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Electrochemical coupling in subnanometer pores/channels for rechargeable batteries

March 2024
Chemical Society Reviews 53(7)

March 2024
53(7)

DOI:10.1039/d3cs01043k

Authors:

Zhao Lingfei

University of Wollongong

Wei-Hong Lai

University of Wollongong

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This review categorizes subnanometer pores/channels (SNPCs) from structural perspective and demonstrates electrochemical couplings in SNPCs for batteries while proposing corresponding challenges and future research directions.

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Cite this: DOI: 10.1039/d3cs01043k

Electrochemical coupling in subnanometer

pores/channels for rechargeable batteries

Yao-Jie Lei,†

Lingfei Zhao, †

Wei-Hong Lai, †

Zefu Huang,

Bing Sun,

Pauline Jaumaux,

Kening Sun,*

Yun-Xiao Wang*

and Guoxiu Wang *

Subnanometer pores/channels (SNPCs) play crucial roles in regulating electrochemical redox reactions

for rechargeable batteries. The delicately designed and tailored porous structure of SNPCs not only

provides ample space for ion storage but also facilitates eﬃcient ion diﬀusion within the electrodes in

batteries, which can greatly improve the electrochemical performance. However, due to current

technological limitations, it is challenging to synthesize and control the quality, storage, and transport of

nanopores at the subnanometer scale, as well as to understand the relationship between SNPCs and

performances. In this review, we systematically classify and summarize materials with SNPCs from a

structural perspective, dividing them into one-dimensional (1D) SNPCs, two-dimensional (2D) SNPCs,

and three-dimensional (3D) SNPCs. We also unveil the unique physicochemical properties of SNPCs and

analyse electrochemical couplings in SNPCs for rechargeable batteries, including cathodes, anodes,

electrolytes, and functional materials. Finally, we discuss the challenges that SNPCs may face in

electrochemical reactions in batteries and propose future research directions.

1. Introduction

The endeavours to achieve high energy density, high power

density, and high cycling stability for various rechargeable

battery systems have been the persistent pursuit of the research

community for decades.

1–4

Among the diverse approaches,

reducing the size of electrode materials with essential phase

engineering for cathodes and morphology design for anodes is

one of the most effective strategies to enhance the electroche-

mical performance of the batteries.

5,6

With the advancement of

systematic characterization techniques for optimal electrode

Centre for Clean Energy Technology, School of Mathematical and Physical

Sciences, Faculty of Science, University of Technology Sydney, Sydney, NSW 2007,

Australia. E-mail: Guoxiu.Wang@uts.edu.au

Institute for Superconducting & Electronic Materials, Australian Institute of

Innovative Materials, University of Wollongong, Innovation Campus, Squires Way,

North Wollongong, NSW 2500, Australia

School of Chemistry and Chemical Engineering, Beijing Institute of Technology,

Beijing 10081, P. R. China. E-mail: sunkn@bit.edu.cn

Institute of Energy Materials Science (IEMS), University of Shanghai for Science

and Technology, 516 Jungong Road, Shanghai, 200093, P. R. China.

E-mail: yunxiaowang@usst.edu.cn

Yao-Jie Lei

Yao-Jie Lei is a Research Associate

working under the supervision of

Prof. Guoxiu Wang at the Centre

for Clean Energy Technology,

University of Technology, Sydney.

He received his bachelor of science

major in chemistry from Lanzhou

University, and research master

degree from the University of

Sydney. He obtained his PhD from

the University of Wollongong. His

research interests include the

synthesis of nanostructured mater-

ials for room-temperature Na–S

batteries.

Lingfei Zhao

Lingfei Zhao is currently an

associate research fellow at the

Institute for Superconducting &

Electronic Materials, University

of Wollongong, where he earned

his PhD in July 2023. His

research interest focuses on

materials design and electrolyte

engineering for high energy

density rechargeable batteries,

including Li/Na-ion batteries

and Li/Na–sulfur batteries.

†These authors contributed equally to this work.

Received 27th November 2023

DOI: 10.1039/d3cs01043k

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materials and in-depth understanding of the electrochemical

mechanisms, the fact that the electrode materials with fine

structures, especially those exhibiting variations at the subnan-

ometer scale, lead to substantial enhancement in electroche-

mical redox processes compared to bulk materials

7–10

drawing attention.

Subnanometer pores/channels (SNPCs) are ubiquitous in

various rechargeable battery systems, yet the vital roles of

SNPCs have long been neglected. Based on the extensive reports

on electrode materials with SNPCs, such as metal oxides, metal

phosphides, metal nitrides/carbides, poly-anionic compounds,

Prussian blue, and carbon materials, the functions of SNPCs

can be summarized as (1) size/channel eﬀects on fast ion

diﬀusion. With shortened ion-diﬀusion length in SNPCs,

fast diﬀusion of ions can be achieved, which is one of the

main indicators for the battery performance i.e., high-rate

capability.

In addition, SNPC-based materials can serve as

artificial protective shelves on the surface of the metal anodes,

which are capable of regulating uniform ion flux and prevent-

ing the side reactions of the metal anodes with the electrolyte

solvents, thus achieving high Coulombic eﬃciency and

dendrite-free stripping/platting processes.

(2) Abundant

active sites for enhanced ion storage kinetics and capacity.

Materials with a larger surface area usually have more active

sites, which can provide more storage sites for ions.

13–15

controlling the size, orderliness, and wettability of SNPCs, the

ion storage performance in batteries can be significantly

improved. For example, modifying the oxygen-containing func-

tional groups in SNPCs can change the surface and bulk

structures, conductivity, wettability, and reaction activity of

the material, thereby improving the electrochemical reaction

kinetics of sodium ion storage.

16,17

(3) Pathway regulation of

redox reactions. The SNPCs could enable selective transport of

various species (ions and/or molecules) through the size effect

of the pore/channel or electrostatic effect of the building

blocks, so as to avoid undesirable side reactions.

For

instance, the small molecule S species (S

2–4

) confined in the

SNPCs of the carbon matrix could achieve solid-state conver-

sion during the charge/discharge process, prohibiting the

formation of soluble polysulfides that lead to parasitic

reactions.

Other than the advantages of SNPCs in perfor-

mance improvement, some key properties of SNPCs and their

underlying relationships with reaction mechanisms are still

unclear and have been barely explored to date.

20–25

These include the synthesis of electrode materials with

uniform SNPCs and maximization of the eﬀective utilization

of SNPCs for ion storage. Understanding the contribution of

SNPCs to ion storage will help us discover electrode materials

with higher capacity and reversibility. In addition, the internal

ion diﬀusion within the SNPCs and the ion diﬀusion from the

interface are the main factors aﬀecting ion kinetics.

26,27

When

the resistance at the interface of two bulk materials signifi-

cantly increases, it can lead to a decrease in electrode potential

and low ion accessible area, especially at high currents, thereby

severely reducing performance. Furthermore, increasing the

thickness or mass loading of the electrodes will also severely

limit ion diﬀusion. Ideally, an eﬃcient SNPC should achieve

fast electrolyte transport through ion diﬀusion and have good

electrolyte accessibility. Also, ions always exhibit close contact

within the SNPCs. In this way, the storage and transport of ions

in individual SNPCs are influenced by collective eﬀects. How-

ever, these eﬀects cannot be described by traditional channel

Yun-Xiao Wang

Yun-Xiao Wang currently holds

the position of Vice Dean at the

Institute of Energy Materials

Science (IEMS), University of

Shanghai for Science and

Technology. She received her

master’s degree from Xiamen

University in 2011 and obtained

her PhD degree from the

University of Wollongong in

2015. She was awarded a

Discovery Early Career

Researcher Award (DECRA) from

the Australian Research Council

in 2017. Her research features elaborate material engineering for

various emerging battery systems and other energy storage

technologies, with a particularly focus on developing room-

temperature sodium–sulfur batteries.

Guoxiu Wang

Guoxiu Wang is the Director of

the Centre for Clean Energy

Technology and a Distinguished

Professor at the University of

Technology Sydney (UTS),

Australia. Professor Wang is an

expert in materials chemistry,

electrochemistry, energy storage

and conversion, and battery

technologies. Currently, he

serves as an Associate Editor for

Electrochemical Energy Reviews

(Springer-Nature), and an

Associate Editor for Energy

Storage Materials (Elsevier). His research interests include

lithium-ion batteries, lithium-air batteries, sodium-ion batteries,

lithium–sulfur batteries, and electrocatalysis for hydrogen produc-

tion. Professor Wang has published more than 700 refereed journal

papers. His publications have attracted over 75 000 citations with

an h-index of 150 (Google Scholar). He has been recognised as a

highly cited researcher in both materials science and chemistry by

Web of Science/Clarivate Analytics.

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theories. Importantly, only by studying the electrochemical

reactions within SNPCs at the atomic scale can these challenges

be fundamentally understood and addressed and their electro-

chemical performance be further improved.

To the best of our knowledge, no review has been reported

yet from the perspective of the electrochemical couplings of

SNPCs in rechargeable batteries. Herein, the SNPC families

have been systematically classified and summarized from the

architecture point of view, i.e., one-dimensional (1D) SNPCs,

two-dimensional (2D) SNPCs, and three-dimensional (3D)

SNPCs. These SNPCs embrace a wide range of materials includ-

ing carbonaceous materials, metal organic frameworks (MOFs),

covalent organic frameworks (COFs), porous organic cages

(POCs), MXenes, layered transition metal dichalcogenides

(TMDs), layered transition metal oxides (TMOs), transition

metal phosphates (TMPs), and various types of cathode materi-

als. Besides, diverse approaches to alter the structure and

building blocks of the SNPCs for anodes, cathodes, electrolytes,

and functional interlayers to enhance the electrochemical

performance of the rechargeable batteries have been intensively

reviewed. Furthermore, the gaps between practical application

and fundamental understanding of SNPCs in rechargeable

batteries have been carefully illustrated, while future research

directions and promising approaches are rationally suggested.

We hope that this review could shed light on the forefront of

this emerging yet underdeveloped field and stimulate further

exploration in this exciting area.

2. Scientific gaps and classifications of

SNPCs

2.1. Scientific gaps for understanding SNPCs in batteries

The last century has witnessed great achievements in manifold

characterization techniques for materials, enhancing the cap-

ability to identify elements, bonds, phase, and morphology of

the samples from micrometer to subnanometer scales. These

powerful tools are indispensable for the development of various

rechargeable batteries, and the progressive understanding of

the working mechanisms inside the batteries. The properties of

the materials can vary significantly with diﬀerent sizes from

micro or nano to atomic scales, for example, the ratio of surface

atoms increases exponentially at subnanometer scales. The

angstrom-scale charge carriers exhibit intimate electrochemis-

try couplings with SNPCs in rechargeable batteries; however,

the capabilities of various characterization techniques to

understand these interactions in batteries at the subnanometer

scale are limited.

Electrochemical studies on SNPCs are expected to overcome

the limitations of previous nanopores and achieve higher

selectivity and electrochemical reaction eﬃciency.

28,29

Although

the application of SNPCs in batteries is still in the early stages,

it is undoubtedly a new topic in the development of next-

generation materials. At the SNPC-level, the operation of the

battery involves ion storage and ion transfer processes. They

typically form atomic and molecular-scale circuits. Exploring

the atomic-level assembly of cathode and anode electrode

materials, electrolytes (solid-state and quasi-solid-state), inter-

mediate layers/isolation layers, and other components from the

perspective of SNPCs to form composite electrode structures

with eﬃcient ionic carriers and both ion and electron conduc-

tivity is of great significance for batteries. This is because the

size, shape, and spatial distribution of each component have a

decisive impact on the ion storage and diﬀusion, thereby

aﬀecting the charge–discharge performance and rate capability

of the battery. As shown in Fig. 1, the research on SNPCs can

effectively upgrade various components of batteries, including

anodes, cathodes, solid-state electrolyte, as well as interlayers/

separators. Optimization of SNPCs can strengthen the interface

stability of anodes, especially for the SEI. An excellent SEI layer

with appropriate SNPCs can selectively transport ions, avoid

excessive SEI formation to reduce electrolyte consumption, and

reduce volume changes during the cycling process. In terms of

insertion-type cathodes, carefully designed SNPC materials can

effectively promote ion diffusion while maintaining material

structure stability, enhancing rate performance; for conversion-

type cathodes, structural stability and reaction kinetics are

crucial performance factors. By improvements in SNPCs, the

Fig. 1 Schematic illustration of the versatile advantages of SNPCs for various battery components.

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active material can be better confined within SNPCs and

accelerate ion diffusion, which not only suppress the ‘‘shuttle

effect’’, but increase kinetic reactions. Moreover, well-designed

SNPCs for solid-state electrolytes can enhance their ionic con-

ductivity, and their strong selectivity advantage can effectively

shield unnecessary ions from passing through, avoiding the

generation of side reactions. Moreover, by leveraging the

advantages of high selectivity and excellent ionic conductivity

of SNPCs, ions can rapidly and orderly diffuse through the

separators/interlayers, avoiding uneven deposition and side

reactions.

However, designing and preparing eﬃcient battery compo-

nent structures are challenging for the following reasons: (1)

there is still insuﬃcient understanding of the dynamic

mechanisms of such complex battery systems; (2) the key ion

storage properties, as well as electronic and ionic transport

properties of many materials have not been determined or

there is uncertainty; and (3) involving multiphase and multi-

scale situations makes the problem more complex. Therefore,

studying batteries from the perspective of SNPCs helps to

comprehensively understand the electrochemical reaction

mechanisms in batteries and achieve high-performance bat-

teries with fast charge–discharge cycles, long life, excellent rate

stability, and high energy/power density. Nevertheless, a sys-

tematic summary of SNPCs and their electrochemical reactions

in batteries has not yet been collected. Therefore, this is the

first review to summarize and report on SNPCs and their

applications in batteries.

2.2. SNPC families

SNPC families represent a wide range of porous or layered

materials with a pore diameter or interlayer spacing of less than

1 nm, including various types of materials such as carbonac-

eous materials, inorganic transition metal compounds, porous

organic materials, and metal–organic materials. The carbonac-

eous materials include carbon nanotubes and layered graphene

analogues such as graphite, graphene oxide, reduced graphene

oxide, graphdiyne, and graphitic carbon nitrides (g-C

Although phosphorene, silicene, and germanene, are not car-

bonaceous materials, they exhibit layer structures and deliver

similar properties to that of graphene and can be reasonably

sorted as GAs.

31,32

Inorganic transition metal compounds

based SNPCs include transition metal oxides phosphates,

dichalcogenides, carbides, and nitrides.

Porous organic

material-based SNPCs include covalent organic frameworks,

porous organic cages, and metal–organic frameworks.

the shape, diameter, and building blocks of the SNPCs have a

crucial influence on the electrochemical performance of the

battery materials, logical classification and detailed discussion

are essentially required. Therefore, we tentatively classify the

SNPCs from the architecture point of view into three categories,

i.e., liner shape one-dimensional (1D) SNPCs, channel shape

two-dimensional (2D) SNPCs, and interconnected three-

dimensional (3D) SNPCs. The typical representatives, distinc-

tive properties, and potential applications of the SNPC families

will be comprehensively illustrated in the following sections.

2.2.1. 1D SNPCs

Carbon nanotubes (CNTs). As presented in Fig. 2, CNTs are

cylinders of one or more layers of graphene with open or closed

ends, which are usually divided into three types according to

the number of the rolling graphitic sheets, i.e., single-walled

CNTs (SWNTs), double-walled CNTs (DWCNTs), and multi-

walled carbon nanotubes (MWNTs).

35,36

Besides, other types

of CNTs with non-perfection structures also deserve wide

attention, since the doped heteroatoms or defective sites in

CNT structures could significantly alter the properties of the

CNTs.

37,38

CNTs can exhibit either metallic or semiconductor

properties, depending on the direction of the graphitic sheets,

Fig. 2 Illustration of representative 1D SNPC materials. (a) Representative materials of CNTs. (b) Representative materials of COFs. (c) Representative

materials of MOFs. (d) Representative materials of TMOs/TMPs.

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e.g. zigzag,

armchair,

or chiral configurations.

SWCNTs

exhibit excellent chemical stability and provide eﬃcient

chemical shielding, which could eﬀectively protect the encap-

sulated species from external influences.

For instance, S has

been confined in the 1D SNPCs of the SWCNTs with a pore

diameter of 0.99 nm, which could facilitate favourable solid-

state reactions in glyme-based electrolytes with inhibited S

dissolution.

Other distinctive properties including good

mechanical stability, excellent electrical conductivity, and tune-

able SNPC size, render them promising as backbones for

various composite materials in battery applications.

Covalent organic frameworks (COFs). COFs are highly crystal-

line, covalently linked, periodically extended organic networks

consisting of only light elements (i.e., H, B, C, N, and O).

They

exhibit high structural, chemical, and thermal stability, as well

as a rich porous structure for a wide variety of applications such

as gas storage, separation, catalysis, and sensors.

45–48

Notably,

there is a growing interest in utilizing COFs in the realm of

electrochemical energy storage, including those with 1D SNPCs

as presented in Fig. 2, such as COF-1, COF-5, COF-6, ACOF-1,

and JUC-505.

The pore size of COFs ranges from subnan-

ometer to nanometer scales, which can be rationally engineered

by altering the building blocks.

50–52

The utilization of COFs

with 1D SNPCs could facilitate fast ionic transport through

SNPCs, while blocking the undesirable species with a diameter

larger than the SNPCs. For instance, a redox-active, crystalline

COF has been reported as a cathode material for LIBs with

excellent rate capability and good cyclability, as a result of

enhanced ion transportation derived from the SNPCs of the

COF structures.

COFs possess distinctive qualities, including

their inherent insolubility in electrolytes, abundant porosity,

ordered open SNPCs that favor ion transportation, and p-

conjugated frameworks that enhance charge transfer.

54–56

Con-

sequently, the prospects of COF-based electrode materials for

rechargeable batteries are undeniably promising.

Metal–organic frameworks (MOFs). MOFs are porous

materials consisting of metal ions or clusters coordinated

with organic ligands, which build up extended crystalline

structures with excellent structural stability upon

intercalation/extraction of guest molecules.

57–59

There are

plenty of MOFs with 1D SNPCs in diverse MOF families,

including ZIF-8, ZIF-69, CPO-27, MIL-53, MOF-74, etc.,as

presented in Fig. 2. In the field of rechargeable batteries, the

SNPCs in MOFs can offer a large surface area and adaptable

pore size, which facilitates quick diffusion of cations.

60–63

These merits make them ideal for intercalation-type

electrodes. Additionally, MOFs with SNPCs possess

confinement effects to effectively trap S species, enabling

their utilization as host materials for conversion-type

electrodes in metal–sulfur batteries. Furthermore, the well-

ordered channels and unique features of MOFs with SNPCs

can enhance the uniformity of cation plating during the

charging and discharging process, which could result in the

formation of a stable interface layer and enhance cycling

stability.

64,65

Consequently, MOFs with SNPCs are also

attractive for applications in solid-state electrolytes (SSEs) and

artificial interfaces. Overall, MOFs with SNPCs have multiple

features that give them enormous potential for various kinds of

batteries.

Transition metal oxides (TMOs) and transition metal phos-

phates (TMPs). Ionic channels are indispensable for various

cathode materials, and the size of these channels falls within

the realm of SNPCs. TMOs and TMPs are among the most

representative cathode materials extensively explored for alkali

metal ion batteries, of which olivine and tunnel structured

cathodes exhibit rich 1D SNPCs.

66,67

As presented in Fig. 2, the

cations of the cathodes are inserted in the 1D SNPCs build by

the M–O (M = transition metals) and/or P–O polyhedrons,

which is the case for LiFePO

, NaFePO

,Na

0.44

MnO

,Li

FeSiO

and KVOPO

. The shape and size of the SNPCs in the cathodes

could be altered using various approaches to modify ion

transportation inside the SNPCs, which will be discussed in

detail in the following sections.

2.1.2. 2D SNPCs. Since the discovery of graphene by Geim

and Novoselov in 2004, 2D materials have surged in various

fields of applications, especially in rechargeable batteries.

68–71

Diverse 2D materials with 2D SNPCs have been successfully

fabricated as promising candidates for rechargeable batteries,

including metal sulfides,

metal oxides,

metal nitrides,

metal carbides,

metallenes,

etc. (Fig. 3) In comparison to

other materials, 2D materials exhibit many unique properties,

such as excellent conductivity, mechanical flexibility, uniform

electronic state and lattice planes, desirable SNPC structures,

etc., making them potential electrode materials for various

rechargeable batteries.

2,77–79

Graphene analogues (GAs). Graphene is the most prestigious

2D material with a single layer of sp

carbon atoms arranged in

a hexagonal lattice structure.

Graphene possesses many

unique properties, including a high surface area, high modulus

of elasticity, good mechanical stability, and excellent electrical

conductivity.

It is worth noting that single-layer graphene is

relatively scarce and diﬃcult to obtain; most of the research has

been carried out on few-layer graphene, which is composed of

several parallel graphene layers with weak interlayer van der

Waals force.

The size of the channel between the graphene

layers falls into the region of SNPCs, which could allow for the

intercalation of various metal ions as well as solvents. For

example, graphene oxide laminates were fabricated by Abra-

ham et al., which exhibit distinctive SNPCs with well-defined

interlayer spacing ranging from 6.4 to 9.8 Å for ion

intercalation.

On the other hand, generating defects in the

graphene layers (holey graphene) could facilitate ion transport

across the graphene layers. For instance, holey graphene with

SNPCs of 0.5 to 0.8 nm have been produced through high-

temperature etching,

and ion permeable SNPCs can be engi-

neered on the graphene layer through plasma etching.

Soon

after the discovery of graphene, the exploration of 2D materials

has been extended to a wide variety of other graphene

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analogues (GAs) with similar 2D layered structures but diﬀerent

chemical compositions, including graphene oxide (GO),

reduced graphene oxide (RGO), graphdiyne, silicene, germa-

nene, g-C

,etc. These GAs with distinctive 2D layered struc-

tures and rich SNPCs have been widely used in various

applications including catalysis, superconductors, sensors, as

well as energy storage and conversion devices including various

batteries.

MXenes. MXenes stand for a wide variety of 2D metal

carbides, nitrides, or carbonitrides with an odd number of

layers in which the metal layers (M) are sandwiched between

carbon or nitrogen (X) layers.

Since its first discovery by Yury

et al. in 2011, their unique features, including electrical con-

ductivity, mechanical stability, and thermal stability, render

them promising for various applications in supercapacitors,

batteries, supercapacitors, catalysis, membranes, and

sensors.

Mxenes exhibit the general formula of M

n+1

where M is the metal, X represents C or N, and T refers to the

terminal groups such as –H, –F, and –OH, which are obtained

by selectively etching the A layer (usually the Al layer) from

pristine MAX precursors. After ten years of development,

MXenes have been extended from Ti

to a large family of

metal carbides/nitrides with metals such as Ti, Sc, Zr, Hf, V, Nv,

Ta, Mo, Cr, Nb, or Ta.

6,86

The interlayer space of MXenes ranges

from about 3.5–5 Å, making them suitable SNPCs for Li and Na

ions storage.

6,88,89

Besides, enriched functional groups in the

SNPCs of MXenes could efficiently trap polysulfides, thereby

inhibiting the shuttle effect in metal–S batteries.

90–92

MXenes

have shown great potential in various applications when

coupled with a diverse range of other materials.

Transition metal dichalcogenides (TMDs). TMDs are layered

materials with a general chemical formula of MX

, where M

stands for transitional metals and X represents chalcogen

elements of S, Se, or Te.

93–95

The properties of TMDs can be

varied from insulators (HfS

) to semiconductors (MoS

and

), semimetals (WTe

and TiSe

), and metallic (NbS

and

VSe

), rendering them capable for a variety of applications.

TMDs always feature multi-crystalline structures.

Taking

MoS

as an example, it has three crystal structures, namely,

2H (hexagonal), 1T (trigonal), and 3R (rhombohedral), each

characterized by distinctive coordination models and staking

orders. Different from graphene, 2D TMDs can expose more

active sites, further improving the electrochemical performance

of TMDs.

74,98,99

In addition, the interlayer spacing of 2D TMDs

at the subnanometer level has strong covalent bonds within the

layer and weak van der Waals forces between layers, providing

an ideal space for intercalation of ions with small ionic radius,

such as Li or Na ions.

2,100–102

Layered TMOs. Due to high structural stability, low material

cost, large specific capacity, high ionic conductivity, good

environmental benignity, and feasible synthesis conditions,

layered TMOs have been developed as one of the most popular

candidates of cathodes for LIBs and SIBs.

103–106

Generally, the

structure of layered TMOs consists of alternating MeO

octahe-

dra layers and alkali metal layers, which can be sorted as O- or

P-type depending on the coordination environment of the alkali

metal ions.

107,108

The interlayer spacings of layered TMOs are

in the range of SNPCs, facilitating quick 2D ion transportation

through the SNPCs and resulting in excellent rate capabilities.

2.1.3. 3D SNPCs

MOFs. 1D SNPCs are ubiquitous in various MOFs. For MOFs

with 1D SNPCs at intersecting directions, 1D SNPCs would

interconnect with each other to generate 3D SNPCs.

109

For

instance, as illustrated in Fig. 4, Prussian blue analogues

(PBAs), one of the earliest discovered MOF materials, exhibit

1D SNPCs at three intersecting directions, generating a 3D

Fig. 3 Illustration of representative 2D SNPC materials. (a) Representative materials of GAs. (b) Representative materials of MXenes. (c) Representative

materials of TMDs. (d) Representative materials of TMOs.

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SNPC network.

110

These PBAs with 3D SNPCs can facilitate

quick diﬀusion of metal ions, together with abundant redox-

active sites and good structural stability, making them an ideal

choice for alkali metal ion batteries. Similarly, other MOFs with

3D SNPCs, such as MIL-125, UIO-66, MOF-177, and HKUST-1,

have also been widely used in various battery systems.

111–113

The advantages of utilizing these MOFs with 3D SNPCs for

batteries will be discussed in detail in the following sections.

COFs. Similar to MOFs with 3D SNPCs, the interconnection

of 1D SNPCs in the COFs results in 3D SNPCs. The COFs with

3D SNPCs exhibit not only cross-linked 3D electrically conduc-

tive frameworks but also interconnected 3D ion permeable

pathways. Therefore, they are promising candidates for active

materials or coating layers in various battery systems.

114–116

Those frequently reported COFs with 3D SNPCs including

COF-102, COF-105, COF-108, COF-300, CTF-1, etc.

117

Porous organic cages (POCs). POCs are a series of micro-

porous organic molecules with intrinsic, guest accessible

cages.

118

They are built through covalent bonds involving

non-metal elements, such as carbon–carbon or carbon-

heteroatoms, imines, boronic esters, amides, etc. Compared

to other porous frameworks, POCs exhibit many merits includ-

ing large surface areas, pore volumes as well as open and

flexible pores, including tuneable SNPCs.

28,119,120

In addition,

their discrete molecular structure provides excellent solubility

in common solvents with high solution dispersion and proces-

sability, which is a rare feature that cannot be achieved in

insoluble extended porous frameworks such as MOFs and

COFs.

121,122

A wide variety of POCs including CPOC-102,

CPOC-104, CPOC-302, RCC1, and CC-8 have been used in

various battery systems, whose functions and advantages would

be detailed in the following sections.

122,123

TMOs and TMPs. Besides, 1D and 2D SNPCs in olivine and

layered type cathodes, 3D SNPCs have also been extensively

reported in various cathodes such as Na

(PO

)

, which has

been widely known as a NASICON (sodium super ionic con-

ductor) type cathode. These NASICON cathodes generally

undergo topotactic insertion/extraction Na

with small volume

changes and minimal structural rearrangements, featuring

outstanding long-term cycling stability.

124,125

Plenty of cathode

materials with 3D SNPCs have been widely investigated to

exhibit high ionic conductivity in the cathode matrix, which

favours high rate performance of the cathodes. Various other

cathode materials with 3D SNPCs, such as LiMn

and

FeP

126

will also be discussed in the following sections.

It should be noted that simply utilizing one kind of porous

material is not the case in most scenarios; instead, hetero-

structures or composite materials that merge the merits

of various components have been frequently reported.

127–129

In particular, the built-in electric field at the heterostructure

interface can promote rapid transport of ions and

electrons.

130,131

Heterostructures composed of adsorption com-

ponents and catalytic components can combine two functions

to achieve synergetic effects.

132,133

For instance, higher energy

density can be achieved in cathode materials by carbon-coating

with three-dimensional sodium diffusion channels.

134

rational designs of heterostructures and hybrid materials will

be illustrated in detail in the following discussions.

2.3. Unique physicochemical properties of SNPCs

As the size of the pore/channel decreases to the subnanometer

level, which is within the scale range for molecules, ions, and

atoms, unique physicochemical properties diﬀering from those

of the bulk materials would emerge.

29,135,136

Some extraordin-

ary properties that are impossible in the view of classic physics

would take place, which makes SNPCs a totally new world of

Fig. 4 Illustration of representative 2D SNPC materials. (a) Representative structures of MOFs. (b) Representative structures of COFs. (c) Representative

structures of POCs. (d) Representative structures of TMOs/TMPs.

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exciting wonders. Generally, the ionic conductivity could be

defined as:

k¼GL

S(1)

where Gis the conductance of an ionic channel, Sis its cross-

sectional area and Lis the length. But in fact, the ionic

conductivity of nanochannels is quite complex. The diﬀusion

of monovalent ions confined within a pore with a width like the

ion diameter can be expressed as:

J¼DrrDrGrCDr

rmax rS

rrS (2)

where Dis the diﬀusion coeﬃcient of the ion (for simplicity, we

will use the same D=D



), r



represents the ion density, c=r



represents the charge (in units of the elementary charge),

and r

represents the total ion density. Additionally, r

max

is the

total ion density at close packing. Gis a parameter that

characterizes the screening of ion–ion electrostatic interac-

tions. To realize G, first, we need to consider the exponential

screening of ion–ion electrostatic interactions caused by the

pores. In addition, we adopt the Borukhov–Andelman–Orland

entropy, S[r



137

The voltage-dependent ‘‘external field’’

includes the electrochemical potential of ions, solvation energy,

and van der Waals and image forces between ions and pore

walls. The voltage-dependent ‘‘external field’’ is composed of

the electrochemical potential of ions, solvation energy, and van

der Waals and image forces between ions and pore walls. The

external field controls the equilibrium ion density inside the

pore, and besides participating in dynamics through initial and

boundary conditions, it does not participate in other processes.

Dynamics is defined by the equations of continuity: q



q



=Gr



(dF/r



), where GG



Tis a

phenomenological mobility parameter, Dis the diffusion con-

stant, and we assume it is independent of pore width, voltage,

and density; k

is the Boltzmann constant. Thus, plugging the

free energy Finto the continuity equation yields eqn (2),

138

G¼4LBRCSðsin pn=2Þ2

nK1pnRC=LðÞ (3)

From eqn (3), it can be determined that Gis constrained by

many factors, including ion density, charge within the channel,

electrostatic forces, gradient of ion density along the pore,

collective properties, etc. By changing the above parameters,

selective transportation of specific ions can be achieved. Addi-

tionally, confining restricted species at the molecular scale with

distinctly diﬀerent properties is another appealing feature. For

battery couplings, SNPCs also possess unique properties, which

can be reasonably classified into six categories size eﬀect,

electrostatic eﬀect, confinements eﬀect, suppression eﬀect,

buﬀering eﬀect, and quantum eﬀect (Fig. 5).

Size eﬀect. The size eﬀect plays an important role in mass

transfer. Due to the small size of SNPCs, smaller ions can be

allowed to diﬀuse from one side to the other side while ions

with larger size will be inhibited from entering the SNPCs. This

function has been widely used in rechargeable batteries, for

example, artificial SEIs with abundant ion diﬀusion channels

have been designed, which often only allow smaller ions such

as Li

,Na

,etc. to pass through while inhibiting the passage

of other larger ions.

139–142

This is beneficial for supporting high

ion flux for homogeneous metal stripping/plating, and also

helps to avoid adverse reactions between larger solvent mole-

cules and ions which are in directly contact with the electrode.

Therefore, by adjusting and improving the specific SNPCs of

the materials, potential barriers to mass transfer and storage

can be reduced.

Electrostatic eﬀect. Mass transport of various species

through the SNPCs via diﬀusion or advection caused by ther-

mal motion or electric force is essential for electrical chemical

reactions in the batteries; one of the most important factors

impacting the mass transport is the electrostatic eﬀect.

143–145

The electrostatic effect of SNPCs can be easily conceived, as the

building blocks would attract species with opposite charges

while repelling those with the same charges.

146–148

It should be

noted that the electrostatic effect of SNPCs is generally induced

by partial charges caused by the asymmetric distribution of

electrons in the chemical bonds, rather than bare charge which

tends to be unstable. For instance, Lewis acidic sites in the

SNPCs of COFs and MOFs can complex with anions in the

electrolyte, which is beneficial for the quick transport of

cations.

149

The surface of graphene oxide (GO) membranes

with SNPCs can be engineered with positive or negative

charges, which can repel ions with same charges while allowing

the transmission of ions with opposite charges.

150

Therefore,

the building blocks of the SNPCs can be rationally designed to

achieve selective ion transportation through electrostatic

effects to screen ions with opposite charges.

Confinements eﬀect. Physical confinement is essential for

electrode materials that have poor electric conductivity or

exhibit undesirable side reactions with the electrolytes, which

is essential for sulfur (S) cathodes since they exhibit both these

problems.

151,152

Whereas the confinement eﬀect of SNPCs for S

cathodes is significantly diﬀerent from that in the larger pores,

where the S molecules are reduced to short chain small

molecules (S

2–4

) instead of long chain S

4–8

species. For example,

Wan et al. demonstrated that S

2–4

molecules can be accommo-

dated in conductive carbon matrix with SNPCs (B0.5 nm),

instead of cyclo-S

which exhibits a size larger than 0.5 nm in

at least two dimensions.

153

As such, the formation and dissolu-

tion of long chain polysulfides can be avoided, so as to achieve

good cycling stability and superior rate capability. Furthermore,

it has been evidenced that S encapsulated in the narrow-

diameter SWCNTs with SNPCs undergoes solid-state reactions,

since the Li ions are de-solvated before they enter the SWCNTs

as a result of the confinement effect of SNPCs.

Similarly, the

confinement effect of SNPCs can be extended to other electrode

materials to prevent them from side reactions with electrolytes.

Suppression eﬀect. SNPCs often exhibit suppression eﬀects

as a result of their good mass transport ability and mechanical

stability, which could allow for ions uniformly transmit

through the SNPCs while suppressing short circuits caused by

dendrite propagation. This property has been widely applied in

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various battery systems. For example, common SPEs (such as

PEO) are diﬃcult to eﬀectively suppress lithium dendrites due

to their low mechanical strength, which can easily lead to

battery failure due to short circuits. However, adding ceramic

fillers (such as LLZAO) with rich SNPC structures and good

mechanical properties to polymer electrolytes can not only

increase the ion transport pathways and boost the speed of

ion migration, but also eﬀectively increase the mechanical

strength of the electrolyte which is beneficial for suppressing

lithium dendrites.

154,155

Buﬀer eﬀect. When the dimensions of the material (such as

the aperture or thickness) are close to the size of a single crystal

cell, nanoscale materials exhibit some polymer-like properties

due to their similarity in size to polymer chains. When the

material dimensions are larger than the nanoscale, they are

typically rigid and linear, but when the dimensions are close to

or smaller than the nanoscale, they become flexible or curved,

like polymer chains.

156,157

In the diﬀusion process of ions, the

conformation of SNPCs changes under shear stress, resulting in

shear stress being disproportionate to shear rate and exhibiting

a good buﬀering eﬀect. For instance, a block polymer was

designed as an interlayer to buﬀer tbe cathode volume change

during discharging and charging processes.

158

Therefore, this

characteristic can be applied to non-viscous electrodes and

solid-state electrolytes in batteries to achieve good mechanical

performance, prevent material fracture and resist volume

expansion eﬀects.

158,159

Quantum eﬀect. The quantum eﬀect refers to a series of

distinctive phenomena observed when the size of transported

particle is close to the Ångstrom scale range, which follow the

rules of quantum mechanics and cannot be explained by

classical physics. From the perspective of classical thermody-

namics, the chemical selectivity mass transfer through nano-

scale channels should be very slow: this limitation is predicted

by the Hagen–Poiseuille equation, as the traditional laminar

flow has zero flow velocity at the pore wall.

160

One of the

quantum effects is tunnelling, which refers to the penetration

of a particle getting through an energy barrier that is higher

than the particle’s kinetic energy.

161,162

The principle of tunnel-

ling has led to the development of the scanning tunnelling

microscope (STM), which has significantly advanced scientific

research to atomic scale resolution.

163

Another quantum effect

for SNPCs is quantum confinement, where the movement of

particles will be restricted within the SNPCs, leading to the

existence of particles only in the form of quantum states when

the size of particles approaches the size of the SNPCs. For

Fig. 5 Schematic illustration of the unique physicochemical properties of SNPCs.

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instance, quantum confinement occurs between the interlayer

space of van der Waals channels.

164

In terms of ions diffusion

in SNPCs, however, the rapid ion transport is precisely caused

by quantum flow, resulting in superfast ion fluid states. A

quantum ions fluid can orderly arrange ions, greatly reducing

the ion diffusion energy barrier and achieving highly efficient

and selective ion diffusion.

3. Electrochemical couplings in SNPCs

As mentioned above, electrochemical coupling of SNPCs in

batteries is ubiquitous. To understand the relationship

between SNPCs and the electrochemical performance, we have

summarized the size of SNPCs and various other electrochemi-

cal parameters in batteries (Tables 1–4). We have tentatively

sorted the specific capacities (for cathodes and anodes) and the

ionic conductivities (for electrolytes and separators/interlayers)

according to the size of the SNPCs, to understand the influence

of SNPCs on the electrochemical performance of the batteries.

As shown in Fig. 6a, capacities of transition metal oxides,

polyanions, PBAs, and polymers exhibit not directly relation-

ship with SNPC size. The possible reason is that these materials

have enough pores to provide ion diffusion and storage, and

the reaction kinetics are all not slow. Instead, their perfor-

mance is more likely to be influenced by electro-conductivity

rather than ionic conductivity. Nevertheless, it is obvious that

with the increase in pore size of S/Se cathodes and COFs

(Fig. 6b), the performance significantly decreases. This

indicates that the reaction kinetics are one of the key factors

determining their capacities. As for the anodic materials in

Fig. 6c, the pore size of phosphides, sulfides, and polymers,

does not directly affect their ion storage. However, for MXenes,

graphite-based materials, and hard carbons shown in Fig. 6d,

the size of the pores is closely related to ion storage. For

MXenes, increasing the size of the pores will lead to a decrease

in ion storage performance, while for graphite-based materials

and hard carbons, the capacity will increase with the increase

in pore size. This indicates that the regulation of the pore size

will affect the ion storage capacity of these carbon-based anodic

materials. For solid-state electrolytes and quasi-solid-state elec-

trolytes, it is commonly known that ionic conductivity can

impact their performance. According to Fig. 3e, however, the

ionic conductivity of some materials does not show a linear

relationship with SNPC size. It may be because when polymers

and MOFs are used as electrolytes, they are usually modified. As

described in eqn (3), changing their electrostatic force, ion

concentration difference, and other conditions can greatly alter

the ion conductivity. Therefore, these materials do not exhibit a

linear relationship with size of SNPCs. However, for some

materials that are difficult to modify, such as NASICONs and

sulfides, their ionic conductivity exhibit a linear relationship

with SNPC size. Thus, as the pore size increases, the ion

conductivity also increases in Fig. 6f. For interlayer/separators,

their research mainly focuses on polymers, oxides, and MOFs.

As illustrated in Fig. 6g, there is no clear correlation between

the ionic conductivity and SNPC size. Nonetheless, it is obvious

that the ionic conductivity of MOFs is affected by the size

of SNPC.

The analysis of Fig. 6 shows that the determining factors of

battery performance are not only the reaction kinetics but also

the redox reaction activity and electronic conductivity of the

materials. Ion diﬀusion is influenced by various factors, which

can alter its kinetic activity and result in diﬀerences in battery

performance. To help readers better understand the main role

of SNPCs in rechargeable batteries, we have compiled and

summarized some representative studies.

3.1. Electrochemical couplings of cathode materials with

SNPCs

During the electrochemical reactions of rechargeable batteries,

the cathode materials coupling with SNPCs serve as the hosts

for cations. The redox reactions during charging and dischar-

ging processes always cause expansion and contraction of

cathode materials, leading to undesired structure distortion,

capacity fading, or even battery failure. The design of SNPCs in

cathode materials can eﬀectively facilitate ion diﬀusion and

buﬀer volume changes, ensuring stable performance in

rechargeable batteries. In this section, we outline the develop-

ment and achievement of SNPC design in cathode materials,

including intercalation-type and conversion-type materials

(Fig. 7).

3.1.1. Intercalation-type cathode materials

3.1.1.1. Tuning SNPCs in layered oxide cathodes. Layered

oxides with SNPCs, which have the chemical formula AMO

(A normally represents Li, Na, K, etc.; M represents transition

metals), are the most popular and well-developed cathode

materials under massive production in the current battery

industry.

543

The first commercial intercalation-type layered

oxide cathode material (LiCoO

) with SNPCs was introduced

by Goodenough et al. This cathode material attracted global

attention due to its high specific capacity (B140 mA h g

1

) and

super high working voltage in organic electrolytes, as well as its

excellent SNPC structure for excellent reversible Li

insertion

and extraction.

544,545

Due to the high cost and geographic

distribution issues of cobalt resources, many alternative layered

oxides with abundant and low-cost transition metals, such as

Ni, Mn, and Fe, were developed to form the layered LiMO

structure.

546–548

Moreover, Li was also replaced with Na or K to

form layered NaMO

and KMO

, which further reduces the

cathode cost.

549,550

However, with the decrease in the cost, the

challenges that affect the structure stabilities, energy density

and cycling performances of layered oxide cathode materials

have become more prominent.

551

The electrochemical energy storage mechanisms of the

layered oxides exploit the SNPCs (B0.4 to 0.7 nm) between

the adjacent MO

layers with edge-shared octahedral structures

to allow the ‘A’ ion insertion/extraction during the cycling

(Fig. 8a).

552–555

This mechanism inevitably subjects the MO

layers to structural distortion during repeated cation insertion/

extraction for long-term cycling, leading to structure degrada-

tion and capacity fading. To maintain the performance of

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Table 1 Summary of the cathode materials with SNPCs (theoretical = T)

Materials Battery types

Theoretical

capacity

(mA h g

1

)SNPC

size (nm) Average

potential (V)

Capacity (mA h g

1

current density (mA g

1

cycle number Ref.

LiCoO

LIBs 274 — 4 123@50@10 165

Oxygen vacancy-Li[Ni

0.2

0.6

LIBs 315 — 3.8 121@60@10

Oxygen vacancy-Li

MnO

LIBs 230 — 2.8 59.5@10@50 166

LiCoO

LIBs 274 — 4 116@100@20 167, 168

LiNi

0.8

0.1

LIBs 190 — — 210@100@50 169

LiNi

0.8

0.15

0.05

LIBs 180 0.47 3.8 170@180@100 170

LiNiO

LIBs 275 — 3.8–3.9 140@275@100 171

LiNi

0.9

0.1x

0.03

LIBs 275 — 3.8–3.9 180@275@50

LiNi

0.9

0.08

0.02

LIBs 275 — 3.8–3.9 120@275@50

LiNi

0.9

0.06

0.04

LIBs 275 — 3.8–3.9 190@275@50

MnO

LIBs 458 0.47 4 140@45@20@10 172, 173

LiNi

0.8

0.15

0.05

LIBs 279 0.47 3.8 155@280@100 174

LiNi

0.6

0.2

LIBs 279 — 3.6 170@280@100 175

1.2

0.54

0.13

LIBs 378 — 3.6 177@280@200 176

1.13

0.30

0.57

LIBs 343 0.79 3.0 85@340@500 177

1.2

0.17

0.56

0.07

O LIBs 465 — 3.8 172@1400@200 178

LiNi

1y

LIBs 276 — 3.7 148.4@27@20 179

LiNi

1x

LIBs 276 — 3.8 175@137@50 180

12x

0.85

0.15

LIBs 180 — — — 181

LiNi

1/3

LIBs 279 — 3.8 186@28@50 175

LiNi

0.7

0.3–x

LIBs 160 — — — 182

LiNi

LIBs 200 0.47 3.8 187@100@100 183

Z-doped LiNi

0.6

0.2

LIBs 160 — 3.8 130@53.3@50 184

F-LNCM LIBs 200 0.55 3.75 153.4@200@200 185

5%P@LLO LIBs 250 — 3.5 200@250@100 186

B@LNMO LIBs 200 0.48 3.6 200@100@300 187

LiNi

0.6

0.2

LIBs 180 0.47 3.8 141@180@200 188

LiNi

0.8

0.15

0.05

LIBs 180 — 3.8 140@36@1500 189

LiNi

0.7

0.15

LIBs 180 — 3.8 130@36@1500

Mo-doped LiNi

0.5

LIBs 180 0.47 3.8 105@50@100 190

Nb modified NCM811 LIBs 200 0.47 3.8 182@66@250 191

LiNi

0.6

0.2

LIBs 180 0.47 3.9 183.3@180@80 192

Ni-rich LiNi

0.8

0.1

LIBs 180 0.47 3.8 178@180@100 193

Ti-doped Ni-rich LiNi

0.8

0.1

LIBs 180 0.47 3.8 130@180@150 194

Ni-rich LiNi

1xy

LIBs 190 — 3.8 140@62.7@600 195

LiCoMnO

LIBs 145 — 4.8 85@14@50 196

LiFe

0.5

1.5

LIBs 147 — 4.2 80@14@50 197

LiFe

0.1

1.9

LIBs 147 — 89@14@50

LiFe

0.3

1.7

LIBs 147 — 70@14@50

LiCu

0.5

1.5

LIBs 145 — 2.6 47@14@14 198

LiNi

0.25

1.5

LIBs 145 — 2.2 57@14@8

LiNi

0.5

1.5

LIBs 145 — 2.7 48@14@20

NaFeO

SIBs 241.8 0.53 2.8 48@200@100 199

NaNi

0.5

/Super P SIBs 240 0.51 2.8 142@12@100 200

NaNi

0.5

/CNT SIBs 240 0.51 2.8 127@12@100

NaNi

0.5

SIBs 240 0.54 2.9 74@240@200 201

2/3

1/3

2/3

SIBs 173 — 3.2 52@346@500 106

3/4

(Li

1/4

3/4

SIBs 291 — 2.6 112@150@100 108

NaNi

0.5

0.2

0.3

SIBs 240 0.54 3.0 93@240@200 201

NaLi

0.1

0.35

0.55

SIBs 268 — 3.1 110@12@100 202

1.2

0.4

SIBs 203 — 2.5 68@20@50 203

NaFe

0.55

0.45

SIBs — 0.55 3.2 32@240@100 204

0.75

0.82

0.12

0.06

SIBs 200 0.55 2.8 80@200@400 205

0.9

0.05

1/3

SIBs 130 — 3.0 102@130@200 206

Na[Li

0.05

(Ni

0.25

0.5

)

0.95

SIBs 170 — 3.4 120@85@40 207

0.85

0.10

0.175

0.525

0.2

SIBs 150 — 3.5 115@150@140 208

Na[NiCoMnTi]

1/4

SIBs 120 0.54 3.0 78@600@400 209

NaMn

0.48

0.2

0.3

0.02

SIBs 240 — 3.0 100@24@100 210

NaCr

1/3

SIBs 200 — 2.7 102@5@12 211

Na[Cu

0.22

0.30

0.48

SIBs 240 — 3.3 100@10@100 212

TiS

LIBs 239 0.57 2.25 200@240@100 213

0.3

MnO

PIBs 82 0.62 2.8 74@28@50 214

0.6

CoO

PIBs 80 — 2.5 44@100@120 215

0.7

0.5

PIBs 164 0.69 2.0 70@500@200 216

0.7

0.5

SIBs 182 0.56 — 68@500@100 211

0.7

0.5

LIBs 204 0.47 — 20@500@100

0.7

CoO

SIBs 175 0.54 2.6 60@30@40 217, 218

100@175@100

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Table 1 (continued )

Materials Battery types

Theoretical

capacity

(mA h g

1

)SNPC

size (nm) Average

potential (V)

Capacity (mA h g

1

current density (mA g

1

cycle number Ref.

NaNiO

SIBs 237 0.53 2.9 100@23.7@20 219

NaFeO

SIBs 244 0.56 3.2 68@12@30 220

NaCrO

SIBs 253 0.53 3.0 121@126@300 221

NaVO

SIBs 255 0.58 1.6 120@52@15 222

0.7

SIBs 190 0.58 1.6 100@38@10

NaNi

0.5

SIBs 240 0.56 3.5 138@24@12 223

0.9

0.1

SIBs 220 — 2.75 60@1100@500 224

2/3

[Mg

0.28

0.72

SIBs 190 — 2.9 83@38@150 225

0.6

[Cr

0.6

0.4

SIBs 167 — 3.6 75@16.7@200 226

0.80

0.12

0.22

0.66

SIBs 214 — 3.4 115@21.4@200 227

0.70

0.60

0.30

0.10

SIBs 179 — 3.5 125@90@10 228

0.41

CoO

PIBs 103 0.56 3.0 56@18@30 229

0.45

MnO

PIBs 116 0.5 2.7 66@20@100 230

0.28

MnO

0.15H

O PIBs 77 — 2.5 71.5@20@100

KCrO

PIBs 218 0.59 2.5 60@10@100 231

0.5

PIBs 67 0.6 2.7 70@20@80 232

0.45

0.5

PIBs 114 — 2.3 47@500@500 233

0.65

0.5

PIBs 154 — 2.2 55@100@350 234

0.44

0.22

0.78

PIBs 112 — 2.4 52@200@500 235

0.67

MnO

PIBs 237 0.61 2.6 78@50@300 236

1.39

PIBs 118 — 2.6 80@50@50 237

0.67

MnO

PIBs 159 0.64 2.5 40@200@400 238

0.5

MnO

PIBs 125 0.64 2.5 40@200@400

KCrO

PIBs 218 — 2.5 60@10@100 231

0.77

MnO

PIBs 176 — — —

0.32

MnO

PIBs 86 — — —

0.6

CoO

PIBs 141 — 2.5 65@100@300 232

KCrS

PIBs 173 — 2.4 60.5@35@300 239

0.69

CrO

PIBs 167 0.68 2.6 74@100@300 240

0.8

CrO

PIBs 186 — 2.5 50@186@300 241

KVO PIBs 253 0.52 2.5 87@10 mA g@50 242

0.5

PIBs 67 1.0 3.2 79.2@100 mA g@100 243

PIBs 149 0.53 1.75 60@20 mA g@200 244

0.83

PIBs 104 — 2.5 54@100 mA g@200 245

0.48

0.4

0.6

PIBs 119 0.5 2.5 27@12@180 246

0.45

0.9

0.1

PIBs 119 — 2.4 20@20@100 247

0.7

0.3

PIBs 179 — 2.75 83.4@100@400 248

2/3

[Ni

1/3

2/3

PIBs 155 — 3.0 74@85@200 249

0.83

[Ni

0.05

0.95

PIBs 187 0.64 3.0 120@52@200 250

0.67

0.83

0.17

PIBs 158 — 2.1 52@500@200 251

0.45

0.5

PIBs 113 — 2.3 82@50@50 252

0.67

0.17

0.66

PIBs 157 — 2.9 76@20@100 253

LiFePO

-with Na doping LIBs 170 1.0 3.45 136@1700@3000 254

LiFePO

-with Ni doping LIBs 170 1.0 3.4 150@1700@5000 255

Cl-doped LiFePO

LIBs 170 1.2 — 105@1700@500 256

Nb-doping LIBs 170 — 3.4 114.3@1700@300 257

LiMnPO

LIBs 170 0.52 4.1 80@170@500 258

LiMn

1x

LIBs 171 0.52 3.8 160@17@50 259

0.92

0.8

0.2

LIBs 154.1 0.52 4.8 121@15@500 260

LiCoPO

LIBs 167.5 0.51 4.8 60@84@140 261

LiNiPO

LIBs 167.5 0.55 — — 262

LiNi

0.5

LIBs 160 — — —

(PO

)

LIBs 197 0.51 3.9 57@133@1000 263

MnP

LIBs 110 0.44 4.7 (T) — 264

NiPO

F LIBs 143 0.44 — — 265

CoPO

F LIBs 143 0.44 — — 266

LiCuSO

F LIBs 145 0.50 5.1 (T) — 267

LiCoSO

F LIBs 149 0.56 4.7 (T) — 268

LiNiSO

F LIBs 149 0.54 5.2 (T)—

LiNiOSO

LIBs 152 — 5.0 (T) — 269

LiCoOSO

LIBs 152 — 5.1 (T)—

NiOSO

LIBs 152 — 5.0 (T)—

LiNi

0.5

1.5

LIBs 147 — 4.7 110@140@200 270

LiNiPO

LIBs 167.5 0.55 5.1 110@167@100 271

LiNi

0.5

LIBs 167.5 0.55 —

CoPO

F LIBs 287 0.47 4.8 50@2870@50 272

LiNiSO

F LIBs 148 0.54 — —

(PO

)

LIBs 132 0.62 4 90@66@40 273

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Table 1 (continued )

Materials Battery types

Theoretical

capacity

(mA h g

1

)SNPC

size (nm) Average

potential (V)

Capacity (mA h g

1

current density (mA g

1

cycle number Ref.

Na-deficient LIBs 117 — 3.0 65@110@1000 274

3.32

2.11

0.23

)

Na deficient LIBs 194 — 2.8 106@550@300 275

3.41

0.59

FeV(PO

)

NaFePO

SIBs 154 — 2.7 110@30@50 276

NaFePO

SIBs 154 0.38 2.3 140@20@300 277

a-FePO

SIBs 178 — 2.3 54@50@300 278

VOPO

SIBs 117 0.6 3.5 100@16.5@250 279

NaVOPO

SIBs 145 0.51 3.5 75@72@1000 280

V(PO

)

SIBs 173 0.69 3.25 70@173200 281

(PO

)

SIBs 117 0.52 3.25 48@118@5000 282

(PO

)

SIBs 117 0.54 3.3 30@4680@30000

(PO

)

SIBs 115 0.58 2.8 96@115@200 283

(PO

)

SIBs 117 0.63 4.5 5@60@20 284

TiV(PO

)

SIBs 178 — 2.2 73@1250@500 285

FeV(PO

)

SIBs 111 — 2.6 100@110@1000 286

MnV(PO

)

SIBs 111 — 3.4 90@110@1000 286

MnZr(PO

)

SIBs 107 0.64 3.5 92@50@500 287

MnTi(PO4)

SIBs 177 0.63 2.4 82@3500@3500 288

MnP

SIBs 195 0.62 3.0 90@39@30 289

CoP

SIBs 96.1 0.51 2.6 85@5@10 290

3.12

2.44

)

SIBs 110 — 3.0 92@220@80 291

)

SIBs 80 — 4.0 52.5@80@600 292

t-Na

(VO)P

SIBs 93.4 0.5 3.5 66@4.6@10 293

NaVP

SIBs 108 — 3.7 30@5.4@20 294

(PO

)

) SIBs 127 — 4.5 70@12.7@100 295

(PO

)

) SIBs 129 — 4.6 100@10@10 296

)

SIBs 92.8 — 3.8 81.4@46@300 297

NaVPO

F SIBs 143 0.55 3.5 101@286@1000 298

(PO

)

F SIBs 130 — 3.7 102@2600@2000 299

FePO

F SIBs 124 3.25 — — 300

CoPO

F SIBs 122 0.59 4.3 40@61@20 301

(SO

)

SIBs 118 — 3.5 80@12@50 302

Fe(SO

)22H

O SIBs 118 — 3.2 61@12@20 303

(SO

)

SIBs 120 — 3.7 97@24@300 304

2.5

1.75

(SO

)

SIBs 106 — 3.6 90@106@200 305

(SO

)

SIBs 120 — 3.7 87.1@240@1000 306

NaFe(SO

)

SIBs 99 0.64 3.0 78@20@80 307

MnSiO

SIBs 278 — 3.0 140@278@500 308

FeSiO

SIBs 276 — 2.4 88@70@200 309

CoSiO

SIBs 272 0.47 3.3 105@5@25 310

(PO

)

) SIBs 129 — 3.1 65@2600@4400 311

(SO

)

SIBs 120 — 3.5 70@60@100 302

KTi

(PO4)

PIBs 64 0.62 1.7 80@32@100 312

KFeSO

F PIBs 255 0.5 3.6 52@20@100 313

(PO

)

PIBs 106 0.47 3.6 50@20@100 314

(PO

)

PIBs 115 0.58 3.75 59@10@50 315

KVOPO

PIBs 133 0.55 3.7 104@66@100 316

[Fe(CN)

]

5.89H

O LIBs 125 1.03 3.0 68@100@10 317

[Fe(CN)

]

LIBs 125 1.02 3.0 70@25@94 318

Fe[Fe(CN)

]

0.71

LIBs 125 1.02 3.0 20@25@30 319

Fe[Fe(CN)

]

0.87

0.133.1H

O LIBs 125 1.02 3.0 96@25@50

LiFeHCF-1 LIBs 170 1.02 3.0 109@190@650 320

LiFeHCF-2 LIBs 170 1.02 3.0 87@190@650

LiFeHCF-3 LIBs 170 1.02 3.0 41@190@650

LiFeHCF-4 LIBs 170 1.02 3.0 61@190@650

LiFeHCF-5 LIBs 170 1.02 3.0 29@190@650

NiFe-PBA SIBs 70 1.03 3.1 100@20@200 321

PB-1 SIBs 112 — 2.9 70@100@100 315

[Fe

(CN)

]

9H

O SIBs 64.8 — 3.2 96@10@50 322

Ni-based PBAs SIBs 85 — 3.4 72@85@4000 323

PB-S1 SIBs 170 — 3.1 70@100@200 324

PB-S3 SIBs 170 2.9 72@100@500

Fe-based PBAs SIBs 157 — 3.0 80@150@500 325

Mn-based PBAs SIBs 140 1.06 3.3 74@500@2700 326

1.7

FeFe(CN)

SIBs 148 1.06 2.9 99@200@100 327

1.54

FeFe(CN)

SIBs 170 1.06 3.0 84@200@500 328

[Fe

(CN)

] SIBs 170 2.9 71@50@100 329

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Table 1 (continued )

Materials Battery types

Theoretical

capacity

(mA h g

1

)SNPC

size (nm) Average

potential (V)

Capacity (mA h g

1

current density (mA g

1

cycle number Ref.

NaFe

III

[Fe

(CN)

] SIBs 140 1.0 3.0 50@50@100

III

[Fe

III

(CN)

] SIBs 64.8 1.0 3.2 6@50@100

PB PIBs 87 — 3.6 80@9@500 330

1.64

Fe[Fe

(CN)

]

0.89

0.15H

O PIBs 155 1.0 3.3 130@30@100 331

1.75

Mn[Fe

(CN)

]

0.93

0.16H

O PIBs 155 1.0 3.6 120@30@100

Mn[Fe(CN)

] PIBs 155 1.02 3.4 150@15@140 332

KFe

III

(CN)

PIBs 155 1.02 3.3 120@10@100 333

KFe[Fe(CN)

] PIBs 155 1.02 3.3 30@500@1100 334

0.6

1.2

[Fe(CN)

] PIBs 155 3.3 62@50@300 335

RGO@PB PIBs 87 3.3 62@50@300 335

1.75

Mn[Fe(CN

)]0.930.16H2O PIBs 155 1.02 3.8 128@30@100 331

1.64

Fe[Fe(CN)

]

0.89

0.15H

O PIBs 155 1.02 3.3 110@30@100 331

KMHCF PIBs 156 — 3.7 85@156@100 336

NI-KMHCF PIBs 156 — 3.7 102@156@100

1.6

Mn [Fe(CN)

]

0.96

0.27H

O PIBs 131 — 3.9 83@50@30 337

0.220

Fe[Fe(CN)

]

0.805

4.01H

O PIBs 125 0.51 3.2 117@125@100 338

FeFe-PW PIBs 119.7 — 3.3 90.4@20@100 339

CoFe-PW PIBs 108.2 — 3.4 43@20@15

NiFe-PW PIBs 70.7 — 3.7 64@20@15

CuFe-PW PIBs 59.1 — 3.7 30@20@15

KFeHCF-S PIBs — — — 78@100@300 340

KFeHCF-M PIBs — — — 108@20@15

KFeHCF-L PIBs — — — 8@20@15

PTCDA LIBs 273 0.35 2.4 120@100@280 341

IEP-11-E12 LIBs — 1–2 2.2 46.7@550@9000 342

CMP LIBs — 1.69 101@1000@1500 343

Py-A-CMP LIBs — 2.1 2.2 125@100@400 344

TPE-A-CMP LIBs — 1.56 2.2 170@100@400

PTTPAB LIBs — 0.75B1 3.8 95@20@50 345

SPTPA LIBs — 1.0 3.75 88@50@1700 346

YPTP LIBs 109.4 1.1, 1.6 3.75 92@50@1700

OPTPA LIBs 109.4 1.7 3.75

SPTPA LIBs 109.4 1, 1.7 3.75

POP SIBs — 1.05 1 180@30@150 347

POP SIBs — 1.4–2 2 200@10@40 348

TAPT-NTCDA SIBs — 1.25 1.5 70@50@50 349

PI PIBs — 4.7 2.2 48.7@50@200 350

PQI PIBs — 4.7 2.2 84.7@50@200

PI-CMP PIBs — 4.7 2.25 93.3@50@200

HAT PIBs 245 0.7–1.4 1.7 169@10000@4600 351

PIBN-G (COF) LIBs 280 1.4 2.3 242.3@280@300 352

BQ1-COF LIBs 773 1.2 2.2 230@1556@1000 353

PIBN LIBs 280 1.45 2.0 206@280@300 352

CT SIBs 454 1.3 2.25 140@500@100 354

N-COF SIBs 515 1.1 1.5 236.5@500@1000 355

DAAQ-COF@CNT PIBs — 2.3 1.5 108@500@500 356

COF PIBs — 1.95 1.5 70@1000@5000 357

MIL-53(Fe) LIBs — 0.65 2.6 75@75@50 358

MIL-132 LIBs 59 — 3.0 50@10@5 359

MOF-1 LIBs — 2 2.3 40@100@50 360

MOF-2 LIBs — 2 2.4 37@100@50

MOF-3 LIBs — 2 2.5 8@100@50

MOF-4 LIBs — 2 2.2 5@100@50

S/MC LSBs 1675 2 1.4 500@167@800 361

AB-S LSBs 1675 2 1.8 400@837@50 362

MICP LSBs 678 1.1 1.8 341@67.8@3000 363

S/OBC LSBs 1675 2.3 2.0 711@167@50 364

S/TBC LSBs 1675 1.4 1.9 401@167@50

S/DBC LSBs 1675 2.5 2.1 291@167@50

FDU/S-40 LSBs 1675 0.46 1.6 780@400@50 365

MPC/Se LSBs 678 1–3 1.7 530@67.8@100 366

ACC SSBs 1675 0.5 1.1 700@1675@2000 367

S/ELSC-40 SSBs 1675 0.7 1.0 518@1675@500 368

APCF-38S SSBs 1675 0.3–0.8 0.9 1000@167@400 369

WBMC SSBs 1675 0.4–1.0 0.9 822@334@100 370

C/S PSBs 1675 0.4–1.0 0.6 868@20@150 371

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Table 2 Summary of the anode materials with SNPCs

Materials Battery types

Theoretical

capacity

(mA h g

1

)SNPC

size (nm) Average

potential (V)

Capacity (mA h g

1

current density (mA g

1

cycle number Ref.

TiS

LIBs 956 0.57 1.6 213@100@200 372

ZnSe/CoSe

-CN SIBs 433 0.38/0.58 1.0 422@500@300 373

TiO

SIBs 335 — 0.3 165@6700@2000 374

CoSi

LIBs 2902 0.34 0.3 891@100@200 375

LIBs 890 — 0.8 — 376

TiNb

LIBs 387.6 2 1.6 — 377

BP LIBs 2596 1 0.8 600@1000@100 378

MoO

LIBs 838 1 0.4 489@100@1050 379

MoS

SIBs 670 0.64 0.3 172@200@200 380

MoS

LIBs 670 0.69 1.6 205@200@1400 381

MoSe

LIBs 422 0.64 0.6 494@422@100 382

e-MoSe

0.98 0.8 80@422@100

MoSe

@C@MoO

SIBs 422 0.65 0.6 450@200@200 383

MoSe

@C SIBs 422 0.64 0.6 200@200@200

MoSe

SIBs 422 0.64 0.6 320@200@150

AlC

SIBs 351 0.93 0.5 — 384

SIBs 351 0.99 0.5 —

a-Ti

SIBs 351 1.25 0.5 50@200@500

PIBs 191 0.99 — —

a-Ti

PIBs 191 1.25 0.25 47@200@500

TiC

PIBs 356 0.99 0.5 140@20@94 385

Pillared-Mo

TiC

PIBs 356 1.12 0.4 250@20@94

SIBs 351 1.2/0.97 0.5 100@20@100 386

SIBs 351 0.99 0.4 76@100@120 387

PIBs 191 0.99 0.3 42@100@120

C SIBs 331 0.77/1.0 0.6 175@20@100 388

C SIBs 335 0.952 0.8 21@1000@300 389

Carbon SIBs 297 0.3/0.5 0.2 280@100@300 390

TiO

LIBs 335 0.95 — — 391

Hard carbon LIBs — 0.62/0.6 0.01 500@217@200 392

a-C-900 SIBs — 0.55 0.6 280@100@5 393

a-C-1300 SIBs — 0.55 0.7 270@100@5

a-C-1800 SIBs — 0.55 0.7 280@100@5

Hard carbon PIBs — 0.42 0.2 200@100@100 394

Graphite PIBs — 0.34 0.25 16@100@100

SiC-CDC-800 PIBs — 0.52 0.5 284@100@200 395

SiC-CDC-900 PIBs — 1.19 0.4 198@100@200

SiC-CDC-1000 PIBs — 1.53 0.5 164@100@200

L-A-900 PIBs — 0.4 0.3 118@1000@1200 396

B1-A-900 PIBs — 0.5 0.3 95@1000@1200

B2-A-900 PIBs — 0.45 0.4 52@1000@1200

Graphene SIBs — 0.4 0.6 120@50@50 397

C-900 SIBs — 0.6 0.5 150@50@50

C-1300 SIBs — 0.7 0.1 297@50@50

Hard carbon SIBs 0.5 0.1 250@50@200 398

PDCzBT SIBs — 1 0.2 117@100@200 399

LIBs — 1 0.25 300@200@400

DBD-CMP1 LIBs — 0.4–0.6 0.2 600@100@300 400

DBD-CMP2 LIBs — 0.25 400@100@300

DBD-CMP1 SIBs — 0.4–0.6 0.3 241@100@100

DBD-CMP2 SIBs — 0.4 83@100@100

CMP-PyBT PIBs — 0.94 0.75 104@500@500 401

CMP-PyBz PIBs — 1.1 0.5 272@500@500

CTF-0 PIBs — 0.5 0.3 113@100@200 402

CTF-1 PIBs — 0.7 0.8 60@100@200

Si@ZIF-8 LIBs 4200 1.1 0.5 830@200@500 403

ZIF-8-C@PP LIBs 2596 0.8/1.3 0.25 786@100@100 404

P@NMC SIBs 2596 0.6/0.8 0.4 450@1000@1000 405

P@HC SIBs 2596 0.6/1.1 0.3 548@1000@1000 406

P@N-CNT LIBs 2595 0.9/1.1 0.3 523@5000@1500 407

OMC@RP SIBs 2596 0.75 0.4 600@5200@1000 408

Cu-OMC@RP SIBs 2596 1.2/1.4 0.5 750@5200@750

MnS LIBs 616 1–2 0.5 460@1600@1500 409

NiP

SIBs 1333 — 0.3 244@2000@1000 410

FeP LIBs 926 0.46 0.6 590@2000@1000 411

GeP

LIBs 2300 — 0.75 2200@200@40 412

ZnP

LIBs 1477 0.48 0.5 100@1000@200 413

CoNi-LDH LIBs 744 0.81 0.8 440@5000@500 414

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layered oxide cathodes, optimizing the size of the SNPC

between the adjacent MO

layers to increase the structure

stability and reaction kinetics is essential. Therefore, except

for the unary transition metal oxides, binary transition metal

oxides (i.e., Mn/Ni, Mn/Fe, and Ni/Fe-based oxides) and ternary

transition metal oxides (LiNi

1xy

) were also inten-

sively investigated to adjust the SNPC for fast ion diffusion

kinetics, which increases both high electrochemical perfor-

mance and low-cost advantages.

556–558

Especially, the well-

recognized ternary transition metal oxides were successfully

applied in industry for large-scale battery packages.

559,560

The above SNPC designs alleviate the structure distortion

and damage to some degree during ion diﬀusion. When the Li

applies as the transport ion ‘A’, the diﬀusion of the ions inside

the MO

layers slowly distorts the order of the layered structure,

which is still aﬀordable for rechargeable batteries. However, if

and K

ions with much larger ionic radii are used as

transport cations, the distortion of MO

layers becomes severe,

damaging the SNPC for the ion transport and significantly

shortens the service life of the layered oxide cathodes. Further

development of layered oxide materials with appropriate SNPCs

to facilitate ion diﬀusion is required.

Currently, heteroatom doping is one of the most popular

strategies to improve the electrochemical performances of

layered oxide cathodes with SNPCs. Many elements, such as

Mg, Ti, Cu, Sn, Zn, etc., have been investigated to optimize the

interlayer distances between adjacent MO

layers to stabilize

the sub-nanochannels for ion diﬀusion. Su et al. demonstrated

that the doping of the Mg element into CoO

layers to form

the Na(Co

0.92

0.08

cathode material could change the

electron density and the valence state of oxygen, and eﬀectively

improve the Na

ion diﬀusion, making it seven times faster by

enlarging and stabilizing the SNPC with stronger Coulombic

repulsion between the adjacent oxide layers (Fig. 8b).

552

et al. designed the Ti-substituted layered oxide cathode

(Na

0.8

0.27

0.68

0.05

) and indicated that the doping of

the Ti element significantly relieved the structure distortion

due to the Jahn–Teller effect, effectively stabilizing the SNPC at

around 0.55 nm for ion transport (Fig. 8c).

553

Furthermore,

Chen et al. discovered that doping Cu element into MO

layers

enlarged the SNPC, preventing the shrinkage of the SNPC

during the stripping of ions and increasing the mobility of

ions. As a result, the Cu-substituted layered oxide cathode

(Na

0.67

0.6

0.2

0.1

) provided a capacity retention of

80.0% after 500 cycles at a high current density of up to 1 A g

1

in SIBs.

562

Yun et al. indicated that the doping of Sn into

lithium-rich layered oxide (Li

IrO

) effectively enlarged the

SNPC and prevented structural collapse at high charging vol-

tage, which benefited from the migration of Sn between the

adjacent IrO

layers during cycling (Fig. 8d).

554

Moreover, Zheng

et al. reported that Zn-substitution in MO

layers of materials

0.02

0.55

0.70

0.25

0.05

) reduced the anisotropic coupling

between Mn

and oxidized O

2

. This Zn doping strategy effec-

tively stabilized the SNPC and provided the layered oxides with a

superior cycling performance in K-ion batteries (97% capacity

retention after 1000 cycles at 100 mA g

1

563

Besides the heteroatom doping strategy, an innovative

method to stabilize SNPCs for ion diﬀusion is to further modify

the MO

layers through high-entropy design. The high-entropy

design achieved by doping five or more elements to form a

single phase and achieve a high entropy situation in layered

oxides aims to provide super stable MO

layers with homo-

genous internal stress for fulfilling the requirement of con-

structing eﬀective SNPCs for fast ion transport. For example,

Zhao et al. reported a high entropy sodium layered oxide

(NaNi

0.12

0.15

0.1

0.04

)by

mixing nine elements (Ni, Cu, Mg, Fe, Co, Mn, Ti, Sn, and

Sb) into MO

layers, which forms very stable SNPCs for fast Na

ion diﬀusion.

561

The high-entropy MO

layers eﬀectively

delayed the phase transformation from O3 to P3 during cycling

and maintained around 60% capacity in the O3 phase region

(Fig. 8e and f). Consequently, the high-entropy layered oxide

Table 2 (continued )

Materials Battery types

Theoretical

capacity

(mA h g

1

)SNPC

size (nm) Average

potential (V)

Capacity (mA h g

1

current density (mA g

1

cycle number Ref.

CoFe-LDH SIBs — 0.7 0.8 209@1000@200 415

CoFe-LDH LIBs — 0.92 0.8 860@4000@1000 416

Graphene sheets LIBs — 0.57 0.3 718@500@40 417

Graphene sheets SIBs — 0.37 0.25 917@50@100 418

Graphene sheets PIBs — 0.35 0.35 400@500@600 419

Graphite LIBs 372 0.335 0.1 306@1000@800 420

Natural graphite PIBs 278 1.2 0.7/0.75 90@500@100 414

Graphite SIBs 278 0.335 1.1/1.2 125@100@100 421

Graphite SIBs — 0.37 0.3 300@20@30 422

MoP

LIBs 676 0.56 0.6 525@160@60 423

FeP LIBs — — 0.7 750@200@100 424

SnP

0.94

LIBs 488 0.4 0.4 670@120@40 425

NaTi

(PO

)

SIBs 485 0.366 — — 426

SIBs 311 0.845 — — 427

LIBs 175 0.835 0.75 220@125@500 428

MnO

SIBs 308 0.693 1.25 72.2@500@100 357

F-COF LIBs 314 1.93 0.2 95@1000@5000 357

COF LIBs 421 1.95 0.2 70@1000@4000 357

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Table 3 Summary of the electrolytes with SNPCs

Electrolyte SNPC size (nm) Ion types Ionic conductivity (S cm

1

) Ref.

PEO-LiTFSI 0.7 Li

— 429

TEA-TFB 0.6 TEA

— 430

1.1 BF

4

SiN

film 0.45 H

— 431

V-CNF 0.6 Zn

0.61 10

3

432

1.3

Zeolite 0.54 Li

0.94 10

3

433

UiO-66-X 0.6 F



,Cl



B10 10

3

434

CuBTC MOF 0.65 Li

B5.0 10

4

435

MOF/polymer 0.8 Li

0.54 10

3

PvDF-LiTFSI-MOF 1.16 Li

4.08 10

4

436

Ce-UiO-66-Li

0.6 Li

2.16 10

4

437

PEO: LiAsF

0.5 Li

— 438

Cellulose nanofibrils 0.9 Li

1.5 10

3

439

MOF-cellulose nanofibers 1.1 Li

7.88 10

4

440

PP/UiO-66-NH

0.4 Li

2.45 10

4

441

9.54

1.74

1.44

11.7

0.3

0.8 Li

2.5 10

3

442

OCl 0.4 Li

6.6 10

5

443

1+x

2x

(PO

)

0.5 Li

— 444

POSS-PEO/LiTFSI 0.74 Li

5.6 10

6

445

POSS-IL-LiTFSI — Li

4.8 10

4

445

EMIM-Cl@UiO-67 0.65 Li

0.68 10

4

446

F-IL-GEL — Li

9.16 10

3

447

PIM-EA-TB — FSI



0.5 10

2

448

1.5

0.5

1.5

0.6 Li

410

4

449

GF@ZIF@PEO 0.38/1.31 Li

1.78 10

4

450

GF@PEO 0.74 Li

1.60 10

4

450

PEO-E 0.74 Li

2.03 10

4

450

MOF-LiCl 2 Li

2.4 10

5

451

MOF-LiBr — Li

3.2 10

5

451

MOF-LiI — Li

1.1 10

4

451

PVDF-HFP/LLZO/LiTFSI 3.41 Li

4.9 10

4

452

(dobdc) 1.1/1.3 Li

3.1 10

4

453

MOF 1.0/2.0 Li

7.41 10

4

454

Li–IL@UIO-67 1.2/1.6 Li

4.3 10

4

455

EMI-TFSA 1.16 Li

0.5 10

4

456

Li-IL@MOF 1.2 Li

3.0 10

4

457

SLE-H 0.6 Li

3.3 10

4

458

SIL/UIO-66 QSSE 0.6 Li

3.7 10

4

459

LIM-L 1.2 Li

1.0 10

4

460

MIL-121/Li 0.87 Li

510

4

461

6.75

1.75

0.25

—Li

1.2 10

4

462

LLZO-polymer 1.2 Li

4

–10

3

463

PEO 0.74 Li

5

464

PAN 1.1 Li

1.07 10

5

465

PVDF 0.56 Li

7.27 10

4

466

PAN — Li

6.5 10

4

460

PEO 0.74 Li

1.4 10

3

467

PEGDA — Li

2.26 10

4

462

NaPF

-PEO 0.74 Na

510

6

468

NaTFSI-PEO 0.74 Na

4.5 10

6

469

NaFNFSI-PEO 0.74 Na

210

6

470

NaTCP-PEO 0.74 Na

6.9 10

5

471

NaClO

-PVP 1.2/1.3 Na

2.5 10

6

472

NaBr-PVA 0.34 Na

1.36 10

6

473

0.37 Na

1.2 10

3

474

3.1

1.95

0.05

0.65 Na

3.5 10

3

475

3.4

1.6

0.4

(SiO

)

(PO

) 0.54 Na

410

3

476

0.4/0.5 Na

3.9 10

4

477

94Na

6Na

SiS

0.5 Na

7.4 10

4

478

0.62

0.38

0.7 Na

1.46 10

3

479

2.9375

3.9375

0.0625

0.4/0.5 Na

1.14 10

3

480

Pse

0.73 Na

1.16 10

3

481

0.98 Na

110

2

482

)

0.5

)

0.5

0.58 Na

910

4

483

PVDF-HFP 0.3 Na

110

3

477

PEO/Na

3.4

1.8

0.2

0.74/0.4 Na

2.4 10

3

484

PEO/KbrO

0.74 K

7.74 10

8

485

PEO/KBr 0.74 K

5.0 10

7

486

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cathode delivered a high-capacity retention of around 83% after

500 cycles at 3C-rate in SIBs.

3.1.2. Tuning SNPCs in polyanionic and spinel-like cath-

odes. Polyanionic materials are another class of cathode mate-

rials coupled with SNPCs to realize redox reactions and cation

storage in rechargeable batteries, showing diﬀerent advantages

compared to layered oxides. Applying polyanionic materials as

cathodes has attracted great interest since the late 1990s, due to

their high operating potential, stable SNPCs (i.e., 3D open

framework) with less volume change and no phase transition,

high thermal stability, and high safety.

564–566

However, the

drawbacks of polyanionic materials are their low specific

capacities, low electronic conductivities, and poor low-

temperature performances, which restrict their wide applica-

tion under harsh environmental conditions.

Polyanionic materials A

(XO

)

consist of tetrahedral

polyanionic units (XO

)

n

and covalently bonded polyhedra

(where A represents Li, Na, and K, X represents P, S, Si,

etc., and M represents transition metals) with SNPCs of around

0.4 to 0.6 nm (Fig. 7b).

311,567–571

This special structure of

polyanionic materials leads to low conductivity because of

the electronic interactions between (XO

)

n

units during the

charge/discharge process. According to X elements, the poly-

anionic materials can be classified as phosphate with X = P

(orthophosphates, fluorophosphates, pyrophosphates, and

mixed pyrophosphates), sulfates with X = S (AM(SO

)

(SO

)

), and silicates with X = Si (A

MSiO

), which share

similar SNPC structures.

566

Similar to the development of

layered metal oxides, the heteroatom doping strategy is

the most popular way for improving the structure stability

and ionic conductivity of the SNPCs inside polyanionic cath-

odes. However, to further improve the electronic and ionic

conductivity of the polyanionic materials, doping modification

is commonly accompanied by carbon coating and particle size

control strategies.

The heteroatom doping strategy used in polyanionic cathode

materials can be categorized as (1) doping in transport ion sites

and (2) doping in transition metal sites. The doping in trans-

port ion sites involves incorporating heteroatom ions with large

radii and high conductivity to control the size of SNPCs and act

as the ‘pillars’ to stabilize the ion diﬀusion paths. For instance,

Lim et al. doped the K element into the Na

(PO

)

/C (NVP/C)

cathode material at the transport Na

ion sites to form K

0.09

NVP/C.

567

Due to the larger ionic radius of K than that of Na,

the K elements act as the pillar and enlarge the SNPC for Na

diﬀusion and accommodation (Fig. 9a). With the pillar eﬀect

provided by K doping, the doped cathode material showed a

significantly smaller volume change than that of the pristine

materials (reduced from 9.02% to 6.64%) (Fig. 9b). Conse-

quently, the K

0.09

-NVP/C cathode achieved a high reversible

capacity of 83 mA h g

1

after 200 cycles at the 1C-rate.

Doping heteroatom ions in transition metal sites aims to

stabilize the framework structure and increase the conductivity

of the SNPC. For example, Shen et al. designed a NASICON-type

cathode (Na

2x

(PO

)

/C) by doping Mn

ions into the

transition metal sites of Na

(PO

)

/C (Fig. 9c).

568

The doping

Table 3 (continued )

Electrolyte SNPC size (nm) Ion types Ionic conductivity (S cm

1

) Ref.

PEO/CH

COOK 0.74 K

2.74 10

7

487

PVP/KIO

—K

110

9

488

PPCB/KFSI 0.74 K

1.36 10

5

489

PEO/KNO

/KI 0.74 K

6.15 10

6

490

0.4 K

3.5 10

2

491

PAF-220 1.3/1.9 Li

210

4

492

PAF-220-Li 1.9 Li

510

4

492

PEO-LiTFSI 0.74 Li

2.3 10

4

493

Halide 0.452 Li

1.0 10

4

493

Molecular sieve 0.32 Na

— 494

AO-PIM-1 0.45 K

,Na

,Li

,Cl



4.4 10

4

495

PVDF-HFP-CPT-[PMPyr][TFSI] — Li

4.2 10

5

496

SSZ-13 + PEO + LiTFSI 0.74 Li

5.34 10

2

497

PEO + LiTFSI + ZYNa 0.74 Li

1.66 10

2

498

PHS — Li

1.36 10

5

499

Mn-PBA 1.0 Na

9.1 10

5

500

Cubic Na

0.4 Na

210

4

501

0.5

2.4

0.4

0.6

0.4 Na

3.5 10

5

502

2.9

0.9

0.1

0.7 Na

4.1 10

2

503

3x

1x

0.2 Na

6.6 10

5

504

2.2

0.4

SbSe

0.5 K

4.45 10

5

505

MgZnTeO

0.6 Na

1.4 10

5

506

TeO

0.55 Na

2.3 10

4

507

CPCSE 0.95 Li

5.2 10

4

508

COF 0.9 Li

1.71 10

4

509

MOF 0.34 Li

6.7 10

4

510

Carbon 0.7 Li

— 159

PPS@TiO

0.3/0.4 Li

,Na

0.6 to 3 10

4

MLM 0.56 K

— 511

MLM-EDTA 0.6 K

— 511

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of Mn

eﬀectively enlarged the SNPC (Fig. 9d), stabilized the

crystal structure, and promoted the ionic and electronic con-

ductivity due to the large radius of Mn

(0.91 Å) compared to

that of V

(0.64 Å) and self-polarization ability. As a result, the

Mn-doped cathode materials achieved a high reversible dis-

charge capacity of 92.5 mA h g

1

after 100 cycles at 5C, which is

around 95.9% capacity retention.

Besides heteroatom doping, another pathway to enlarge the

ion diﬀusion channels and increase the ion conductivity of

SNPC inside the polyanionic materials is by combining them

with high-conductive materials. Li et al. introduced carbon

nanotubes into Na

(PO

)

(NVPF), which significantly

improved the NVPF crystallinity and ion transport (Fig. 9e

and f).

569

The NVPF@CNT cathode oﬀered a super cycling

performance with 77.3% capacity retention after 5000 cycles

at 20 C. Guo et al. designed a heterogeneous NASICON-type

composite by combining Na

(PO

)

with Na

(PO

)(P

)

(NVFPP).

570

The introduced NVFPP phase provided enlarged

SNPCs. As a result, after 500 cycles, their cathode delivered a

78.6% capacity retention rate at 5C.

Moreover, the conventional polyanionic cathode usually

contains the V element, which is expensive and bio-toxic.

Substituting the V element with other cheap and eco-friendly

transition metals while maintaining the stability and conduc-

tivity of SNPCs in polyanionic materials is also worth

studying for practical applications. Chen et al. reported a

3.32

2.34

)

/C composite as the cathode material with

obvious eco-friendly advantages. Their V-free cathode also

provided suﬃcient SNPCs for Na

ion transport.

571

Later, they

further designed an eco-friendly cathode with a tenable nano-

sized Na

(PO

)

)/C (NFPP-E) composition, exhibiting

enhanced air stability and suitability for all-climate operation

conditions. After 4400 cycles at 20C, the SNPC of NFPPE could

be maintained at around 0.5 nm.

311

The robust 3D frameworks provide the polyanionic cathode

with a more stable SNPC than that of the conventional layered

oxide materials. In addition, the spinel engineering design can

provide a 3D framework for transition metal oxides and form

AM[M

(M = Fe or Mn) spinel-like cathode materials, which

is worth mentioning here. In spinel-like materials, the [M

units form a spinel framework that stabilize the whole struc-

ture, allowing the reversible alkali ion insertion and extraction.

The spinel-like cathodes cannot oﬀer a high energy density as

the traditional layered oxide materials, but they can provide

relatively lower costs and high safety like the polyanionic

cathode.

574

Spinel-like cathodes with 3D SNPCs have been

commercialized in LIBs, and their application in sodium-ion

batteries is currently attracting researchers.

A popular strategy to improve the electrochemical perfor-

mance and SNPC stability of spinel-like cathodes is the

chemical substitution to form the A[Mn

2x

, where M is

the substituted metal. For example, the well-known

LiNi

0.5

1.5

(LNMO) is Ni-substitution modified LiMnO

spinel-like cathodes. The Ni substitution significantly improves

the cathode’s capacity (B130 mA h g

1

) and operating voltage

(B4.7 V vs. Li). Furthermore, due to the high voltage and less

involvement of the Mn

redox reaction during cycling, the

Jahn–Teller distortion is effectively reduced in the LNMO

cathode, stabilizing the SNPC for ion transport.

574,575

Chiring

and Senguttuvan reported a spinel-NaMnSnO

cathode

(Na

0.877

MnSnO

) for SIBs with Sn substitution (Fig. 9g).

572

The Sn

in the spinel framework effectively reduced the ion

diffusion barriers, suppressed the Jahn–Teller effect with no

Table 4 Summary of the functional interlayers/separators with SNPCs

Materials SNPC

size (nm) Ion

types Ionic conductivity

(S cm

1

) Ref.

ZIF-7@PCF 0.3 Li

2.87 10

6

/8.09 10

7

512

N,S-Mo

C/C-ACF 1.2 Li

1.04 10

3

513

N-Mo

C/C-ACF 1.4 Li

1.31 10

3

N-C-AMP 0.5/0.8 Li

1.28 10

3

Celgard — Li

7.6 0.15 10

4

514

P(VDF-HFP) — Li

2.6 0.04 10

4

515

Li-Nafion — Li

2.1 0.04 10

5

Li-PFSD — Li

1.2 0.02 10

4

Z-PE 2 Na

7.0 10

4

516

UiO-66 MMM 0.8 Li

0.67 10

3

147

LMA 1.1 Li

2.310

6

149

MOF-coated LMA 1.1 Li

3.3 10

3

MOF@GO 0.9 Li

3.8 10

4

517

MOF@GO 0.9 Li

710

5

S-PE — Li

3.5 10

4

518

S-GE — — 8 10

4

S-CE/S-PE — — 3 10

3

S-CE/S-GE — — 8 10

3

LLZO 0.35 Li

1.03 10

3

LLZTO 0.4 Li

210

3

Azo-TbTh 0.36 Na

6.9 10

3

519

TA/Fe

III

MOF-PP 1.9 Li

1.1 10

3

520

Spim-SBF-0.53 0.55 Li

5.5 10

3

521

Spim-SBF-0.98 0.54 Li

1.2 10

2

Spim-SBF-1.4 0.54 Li

2.6 10

2

Spim-SBF-1.67 0.54 Li

6.5 10

2

Spim-SBF-1.86 0.52 Li

7.6 10

2

Spim-SBF 0.55 Li

2.8 10

2

TiO

/PP 0.38 Li

0.246 10

3

MIL-125(Ti)-PP/PE 0.77 Li

522

Cpim-1 0.55, 0.9 — 4 10

2

523

AO-PIM-1 0.55, 0.9 — 5 10

6

MGEs-S0 2 Li

9.77 10

5

524

MGEs-S1 2 — 1.80 10

4

MGEs-S2 2 — 5.37 10

4

MGEs-S3 2 — 6.76 10

4

PAN-C — Li

1.04 10

3

525

oxy-PAN-60 — Li

0.461 10

3

oxy-PAN-120 — Li

0.459 10

3

PVDF membrane — Na

7.38 10

4

526

PVDF coated PP — Na

1.25 10

3

527

PEO-KFSI 0.74 K

2.7 10

4

528

Poly (PC) (PPC)-KFSI — K

1.36 10

5

529

—Na

6.3–6.8 10

3

530

NaAlO

—Na

5.5–6.5 10

3

MATEPP/MMA/TFMA 0.74, 0.88 Na

6.29 10

3

531

LLTO/Li

/polymer 1.2 Li

5.1 10

4

532

2D-SPE — Li

7.14 10

5

533

SHCPE 0.3 Li

810

5

534

P(MMA-AN-VAc) 0.57, 0.88, Li

1.54 10

3

535

P(AN-co-MA) 1.1 Li

6.7 10

4

536

PVN-GPE 0.78 — 2.6 10

4

537

PDMS/PVDF 0.56 — 1.17 10

3

538

PEO/LiBOB/LLZTO 0,74 Li

2.4 10

5

539

PEGBCDMA based PEM — Li

810

4

540

HPEI-PGC-PCL — Li

5.36 10

4

541

PEO — K

4.3 10

3

ZIF-67@PP 1.1 Li

1.64 10

3

542

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observed change in the axial bonds in Mn

centers (Fig. 9h),

and thus promoted highly stable SNPCs (B0.5 nm).

Furthermore, the coating strategy is also commonly used on

the surface of spinel-like cathodes against transition metal

Fig. 6 (a) The summary of SPNC size and theoretical capacities for oxides, polyanions, PBAs, polymers, and (b) the summary of SPNC size and capacities

for COFs, and S/Se cathodes in rechargeable batteries. (c) The summary of SPNC size and theoretical capacities of oxides, phosphides, sulfides, and

polymers, and (d) the summary of SNPC size and capacities of MXenes, graphite-based materials, and hard carbons in rechargeable batteries. (e) The

summary of SPNC size and ionic conductivity of polymers and MOF and, (f) the summary of SPNC size and ionic conductivity of NASICONs, sulfides, and

hydrides for quasi-solid-state and solid-state electrolytes in rechargeable batteries. (g) The summary of SPNC size and ionic conductivity of polymers and

oxides, and the summary of SNPC size and ionic conductivity for interlayers/separators in rechargeable batteries. (Red, green, and blue represent Li, Na,

and K, respectively.)

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dissolution, impedance rise, and capacity fade under harsh

operating conditions such as high temperatures. For instance,

Chu et al. coated AlF

onto the LNMO.

573

They found that the

1 wt% AlF

-coating (B5.2 nm) can eﬀectively prevent the

transition metal dissolution of the spinel-like cathode and

maintain the structure integrity of SNPCs (B0.47 nm)

(Fig. 9i). Consequently, the 1 wt% AlF

-modified LNMO cathode

delivered enhanced cycling stability with a high-capacity reten-

tion of around 81.7% after 100 cycles at 0.2 C and 55 1C,

whereas the pristine LNMO cathode only delivered 70.1%

capacity retention.

3.1.3. Tuning SNPCs in MOF- and COF-based cathodes.

Metal–organic frameworks (MOFs) are another type of popular

cathode materials applied in alkali metal ion rechargeable

batteries. After decades of investigation, more than twenty

thousand types of MOFs have been reported.

576

MOFs have

structures with metal ion centers (Fe, Co, Ni, Cu, Mn, etc.) and

organic ligands (polyamines, carboxylates, hydroxyl, etc.),

which give the advantages of tenable porous structures,

high surface areas, and homogeneous metal sites to these

materials and thus benefit the fast kinetic and ion diffusion

(Fig. 7c).

577,578

However, this structure also presents significant

drawbacks. First, MOFs cathode usually deliver a low specific

capacity and limited electric conductivity due to limited redox-

active sites that are only based on the metal center (M

(n+1)+

)

in the framework. Second, the porous framework not only

benefits the ion insertion/extraction by providing sub-

nanochannels but also leads to easy structure collapse during

the charge/discharge and low volumetric energy density. Third,

the existence of crystalline water and lattice vacancies

inside the MOFs can lead to low coulombic efficiency and poor

cycling stability.

The first MOF-based cathode material for LIBs was MIL-

53(Fe) reported by Ferey et al. in 2007. The MIL-53(Fe)

cathode provided a low capacity of around 70 mA h g

1

only exploiting the Fe

/Fe

redox reduction inside the

frameworks.

358

After that, researchers endeavor to increase

the redox-active sites and stabilize the SNPC of MOFs by

designing the organic ligands, selecting the metal node, and

modifying the nanostructure.

The organic ligand design aims to create redox-active sites

on the organic linkers of the MOFs and maintain the structure

stability simultaneously. For example, Peng et al. used tricar-

boxytriphenyl amine (TCA) to replace the conventional

quinone-type ligands and form the Cu-TCA cathode for LIBs

(Fig. 10a).

579

In addition to the redox change of Cu

/Cu

in the

center of MOFs, the N atoms in TCA also provide redox-active

sites by transitioning between neutral and cationic forms in the

voltage range from 3.8 to 4.3 V. In the meantime, the TCA

ligands also oﬀered good stability to support the frameworks

and sub-nanochannels (B0.5 nm).

The metal node design involves heteroatom doping and

high entropy design. The heteroatom doping can eﬀectively

change the electronic state of the original metal node, promote

the ion transport inside sub-nanochannels, stabilize the frame-

works, and enhance the cycling voltage. For instance, Huang

et al. successfully doped Ni ions into the Prussian blue analo-

gue (PBA) K

FeFe(CN)

to form KNi

0.05

0.95

Fe(CN)

with a sub-

nanochannel of around 0.5 nm, which eﬀectively changed the

electronic state of the Fe ions and enhanced K ion diﬀusion

inside the channels (Fig. 10b).

580

The Ni substitution promoted

the redox reaction of Fe

/Fe

and thus improved the

capacity from 40 to 53 mA h g

1

at high charge voltage plateaus.

Consequently, their enhanced MOF-based cathode provided a

Fig. 7 Illustration of the material structure with SNPC and the improvement strategies for (a) layered oxide cathodes, (b) polyanionic cathodes, (c) metal

organic frameworks (MOF), and (d) covalent organic framework (COF) cathode materials.

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stable cycling performance with 83.1% capacity retention after

300 cycles at 0.1 A g

1

. A high entropy design acts the same way

as heteroatom doping but with five or more elements sharing

the same lattice sites, which further stabilizes the ion diﬀusion

pathways and framework structure. Ma et al. reported a high-

entropy design on the PBA (Na

(FeMnNiCuCo)–[Fe(CN)

]) with

the sub-nanochannels of around 0.6 nm and employed it as the

cathode in SIBs (Fig. 10c).

581

The high entropy (HE) structure

provided a nearly zero-strain operation during the desertion/

insertion of Na

ions, and thus offered a better structure

stability. As a result, the HE–BPA cathode delivered 94%

capacity retention after 150 cycles at 0.1 A g

1

There have been relatively fewer studies on modifiying

thestructure morphology of MOF cathodes than the above

two strategies, but it can eﬀectively increase the intrinsic

electronic conductivity, provide a much higher density of

redox-active sites, promote ion diﬀusion, and oﬀer stable sub-

nanochannels for the intercalation of large-size alkali metal

ions. For example, Wada et al. reported a 2D-MOF cathode

material (NiDI) applied in LIBs.

582

Their 2D-MOF cathode has a

bis(diimino)nickel framework with a high density of redox-

active sites and several redox states provided by both organic

ligands and metal ions. Especially, the energy storage mecha-

nism in this 2D-MOF cathode involves the insertion/desertion

Fig. 8 (a) Illustration of Mg doping into CoO

layers. (b) The electron density diﬀerences of NaCoO

(up) and Na(Co

0.92

0.08

(down). Reproduced

0.8

0.27

0.68

0.05

Ti-doping cathode.

change during the charge of the typical NaMO

(left) and high entropy NaMO

(right), where the diﬀerent colors of balls represent diﬀerent elements and

the diﬀerent sizes of ball represent the diﬀerent oxidation states. (f) Schematic of the change between P3 and O3 phase of high entropy NaMO

during

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of both cations (Li

) and anions (PF

6

) (Fig. 10d), providing a

high specific capacity of around 155 mA h g

1

at a current

density of 10 mA g

1

. Moreover, Jiang et al. designed a 2D-MOF

cathode with a copper–benzoquinoid framework (Cu-THQ

MOF) and sub-nanochannels (B1 nm) using a similar energy

storage mechanism with cation and anion insertion/desertion

(Fig. 10e).

583

Due to the highly porous structure and intrinsic

redox characteristics of Cu-THQ, their 2D MOF cathode pro-

vides abundant and highly conductive channels for promoting

ion transport. As a result, the 2D Cu-THQ MOF achieved a

Fig. 9 (a) Illustration of doping K

ions into transport ion sites in Na

(PO

)

. (b) The volume shrinkage between the charge and discharge of

(PO

)

of doping Mn

ions into transition metal sites in Na

(PO

)

. (d) HRTEM image of the Mn doped Na

(PO

)

with 0.373 nm SNPC. Reproduced from ref.

0.877

MnSnO

structure (h) Schematic showing the bond lengths of (Mn

/Sn

and (Mn

/Sn

octahedra inside the Na

0.877

MnSnO

.by viewing along

AlF

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very high capacity of 387 mA h g

1

during the second cycle and

maintained a stable cycling performance with 340 mA h g

1

capacity retention after 100 cycles at 50 mA g

1

Covalent organic frameworks (COFs) are similar to MOFs,

but instead of having metal nodes inside the framework, COFs

are formed by covalently bonded organic ligands (Fig. 7d).

COFs, as a kind of crystalline porous material, possess abun-

dant well-defined directional meso- and nano-size channels for

ion transport, rich redox-active sites, and a stable framework

structure, oﬀering them excellent ion diﬀusion capacity.

However, the drawbacks of limited specific capacity and poor

electronic and ion conductivity similar to MOFs pose chal-

lenges to the application of COFs as cathodes in alkali metal

ion batteries. The COF material was first reported by Yaghi’s

group in 2005 and named COF-1 and COF-5.

584

After ten years,

Jiang’s group first designed the COF-based cathode applied in

Li-ion batteries by growing mesoporous COFs (D

-A

NDI

-COF

with channel size of around 5.06 nm) on carbon nanotubes

(CNT).

However, their cathode only delivered a capacity of

67 mA h g

1

at 200 mA g

1

Schematic of the crystal structure of the K

FeFe(CN)

(up) and Ni doping KNi

0.05

0.95

Fe(CN)

(down). Reproduced from ref. 580 with permission from

(FeMnNiCuCo)–[Fe(CN)

] crystal structure. Reproduced from ref. 581

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In recent years, several strategies, such as SNPC design, pore

wall decoration, and morphology modification (exfoliation,

crystallinity regulation and orientation, secondary material

combination, etc.) have been developed to improve the perfor-

mance of COF-based cathodes. Generally, the large pores can

provide more free space for ion transport, and small pores can

be more conductive due to the interaction between the pore

wall and transport ions. Combined with the development of

enriching redox-active centers on the pore walls, COF-based

cathodes can oﬀer significantly enhanced electric and ionic

conductivities and excellent electrochemical performance. For

example, Shi et al. developed a nitrogen-rich COF with triqui-

noxalinylene and benzoquinone units (TQBQ-COF).

355

The

TQBQ-COF has a honeycomb-like and AB stacking structure

with well-defined directional SNPCs of around 1 nm (Fig. 11a

and b). The SNPC provided the TQBQ-COF with a high electro-

nic conductivity of 1.973 10

9

Scm

1

, and the abundant N

atoms on the pore walls eﬀectively decrease the energy gap

between the lowest and highest occupied molecular orbitals,

thus promoting the ionic and electronic conductivity. Conse-

quently, the TQBQ-COF cathode in SIBs provided a very high

capacity of 327.2 mA h g

1

and around 89% capacity retention

after 400 cycles at 0.1 A g

1

The most popular structural morphology modification of

COFs is the 2D morphology obtained through direct synthesis

or exfoliating from 3D COFs, which can eﬀectively enlarge their

surface area, improve the accessibility of redox-active sites, and

promote ion diﬀusion. For example, Wang et al. exfoliated the

anthraquinone-based COF (DAAQ-TFP-COF) to redox-active

ECOF (DAAQ-ECOF), providing an approximately three times

faster Li

diﬀusion rate than its non-exfoliated counterpart due

to the significantly shortened ion transport paths (Fig. 11c).

585

Wu et al. reported a 2D COF cathode (BQ1-COF) through the

polycondensation reaction between C

and C

deliver CRO and CRN groups (Fig. 11d).

353

This design

provided SNPCs of B1 nm and minimized the inactive group

inside the BQ1-COF (Fig. 11e). As a result, the BQ1-COF cathode

in LIBs oﬀered an excellent reversible capacity of around

502 mA h g

1

at 0.05C and very stable cycling performance

with 81% capacity retention after 1000 cycles at 1.54 A g

1

It is worth mentioning that conjugated microporous poly-

mers (CMPs), from some perspectives, can be regarded as

amorphous COFs. They are another type of microporous mate-

rial with promising potential as cathode materials in alkali

metal ion batteries.

588

CMPs have a very similar composition to

COFs, but instead of a crystalline structure, CMPs are amor-

phous. This characteristic not only makes the CMPs more

challenging to characterize and process than COFs but also

gives CMPs the advantages of high thermal and chemical

stability. Moreover, CMPs have a highly conjugated structure

and extended p-conjugation system, which benefits the stability

of the framework and the ion transport in SNPCs. For instance,

Li et al. designed a CMP-based cathode applied in SIBs by cross-

linking 1,8-diaminopentacene-5,7,12,14-teraone (DAPT) and

1,3,5triformylphloroglucinol (TFP) to form p-conjugated porous

frameworks (DAPT-TFP-CPFs) (Fig. 11f).

586

The DAPT-TFP-CPF

cathode resulted in fast ionic diﬀusion thanks to the sub

nanometer pores (B0.8 nm) and the lamellar structure.

Furthermore, the extended p-conjugation backbones eﬀectively

stabilized the SNPC inside the framework, improving the

charge transport stability in cycling. As a result, the DAPT-

TFP-CPF cathode exhibited a very stable cycling performance

with a high-capacity retention of 145 mA h g

1

after 1000 cycles

at 100 mA g

1

It is worth noting that, in addition to monovalent (Li

,Na

and K

) ion batteries, tuning of SNPCs in cathodes of multi-

valent ion (Zn

,Mg

,Ca

,Al

) batteries can also remarkably

enhance their electrochemical performance. Compared with

monovalent ion batteries, multivalent ion batteries oﬀer advan-

tages including more aﬀordable cost, higher safety and lower

environmental impact. However, challenges such as unstable

electrode materials, poor ion diﬀusion kinetics, and a narrow

electrochemical stable potential window hinder the application

of multivalent ion batteries. Tuning SNPCs in the cathode

materials, through methods such as the abovementioned het-

eroatom doping, size regulation, pre-intercalation, defect engi-

neering, and freestanding configuration design, could pave the

way for breakthroughs and potential applications in these

multivalent ion batteries.

589

For instance, Zhu et al. designed

a freestanding design Mn-based cathode (SSWM@Mn

) for

Zn-ion batteries using stainless steel welded mesh (SSWM) to

grow the flower-like Mn

(Fig. 11g and h). The cathode

provided SNPCs of around 0.61 nm (Fig. 11i), allowing Zn

intercalation/extraction and eﬀectively improving the cycling

stability up to 500 cycles at 500 mA g

1

587

Nam et al. intro-

duced crystal water into the SNPCs (B0.7 nm) inside the

layered manganese oxide to form an enhanced stable cathode

for Mg-ion batteries at high voltage (2.8 V vs. Mg/Mg

590

The

Mg-ion batteries with their cathode oﬀered 62.5% capacity

retention after 10 000 cycles. Furthermore, Li et al. reported a

microsphere cathode material for Al-ion batteries.

591

The

microsphere provided about 0.2 nm SNPCs for Al

intercalation/deintercalation and a porous structure for electro-

lyte penetration. With this unique structure design, the Al-ion

batteries with Co

microsphere cathodes delivered a reversi-

ble capacity of 90 mA h g

1

after 150 cycles at 50 mA g

1

3.1.4. The design of SNPCs in conversion-type cathode

materials. Cathode materials based on conversion reactions,

such as S and selenium (Se) have been intensively investigated

in the past decades due to their high theoretical specific

capacities (Fig. 12a and b).

592,593

At room temperature, the

reactions of S/Se cathodes during charge and discharge

processes involve multiple phase-transition steps with the

formation of soluble polysulfides (PSs)/polyselenides (PSes) as

intermediates. The major challenges faced by these conversion-

type cathode materials include poor electronic conductivity of

the cathode materials, the ‘‘shuttle eﬀect’’ of PS/PSe intermedi-

ates, significant volume variations during cation insertion and

extraction, and sluggish reaction kinetics. To solve the above-

mentioned issues, a strategy which involves introducing multi-

functional hosts with appropriate SNPC design to form S/Se-

based nanocomposites has made significant achievements so

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far. The host materials with SNPCs, such as nanostructured

porous carbon materials, provide sub-nanoscale conductive

networks that significantly increase the electronic conductivity

of the S/Se cathodes and buﬀer the volume change during

cation insertion and extraction in diﬀerent battery systems (e.g.,

Li/Na/K–S batteries and Li/Na/K–Se batteries). More impor-

tantly, the confinement effects of SNPC suppress the ‘‘shuttle

effect’’ (i.e., restricting the dissolution of PS/PSe intermediates

into the electrolytes), reducing the loss of active materials and

the side reactions on the anode counterparts.

Carbon-based materials with SNPCs, ranging from 1D CNTs

to 2D graphene and 3D porous carbon spheres, are the most

intensively investigated hosts for sulfur cathodes.

598–604

Com-

pared with the traditional porous structure design, carbon

materials with SNPCs have been found to show unusual elec-

trochemical reaction behaviours in the S cathode. For instance,

Fig. 11 (a) Schematic of the TQBQ-COF chemical structure, electrochemical redox mechanism, and the theoretical capacity of 515 mA h g

1

.(b)

Illustration of the AB stacking model of TQBQ-COF layers with a packing distance of 3.07 Å. Reproduced from ref. 355 with permission from Springer

inside the skeleton. (e) TEM images of the BQ1-COF showing the interlayered spacing between the adjacent 2D COF nanosheets. Reproduced from ref.

cathode material. (h) SEM

image of SSWM@Mn

. (i) HRTEM image of the SSWM@Mn

cathode showing the SNPCs. Reproduced from ref. 587 with permission from The Royal

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two types of single-walled carbon nanotubes (SWCNTs) with

different diameters were prepared as hosts to study the 1D

confinement effects of SNPCs on the lithiation/delithiation

process of S cathodes in Li–S batteries (Fig. 12c).

594

The long-

chain S diradicals were formed inside the as-prepared SWCNTs

via infusion and polymerization processes. The SWCNTs pre-

pared by the electric arc method (EA-SWCNTs) have an average

diameter of B1.55 nm with an average inner van der Waals

diameter of 12.1 Å for EA-SWNTs. The other SWCNTs obtained

from high-pressure carbon monoxide (HiPc0-SWCNTs) have an

average diameter of B1.0 nm with an average inner van der

Waals diameter of 6.6 Å for HiPco-SWNTs. The conventional

solid–liquid–solid reactions occurred in the S cathode with

EA-SWCNTs in both tetraethylene glycol dimethyl ether

(TEGDME)-based and 1,4,7,10,13-pentaoxacyclopentadecane

(15-crown-5)-based electrolytes. In contrast, unusual continu-

ous solid-state reactions were observed in S cathodes with

HiPc0-SWCNTs. The distinct electrochemical behaviors were

explained because of the unique SNPC feature of HiPc0-

SWCNTs. The largest van der Waals dimensions of the solvated

[Li(TEGDME)]

and [Li(15-crown-5)]

ions are 10.87 Å and

11.34 Å, respectively, which are smaller than the diameter of

EA-SWCNTs but larger than that of HiPc0-SWCNTs. Therefore,

the S cathode with EA-SWCNTs showed similar phase transfor-

mation processes to the normal S cathodes as the solvated

[Li(TEGDME)]

and [Li(15-crown-5)]

ions could still access the

inner channels of EA-SWCNTs and react with S. However, the

sulfur inside HiPc0-SWCNTs could not directedly react with

the solvated cations. Instead, the sulfur was reduced through

the wall of SWCNTs via an out-of-plane p-electron interaction.

A 2D graphene material with an SNPC structure (i.e.,an

interlayer spacing of B0.4 nm) was developed as the S host for

Li–S batteries. Through a solvothermal method or an interla-

mellar reaction method, S molecules were intercalated into the

graphene interlayers to form a S/reduced graphene oxide

(S/RGO) composite (Fig. 12d). The electrochemical performance

of the S/RGO composite showed similar phase-transfer beha-

viors to that of small S molecules in a carbonate-based electro-

lyte (1 M LiTFSI in DOL/DME), demonstrating that this 2D

SNPC design effectively facilitates phase transformation

during electrochemical conversion reactions from S to lithium

sulfide.

595

Another carbon host with 3D SNPC design, micro-

mesoporous carbon nanospheres (MMPCS), was reported by

Wu et al. for RT Na–S batteries.

596

Porous carbon spheres with

tailored continuous carbonaceous pores ranging from micro-

meters to sub-nanometers were synthesized as S hosts

(Fig. 12e). Similarly, the design of the 3D SNPC carbon host

has been widely applied in the Li/Na–Se battery system. Aboo-

nasr Shiraz et al. synthesized microporous carbon (MPC) with

SNPCs of around 1 nm from the PVDF precursor. When

employed as a host for Se in Li–Se batteries, the MPC could

confine the LiPSes and effectively reduce the side reaction

between the Se cathode and the electrolyte (Fig. 12f).

366

As a

result, the Li–Se batteries exhibited a reversible capacity of

508.8 mA h g

1

after 100 cycles at 0.1C. Furthermore, Zhang

et al. designed interconnected conductive polyaniline (PANI)

coated hierarchical porous carbon (i-PANI@NSHPC) to accom-

odate up to 65.7 wt% Se in SNPCs applied as cathodes in Na–Se

batteries.

595

This cathode offered an excellent reversible capa-

city of 617 mA h g



1 at 0.2C after 200 cycles due to the

enhanced electronic and ionic conductivity even at high Se

areal mass loading. The S material confined within those

multifunctional channels is highly reactive with full access to

ions. In addition, a highly Na-ion conductive and contin-

uous solid interphase containing sodium sulfide was confor-

mally formed inside the pores, significantly stabilizing the

cathode/electrolyte interfaces, and promoting the kinetics of

S-involved redox reactions. In addition to the carbon-based

materials, MOF and COF 3D frameworks with SNPCs have also

been used as hosts for S/Se cathodes. For instance, Su et al.

reported a 3D SNPC framework by using the Prussian blue

analogues (PBAs) coated with PEDOT (Na

Fe[Fe(CN)

poly(3,4-ethylenedioxythiophene)) to capture the sulfur and

polysulfides for Li–S batteries (Fig. 12g).

597

The MOF-based

host significantly enhanced the confinement of soluble Li

polysulfides through the Lewis acid–base interaction between

the rich open metal sites in the SNPC of the MOF host and

polysulfide anions. Finally, their S@Na

Fe[Fe(CN)

]@PEDOT

cathode exhibited a stable cycling performance with a capacity

retention of 697 mA h g

1

after 100 cycles at 2C. Recently,

redox-active polymers have emerged as an attractive option

among organic materials for seving as S hosts, offering advan-

tages such as cost-effectiveness, diversity, good processability,

unique electrochemical properties, and precise tuning for

energy storage applications.

605

e.g., Park et al. the reported S-

rich polymers on the gram scale derived from the vulcanization

of trithiocyanuric acid-based materials. The resulting cathode

material exhibited stable cycling over 450 cycles, with a reten-

tion rate of 83% and excellent rate performance with a current

density of C/10 (1210 mA h g

1

) to 5C (730 mA h g

1

). This

performance is attributed to strong bonding energy between

redox-reactive polymers and S.

606

In conclusion, the SNPCs play an important role in both

intercalation-type and conversion-type cathode materials. The

size, distribution, and amount of SNPCs inside cathode materi-

als directly aﬀect the accommodation and transportation of

metal ions and the confinement of active materials. The

advanced material designs to modify the morphology and

catalytic functions of the SNPCs in cathodes can further

improve the electrochemical performance of rechargeable

batteries.

3.2. Electrochemical couplings of anode materials with

SNPCs

In addition to their significant role in cathode materials, SNPCs

also play critical roles in various anodes. It has been widely

reported that the SNPCs can be engineered on the surface of the

anodes as artificial solid–electrolyte interphase (SEI) layers,

which could facilitate feasible selective ion transport, avoid

excessive SEI formation, and alleviate the volume changes upon

cycling. The SNPCs can also be engineered inside the nano-

particles of the anode materials, which could generate fast ion

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transportation to achieve enhanced rate performance. Hereby,

the rational design of SNPCs for various types of anode materi-

als has been systematically sorted and discussed.

3.2.1. Intercalation-based anodes. The intercalation pro-

cess to insert diversified working ions into the interlayers of the

crystal planes represents a wide variety of anode materials for

versatile battery systems, of which the intercalation of Li

into

the graphite layers has been the fundamental working mecha-

nism for commercial LIBs since 1990s. Carbonaceous materi-

als, conjugated microporous polymers CMPs, titanates, TMDs,

and Mxenes generally working as intercalation-based anodes,

which exhibit vital importance in practical batteries due to their

Fig. 12 (a) Schematic illustration showing the mass/charge transfer at the cathode–electrolyte interface in liquid-electrolyte-based Li–S batteries. S is

reduced to generate LiPSs, which could dissolve in the liquid electrolyte and shuttle between two electrodes. Reproduced from ref. 592 with permission

the fabrication processes of the sulfur intercalated reduced graphite oxide by two wet chemical methods. Reproduced from ref. 595 with permission

transmission in the internal structures of MMPCS-800@S. Reproduced from ref. 596

Fe[Fe(CN)

] and polysulfide Li

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outstanding cycling performance. These anodes with SNPCs

could deliver enhanced electrochemical performance, as a

result of the benefits derived from the SNPCs.

3.2.1.1. Carbon-based anodes. Carbon-based materials

including graphite, graphene, graphdiyne, hard carbon, soft

carbon, carbon nanotubes (CNTs), etc. are all promising anode

materials for alkali metal ion batteries. Numerous research

studies have incorporated SNPCs into these carbonaceous

anodes to achieve outstanding electrochemical performance.

For instance, hard carbon has been widely recognised as a

versatile anode for alkali metal batteries, the abundant SNPCs

in the hard carbon resulting from randomly stacked graphitic

layers render it capable of accommodating more ions both

between the layers and also in the sub-nano pores, as presented

in Fig. 13.

607

It is worth noting that, the SNPCs in the hard

carbon anodes could contribute a considerable amount of low

voltage capacity, which is achieved probably by pore-filling of

quasi-metallic Na clusters.

608

The size of the SNPCs in the

carbon anodes is crucial for the accommodation of alkali metal

ions, especially for K

with a larger diameter. For instance, a

nitrogen-doped porous carbon (NPC) has been reported for

KIBs, the SNPC size was enlarged from 0.335 to 0.383 nm due to

the decomposition of the Na

during pyrolysis, as presented

in Fig. 13b.

609

As a result, the NPC delivered a high reversible

capacity of 382 mA h g

1

for more than 500 cycles and good rate

capability of 185 mA h g

1

at 10.0 A g

1

. The improvements in

the performance were attributed to the surface driven K

storage by the enlarged SNPCs, as well as enhanced K

aﬃnity

provided by N-doping sites. Similarly, it has been reported that

the interlayer spacing of the graphitized domains in the hard

carbon can be expanded to 0.42 nm by incorporating graphene

oxide in the precursors; the expanded spacing could serve as

fast K

diﬀusion channels.

394

As a result, high reversible

capacity, excellent rate capability, and good cycling stability

have been achieved for PIBs.

Alternatively, Mai and colleagues reported soft carbon

nanosheets with SNPCs of 0.45–0.90 nm, exhibiting a high

surface area, large pore volume, and rich defective sites.

610

Excellent capacitance-dominated Na

and K

storage was

achieved, as a result of the extra ion storage sites derived from

abundant SNPCs. Significantly, Li and co-workers reported the

synthesis of graphdiyne with a channel of 0.546 nm as anode

materials for LIBs, which could be expanded to 0.596 nm upon

intercalation, as illustrated in Fig. 13c.

611

The self-

expanding channel could reduce the energy barrier and elec-

trostatic repulsion for Li

transport, facilitating fast solid-state

diffusion. Benefiting from self-expanded SNPCs, graphdiyne

delivered higher capacity, better cycling stability, enhanced

capacity retention, and broaden working temperature range

at high current rates. Besides, S-doped hollow carbon

nanosheets,

612

hard carbon,

613

and N,P co-doped hollow micro-

porous carbon,

614

have also been reported to deliver

enhanced electrochemical performance due to the incorpora-

tion of SNPCs, as a result of enhanced ion transportation,

improved electrolyte wettability, and decreased SEI thickness.

Furthermore, the advantage of the SNPCs in various carbo-

naceous materials including graphite nanomesh,

615

holey

graphite,

616

and microporous carbon

617

have also been

revealed via theoretical calculations, further demonstrating

the significance of SNPCs for various carbon anodes.

3.2.1.2. Titanates, TMDs, and MXenes. Titanates are widely

used intercalation-based anode materials for alkali metal ion

batteries, which exhibit good cycling stability and excellent rate

performance.

618

Various TMDs and MXenes with a well aligned

layer structure could also deliver excellent intercalation perfor-

mance for rechargeable batteries, benefiting from the stable

layered structure with SNPCs. Previous research by Geng and

co-workers reported stacked titania sheets with pillared inter-

layer spacing ranging from 0.76 to 1.15 nm, which could

facilitate ultrafast intercalation of Li

,Na

and K

with high

cycling stability, as presented in Fig. 13d.

619

The ultrafast ion

transportation could be attributed to the open 2D SNPCs,

which could even achieve good rate performance for PIBs with

a thick electrode of up to 80 mm. Besides, several research

groups reported MoS

and MoO

based TMDs for LIBs and

sodium-ion batteries (SIBs) with SNPCs of B1 nm, which

delivered excellent cycling stability and rate capability.

620,621

The improved electrochemical performance can be attributed

to SNPCs between the layered structures, which could acceler-

ate ion transportation and also decrease the ion diﬀusion

pathway. A wide variety of Mxenes with layered structures

and abundant SNPCs have also been widely used as anode

materials. For instance, Yamada and colleagues reported a TiC

MXene for Na

storage in hybrid capacitors and SIBs, which

could retain a stable SNPC of 1.01 nm after the first activation

process as a result of the Na

pillars, as illustrated in Fig. 13e.

388

The SIB full cells delivered a high specific energy of

260 W h kg

1

at a high specific power of 1.4 kW kg

1

, as a result

of the rich and stable SNPC structures. Similarly, a pillared

MXene with an expanded interlayer pacing of 1.02 nm has been

reported for LIBs, which could enhance the specific capacity,

rate capability, and also the cycling stability.

622

The improved

performance was attributed to SNPCs, which could accelerate

ion transportation and provide more ion storage sites. The

benefits of the SNPCs for various intercalation based anodes

were further verified by numerous previous reports, demon-

strating the universality of the SNPCs for layered anodes in

delivering enhanced rate performance as a result of the boasted

ion transportation in the confined channels between the

layers.

623–625

3.2.2. COFs. The structure of COFs could enable good

electron transport in conductive polymer backbones, as well

as eﬀective ion transport through SNPCs. Therefore, COFs with

redox active building blocks to accommodate versatile metal

ions in SNPCs have been frequently reported as anode materi-

als for various batteries, working with a similar mechanism to

that of the Li

intercalation into the graphite anode. Among

which, CMP is a distinctive family of COFs, featuring extended

p-conjugation backbones and permanent nanopores.

626,627

presented in Fig. 13f, Chen and colleagues reported a

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phenazine based CMP with rich SNPCs, which could host

various mono- and multi-valent charge carriers (H

,Li

,Na

,Zn

, and Al

) for diverse aqueous rechargeable batteries

combining rapid kinetics, ultralong lifespan, and chemical

rechargeability.

543,628

The highly reversible redox activity, facile

intramolecular electron transfer, and high ion diﬀusion coeﬃ-

cient were attributed to the high density of accessible redox

sites derived from the cross-linked structure with rich SNPCs.

Alternatively, a 2D nitrogen rich CMP with regular SNPCs of 0.7

and 1.1 nm has been rationally designed for LIBs, delivering a

high reversible capacity of 701 mA h g

1

at 1 A g

1

and

remarkable cycling stability for more than 500 cycles.

629

The

superior rate performance can be attributed to excellent con-

ductive backbones, as well as the reduced Li

diﬀusion pathway

derived from the SNPCs. Several excellent reviews have system-

atically summarized the synthesis, properties, and applications

of various COFs,

34,44,49,116,626,627

which should be enlightening

for follow up research on rational design of high performance

CMP anode materials for various rechargeable batteries.

3.2.3. Conversion-based anodes. Conversion based anodes

are promising candidates for rechargeable batteries with high

specific capacity, whereas suﬀering from poor cycling stability

and rapid capacity degradation.

630,631

Recent reports demon-

strate that the drawbacks of the conversion based anodes can

be significantly relieved by incorporating with SNPCs. As pre-

sented in Fig. 14a, ultrathin Co

nanosheets with an inter-

layer spacing of 0.6 nm have been reported for LIBs, which

delivered high specific capacity (1230 mA h g

1

at 0.2 A g

1

Fig. 13 (a) Schematic illustration of the accommodation of Li

/Na

in hard carbon anodes through intercalation, adsorption, and pore filling in the

SNPCs.

603

porous carbon and its working mechanism for K

storage.

594

of the working mechanism of graphdiyne for Li

storage.

596

illustration of the intercalation of Li

/Na

in titania sheets.

610

Schematic illustration of the synthesis of MXene and the structural stability of the SNPC upon Na

intercalation/deintercalation.

387

Reproduced from ref.

organic electrode for diverse aqueous battery chemistry.

611

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excellent rate performance, and excellent cycle capability (1500

cycles).

632

The enhanced performance can be attributed to the

SNPCs between the layers, which could establish 2D nanoflui-

dic channels oﬀering extra lithium storage sites, accelerate

horizontal and vertical Li-ion transport, and alleviate volume

changes during the cycling. Alternatively, Park and colleagues

reported an exfoliated 2D TMD (MoS

) nanosheets with inter-

layer channels of E1 nm for LIBs, which delivered a high

specific capacity of 933.1 mA h g

1

at 0.1 A g

1

and excellent

cycling stability with 90% retention after 1000 cycles.

633

The

SNPCs between the layers with good tolerance to volume

expansion and negatively charged channels for fast ion trans-

portation were attributed to the enhancement of the electro-

chemical performance. It has also been reported that Ni

anchored in nitrogen doped carbon (Ni

P@N–C) with rich

SNPCs could deliver enhanced rate capability (197 mA h g

1

at 2 A g

1

) and excellent cycling stability (0.06% capacity decay

per cycle), as a result of the high electrical conductivity of the

matrix and confinement effect of the SNPCs (Fig. 14b).

634

The

advantages of SNPCs have also been reported for other

conversion-based anodes including silicon oxide,

635

SnO

636

and others high capacity conversion-based anodes with SNPCs

can be expected in the following research.

3.2.4. Alloy-based anodes. Alloy based anodes including Si,

Ge, Sn, P, Sb, Bi, etc. are well known for their ultrahigh specific

capacities resulting from alloying reactions, while their prac-

tical applications have been seriously impeded as a result of the

huge volume change, unstable SEI layers, and poor cycling

stability.

637–639

Confining the alloy based anodes in SNPCs has

been reported to be an effective approach to address these

issues. For instances, Lou and colleagues reported a COF based

artificial SEI layer coating on Si nanoparticles, the anode

delivered a high specific capacity of 1864 mA h g

1

at a high

current density of 2000 mA g

1

and a high capacity retention of

more than 60% after 1000 cycles.

640

The COF based artificial

SEI with SNPCs could facilitate fast ion transportation, reduced

electrolyte decomposition, enhanced Coulombic efficiency, as

well as improved cycling stability, as illustrated in Fig. 14c.

Alternatively, carbon coating layers on Si with abundant SNPCs

derived from pyrolyzed metal–organic frameworks (MOF) have

been reported for LIBs, resulting in high specific capacity and

exceptional cycling stability.

403

The increased electrical con-

ductivity, relieved volume change, and enhanced ionic trans-

portation derived from the SNPCs are all responsible for the

dramatically enhanced electrochemical performance of the Si

anode. Similarly, Yu and coworkers reported a MOF-derived

SNPCs (o1 nm) rich carbon to accommodate amorphous Red P

as anode material for SIBs (Fig. 14d), the composite anode

delivered a high specific capacity of 600 mA h g

1

and excellent

cycling performance for 1000 cycles.

405

The enhanced perfor-

mance can be attributed to the buffering effect, enhanced ionic

conductivity, and improved electronic conductivity derived

from the SNPCs. Various recent research also reported the

encapsulation of red P into SNPCs to achieve dramatically

enhanced electrochemical performances.

404,406–408

With attrac-

tive size, buffering, and confinement effects, the enormous

potential of SNPCs for various other kinds of conversion-based

anodes should be further explored.

3.2.5. Metal anodes. The ultimate choice of anode materi-

als for the rechargeable batteries should be metal anodes, i.e.,

Li, Na, K, and Zn metal anodes for LIBs, SIBs, PIBs, and

aqueous zinc ion batteries (AZBs), respectively.

641

For instance,

Li metal anodes could deliver the highest theoretical capacity of

3860 mA h g

1

for LIBs as compared to all other kinds of

anodes.

642,643

Whereas metal anodes exhibit all the problems of

other types of anodes, and the extent is much more serious.

Besides, the metal anodes are prone to dendrite growth caused

by internal short circuits, posing serious safety concerns for the

practical application of the metal batteries.

3.2.5.1. Li/Na/K metal anodes. cLi metal anodes have been

considered as the ‘‘Holy Grail’’ for LIBs due to their highest

specific capacity and lowest redox potential, to Na and K metals

for SIBs and PIBs. The alkali metal anodes generally exhibit

huge volume change, unstable SEI layers, low Coulombic

eﬃciency, and continuous dendrite growth during repeated

cycling.

644,645

Various species with SNPCs have been reported

as artificial SEI layers to protect the metal anodes. For example,

an ACOF coating layer with rich SNPC structures has been used

for Li metal anodes (Fig. 15a), exhibiting a size eﬀect that

enables selective Li

transport through the SNPCs while pre-

venting the penetration of electrolyte solvents.

646

As a result of

eﬀective protection from the ACOF coating layers, significantly

enhanced cycling stability for Li metal anodes and Li metal full

cells has been achieved. Here, 3D porous frameworks have

attracted tremendous interest as metal anode protective layers

for rechargeable batteries because of their large active surface

areas. Yun et al. demonstrated 3D microporous frameworks

grown on Li anodes. Benefiting from the 3D microporous

framework induced interfacial activity gradient, Li ions under-

goe a uniform deposition, boosting the cycle performance of Li

metal batteries.

647

As the most representative type of material

in the 3D framework, MOFs, COFs and their derived materials

have also received a lot of attention. For instance, similarly, a

COF film with size eﬀects to block TFSI



while allowing for the

selective permeation of Li

was designed as an artificial SEI

layer for Li metal anodes (Fig. 15b), which could generate

uniform Li metal plating as compared to the bare Li metal

anodes with serious dendrite growth.

648

Significantly, Man-

thiram and co-workers reported the room temperature in situ

growth of a COF layer on the Li metal anode, as illustrated in

Fig. 15c, which exhibits a suppression eﬀect to prevent dendrite

growth, as well as a size eﬀect to achieve uniform Li

flux.

649

Benefiting from the COF protective layer with rich SNPC

structures, the Li–S cells delivered exceptional cycling stability

for more than 600 cycles with a low-capacity decay of 0.05% per

cycle under lean electrolyte conditions. Besides, CMP-based

protective layers with SNPCs of 0.5–0.6 nm as ion-selective

nanofluidic transport have been reported for Li metal anodes,

which delivered extraordinary cycling stability for 2550 h at a

high areal current density of 20 mA cm

2

139

The dramatically

enhanced cycling performance of the Li metal anode can be

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attributed to SNPCs with Li

selective channels, so as to prevent

the side reactions of Li metal with anions and electrolytes.

Similarly, MOF-based protective layers have been coated on Cu

current collectors as artificial SEI layers for Li and Na metal

anodes with excellent cycling stability.

650,651

Furthermore,

expanded graphite with SNPCs of around 0.7 nm as molecular

tunnelling has been designed as a host material for Li metal,

which could realize dendrite-free Li metal anodes and Li metal

full cells with no noticeable capacity degradation after 370

cycles.

652

After that, other MOF- and COF-derived materials

have also been successfully prepared as protective layer for

metal anodes.

653–656

The performance enhancement was attrib-

uted to the bulk diffusion of superdense Li into SNPCs. It can

be anticipated that various SNPC-based artificial SEI layers and

host materials could further enhance the cycling stability of

alkali metal anodes, paving the way for the practical application

of metal anodes for next-generation high energy density

rechargeable batteries.

3.2.5.2. Zn metal anodes. Aqueous zinc ion batteries (AZBs)

have been intensively investigated as alternatives for alkali

metal batteries with organic electrolytes, which could deliver

high specific capacity and non-flammable properties.

659

Low

Coulombic eﬃciency due to hydrogen evolution and short life

span as a result of Zn dendrite growth are the prevailing

challenges for AZBs. To address these issues, a zeolite based

protective layer with SNPCs of 0.349 nm has been designed for

Zn metal anodes, which could facilitate selective Zn

transpor-

tation through channel size restriction and electric field repul-

sion to the anions, as presented in Fig. 15d.

657

As such, the side

reactions can be restricted to achieve enhanced Coulombic

eﬃciency. Besides, dendrite-free Zn metal deposition can be

achieved due to the homogenized Zn

flux derived from uni-

form SNPCs. Consequently, a long lifespan of 2400 h, a high

current tolerance of 100 mA cm

2

, and a high capacity reten-

tion of 76.4% after 7500 cycles have been achieved. Similarly,

an ion regulating interface has been developed for Zn metal

anodes, which delivered a high Coulombic eﬃciency of 99.9%

and stable cycling for 2500 h, as a result of the homogeneous

flux derived from the coating layer with rich SNPCs

(Fig. 15e).

658

Interestingly, a vermiculite (VRM) coating with

rich negatively charged SNPCs has been designed for Zn metal

anodes (Fig. 15f), which could accelerate the transport of Zn

via electrostatic eﬀects while reducing the water molecules in

the Zn

solvation shell.

635

Therefore, the VRM@Zn anode

delivered excellent cycling stability for 5000 cycles at 1A g

1

The feasibility of protective coating layers for Zn metal anodes

could be further extended to other SNPC based materials.

Versatile anode materials incorporating SNPCs to achieve

enhanced electrochemical performance for various battery sys-

tems have been summarized in Table 5. Further exploration of

SNPCs for various anode materials is essentially required,

which holds promise for enhancing the performance of anodes

for next-generation batteries with high energy density, high

power density, and desirable cycling stability.

3.3. Electrolyte

An electrolyte is the medium which carries the ionic charges

between the electrodes. Although its role seems trivial, the

electrolyte properties drastically influence the electrochemical

Fig. 14 (a) Schematic illustration of ultrathin functionalized Co

nanosheets with massive arrays of 2D nanofluidic channels for Li-ion transport.

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battery performances. Ideally, the electrolyte should (1) be

electrochemically stable at the voltage required for oxidation

and reduction reactions at the electrodes; (2) have a high ionic

conductivity of 410

3

Scm

1

, and a cation transference

number close to 1; (3) present high safety; (4) operate over a

wide temperature range; and (5) represent a small volume or

weight fraction of the battery. Currently, in LIBs, the common

electrolytes are based on liquid organic solvent and thermally

unstable Li salts. As largely demonstrated in the literature,

these types of electrolytes are not satisfactory to further

improve the energy density and safety of the next battery

generation.

665

Quasi-solid and solid-state electrolytes are pro-

mising for solving these issues.

666

Quasi-solid electrolytes are

defined by a liquid electrolyte enclosed in the pores of a solid

matrix (polymer matrix, MOFs, etc.), whereas solid-state elec-

trolytes are solely composed of a solid ionic conductor.

667

The

unique properties of ionic movement in SNPCs have been

recently highlighted as a promising way of improving ionic

conductivity and resolving electrolyte side reactions in quasi-

solid and solid-state electrolytes.

668

The following part reviews

the latest advance of the application of SNPCs in quasi-solid

and solid-state electrolytes.

3.3.1. Quasi-solid-state electrolytes

3.3.1.1. SNPCs in gel polymer electrolytes. Although gel poly-

mer electrolytes (GPEs) present high safety and relatively good

electrochemical properties, the quest to increase the cation

transference number (to achieve high-rate performance and

suppress dendritic growth) and reduce the side reactions at the

electrolyte/electrode interface continues. During the past dec-

ades, nanometre and sub-nanometre polymeric matrices have

been investigated through intensive experimental and theore-

tical practices. For instance, in 2011, Li et al. employed multi-

axis pulsed-field-gradient nuclear magnetic resonance (NMR),

H NMR spectroscopy and synchrotron small-angle X-ray scat-

tering to understand how the PEM structure and morphology

influence the ion transport from the sub-nanometre to micro-

metre scale.

669

Theoretical models such as molecular dynamics

simulations showed that the ionic transport in SNPC polymer

films is ascribed to the negatively charged nanopores (radius of

E0.3 nm).

670

More recently, machine learning was employed to

elucidate the energy barrier descriptors from 126 features, this

approach could reveal key attributes for the design of ion

selectivity sub-nanopores membranes.

671

Coupling cutting-

edge experimental characterisation studies with theoretical

calculations and computing tools could revolutionise the for-

mulation of electrolytes in energy storage systems.

Several research groups demonstrated that Li ions can

penetrate SNPC whereas larger anions and solvent molecules

remain stranded.

392,429

Therefore, employing SNPCs in bat-

teries introduces specific ion selectivity, which leads to a high

Fig. 15 (a) Schematic illustration of ACOF coating with ion selective SNPCs for Li metal anodes. Reproduced from ref. 646 with permission from Wiley-

illustration of VRM coating on Zn metal with ion accelerating SNPCs for stable Zn metal anodes. Reproduced from ref. 635 with permission from Elsevier,

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cation transference number and provides a physical barrier

limiting the electrolyte decomposition. Depending on the ion

solvation sheath and on the SNPC internal functional groups,

various electrostatic interactions dictate the ion selectivity

and transport. In organic electrolytes, cations and anions

can penetrate the sub-nanochannels with partial solvation

sheath.

430

As the pore size decreases, the number of solvent

molecules removed from the solvation shell increases. Analo-

gically, Lu et al. in situ characterised the dehydration phenom-

ena of alkali metal ions (Li

,Na

and K

) during ion transport in

polymeric SNPCs.

431

Interestingly, they observed partial shred-

ding of water molecules from the hydration sheath, which

allowed the ions to penetrate pores with smaller size than their

solvated size. This fundamental characterization opens exciting

routes for aqueous electrolytes to enlarge the electrochemical

stability window of the electrolyte and suppress water splitting

side reactions. For instance, Li et al. developed a composite

membrane based on 2D vermiculite and 1D CNFs with ZnSO

aqueous electrolyte. Based on dielectric relaxation spectroscopy

and molecular dynamics studies, two types of channels form

two corresponding types of confined water molecules, with

diﬀerent water relaxation processes and water activities. Due

to the fast relaxation process of water in 1D fiber-expanded 2D

capillaries, increasing the CNF ratio to 75% will result in the

maximum Zn

conductivity of 1D/2D membranes, which is far

higher compared to the original 2D vermiculite and 1D CNF

membranes. Meanwhile, the electrochemical activity of con-

fined water restricted by 1D/2D is limited, including a 78%

reduction in corrosion current, and the unique egg-like struc-

ture of the elastic modulus of the pebble-like structure is

further increased by 155% compared to the vermiculite

membrane. Due to the confinement eﬀect of controlled water

and enhanced mechanical strength, non-dendritic zinc electro-

deposition has been achieved, and the permeation of zinc in

the battery is significantly reduced.

432

A diﬀerent quasi-solid electrolyte formulation approach

involves introducing SNP particles as fillers in gel electrolytes

to promote the cation transference number. Yang et al. engi-

neered a gel polymer electrolyte consisting of a PvDF-HFP

micro-structured matrix and two inorganic fillers (SiO

nano-

particles and Zeolite Socony Mobil-5, ZSM-5).

433

As schemati-

cally explained in Fig. 16a, the SiO

nanoparticles adsorb PF

6

anions owing to Lewis acid interactions, which favours Li salt

dissociation. Meanwhile, the ZSM-5 particles provide many

sub-nanopores which enhance the ionic conductivity of Li

thereby eﬃciently hindering Li dendrite growth (Fig. 16b). To

demonstrate its practical application, the gel polymer electro-

lyte was applied in Li||NMC811 and Li||LFP batteries. The cells

exhibited excellent cycling stability, i.e., 300 cycles with 92%

capacity retention for Li||NMC811 batteries and 500 cycles with

96% capacity retention for Li||LFP batteries. In addition, gel

polymers are also performed as quasi-solid-state electrolyte

for Na batteries. As shown as Fig. 16c, a polyvinylidene

fluoride-hexafluoropropylene copolymer (PH) membrane is

used as a flexible three-dimensional porous polymer matrix

that can incorporate additional microporous polymers.

672

introducing super-crosslinked microporous polymers into the

PH host membrane, a continuous polymer network is created

that can capture liquid electrolytes and create ‘‘liquid SNPCs’’.

Compared to modern separators used in liquid electrolyte

systems, these quasi-solid polymer electrolytes oﬀer higher

safety and flexibility without sacrificing the high ion conduc-

tivity of traditional liquid electrolytes. Specifically, we synthe-

sized super-crosslinked microporous polymer membranes

incorporating polyfuran or polypyrrole into the 3D PH struc-

ture. These membranes demonstrate the ability to immobilize

liquid electrolytes within the microporous polymer matrix,

resulting in quasi-solid electrolytes with high ion conductivity,

stability, and cycling life when applied in lithium and sodium

metal batteries. Due to a certain aﬃnity for liquids, electrolytes

are easily trapped in the microporous polymer. Therefore, GPEs

can provide key advantages over SPEs and liquid electrolytes,

including acceptable ion conductivity (410

at room tempera-

ture), good wetting of alkali metal anodes, and maintaining

close interface contact with the cathode and anode. More

Table 5 Summary of the application of SNPCs for anode materials in

various battery systems

Materials Categories SNPCs size (nm) Batteries Ref.

HC Carbon o1 PIBs 394

Graphdiyne Carbon 0.55–0.56 LIBs 611

HPCNS Carbon 0.7–1.3 PIBs 612

SiC-CDC Carbon 0.52–1.0 PIBs 395

HC Carbon 1.0 SIBs 613

SC-NSs Carbon 0.45–0.90 SIBs/PIBs 610

Soft carbon Carbon o1 PIBs 396

C-1300 Carbon 0.8 SIBs 397

PC Carbon 0.43–0.73 PIBs 609

HC Carbon o0.5 SIBs 398

CMP Polymer o1 LIBs/SIBs 660

CMP Polymer 0.4–0.6 LIBs/SIBs 400

CMP Polymers 0.7–1.1 LIBs 629

CMP Polymers 0.5–1.5 SIBs 347

CMP Polymers 0.5 PIBs 402

CMP Polymers o1 ABs 628

1.73

41.04

Intercalation 1.15 LIBs/SIBs/PIBs 619

MoS

/Gr/C Intercalation 0.98 LIBs 620

DMcT-MoO

Intercalation 1.04 SIBs 621

MXene Intercalation 1.02 LIBs 622

HTO-PANI Intercalation 9.3–9.9 SIBs/PIBs 625

SUCNs-SF Conversion 0.6 LIBs 632

Graphene/MoS

Conversion o1 LIBs 661

MoS

Conversion o1 LIBs 633

P@C-N Conversion 1.0 SIBs 634

Si@ZIF-8 Alloying B1.1 LIBs 403

ZIF-8-C@PP Alloying 0.5–1.0 LIBs 404

P@N-MPC Alloying o1 SIBs 405

HPCNS/P Alloying o1 SIBs 406

N-CBCNT@rP Alloying 0.9 LIBs 407

Cu-OMC@RP Alloying o1 LIBs 408

CMP-Li Li metal 0.5–0.6 LMBs 139

ACOF-coated Li Li metal 0.6 LMBs 646

COF-Li Li metal 0.6 LMBs 648

COF-F6@Li Li metal 0.93 LMBs 662

Ploymer-Li Li metal 0.6–1.2 LMBs 12

BDLC Li Metal 0.68 LMBs 652

UiO-66-Li Li metal 1.0–1.2 LMBs 149

ZnA@Zn Zn metal 0.35 AZBs 657

VRM@Zn Zn metal 0.4–1.2 AZBs 663

Zn@MGs Zn metal 0.92 AZBs 664

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importantly, microporous polymer candidate materials with

small pore sizes and high porosity can absorb large amounts

of liquid electrolyte while providing minimal electrolyte leakage

and maintaining the ability to suppress the formation and

growth of dendritic substances due to their small pore size.

Because of this, the method of trapping liquid electrolytes in

microporous polymers has been widely used as gel polymer.

Full-cell lithium and sodium batteries containing these micro-

porous polymer electrolyte membranes exhibit comparable rate

and interface performance to traditional liquid electrolytes, but

with significantly improved cycling performance and coulom-

bic eﬃciency. Furthermore, the polymer of inherent micropor-

osity (PIMs) has been widely used in functional membranes in

recent years because of the stable structure micropores formed

by ineﬃcient molecular stacking. Thus, GPE was prepared

using bacterial cellulose (BC) as a support membrane and

partially acylated PIM-1 (named PIM-CONH

) as a functional

layer for use in lithium metal batteries (LMBs), as shown in

Fig. 16d. Due to the presence of amide groups, the formed PIM-

CONH

/BC GPE exhibits a high Li

transport number (0.76),

good cycling performance (retains 83% capacity after 200 cycles

at 0.5C), and good rate capability in LiFePO

|GPE|Li batteries.

The layered porous structure in PIM-CONH

/BC GPE can reg-

ulate the Li

transport behavior, and the presence of amide

groups promotes the uniform dissolution/deposition of Li

(Fig. 16e). Acylated PIMs in GPE can play an important role in

improving interface aﬃnity and suppressing lithium dendrite

growth. Similarity, Zou et al. employed bacterial cellulose (BC)

as the support membrane and partially acylated PIM-1 (named

PIM-CONH

) as the functional layer, which was performed as

the electrolyte membrane of lithium metal batteries (LMBs).

673

The PIM-CONH

/BC GPE, designed using the vascular system

as a basis, had a multilayer porous structure. This structure

enhanced charge transport and reduced volume changes dur-

ing the cycling process. The amide group in GPE acted as the

main transport site. It regulated the nucleation mode of

lithium, induced uniform deposition of Li, and inhibited the

growth of lithium dendrites. This study provides a new strategy

for improving the safety and stability of LMBs to meet the

demand for functionalized LMB electrolytes.

3.3.1.2. SNPCs in MOF quasi-solid electrolytes. Solid-state

batteries are gaining attention as a potential energy storage

system due to their high energy density and improved safety.

However, the high resistance between the solid-state electrolyte

and electrode leads to slow cation transport. MOF formulation

is adaptable to create high specific area SNPC structures, which

can accommodate ions and small molecules. Sub-nano con-

fined ions/solvent molecules exhibit chemical and physical

properties that are dramatically altered from those in bulk

electrolytes. The physical confinement and chemical interac-

tions between the ions/solvent molecules with metal sites

inside the MOF nano-channels can facilitate the ion transport,

regulate the SEI formation, increase the temperature decom-

position of the electrolyte and adjust the electrolyte up-

take.

18,434,435

Inspired by this, a quasi-solid-state electrolyte

(QSSE) based on a solvate ionic liquid (SIL) confined in nano-

cages of UIO-66 (SIL/UIO-66) is developed. The SIL/UIO-66 QSSE

benefits from the spatial confinement of TFSI



by the UIO-66

pores and the strong chemical interactions between SIL and

metal atoms. Consequently, the SIL/UIO-66 QSSE exhibits high

ionic conductivity and compatibility with electrodes. As a

Fig. 16 (a) Schematic illustration of SZ-GPE. (b) Current–time response of SZ-GPE in Li||Li symmetric cells after applying a constant potential (10 mV).

Schematic representation of Li or Na plating/stripping on traditional liquid/separator-based (CG or GF) cells compared to cells based on advanced Li-

formation of the PIM-CONH

/BC composite GPE. (e) Mechanism of lithium dendrite growth inhibition by PIM-CONH

/BC GPE. Reproduced with

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result, Li|QSSE|LFP cells demonstrate excellent rate capability

and cycle stability in a wide temperature range of 25–90 1C. This

study presents a practical approach for fabricating safe solid

electrolytes with excellent compatibility and long cycle life for

high-performance QSSE LIBs.

Chang et al. prepared a safe quasi-solid electrolyte by con-

fining a Li-based organic liquid electrolyte inside the SNPCs of

a MOF.

435

The as-prepared quasi-solid electrolyte exhibits high

safety (non-flammability) and a large electrochemical stability

window (5.4 V vs. Li/Li

), owing to electrolyte confinement; the

Li solvation sheath became more compact and therefore more

energy is needed for the solvated PC molecules to be oxidized

(Fig. 17a). Meanwhile, the energy density was also improved

since only a small amount of liquid electrolyte was necessary to

fill the MOF sub-nanochannels. The Li||NMC811 pouch cells

cycled for more than 300 cycles at room temperature and at

90 1C with an excellent Coulombic eﬃciency even though the

cathode loading was 20 mg cm

2

and electrolyte up-take was

0.23 mLcm

2

. Similarly, ionic liquids, which are considered as a

safer alternative to organic solvent, have been infiltrated in the

pores of a self-assembled zeolite imidazole framework (ZIF-8)

3D structure (Fig. 17b).

436

Recently, a MOF was decorated with

halogen atoms inside the channels, leading to a high ionic

conductivity of 2.16 10

4

Scm

1

at room temperature, a large

electrochemical stability window (4.8 V) and dendrite

suppression.

437

Besides, the MOF nanocrystals were continu-

ously grown on polyimide fibres. The SNPCs of the MOF were

infiltrated with a Li-containing ionic liquid electrolyte; mean-

while, the SNPCs between the interconnected fibres were filled

in with the PvDF–LiTFSI polymer composite. The SNPCs of the

Fig. 17 (a) Schematic illustration of the porous PSS polymer with CuBTC MOF decorated inside its channels and its advantages. Reproduced with

conductor with continuous Li

based SSI formed on LMA with immobilized anions and ionic channels for fast Li

Elsevier. (e) Schematic illustration of MOF–PVDF GPE with anions immobilized for lithium–sulfur batteries. Reproduced with permission from ref. 674

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MOF network provided high Li

conductivity owing to the

spatial anion confinement in the sub-nanopores and the

Lewis acid interactions between anion-metal sites. Such a

quasi-solid electrolyte presented a high ionic conductivity of

4.08 10

4

Scm

1

at 30 1C and enhanced the cycling

performance of Li||LFP batteries. Furthermore, the MOF struc-

ture can be tuned by altering the ligands or the metal sites. In

addition, solid-state electrolytes are widely used in solid-state

lithium batteries to help improve the slow transmission

kinetics caused by high interfacial resistance between the solid

electrolyte and the electrode. Thus, a quasi-solid-state electro-

lyte (QSSE) based on solvent ionic liquid (SIL) confined in

UIO-66 nanocages is prepared.

459

Due to the effective spatial

confinement of TFSI



through UIO-66 SNPCs and the strong

chemical interaction between SIL and metal atoms, SIL/UIO-66

QSSE exhibits high ion conductivity and good electrode com-

patibility (Fig. 17c). Therefore, Li|QSSE|LFP batteries demon-

strate excellent rate performance and cycling stability in a wide

temperature range of 25–90 1C. This study provides a practical

strategy for preparing safe solid electrolytes for high-

performance QSSE lithium-ion batteries. Apart from improve-

ment in ionic conductivity, the high interfacial resistance

between electrolyte and electrolyte is also a crucial factor to

suppress cations transportation. A QSSE based on a solvent-

type ionic liquid (SIL) confined in the UIO-66 nanocage was

prepared (Fig. 17d).

149

Due to the effective space restriction of

TFSI- in the UIO-66 pore and the strong chemical interaction

between SIL and metal atoms, SIL/UIO-66 QSSE exhibits low

interfacial resistance and good electrode compatibility. There-

fore, the Li|QSSE|LFP battery shows excellent rate performance

and cycle stability over a wide temperature range of 25–90 1C.

Additionally, a universal interphase design protocol for durable

lithium metal anodes has been proposed by Wu’s group. It is

recommended to cycle high-capacity Li metal anodes using ion

conductors with high lithium transport numbers and high

diffusion coefficients. An anion-binding semi-solid interphase

constructed with metal–organic frameworks as an ion transport

rectifying layer has been used to meet the requirement of

suppressing Li dendrite growth on practical Li metal anodes.

By using protected thin Li metal, high-loading cathodes, and

low electrolyte usage, high energy density Li metal batteries

have been demonstrated.

S/Se cathode batteries are also attracting great attention for

promising next-generation rechargeable energy storage sys-

tems. They oﬀer advantages like traditional liquid metal oxide

batteries and address the drawback of liquid-based metal-

chalcogen batteries, which is the ‘‘shuttle eﬀect’’. However,

the poor compatibility of the electrode/electrolyte interface and

the low ion conductivity of solid-state electrolytes are key

issues hindering their practicality. Thus, a gel polymer electro-

lyte (GPE) modified with a metal–organic-framework (MOF) is

utilized to stabilize the lithium anode in a Li–S battery

(Fig. 17e).

674

The MOF skeleton contains abundant pores,

which immobilize large-size polysulfide anions and cage elec-

trolyte anions, resulting in a uniform flux of Li

and homo-

geneous Li deposition. In addition, Wu et al. have designed

MOFs by incorporating two types of ionic liquids (ILs) for

creating quasi-solid electrolytes.

675

The resulting MOF-IL elec-

trolytes provide uninterrupted ion transport channels with

functional sulfonic acid groups that serve as lithium ion hop-

ping sites, thus enhancing Li

transport in both the bulk

and at the interfaces (Fig. 17f). These quasi-solid MOF-IL

electrolytes exhibit competitive ionic conductivities of over

3.0 10

4

Scm

1

at room temperature, wide electrochemical

windows over 5.2 V, and good interfacial compatibility. Apart

from employing electrolytes, MOFs can also be used as an

electrolyte additive to effectively suppress the generation of

side reactions. For example, when Li

Cl (LPSCl) is used as

an electrolyte, it is easy to release hydrogen sulfide (H

S) in a

humid environment, which affects the performance of bat-

teries. To solve this problem, the Jin group used ZIF-8 as a

desiccant in LPSCl without changing the Li

Cl electrolyte or

electrode structure. By introducing highly ordered porous

materials, we have demonstrated the stable cycling perfor-

mance of the configured LPSCl SSEs battery, due to the effective

and lasting desiccating effect.

676

Porous organic frameworks (POFs) are porous materials

constructed from organic matrices. The inherent pores of POFs

meet the demand for constructing rapid Li

diﬀusion SNPCs to

achieve high ion conductivity in solid polymer electrolytes

(SPEs). Although some studies have reported SPEs on POF

substrates, most are limited to thin-film frameworks of func-

tional groups (such as boronic esters, b-ketoimines, and tria-

zines), and the transport capacity of Li

is restricted. In

addition, stable covalent bonds are necessary to construct

porous materials with rich porous structures to ensure the

stability of fast Li

transport channels in SPEs. Porous aromatic

frameworks (PAFs) are a new type of POFs with rigid skeletons,

open structures, high specific surface areas, and excellent

stability, composed of irreversible carbon–carbon bonds. The

abundant SNPCs of PAFs allow for free diffusion of Li

. There-

fore, constructing imidazole anion-type PAFs enables easy

dissociation and efficient transport of Li

in PAF-based SPEs.

To ensure high Li

transport in SNPCs, a high Li

content is

necessary according to the classical equation: s(T)=Pn

The Sonogashira–Hagihara coupling reaction was applied to

prepare a new imidazole-based PAF (PAF-220), which was then

lithiated to obtain a highly lithium-ion conductive lithium-rich

anionic PAF (PAF-220-Li) (Fig. 18a).

677

The binding energy

between imidazole anions and Li

is low, which facilitates the

dissociation of Li

. The conjugated structure of benzimidazole

can delocalize negative charges and further reduce the binding

energy between imidazole groups and Li

. In addition, the

anionic framework can restrict the movement of anions, while

the abundant channels in the single-ion PAF-220-Li only allow

diffusion (Fig. 18b). PAF-220-Li was further vacuum-injected

with LiTFSI and combined with (polyvinylidene fluoride-co-

hexafluoropropylene, PVDF-HFP) to obtain a quasi-solid-state

polymer electrolyte (PAF-220-QSPE) with an ion conductivity of

0.206 mS cm

1

at room temperature, up to 0.76. It is worth

noting that the rigid structure of PAF-220-Li grants it good

stability, providing excellent physicochemical stability with a

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wide electrochemical window (5.0 V) for PAF-220-ASPE. There-

fore, this work provides a valuable strategy for high-

performance SPE based on functional PAF and may become a

practical means for the design of solid-state LIBs. Similarity,

Wang’s group reported a strategy to confine low molecular

weight polyethylene glycol (PEG, molecular weight = 800) into

the channels of COFs, a solvent-free strategy is used to effi-

ciently promote Li

ion movement within the SNPCs of COFs,

enabling rapid and stable conduction of cations over a wide

temperature range (Fig. 18c and d).

678

SNPCs applied in quasi-solid-state electrolytes provide

many benefits. The SNPCs can be tailored to achieve specific

properties depending on the application, which can increase

the cation transference number by allowing cation conduction

while hindering anion movement. This property is critical in

metal batteries to mitigate dendrite growth in metal anodes

and improve the cycling rate performance for metal-ion bat-

teries. Nonetheless, fully understanding the local properties of

ions inside the SNPCs as well as at the interface of bulk

electrolyte/SNPCs remains challenging.

3.3.2. Solid-state electrolytes

3.3.2.1. SNPCs in solid polymer electrolytes. Solid-state poly-

mer electrolytes (SPEs) have garnered significant interest due to

their exceptional properties in lithium-ion batteries, including

Fig. 18 (a) Schematic representation of the preparation of PAF-220-SPE and PAF-220-ASPE. (b) Illustrative drawings showing the Li

transport

illustrations of Li

transport in COFs and (d) structural representations of CD-COF, COF-5, COF-300, and EB-COF. Reproduced with permission from ref.

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low flammability, resistance to leakage, superior thermal sta-

bility, excellent processability, high flexibility, and enhanced

safety levels. Polyethylene oxide (PEO) is commonly reported as

SPEs since it was discovered that Li ions can hop from one

ethylene oxide (EO) group to the next with polymer chain

motion, thereby demonstrating some ion conduction.

679,680

By definition, in crystalline PEO, the molecular chains are

static, thereby hindering ionic conduction. Therefore, PEO-

based solid polymer electrolytes suﬀer from extremely low

ionic conductivity at room temperature due to the crystallinity

of the PEO chains and can only be applied as electrolyte above

their temperature (application above B60 1C). Contrarily,

Bruce et al. reported Li conduction in a highly ordered crystal-

lized PEO

:LiAsF

system.

681

According to X-ray diﬀraction

(XRD) analysis and ab initio simulations, they demonstrated

that in the EO : Li ratio 6: 1, the PEO chains adopt a double

helical structure forming a cylinder shape.

438

The Li ions are

located inside the cylinder whereas the anions remain outside.

This structure acts as SNPCs with the distance between Li

and EO units ranging from 2 to 2.3 Å. In order to increase

the ionic conductivity of solid polymer electrolytes, another

polymer was explored by Qi and Hu’s groups.

439

They demon-

strated the intercalation of Li ions in elementary cellulose

nanofibrils (CNFs). The copper (Cu) coordination with the

CNFs allowed the expansion of the interspacing between mole-

cular chains from 0.39 nm to 0.87 nm (Fig. 19a and b).

The decoupling of Li ions resulted in excellent ionic conductiv-

ity and transference number (Fig. 19c) and cost-eﬃciency,

scalability, and flexibility (Fig. 19d). To prove the practical

application of the as-prepared solid polymer electrolyte,

an all-solid-state pouch cell based on Li metal anodes and

LFP cathodes demonstrated exceptional cycling performance

with a capacity retention of 94% after 200 cycles at room

temperature (Fig. 19e and f). Furthermore, other ions (Na

and Zn

) and polymer (chitosan, CMC, alignate, XG/CNF)

combinations are also suitable for creating analogous solid

polymer electrolytes.

Another approach to improve the ionic conductivity of solid

polymer electrolytes through SNC engineering involved utiliz-

ing MOFs grown on polymer networks. Zeng et al. in situ grew a

MOF functionalized with high-density electronegative groups

(Zr-BPDC-2SO

H) on bacterial cellulose (Fig. 19g and h).

440

The

in situ growth enabled minimization of the interfaces between

MOF particles and provided a continuous ion conduction

pathway. They demonstrated a Li transference number of 0.88

(Fig. 19i), achieving a high specific capacity of 119 mA h g

1

at a

high cycling rate (3C). Recently, Hu et al. employed a layered

composite solid polymer electrolyte composed of Uio66-NH

MOF particles and the PVDF-HFP-LiTFSI-SN-FEC solid

polymer.

441

The MOF layer acted as an anion sieve owing to

the sub-nanopores of the MOF particles,while facilitating high

Li conduction. Therefore, the composite solid electrolyte exhib-

ited an ionic conductivity of 0.245 mS cm

1

. The Li ions forced

through the sub-nanopores of the MOF layer generated a uni-

form Li flux, which benefit excellent Li plating and stripping

cycling performance.

3.3.2.2. SNPCs in inorganic solid electrolytes. Inorganic solid

electrolytes can be categorized into three large families accord-

ing to their chemical structure:

682,683

oxides, which regroups

perovskite conductors (ABO

–type, the general formula is

2/3x/3

TiO

, LLTO), anit-perovskite conductors (e.g.,Li

OCl

and Li

OBr), NASICON conductors (Na

1+x

3x

and

LiM

(PO

)

(M = Zr, Ti, Hf, Ge or Sn)) and garnet-type con-

ductors (e.g.,Li

(M = Nb, Ta), orthosilicate garnets

3II

2III

(SiO

)

), A

(A = Ca, Mg, Y or Ln = La, or rare-earth

elements; B= Al, Fe, Ga, Ge, Mn, Ni, and V), cubic Li

(LLZO)); sulfide-type, which reassembles thio-LISICONs

with the formula Li

4x

1y

(M = Si, Ge, and M’ =P, Al,

Zn, and Ga), LGPS family (Li

GeP

,Li

SnP

, and

9.54

1.74

1.44

11.7

0.3

), arygodrites-type with the common

formula Li

X (X =Cl, Br, and I); halide-type with the for-

mula—Li

, where X represents I, Br, Cl, and F while M is a

metal element (e.g.,Li

InCl

,Li

YCl

,Li

ErCl

, and Li

ZrCl

Recently, Kang et al. reported the control of superionic

conduction in ternary halides (e.g.,Li

MCl

[where the metal

(M) is Y or Er]) by manipulating the in-plane lithium diﬀusion

pathways and the stacking layer distances. These two factors

are negatively correlated with each other through the partial

occupancy of M, which acts as both a diﬀusion inhibitor and a

pillar to maintain interlayer distances. The authors demon-

strated the critical range or ordering of M in ternary halides and

showed the achievement of high ion conductivity by adjusting

the simple M ratio. This work provides a general design

standard for superionic ternary halide electrolytes.

684

Besides,

the inorganic solid electrolytes contain metal cations, which

take part in electrochemical reactions. As shown in Fig. 20a, the

conduction occurs through diﬀerent mechanisms: intersti-

tial hopping, interstitial knock-oﬀ and vacancy hopping.

666,685

The atomic sites in inorganic solid state electrolytes can be

compared to sub-nanopores and the cation conduction analo-

gously occurs through sub-nanochannels. Kato et al. discovered

a superionic conductor Li

9.54

1.74

1.44

11.7

0.3

, which showed

the highest Li

conduction reported for inorganic solid-state

electrolytes (Fig. 20d).

442

They demonstrated that the double

substitution with aliovalent-ion doping (Si and Cl atoms)

creates a 3D Li

conduction pathway in Li

9.54

1.74

1.44

11.7

0.3

The 1D pathway is characteristic of the LGPS family, while the

2D pathway could be attributed to the small amount of Cl

atoms located in the Cl(1) (8g) sites situated in P(2b)X

tetra-

hedra (Fig. 20d and e). Therefore, the ionic conductivity in

solid-state electrolytes is closely related with the conduction

pathways. Inorganic solid electrolytes are polycrystalline, i.e.,

contain grains and grain boundaries. The ionic conductivity in

the grains, across the grain boundaries and in the grain

boundaries varies largely depending on the crystallographic

structure of the inorganic solid electrolyte. This leads to two

competing conduction pathways: from one grain to the neigh-

bouring grain, i.e., across the grain boundary, named ‘‘the

granular pathway’’, and within the grain boundaries, named

‘‘the grain boundary pathway’’ (Fig. 20b and c). The granular

pathway will be preferential when the grain boundaries are

more resistive than the grain, for instance, in LATP and Li

OCl.

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Otherwise, the grain boundary pathway will dominate, which is

the case for sulfide-based electrolyte and some oxides such as

LLZO.

443

Several strategies have been explored to increase the ionic

conductivity in inorganic solid-state electrolytes. Although not

fully understood yet, it was demonstrated that employing a

doping and/or substitution strategy can dramatically increase

the ionic conductivity. For instance, the introduction of 0.3 Al

mol per unit in the LTP crystal enriches the M3 site in Li atoms,

thereby opening a new conduction channels M1-M3-M1 site

with an activation energy between M1/M3 and M3/M1 much

lower than that between M1/M1.

444

The new conduction chan-

nels enable LATP to exhibit a much higher ionic conductivity

than the parent LTP crystal. However, substituting Ge

by Si

or Sn

in LGPS-type solid electrolytes resulted in lower ionic

conductivities. It is thought that Si doping narrows the sub-

nano channels for Li

migration; further fundamental investi-

gations on Li

conduction pathways at a sub-nanoscale are

necessary to develop novel superionic conductors.

683

The

substituted and/or doped element intrinsic characteristics

Fig. 19 (a) Schematic illustration of the structure of CNFs. Bottom: Coordination of Cu

ions with the hydroxyl groups of cellulose which opens the

spacing between the molecular chains, creating cellulose molecular Li

-conducting channels in the CNFs. (b) Scanning electron microscopy (SEM)

image of the CNFs. (c) Transference number is plotted against Li

ionic conductivity for Li–Cu–CNF and for other SPEs PEO-inorganic composites,

cross-linked polymers, and a high-Li-concentration electrolyte. (d) Digital photograph of a 1-m-long roll of Li–Cu–CNF membrane. (e) Illustrationofa

Li|Li-Cu-CNF|LFP all solid-state battery Li-metal as anode, Li–Cu–CNF paper as electrolyte and LFP/CNT/Li–Cu–CNF as a cathode. The Li–Cu–CNF

(green fibres) enables transport of Li

ions (yellow arrows), and CNTs (red fibres) in the cathode enable electron transport (red arrow). (f) Cycle

performance of a solid-state LiFePO

cell made using Li–Cu–CNF ion-conducting binders in the cathode, Li–Cu–CNF electrolyte, and a Li-metal anode.

crystal structure of Zr-BPDC-2SO

H. Color code: Zr, purple; O, blue; C, gray; and S, yellow. (h) Bottom–up synthesis of cross-linked MOF chains on the

BC skeleton. (i) The ionic conductivities of Zr-BPDC-2SO

HforLi

,Na

, and Zn

American Chemical Society.

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(e.g., atoms size, valence, etc.) greatly influence greatly the bulk

ionic conductivity. Besides, the crystal phase also seriously

impacts the ionic conductivity due to the diﬀerent arrangement

of atoms. For instance, LLZO solid-state electrolyte has two

crystal structures, the tetragonal phase (t-LLZO) and cubic

phase (c-LLZO). In t-LLZO, all the Li

positions in the crystal

structure are occupied, whereas in c-LLZO, one site is occupied

while the two neighbouring sites are vacant. The c-LLZZO

exhibits approximatively twice the ionic conductivity of t-

LLZO.

686

Another challenge suppressing the development of all-solid-

state batteries is the high interface resistance between the

electrolyte and the electrode, which has a significant impact

on the overall performance of the battery.

687

In all-solid-state

batteries, electrochemical reactions occur at the solid–solid

electrolyte–electrode interface. Ions diffuse from the electrolyte

to the electrode through their interconnected region and

undergo oxidation–reduction reaction at the electrolyte–

electrode interface in contact with the active material and

electrons. Therefore, maintaining a good solid–solid electro-

lyte–electrode interface in the battery is crucial for achieving

stable charge transfer reactions. One of the main causes of high

interface resistance is the chemical and electrochemical

instability between the solid electrolyte and the electrode, such

as the space charge layer of local ion vacancies in the electrolyte

near the electrode, which severely limits the rate capability of

the battery due to the chemical potential difference between the

electrode and the electrolyte, causing ions to be extracted from

the electrolyte to the electrode side.

688

In addition, poor contact

between the solid electrolyte (especially inorganic solid electro-

lyte) and the electrode is also a major issue affecting ion

diffusion.

689

The volume changes of cathodic and anodic

materials during charge and discharge processes may lead to

the loss of effective contact between the electrode and the solid

electrolyte, thereby limiting the conduction of ions in the

interface area. Furthermore, it is worth noting that the diffu-

sion layer of elements formed at the electrolyte–electrode inter-

face is also an important resistance for the deterioration of

interface stability during the cycling process.

690

Since the solid

electrolyte is physically inflexible, the battery manufacturing

process usually requires additional heating steps to improve

the adhesion between the electrode and the electrolyte (oxides).

Therefore, an element mutual diffusion region forms at the

solid–solid interface, accompanied by the formation of signifi-

cant and inevitable interface resistance.

Various methods have been proposed to improve the inter-

face between the solid-state battery electrolyte and electrode.

Interface resistance is mainly attributed to the incompatibility

between the solid-state electrolyte and electrode, due to eﬀects

like space charge, chemical and electrochemical instability, and

interdiﬀusion. Coating ion-conductive and electron-insulating

buﬀer layers on the electrode is an eﬀective way to reduce

American Chemical Society. (c) Arrhenius conductivity plots for the LGPS family and Li

9.54

1.74

1.44

11.7

0.3

. (d) Crystal structure of

9.54

1.74

1.44

11.7

0.3

. The framework structure consists of 1D polyhedral chains. (e) Nuclear distributions of Li atoms in Li

9.54

1.74

1.44

11.7

0.3

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incompatibility. Ohta et al. found that coating Li

0.33

0.557

TiO

(LTO) on LiCoO

(LCO) particles significantly improved the rate

performance of all-solid-state lithium metal batteries based on

sulfide electrolytes, due to reduction in the space charge layer

eﬀect.

691

Besides, introducing an artificial SEI layer with elec-

tron insulation and ion conduction is also an eﬀective method

to reduce interface instability. Goodenough’s team illustrated

the formation of an ion-conductive passivation layer composed

of Li

P and Li

ZrO

on LiZr

(PO

)

solid electrolyte, in contact

with Li metal.

692

In addition, enhancing the electrode–electro-

lyte contact area through electrode–electrolyte nanocomposites

is a commonly employed method, using techniques such as

ball milling, pulsed laser deposition (PLD), and softening glass

electrolytes. Hayashi et al. reported that a significant improve-

ment in the solid–solid interface contact area between the

electrode and electrolyte was achieved by obtaining electrode–

electrolyte nanocomposites through mechanochemical balling.

The large volume changes in the electrode during charge and

discharge processes would lead to significant interface stress

changes, posing a serious problem. Decorating an interface

layer that can closely contact the electrode is an interesting

approach. Yamamoto et al. reported that introducing an NbO

layer at the LCO electrode–solid electrolyte interface effectively

mitigated interface stress during delithiation.

693

Solid-state electrolytes are showing increasingly attractive

prospects and potential. Scientists and engineers still need to

work hard to develop solid-state electrolytes that are commer-

cially competitive in terms of ion conductivity, interface impe-

dance, mechanical strength, and electrode compatibility, while

also being cost-eﬀective. It should be noted that diﬀerent

advantages should be eﬀectively utilized according to diﬀerent

applications, such as high-power density for portable electronic

products and electric vehicles, and low maintenance costs for

smart grid energy storage, in addition to the required high

energy density. Exploring new technologies, such as optimizing

battery design structures to improve overall performance, is

also essential. Furthermore, modifying existing battery manu-

facturing processes or reinventing new manufacturing technol-

ogies for all-solid-state lithium metal batteries is also important

for short-term practical applications.

3.4. SNPCs in separators/interlayers

For rechargeable batteries, the separator plays a crucial role,

whose main function is to separate the cathode and anode

electrodes to prevent short-circuiting while allowing for the

rapid transfer of the ionic charge carrier required by the circuit

as the current passes through the cell.

694,695

They should be

good electronic insulators and could conduct ions through

intrinsic ionic conductors or by soaking electrolytes. They

should minimize any processes that adversely aﬀect the elec-

trochemical energy eﬃciency of the battery.

For example, the separator is a very crucial component that

influences the mass transport of cations across the electrodes,

which aﬀects the anode dendrite growth.

435,696

However, the

separator currently in use is prone to cause an in-homogenous

cation flowing pattern, leading to nonuniform cation transfer

that renders dendrite growth.

697

To address this issue, to

design a separator with appropriate and uniformly distributed

SNPCs may aid in the propagation of anode dendrites. For

instance, Rajendran et al. discovered a carbon nanomembrane

(CNM) with an incredibly thin thickness of 1.2 nm (Fig. 21a).

159

This remarkable CNM contained SNPCs measuring 0.7 nm,

which acted as an interlayer to control the movement of Li

during mass transport. The presence of these SNPCs improved

the contact and wetting properties at the electrode and electro-

lyte interface, promoting rapid ion diﬀusion. Compared to

using a Celgard separator alone, the Li-ion transference num-

ber increased to 0.67 when the CNM/Celgard separator was

employed. A higher Li

transference number eﬀectively delayed

dendrite nucleation, resulting in nearly stable cycling for more

than 600 hours. This extended cycling time demonstrated

successful dendrite suppression, in contrast to the control

experiment where Li dendrites were observed. Additionally,

the CNM/Celgard separator exhibited exceptional mechanical

strength (Young’s modulus B10 GPa), preventing dendrite

penetration. Besides, the materials with low mechanical

strength restrain their application as separator in batteries.

The larger and wider pore size distribution of the separator can

create steep local concentration gradients at the electrode–

electrolyte interface, which further increases the uneven

deposition of ions and the formation of fibrous, mossy, and

dendritic anode metals.

698,699

Recently, in-depth research on

separator modification has been implemented. A separator

with high mechanical strength can prevent dendrite penetra-

tion. A separator with SNPCs can regulate the uniform ion flux

near the electrode surface, thereby promoting uniform metal

nucleation and growth. Archer and colleagues developed a porous

separator with high mechanical moduli and easy ion transport.

It comprises a well-ordered porous Al

sheet between micro-

porous poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-

HFP) polymer layers, forming a sandwich-type composite

architecture. The physical properties, including the elastic mod-

ulus and ionic conductivity, were influenced by the pore size,

which is crucial for electrochemical performance.

700

The elastic

modulus of the PVDF-HFP/Al

separator is approximately

0.4 GPa. The ionic conductivity of the PVDF-HFP/Al

separators

was measured at 1 10

3

Scm

1

. Following optimization, the

separators utilizing Al

demonstrated superior performance in

terms of low internal resistance, high CE, and long cycling

performance. Additionally, MOFs and COFs with a highly uniform

SNPC structure make them a promising candidate for construct-

ing separators. Qi et al. prepared a Ti-MOF modified polypropy-

lene/polyethylene separator for rechargeable batteries. Thanks to

the better electrolyte wettability, less resistance, highly intrinsic

SNPCs and Lewis acid characteristics of Ti-MOFs, this modified

separator exhibited the smooth transport of Li

522

Similarity, a

thin film of covalent organic frameworks (COFs) with azobenzene

side groups branching from the pore walls was employed as a

separator,whichactsasion-hoppingsitesthuspromotingNa

migration.

519

For metal–chalcogen batteries, SNPC modified membrane

separators are not only beneficial for cation transport, but also

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exhibit blocking capability for poly-chalcogen intermediates.

On the other side, excessively small pore sizes may hinder the

diffusion of cations, resulting in retarded redox kinetics. There-

fore, precisely adjusting the size of SNPCs is the key factor for

improving the performance of metal-chalcogen batteries. The

DFT calculations indicate that the SNPCs with a smaller pore

size always exhibit a narrow band gap, which could efficiently

block polysulfide shuttling.

701

Sun’s team synthesized two-

dimensional polymer nanosheets, and then deposited the

modified layers on a separator to form a composite membrane

rich in phenol and triazole units, as well as lithium sites in the

ordered channels of the polymer nanosheets.

702

Due to its

unique SNPCs, Li-COF-based membrane separators can greatly

facilitate the transport of lithium ions while limiting the

diffusion of polysulfides. As a result, the cells obtained showed

higher specific volumes at different rates. Another example

involves the synthesis of a porous SNPC aromatic framework

(SAF) modified separator, which was designed for all-climate

operation of Li–S batteries.

703

After rational molecular engi-

neering design, we developed fully conjugated SAF-3 with

SNPCs (0.97 nm) and the polysulfide migration barrier up to

33.21 eV (Fig. 21b). In addition, Bader charge calculations

(Fig. 21c and d) revealed that SAF-3 transferred more electrons

when interacting with Li

.In situ X-ray photoelectron spectro-

scopy (XPS) and in situ XRD tests show that the SA3-modified

separators can inhibit the transfer of polysulfide and promote

Fig. 21 (a) Schematic representation of the synthesis and transfer process of the CNM onto Celgard separators. Reproduced with permission from ref.

on the SAF-3 skeleton; purple colour represents the electron-rich zone and yellow colour represents the electron-deficient zone, respectively. (d)

Charge transfer analysis between Li

Sons. (e) Schematic of the fabrication process to produce MOF@GO separators. The MOF nanoparticles and introduced GO laminates synergistically

comprise a MOF@GO separator. (f) An illustration of the microporous crystalline structures (HKUST-1). The homogeneous coordinated structures are

Springer Nature.

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its redox conversion. As a result, SAF-3 modified batteries can

work well in a wide temperature range of 40 to 60 1C, showing

all-weather battery performance.

Moreover, MOFs with SNPCs can function as a sieve to

separate specific ions from an ionic solution based on their

sizes and shapes, making them akin to an ionic sieve. MOF-

based materials possessing a significant surface area and well-

structured pores with adjustable porosity are ideal choices as

ionic sieves for reducing the migration of polysulfide ions.

Thus, MOF modified separators are tailored for lithium–sulfur

batteries. This MOF acts as a battery separator by selectively

filtering Li

ions while preventing polysulfides from passing

through. Cu

(BTC)

(HKUST-1) is selected as the MOF to con-

struct the MOF@GO separator due to its three-dimensional

channel structure (Fig. 21e), which contains highly ordered

micropores. These micropores have a size window of about 9 Å

(Fig. 21f), making them significantly smaller than the dia-

meters of lithium polysulfide (Li

,4onr8). This property

makes it ideal for blocking polysulfides. The MOF@GO separa-

tor has demonstrated high efficiency in blocking polysulfides

and remarkable stability over long-term cycling in a lithium–

sulfur battery.

517

Advanced separators are beneficial for battery performance.

However, there are still many issues that separators cannot fully

solve. Due to the inevitable ion concentration gradient during

battery cycling, there can be uneven ion transport eﬃciency,

which can lead to dendrite formation on the anode side. In

addition, in metal–chalcogen battery systems, although multi-

functional separation membranes can block polysulfide spe-

cies, the unstable polysulfides species can still result in their

migration across the separator, which leads to irreversible loss

of active materials and continuous degradation of battery

performance. Therefore, embedding an interlayer is crucial

for metal-ion batteries with long cycle life, metal anode bat-

teries, and metal–chalcogen batteries. The Manthiram group

first proposed the important concept of ‘‘interlayer’’ in 2012

(Fig. 22a). Since then, extensive research has been conducted

on interlayer materials resulting in significant improvements.

Here, the interlayer of SNPCs plays an important role. In 2012,

Yu et al. first prepared the SNPCs hard carbon (HC) to encap-

sulate Li metal in these SNPCs (Fig. 22b and c), which can

prevent the direct contact between electrolyte and anode Li

while providing large accommodation space for Li storage,

restricting the dendrite growth of Li metal.

392

Recently, a

MoS

nanosheet has been used as an interlayer loaded on the

Celgard separator, seving as an effective polysulfide barrier,

resulting in high Coulombic efficient cycling stability

(Fig. 22d).

254

It is because the interspace between MoS

can

serve as an ionic sieve to selectively allow Li ion transport while

suppressing the shuttle effect. It was also found that chemical

reactions could occur between polysulfide and tungsten at the

edge of the micron-sized WS

wafer, effectively improving the

performance of Li–S cells.

704

When SNPC interlayers are

applied on the anode side, the interlayers are commonly

anchored to the separator facing the anode side or grown on

the surface of the anode. SNPCs can guarantee the smooth ion

transfer and avoid the corrosion reaction between the electro-

lyte and anode side. Moreover, preparing inherent regular

SNPCs on the SEI membrane could lead to uniform cation flux

at the electrode/electrolyte interface, causing uniform metal

deposition. A COF-based ultrafine artificial SEI was fabricated

by Guo’s group to regulate LiF formation and distribution in

the SNPCs in COFs. As illustrated in Fig. 22e, the high Li

affinity of COFs facilitates the adsorption of lithium salts from

the dilute electrolyte, resulting in an increase in the local

electrolyte concentration by an electrical double layer (EDL)

around the COF skeletons. Upon electrochemical lithiation of

the COF film during the first cycle, the reductive decomposition

of the strongly bound Li-salts locally generates uniformly dis-

tributed LiF domains. Such a homogeneous COF-LiF film

serves as a desirable SEI. The discrete LiF grains are confined

within the periodic microporous frameworks, endowing the

lithium/electrolyte interphase with considerably enhanced pas-

sivation and mechanical properties against dendrite growth

and electrolyte penetration. Meanwhile, the lithophilic moiety

of COFs facilitates Li

ion transport through the periodic COF

skeletons. Consequently, long-cycling stability of symmetric

lithium metal batteries has been attained in both ether- and

carbonate-based electrolytes.

705

Qiu’s research group prepared

a composite interlayer composed of carbon nanofibers (CNFs)

grown from a metal–organic framework (ZIF-67) enriched with

Co (Fig. 22f).

706

It is worth noting that the ZIF/CNF composite

interlayer can synergistically achieve physical blocking and

chemical capture capabilities, thereby inhibiting the dissolu-

tion of polysulfides and mitigating the shuttle effect. In addi-

tion, the three-dimensional fibrous network provides an

interconnected conductive framework between each ZIF

micro-reactor, facilitating rapid electron transfer during the

cycling process, which contributes to excellent rate and cycling

performance. The interlayer is also used in quasi-solid-state

electrolyte to reduce the loss of liquid electrolyte by adjusting

the solvation environment of moving ions in the layer. Thus,

Kim et al. introduce a novel approach to enhance the stability

and performance of Li metal batteries (LMBs). They present a

composite layer consisting of a single-ion-conducting ceramic

electrolyte (S-CE) and a single-ion-conducting polymer (S-PE)-

based gel electrolyte (S-GE).

518

This composite layer, referred to

as S-CE/S-GE, acts as a modulator for the reactivity of liquid

electrolyte components. By applying the S-CE/S-GE layer onto a

Li metal electrode, the loss of liquid electrolyte on the electrode

is significantly reduced. This layer also improves the cycling

stability of LMBs by altering the solvation environment of Li

ions within the layer (as shown in Fig. 22g). Interestingly, this

effect is not observed when using a composite layer comprising

S-CE and a bi-ion-conducting polymer (B-PE)-based gel electro-

lyte (B-GE). Furthermore, the researchers demonstrate that the

S-CE/S-GE layer has an impact on the morphology of Li anodes

and the stability of the cathode–electrolyte interface in Li metal

batteries. Leveraging the benefits of the S-CE/S-GE composite

layer, they successfully developed an energy-dense Li metal

pouch (Fig. 22h), which exhibits operation for over 400 cycles

with a low mass of electrolyte content of 2.15 g Ah

1

. The

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careful engineering of the solvation structure and the resulting

outcomes provide valuable insights into the control of inter-

facial reactions and offer a practical methodology to enhance

the performance of LMBs.

4. Practical challenges

As comprehensively discussed above, electrochemical coupling

of SNPCs in a wide variety of electrode materials has been

crucial to enhance the performance of the batteries, which is

Fig. 22 (a) Schematic configuration of the cell with a bifunctional microporous carbon interlayer inserted between the sulphur cathode and the

separator. (b) SEM image of the surface of the MCP and (c) transmission electron microscope image of the microporous carbon particles. Reproduced

/Celgar separator.

illustration of the effects of the S-CE/B-GE and S-CE/S-GE composite layers on the cycling stability of liquid electrolyte-based LMBs and (h) cycling

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anticipated to be widely recognized and further explored in

future research studies. Despite significant advances in the past

few years, the employment of SNPCs in rechargeable batteries

is still in its infancy. To pave the way for future investigations, it

is essential to emphasize the practical challenges for SNPCs at

the current stage, as presented in Fig. 23.

4.1. Angstrom resolutions

The understanding of SNPCs has long been scarce, and one of

the major obstacles is the resolution limitations of traditional

characterization methods. To acquire accurate structural infor-

mation of the SNPCs, angstrom scale resolution is required.

The surface morphology of the samples is generally obtained

using a scanning electron microscope (SEM) which collects

scattered electrons for analysis, and the optimal spatial resolu-

tion achievable is about 0.5 nm, while transmission electron

microscopy (TEM), which collect transmitted electrons for

analysis, oﬀers a much better spatial resolution with more

structural information such as lattice fringes and crystal struc-

tures. TEM can analyze the elemental composition of the

samples at high resolution when coupled with energy-

dispersive X-ray spectroscopy (EDS) or electron energy loss

spectroscopy (EELS); the former is particularly sensitive to

heavier elements while the later tends to work best for elements

with low atomic numbers. Whereas the specimen for TEM

analysis should be very thin (o150 nm) to permit electron

transmission, and even below 30 nm is generally required for

high resolution images. Scanning transmission electron micro-

scopy (STEM) can be deemed as the combination of SEM

and TEM, which can analyze both scattered and transmitted

electrons; it requires stable room environments (limited

temperature fluctuations, electromagnetic waves, acoustic

waves, etc.) and can deliver an optimal spatial resolution of

0.5 Å.

707

With the advancement of detectors and computational

power, 4D STEM with beam rasters across a 2 dimensional

region in real space has been invented.

708

It does not necessa-

rily result in higher resolution for 4D STEM; however it can be

extremely helpful for specimens with distorted structures due

to high strain. It is worth noting that, it generally requires to

apply a high dose of electron on a small sampling area to get

enough yield of electrons for high resolution analysis, whereas

many samples are less tolerable to electrons and can get

damaged by the focused electrons. Cryogenic electron micro-

scopy (cryo-EM) is another extension of TEM technology, which

can operate at cryogenic temperatures to minimize the sample

movement or damage. Cryo-EM has been widely used for

structure determination of biomolecules, which has recently

been utilized for battery materials, oﬀering significant contri-

butions to the field.

709

The invention of cryo-EM enabled the

acquisition of atomic structures for a wide variety of sensitive

battery materials at the angstrom scale, such as, air and

electron sensitive Li/Na metal, air and electron sensitive SEI

layers, and volatile S elements.

710

In addition to various electron microscopy techniques, other

morphology and structural information from diverse character-

ization techniques are also essentially required. X-ray diﬀrac-

tion (XRD) has been a powerful tool to characterize the lattice

patterns of nanocrystals at the angstrom scale, while the lattice

distortion may cause broadening and overlap of the diﬀraction

peaks.

711

High spatial and angular resolution XRD can be

achieved by reducing the beam divergence in high photon

fluxes synchrotron sources. For instance, synchrotron XRD with

Fig. 23 The practical challenges associated with SNPCs for rechargeable batteries.

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a high resolution of 1.9 Å has been achieved, which could

identify light elements such as oxygen and water molecules.

712

Besides, X-rays are suited for superficial analysis of shallow

depths or thin specimens, while neutron diﬀraction with its

high penetration depth is suited for bulk samples.

713

Other

angstrom characterization techniques, such as, atomic force

microscopy (AFM) and tip-enhanced Raman spectroscopy

(TERS) should be further investigated for SNPCs.

714

Since the

SNPCs cover a wide range of material families with diverse

physicochemical properties, it is necessary to choose suitable

specimens for characterization of angstrom resolutions to

acquire the desired information.

4.2. Operando characterization

For the electrochemical coupling of SNPCs in various batteries,

dynamic evolution of various species during the electrochemi-

cal reactions is of particular interest. Whereas most of the

results were achieved through post-mortem analysis, for which

the composition of the electrodes may have changed during the

sampling process. Therefore, it is essential to develop various

operando or in situ characterization techniques to investigate

the dynamic electrochemical evolutions under real time work-

ing conditions. Here, the high-resolution in situ transmission

electron microscope (TEM) electrochemical experimental plat-

form is very important for observing battery reactions. This

technology allows direct visualization and timely discovery of

changes in materials during the charging and discharging

process, helping researchers to deeply understand the mecha-

nism of SNPCs for ion storage. In addition, high-resolution

in situ TEM can also observe the phase change process of the

cathode material during battery operation, which helps

researchers understand the working mechanism of the battery

and make timely adjustments. The development of high-

resolution in situ TEM allows researchers to observe the struc-

tural changes of materials during charging and discharging at

the atomic level in real time. This is crucial for understanding

the mechanism of battery reactions and optimizing battery

adjustments. Compared with traditional post-reaction charac-

terization, high-resolution in situ TEM can precisely control and

capture the dynamic changes of materials, revealing the rela-

tionship between the structure and performance. However, the

current in situ TEM technology still faces great challenges; first,

it is diﬃcult to carry out high-rate (atomic level) characteriza-

tion; second, the ability to combine other technologies such as

EDS and EELS is still weak. The high-resolution in situ TEM

would become a powerful tool, not only capturing structural

information of nanomaterials in specific environments, but

also guiding the design of functional materials. In addition,

another feasible option is to use a high-throughput synchrotron

light source to penetrate the seal of the battery and generate

enough signals for analysis, for instance, synchrotron-based

XRD, synchrotron-based X-ray absorption spectroscopy

(XAS),

715

and synchrotron-based scanning transmission X-ray

microscopy (STXM).

716

In situ synchrotron XRD has been widely

used for various battery systems to investigate the lattice

parameters, phase transitions, and strain evolution of electrode

materials under real time operando conditions, which are

extremely useful for an in depth understanding of the working

mechanisms. In situ synchrotron XAS could provide the oxida-

tion state and coordination environment of the elements (X-ray

absorption near edge structure, XANES), and also the coordina-

tion numbers, bonding distances, and the chemical identity of

nearest neighbours (X-ray absorption fine structure, EXAFS).

717

In situ synchrotron STXM could achieve site-specific informa-

tion on chemical and structural changes of the electrode

materials within single particles at high spatial resolution

(B20 nm), therefore, it is powerful for understanding the

working mechanisms of the electrode materials under operando

conditions. Other synchrotron-based characterization techni-

ques, for instance, synchrotron micro-computed tomography

(MCT) while unable to achieve high resolution at the angstrom

scale, could also be further explored for SNPCs due to their

capability of acquiring various structural information under

operando conditions.

4.3. Atomic perceptions

Up to now, most of the reports on SNPCs for battery applica-

tions are focused on the microstructures and electrochemical

performance of the electrodes, whereas an in depth under-

standing of the working mechanisms at the atomic level is

insuﬃcient. Accompanied by the abovementioned angstrom

resolution and operando characterization studies, it is much

more desirable to decipher the working mechanism with

atomic perceptions. For instance, the encapsulation of S in

SNPCs could alter the atomic configuration from cyclic S

short chain S

2–4

species, which could bypass the generation of

soluble long chain polysulfides to minimize S dissolution. This

is a good example of the process from quantitative change to

qualitative change, in which the impact of the SNPCs should be

carefully considered with atomic perceptions. Besides, the

atomic configurations of the doping elements in SNPCs, e.g.,

S doping at different sites in hard carbon, could result in

significantly different electrochemical performance due to dif-

ferent working mechanisms, further verifying the significance

of angstrom resolution characterization studies and atomic

perceptions. For the electrochemical coupling of SNPCs in

various batteries, it is highly important to have a closer look

at the working mechanisms from an atomic perspective. Espe-

cially, the solvation structure of the ions, the composition of

the SEI layers, the influence of the doping elements with

different atomic configurations, the atomic configuration of

the species restricted in the SNPCs, and the interaction of

various species with the building blocks of SNPCs should be

investigated with atomic perceptions to explore the underlying

working mechanisms.

4.4. Theoretical calculations

With the significant advancement of theoretical calculations in

the last two decades, many key properties of the batteries can

be accurately predicted. The capabilities of theoretical calcula-

tions for batteries including theoretical capacity, equilibrium

voltage, ion diﬀusion pathways, electronic conductivity, rate

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capability, thermal stability, etc.

718

These properties are invalu-

able for battery research community, oﬀering an alternative

‘‘prediction and validation’’ route instead of ‘‘trial and error’’

routine for experimental research. Therefore, the potential of

theoretical calculations for electrochemical coupling of SNPCs

in carious batteries should be further explored to enhance the

fundamental understanding of the working mechanisms. For

instance, selective ion transport in SNPCs of MOF based SSEs

has been validated through density functional theory (DFT)

calculations and molecular dynamics (MD) simulations, which

are essential for the atomic understanding of the working

mechanism.

719

While theoretical calculations for various bat-

tery materials have been frequently carried out for crystalized

inorganic materials, modelling and calculation of organic and/

or amorphous materials have been challenging. The SEI layers

on the anode surfaces which are generally composed of organic

and inorganic composites are very meaningful yet challenging

for DFT calculations. As for the SNPCs, one must consider the

size eﬀect of the nano particles, for which the properties may be

dramatically changed at the subnanometer scale. For example,

nanosized LiFePO

could deliver ultrafast Li

extraction, for

which the low-energy surfaces of the nanocrystals account for

up to 85% of the total surface area.

720

Besides, calculations

for solid-state materials with known crystal structures have

been widely achieved, while those with multiple phases and/or

physical fields are diﬃcult, e.g., the interfaces of the electrodes

with complex interactions such as electric field, electrostatic

field, steric hindrance, solvation structure, ion dissociation,

electrochemical voltage window, etc.

Furthermore, with the development of computational power

and artificial intelligence, a new branch of computation known

as ‘‘machine learning’’ has recently surged. Machine learning is

a protocol to feed the program with plenty of known results for

the computer and establish an approximate model between

input and output, with which artificial intelligence could learn

and discover an optimal algorithm to summarize the results

with minimum deviation.

721

After numerous optimizations, the

algorithms can be used to predict the results for unknown

species or systems. It is remarkable that we can find the

algorithms before understanding the underlying correlations

between the properties and the performance, the algorithms in

turn could be helpful to discover the decisive parameters for

the systems. The capabilities of machine learning should be

further explored for SNPCs in batteries, which could certainly

lead to a new era for close combination of theories with

experiments by data-driven computations.

5. Conclusion and perspectives

To meet the growing demand for batteries, the development of

new materials that improve the eﬃciency of energy conversion

and storage systems is crucial. The materials with SNPCs oﬀer

opportunities in energy conversion and battery storage applica-

tions due to their unique physio-chemical properties. As illu-

strated in Fig. 24, the most straightforward advantage of the

SNPCs is that they could achieve regulated ion transportation,

facilitate selective and fast ionic transport through the size

eﬀect or electrostatic eﬀect through the SNPCs.

435,722–724

Besides, the SNPCs with carbon layers or conductive polymers

can serve as an electrically conductive matrix, realizing superior

electrical conductivity. The combination of fast ion transfer and

high overall electrical conductivity could contribute to high-rate

capabilities.

392,725

In addition, some SNPCs as artificial SEIs or

protecting layers could relieve the volume change of the elec-

trode materials as a result of the suppression effect, to

enhance the cycling stability of the electrodes.

726,727

The SNPC

protecting layers can also deliver good ion and electron

conductivity, to enhance the rate performance of the

electrodes.

728,729

Furthermore, by introducing SNPCs into the

materials, higher surfaces area with additional active sites can

be achieved; therefore the reversible specific capacity can be

increased.

730,731

Noticeably, the void formation should be

avoided during the SNPCs fabrication process. The generation

of voids will greatly affect the inherent electrical conductivity of

the matrix. When the void exists, the electrons transformation

will be greatly suppressed. The electrons must achieve more

energy to overcome the transfer barrier created by the voids. In

a word, the SNPCs in the battery materials can enhance the rate

capability, enhance the cycling stability, and increase the

reversible specific capacity of the anodes. Thereafter, the sig-

nificance of SNPCs for various anode materials should be

further explored in the following research.

This review comprehensively covers all aspects of SNPCs and

their involvement in electrochemical reactions within batteries

for the first time. We first define SNPCs and then, we rationally

sorted the families of SNPCs materials and summarize the

unique physicochemical properties of SNPCs. With respect to

the electrochemical applications of SNPCs in rechargeable

batteries, we have systematically summarized the electroche-

mical reactions occurring on various components of the battery

in SNPCs. The challenges for the practical application of SNPCs

in batteries have also been discussed in detail. Furthermore, to

further explore the huge potentials of SNPCs for rechargeable

batteries, we have summarized the perspectives for future

research as followed.

Synthesis of SNPCs

With the highly sought-after attributes of simplicity, environ-

mental friendliness, and controllability of SNPCs structure

synthesis materials, an increase in supply will inevitably lead

to a wider range of applications. Compared to the synthesis of

materials with larger pores, mesopores, and micropores, the

synthesis of SNPCs structures requires carefully designed pre-

paration schemes because their sensitivity to reaction condi-

tions depends on each composition and intermediate phase. In

most methods, such as template methods, they may not be

applicable to the reconstruction of controllable SNPCs. In

addition, the size, structure, and interaction of the components

will greatly aﬀect the synthesis of SNPCs structures. Consider-

ing these factors, it is crucial to find a template-free, simple,

and eﬀective technique to control the synthesis of SNPC

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materials, like the use of metal–organic frameworks in chem-

istry. In energy conversion and storage devices, controlling the

overall particle size, surface structure, morphology, packing

density, orderliness, and high density is also crucial. At the

same time, favorable structural parameters are different for

different applications. Methods for systematically controlling

and optimizing these parameters for specific application sys-

tems have not yet been developed.

High specific surface areas and porosity are ideal conditions

for improving activity. Nevertheless, these advantages provide

more opportunities for adverse reactions. This is particularly

evident in batteries, where the combination of a high specific

surface area increases reactivity with the electrolyte and leads to

uncontrolled solid electrolyte interface reactions. Additionally,

in relation to volumetric energy and power density (reflecting

how much and how fast energy can be stored in a unit volume

of packaging equipment), the low packing density of SNPC

materials may be another disadvantage. Furthermore, SNPC

materials with nanoscale frameworks and high surface energy

often have lower thermal stability, which aﬀects the catalytic

performance at high temperatures. Thus, SNPC materials with

ultra-high specific surface area will further increase the burden

of electrolyte infiltration. SNPCs materials with ultra-high

specific surface area typically have lower density. Therefore,

the key future research direction is how to use less electrolyte to

wet high-load mass electrodes to achieve high utilization of

active materials. In addition, the mechanical stability of the

materials is also crucial, as excessive porosity may pose a risk of

local collapse, and more inconsistent porosity may severely

aﬀect the improvement in battery performance. In summary,

the synthesis of future sub-nanometer pores should be devel-

oped based on applications, and the development of sub-

nanometer pores should be beneficial for the reactions

involved in those applications. For batteries, the future SNCP

designs should prioritize characteristics such as ease of synthe-

size, high-density, controllable, high toughness and mechan-

ical performance, easy wetting by electrolyte, better

compatibility with electrolyte or chemical materials, non-toxic

and environmentally friendly, and low-cost, similar to current

nanometer pore designs.

Stability of materials with SNPCs

Due to the large surface area of SNPCs, SNPCs can theoretically

provide more space to accommodate active materials or

cations, which makes the matrix materials more resilient to

volume changes and preserve structural stability. However, it is

intractable to maintain the SNPC stability for intercalation-type

electrodes due to intrinsic working mechanisms. Taking

intercalation-type electrodes as examples, the structure will

undergo transformation due to intercalation/deintercalation

during charge/discharge processes, which make the lattice ions

deviate from their original positions, leading to potential risks

of structural collapse.

732,733

In terms of conversion-type electro-

des, especially for metal–sulfur batteries, the structural stability

of the SNPCs is relatively hard to maintain. As a S host, the

SNPCs have to sustain large volume deformation due to the

severe volume expansion of S during redox reactions, causing

serious structure damage or even physical disintegration.

734

addition, whether it is an intercalation-or alloy-type anode,

unevenly sized and inappropriate SNPCs would result in non-

uniform deposition of metal ions during the charging process.

As the cycles progress, the structure of the anode electrode will

be severely damaged.

735,736

Overall, the structural stability of

SNPCs is wildly considered one of the main research directions.

Fig. 24 Summary of the versatile functions of the SNPCs for rechargeable batteries.

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Therefore, more research attention should be given to enhance

stability of materials with SNPCs.

Characterization of SNPCs

This includes the characterization of the sub-nanometer pores

themselves as well as the characterization of electrochemical

reactions in sub-nanometer pores. Current technological lim-

itations result in material characterization only reaching the

nanometer level. Therefore, upgrading and developing new

generation characterization devices is crucial and urgent.

Three-dimensional atom probe tomography (APT) can provide

visual and quantitative analysis of materials. Visual analysis

includes observing the internal grain boundaries, phase bound-

aries, structural interfaces, as well as dislocations and defects at

diﬀerent locations. Quantitative analysis includes determining

the composition of materials, calculating the quantity, density,

and volume of precipitation and segregation at interfaces or

grain boundaries. Moreover, nanoscale electrochemical reac-

tions need to be characterized, such as the confinement of

SNPCs, ion diﬀusion, sub-nanometer solvent eﬀects, etc. How

to characterize these eﬀects is a top priority for future research.

For this, more advanced characterization techniques need to be

combined with advanced electron microscopy for further judg-

ment. For instance, wide-angle X-ray scattering (WAXS) mea-

surements provide a spatial resolution in the range of 0.2 nm–

1 nm; By combination of WAXS and SXAS, the capability can be

extended to determine the microstructural features for porous

materials with SNPCs.

In addition to the characterization of the nanopores them-

selves, further development is needed for the characterization

of electrochemical reactions within nanopores. Due to techni-

cal limitations, it is diﬃcult to directly obtain external char-

acterization of the electrochemical reactions of SNPCs, such as

transmission electron microscopy (TEM), X-ray photoelectron

spectroscopy (XPS), scanning electron microscopy (SEM), XRD,

Raman spectroscopy, Fourier transform infrared spectroscopy

(FTIR), etc. To fully understand the integrated multi-scale

regulation mechanism, several challenges related to character-

ization techniques need to be addressed. The first challenge is

the time scale and operating environment. Although oﬄine

characterization studies provide valuable information at rela-

tively low cost, their limitations restrict their application: on

one hand, there is a lack of direct observation of the movement

processes of molecules, atoms, ions, etc., as well as the direct

reaction intensity. On the other hand, due to the sensitivity of

electrolytes and metal ions to air and moisture, oﬄine char-

acterization cannot accurately represent the reaction processes

in batteries. Therefore, in situ/real-time characterization tech-

niques are crucial for a deep understanding of the solvation

chemistry in various rechargeable batteries. In addition to

using more advanced high-resolution electron microscopy,

more instrumental methodologies need to be developed, such

as how to further transfer the high-resolution electron micro-

scopy imaging technology to digital intensity, which can help

us improve this aspect. Through this means, not only can we

observe whether local reactions are intense or not, but we can

also observe the movement and reactions of ions, atoms, and

molecules. Combined with in situ techniques, this will elevate

our understanding of battery reactions from the nano scale to

the sub-nano scale.

Advanced theoretical calculation and simulation techniques

Here, we propose the use of material knowledge supported

machine learning (MIML) to enhance current material compu-

tation methods.

737

MIML combines machine learning techni-

ques with explicit prior material knowledge. In fact, many

successful cases in materials science already utilize specific

forms of MIML, such as deep density functions, chemical

synthesis planning, and the use of deep neural networks for

ab initio calculations in multi-electron systems. By employing

MIML-based algorithms, the computational workflow becomes

partially interpretable, and the need for extensive training data

is greatly reduced due to the incorporation of prior knowledge

or mathematical models. In some cases, it may even achieve

zero-data training. Our goal, from the perspective of multiscale

simulation in material design, is to develop a general partial

diﬀerential equation (PDE) solver for subnanometer-scale

simulations based on MIML. Additionally, we aim to propose

a neural network alternative model for solving ab initio Schro

¨-

dinger equations with built-in physical constraints in the

future. Overall, MIML-based material computation platforms

have the potential to extend multiscale simulations to larger

systems with higher accuracy.

Furthermore, this is a comprehensive platform based on

‘‘artificial intelligence + big data’’. Due to its eﬃciency, artificial

intelligence (AI) (whose core is machine learning (ML), high-

throughput simulation, and experimentation) and big data

technology have attracted more and more attention in molecu-

lar design, material development, performance prediction,

mechanism analysis, relationship mining, and other fields.

Therefore, we propose a comprehensive platform based on

‘‘artificial intelligence + big data’’. According to the needs,

high-throughput computation and simulation based on

machine learning are first used to screen and simulate feasible

molecules and ions with suitable pore sizes, and then high-

throughput synthesis, characterization, and battery testing are

carried out by mobile robot technicians. All the results obtained

in the above process are stored in the database, providing

enough data for machine learning to optimize the design and

performance prediction of SNPCs or sub-nanometer structures.

Finally, high-performance ideal materials are obtained eﬃ-

ciently and quickly. In addition, this comprehensive platform

is an eﬃcient tool for understanding sub-nanometer scale

mechanisms or reactions, such as electrochemical reactions

in SNPCs that are still diﬃcult due to insuﬃcient experimental

techniques.

To better regulate and improve batteries fundamentally

and enhance battery performance, a deeper understanding of

the structure, electron, surface characteristics, and transfer

mechanisms of SNPCs materials at the level of battery and

electrochemistry need to be achieved. Given that energy con-

version and storage devices will be at the forefront in the

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coming years, SNPCs materials are bound to become the next

material trend. Of course, this not only depends on the devel-

opment of materials but also relies on the innovation and

manufacturing of advanced characterization equipment. There-

fore, similar to nanomaterials, it is necessary to conduct

fundamental research, manufacturing, and techno-economic

analysis on SNPCs materials in order to successfully produce and

characterize SNPC materials in a controllable manner and inte-

grate them with cost-eﬀective battery industrial systems. Although

there seem to be many diﬃculties, we still believe that through

collaboration and interdisciplinary eﬀorts, there will be more and

more exciting results, enabling sub-nanotechnology to be widely

applied like current nanotechnology.

Abbreviations

SNPCs Subnanometer pore/channels

MOFs Metal–organic frameworks

COFs Covalent organic frameworks

POCs Porous organic cages

TMDs Transition metal dichalcogenides

TMOs Transition metal oxides

CNTs Carbon nanotubes

GAs Graphene analogues

g-C

Graphitic carbon nitrides

MWCNTs Multi-walled carbon nanotubes

SWCNTs Single-walled carbon nanotues

DWCNTs Double-walled carbon nanotubes

TMPs Transition metal phosphates

MXenes Transition metal nitrides/carbides

TMDs Transition metal dichalcogenides

POCs Porous organic cages

SSIC sodium super ionic conductor

PBAs Prussian blue analogues

POCs Porous organic cages

LIBs Lithium-ion batteries

SIBs Sodium-ion batteries

PIBs Potassium-ion batteries

LSBs Lithium–sulfur batteries

SSBs Sodium–sulfur batteries

PSBs Potassium–sulfur batteries

SEI Solid–electrolyte interphase

CMPs Conjugated microporous polymers

QSSEs Quasi-solid-state electrolytes

GPEs Gel polymer electrolytes

PIMs Polymer of inherent microporosity

PAFs Porous aromatic frameworks

POFs Porous organic frameworks

SPEs Solid polymer electrolytes

HR-TEM High resolution transmission electron microscopy

HAADF-STEM High angle annular dark field scanning trans-

mission electron microscopy

ABF-STEM Annular bright field scanning transmission

electron microscopy

iDPC Integrated diﬀerential phase contrast

XPS X-ray photoelectron spectroscopy

HAXPES Hard X-ray photoelectron spectroscopy

XANES X-ray absorption near edge structure

EELS Electron energy loss spectroscopy

XRPD X-ray powder diﬀraction

NPD Neutron powder diﬀraction

EDT Electron diﬀraction tomography

SAED Selected area electron diﬀraction

PDF Pair distribution function analysis

RIXS Resonant inelastic X-ray scattering

NMR Nuclear magnetic resonance spectroscopy

WAXS Wide angle X-ray/neutron scattering

XCT X-ray computed tomography

XRD-CT X-ray diﬀraction computed tomography

APT Atom probe tomography

NMRC Nuclear magnetic resonance nano pore analysis

Author contributions

Conceptualization, Y. -J. Lei., W. -H. Lai., Y.-X. Wang. and

G. Wang.; visualization, Y. -J. Lei., L. Zhao., Z. Huang, and

P. Jaumaux.; writing – original draft, Y.-J. Lei., L. Zhao., Z.

Huang., and P. Jaumaux.; writing – review and editing, Y.-J. Lei.,

L. Zhao., W. -H. Lai., B. Sun., Y.-X. Wang., and G. Wang.;

funding acquisition, W. -H. Lai., Y. -X. Wang., B. Sun., and G.

Wang.; and supervision, G. Wang.

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

We would like to acknowledge the support from the Australian

Research Council (ARC) through the Discovery Projects

(DP210101389 and DP220103301), the ARC Future Fellowship

(FT180100705), the ARC Discovery Early Career Researcher Award

(DE220101113), the ARC Linkage project (LP200200926), and the

ARC Research Hub for Integrated Energy Storage Solutions

(IH180100020). The authors thank Dr Tania Silver for critical

discussion.

References

1 Z. Zhang, X. Yang, P. Li, Y. Wang, X. Zhao, J. Safaei,

H. Tian, D. Zhou, B. Li, F. Kang and G. Wang, Adv. Mater.,

2022, 34, 2206970.

2 F. Liu and Z. Fan, Chem. Soc. Rev., 2023, 52, 1723–1772.

3 D. Luo, M. Li, Q. Ma, G. Wen, H. Dou, B. Ren, Y. Liu,

X. Wang, L. Shui and Z. Chen, Chem. Soc. Rev., 2022, 51,

2917–2938.

4 Y. Yang, P. Li, X. Zheng, W. Sun, S. X. Dou, T. Ma and

H. Pan, Chem. Soc. Rev., 2022, 51, 9620–9693.

5 J. M. Tarascon and M. Armand, Nature, 2001, 414, 359–367.

Chem Soc Rev Review Article

Published on 04 March 2024. Downloaded by University of Wollongong on 3/8/2024 12:31:15 AM.

View Article Online

6 Y. Zhao, J. Zhang, X. Guo, X. Cao, S. Wang, H. Liu and

G. Wang, Chem. Soc. Rev., 2023, 52, 3215–3264.

7 Y. Wan and D. Zhao, Chem. Rev., 2007, 107, 2821–2860.

8 X. Li, F. Zhang and D. Zhao, Chem. Soc. Rev., 2015, 44,

1346–1378.

9 T. Zhao, A. Elzatahry, X. Li and D. Zhao, Nat. Rev. Mater.,

2019, 4, 775–791.

10 M. R. Palacı

´n, Chem. Soc. Rev., 2009, 38, 2565–2575.

11 W. Song, Q. Jiang, X. Xie, A. Brookfield, E. J. L. McInnes,

P. R. Shearing, D. J. L. Brett, F. Xie and D. J. Riley, Energy

Storage Mater., 2019, 22, 441–449.

12 S. Li, J. Huang, Y. Cui, S. Liu, Z. Chen, W. Huang, C. Li,

R. Liu, R. Fu and D. Wu, Nat. Nanotechnol., 2022, 17,

613–621.

13 L. Kong, M. Zhong, W. Shuang, Y. Xu and X.-H. Bu, Chem.

Soc. Rev., 2020, 49, 2378–2407.

14 C. Liu, F. Li, L.-P. Ma and H.-M. Cheng, Adv. Mater., 2010,

22, E28–E62.

15 Y. Zhai, Y. Dou, D. Zhao, P. F. Fulvio, R. T. Mayes and

S. Dai, Adv. Mater., 2011, 23, 4828–4850.

16 H. Wang, F. Sun, Z. Qu, K. Wang, L. Wang, X. Pi, J. Gao and

G. Zhao, ACS Sustain. Chem. Eng., 2019, 7, 18554–18565.

17 C. Chen, Y. Huang, Y. Zhu, Z. Zhang, Z. Guang, Z. Meng

and P. Liu, ACS Sustain. Chem. Eng., 2020, 8, 1497–1506.

18 G. Cai, Y. Yin, D. Xia, A. A. Chen, J. Holoubek, J. Scharf,

Y. Yang, K. H. Koh, M. Li and D. M. Davies, Nat. Commun.,

2021, 12, 3395.

19 P. Wang, N. Kateris, B. Li, Y. Zhang, J. Luo, C. Wang,

Y. Zhang, A. S. Jayaraman, X. Hu, H. Wang and W. Li, J. Am.

Chem. Soc., 2023, 145, 18865–18876.

20 C. Wu, Y. Lei, L. Simonelli, D. Tonti, A. Black, X. Lu,

W.-H. Lai, X. Cai, Y.-X. Wang, Q. Gu, S.-L. Chou, H.-K.

Liu, G. Wang and S.-X. Dou, Adv. Mater., 2022, 34,

2108363.

21 M. Shen and H. Ma, Coord. Chem. Rev., 2022, 470,

214715.

22 E. Detsi, X. Petrissans, Y. Yan, J. B. Cook, Z. Deng,

Y.-L. Liang, B. Dunn and S. H. Tolbert, Phys. Rev. Mater.,

2018, 2, 055404.

23 A. D. Roberts, X. Li and H. Zhang, Chem. Soc. Rev., 2014, 43,

4341–4356.

24 V. Augustyn, J. Mater. Res., 2017, 32, 2–15.

25 Y. Guo, Y. Wei, H. Li and T. Zhai, Small, 2017, 13,

1701649.

26 Z. Liu, L. Qin, X. Cao, J. Zhou, A. Pan, G. Fang, S. Wang and

S. Liang, Prog. Mater. Sci., 2022, 125, 100911.

27 A. Van der Ven, J. Bhattacharya and A. A. Belak, Acc. Chem.

Res., 2013, 46, 1216–1225.

28 D. He, L. Zhang, T. Liu, R. Clowes, M. A. Little, M. Liu,

M. Hirscher and A. I. Cooper, Angew. Chem., Int. Ed., 2022,

61, e202202450.

29 B. Ni, Y. Shi and X. Wang, Adv. Mater., 2018, 30, 1802031.

30 P. Zhang, F. Wang, M. Yu, X. Zhuang and X. Feng, Chem.

Soc. Rev., 2018, 47, 7426–7451.

31 Y. Chen, C. Tan, H. Zhang and L. Wang, Chem. Soc. Rev.,

2015, 44, 2681–2701.

32 N. Liu, K. Xu, Y. Lei, Y. Xi, Y. Liu, N. Wang, Y.-X. Wang,

X. Xu, W. Hao, S. X. Dou and Y. Du, Small Struct., 2021,

2, 2100041.

33 X. Xiao, H. Wang, P. Urbankowski and Y. Gogotsi, Chem.

Soc. Rev., 2018, 47, 8744–8765.

34 C. Li, L. Liu, J. Kang, Y. Xiao, Y. Feng, F.-F. Cao and

H. Zhang, Energy Storage Mater., 2020, 31, 115–134.

35 D. S. Bethune, C. H. Kiang, M. S. de Vries, G. Gorman,

R. Savoy, J. Vazquez and R. Beyers, Nature, 1993, 363,

605–607.

36 M. T. Pettes and L. Shi, Adv. Funct. Mater., 2009, 19,

3918–3925.

37 J. P. Paraknowitsch and A. Thomas, Energy Environ. Sci.,

2013, 6, 2839–2855.

38 J. C. Charlier, Acc. Chem. Res., 2002, 35, 1063–1069.

39 A. Saha, B. J. Giﬀord, X. He, G. Ao, M. Zheng, H. Kataura,

H. Htoon, S. Kilina, S. Tretiak and S. K. Doorn, Nat. Chem.,

2018, 10, 1089–1095.

40 Y. Shim and H. J. Kim, ACS Nano, 2009, 3, 1693–1702.

41 X. Yi, X. Liu, R. Dou, Z. Wen and W. Zhou, J. Phys. Chem. C,

2021, 125, 22570–22580.

42 H. Tabassum, A. Mahmood, B. Zhu, Z. Liang, R. Zhong,

S. Guo and R. Zou, Energy Environ. Sci., 2019, 12, 2924–2956.

43 C. Fu, M. B. Oviedo, Y. Zhu, A. von Wald Cresce, K. Xu,

G. Li, M. E. Itkis, R. C. Haddon, M. Chi, Y. Han,

B. M. Wong and J. Guo, ACS Nano, 2018, 12, 9775–9784.

44 Y. Cao, M. Wang, H. Wang, C. Han, F. Pan and J. Sun, Adv.

Energy Mater., 2022, 12, 2200057.

45 H.-S. Xu, S.-Y. Ding, W.-K. An, H. Wu and W. Wang, J. Am.

Chem. Soc., 2016, 138, 11489–11492.

46 N. Huang, L. Zhai, D. E. Coupry, M. A. Addicoat,

K. Okushita, K. Nishimura, T. Heine and D. Jiang, Nat.

Commun., 2016, 7, 12325.

47 F. Yu, W. Liu, B. Li, D. Tian, J.-L. Zuo and Q. Zhang, Angew.

Chem., Int. Ed., 2019, 58, 16101–16104.

48 Y.Zeng,R.ZouandY.Zhao,Adv. Mater., 2016, 28, 2855–2873.

49 Z. Wang, J. Hu and Z. Lu, Batter. Supercaps, 2023,

6, e202200545.

50 L. Liu and A. Corma, Nat. Rev. Mater., 2021, 6, 244–263.

51 Y. Yang, X. Chu, H.-Y. Zhang, R. Zhang, Y.-H. Liu,

F.-M.Zhang,M.Lu,Z.-D.YangandY.-Q.Lan,Nat. Commun.,

2023, 14, 593.

52 W. Xin, J. Fu, Y. Qian, L. Fu, X.-Y. Kong, T. Ben, L. Jiang

and L. Wen, Nat. Commun., 2022, 13, 1701.

53 F. Xu, S. Jin, H. Zhong, D. Wu, X. Yang, X. Chen, H. Wei,

R. Fu and D. Jiang, Sci. Rep., 2015, 5, 8225.

54 C. Zhang, C. Lu, F. Zhang, F. Qiu, X. Zhuang and X. Feng,

J. Energy Chem., 2018, 27, 86–98.

55 X. Ma and T. F. Scott, Commun. Chem., 2018, 1, 98.

56 X. Zhan, Z. Chen and Q. Zhang, J. Mater. Chem. A, 2017, 5,

14463–14479.

57 R.-B. Lin, Z. Zhang and B. Chen, Acc. Chem. Res., 2021, 54,

3362–3376.

58 J. Wang, Y. Zhang, Y. Su, X. Liu, P. Zhang, R.-B. Lin,

S. Chen, Q. Deng, Z. Zeng, S. Deng and B. Chen, Nat.

Commun., 2022, 13, 200.

Review Article Chem Soc Rev

Published on 04 March 2024. Downloaded by University of Wollongong on 3/8/2024 12:31:15 AM.

View Article Online

59 P. Yan, F. Ai, C. Cao and Z. Luo, J. Mater. Sci.: Mater.

Electron., 2019, 30, 14120–14129.

60 J. Lu, H. Zhang, J. Hou, X. Li, X. Hu, Y. Hu, C. D. Easton,

Q. Li, C. Sun, A. W. Thornton, M. R. Hill, X. Zhang,

G. Jiang, J. Z. Liu, A. J. Hill, B. D. Freeman, L. Jiang and

H. Wang, Nat. Mater., 2020, 19, 767–774.

61 P. Xiong, F. Zhang, X. Zhang, Y. Liu, Y. Wu, S. Wang,

J. Safaei, B. Sun, R. Ma, Z. Liu, Y. Bando, T. Sasaki,

X. Wang, J. Zhu and G. Wang, Nat. Commun., 2021,

12, 4184.

62 W. Li, R. Fang, Y. Xia, W. Zhang, X. Wang, X. Xia and J. Tu,

Batter. Supercaps, 2019, 2, 9–36.

63 S. Dang, Q.-L. Zhu and Q. Xu, Nat. Rev. Mater., 2017,

3, 17075.

64 P. Liu, J. Yan, Z. Guang, Y. Huang, X. Li and W. Huang,

J. Power Sources, 2019, 424, 108–130.

65 C. Gao, F. Lyu and Y. Yin, Chem. Rev., 2021, 121, 834–881.

66 W. Liu, P. Oh, X. Liu, M.-J. Lee, W. Cho, S. Chae, Y. Kim

and J. Cho, Angew. Chem., Int. Ed., 2015, 54, 4440–4457.

67 P.-F. Wang, Y. You, Y.-X. Yin and Y.-G. Guo, Adv. Energy

Mater., 2018, 8, 1701912.

68 K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang,

Y. Zhang, S. V. Dubonos, I. V. Grigorieva and A. A. Firsov,

Science, 2004, 306, 666–669.

69 Z. Xu, Z. Jiang, C. Kuai, R. Xu, C. Qin, Y. Zhang,

M. M. Rahman, C. Wei, D. Nordlund, C.-J. Sun, X. Xiao,

X.-W. Du, K. Zhao, P. Yan, Y. Liu and F. Lin, Nat. Commun.,

2020, 11, 83.

70 K. Ji, J. Han, A. Hirata, T. Fujita, Y. Shen, S. Ning, P. Liu,

H. Kashani, Y. Tian, Y. Ito, J.-I. Fujita and Y. Oyama, Nat.

Commun, 2019, 10, 275.

71 J. Xiao, M. Long, X. Li, H. Xu, H. Huang and Y. Gao, Sci.

Rep., 2014, 4, 4327.

72 Z. Hu, Q. Liu, S.-L. Chou and S.-X. Dou, Adv. Mater., 2017,

29, 1700606.

73 J. Mei, T. Liao, L. Kou and Z. Sun, Adv. Mater., 2017,

29, 1700176.

74 S. Wang, S. Zhao, X. Guo and G. Wang, Adv. Energy Mater.,

2022, 12, 2100864.

75 C. Eames and M. S. Islam, J. Am. Chem. Soc., 2014, 136,

16270–16276.

76 W. Zhang, L. Sun, J. M. V. Nsanzimana and X. Wang, Adv.

Mater.,2018, 30, 1705523.

77 H. Jin, C. Guo, X. Liu, J. Liu, A. Vasileﬀ, Y. Jiao, Y. Zheng

and S.-Z. Qiao, Chem. Rev., 2018, 118, 6337–6408.

78 H. Jin, H. Yu, H. Li, K. Davey, T. Song, U. Paik and

S.-Z. Qiao, Angew. Chem., Int. Ed., 2022, 61, e202203850.

79 Y. Wu, D. Li, C.-L. Wu, H. Y. Hwang and Y. Cui, Nat. Rev.

Mater., 2023, 8, 41–53.

80 A. K. Geim, Science, 2009, 324, 1530–1534.

81 Z. Chen, C. Liu, L. Sun and T. Wang, ACS Catal., 2022, 12,

8936–8975.

82 C. N. R. Rao, A. K. Sood, K. S. Subrahmanyam and

A. Govindaraj, Angew. Chem., Int. Ed., 2009, 48, 7752–7777.

83 J. Abraham, K. S. Vasu, C. D. Williams, K. Gopinadhan,

Y. Su, C. T. Cherian, J. Dix, E. Prestat, S. J. Haigh,

I. V. Grigorieva, P. Carbone, A. K. Geim and R. R. Nair,

Nat. Nanotechnol., 2017, 12, 546–550.

84 A. W. Robertson, G.-D. Lee, K. He, C. Gong, Q. Chen,

E. Yoon, A. I. Kirkland and J. H. Warner, ACS Nano,

2015, 9, 11599–11607.

85 X.Chen,S.Zhang,D.Hou,H.Duan,B.Deng,Z.Zeng,B.Liu,

L.Sun,R.Song,J.Du,P.Gao,H.Peng,Z.LiuandL.Wang,

ACS Appl. Mater. Interfaces, 2021, 13, 29926–29935.

86 A. VahidMohammadi, J. Rosen and Y. Gogotsi, Science,

2021, 372, eabf1581.

87 M. Naguib, M. Kurtoglu, V. Presser, J. Lu, J. Niu, M. Heon,

L. Hultman, Y. Gogotsi and M. W. Barsoum, Adv. Mater.,

2011, 23, 4248–4253.

88 Y. Sun, S. Li, Y. Zhuang, G. Liu, W. Xing and W. Jing,

J. Membr. Sci., 2019, 591, 117350.

89 C. Tang, Y. Min, C. Chen, W. Xu and L. Xu, Nano Lett.,

2019, 19, 5577–5586.

90 J. Luo, J. Zheng, J. Nai, C. Jin, H. Yuan, O. Sheng, Y. Liu,

R. Fang, W. Zhang, H. Huang, Y. Gan, Y. Xia, C. Liang,

J. Zhang, W. Li and X. Tao, Adv. Funct. Mater., 2019,

29, 1808107.

91 Z. Wang, X. Zheng, A. Chen, Y. Han, L. Wei and J. Li, ACS

mater. lett., 2022, 4, 1436–1445.

92 W. Zhao, Y. Lei, Y. Zhu, Q. Wang, F. Zhang, X. Dong and

H. N. Alshareef, Nano Energy, 2021, 86, 106120.

93 Q. Yun, L. Li, Z. Hu, Q. Lu, B. Chen and H. Zhang, Adv.

Mater.,2020, 32, 1903826.

94 X. Chia and M. Pumera, Nat. Catal., 2018, 1, 909–921.

95 D. Monga, S. Sharma, N. P. Shetti, S. Basu, K. R. Reddy and

T. M. Aminabhavi, Mater. Today Chem., 2021, 19, 100399.

96 M. Chhowalla, H. S. Shin, G. Eda, L.-J. Li, K. P. Loh and

H. Zhang, Nat. Chem., 2013, 5, 263–275.

97 M. K. Aydinol, A. F. Kohan, G. Ceder, K. Cho and

J. Joannopoulos, Phys. Rev. B, 1997, 56, 1354–1365.

98 C. Zhu, D. Gao, J. Ding, D. Chao and J. Wang, Chem. Soc.

Rev., 2018, 47, 4332–4356.

99 Q. Yun, Q. Lu, X. Zhang, C. Tan and H. Zhang, Angew.

Chem., Int. Ed., 2018, 57, 626–646.

100 X. Yin, C. S. Tang, Y. Zheng, J. Gao, J. Wu, H. Zhang,

M. Chhowalla, W. Chen and A. T. S. Wee, Chem. Soc. Rev.,

2021, 50, 10087–10115.

101 M. Faizan, S. Hussain, D. Vikraman, B. Ali, H.-S. Kim,

J. Jung and K.-W. Nam, J. Mater. Res. Technol, 2021, 14,

2382–2393.

102 L. Shi and T. Zhao, J. Mater. Chem. A, 2017, 5, 3735–3758.

103 C. Vaalma, D. Buchholz, M. Weil and S. Passerini, Nat. Rev.

Mater., 2018, 3, 18013.

104 Y. Wang, X. Yu, S. Xu, J. Bai, R. Xiao, Y.-S. Hu, H. Li,

X.-Q. Yang, L. Chen and X. Huang, Nat. Commun., 2013,

4, 2365.

105 J.-Y. Li, H.-Y. Hu, L.-F. Zhou, H.-W. Li, Y.-J. Lei, W.-H. Lai,

Y.-M. Fan, Y.-F. Zhu, G. Peleckis, S.-Q. Chen, W.-K. Pang,

J. Peng, J.-Z. Wang, S.-X. Dou, S.-L. Chou and Y. Xiao, Adv.

Funct. Mater., 2023, 33, 2213215.

106 Y. Xiao, H.-R. Wang, H.-Y. Hu, Y.-F. Zhu, S. Li, J.-Y. Li,

X.-W. Wu and S.-L. Chou, Adv. Mater., 2022, 34, 2202695.

Chem Soc Rev Review Article

Published on 04 March 2024. Downloaded by University of Wollongong on 3/8/2024 12:31:15 AM.

View Article Online

107 F. Wei, Q. Zhang, P. Zhang, W. Tian, K. Dai, L. Zhang,

J. Mao and G. Shao, J. Electrochem. Soc., 2021, 168, 050524.

108 J. Zhang, J.-B. Kim, J. Zhang, G.-H. Lee, M. Chen,

V. W.-H. Lau, K. Zhang, S. Lee, C.-L. Chen, T.-Y. Jeon,

Y.-W. Kwon and Y.-M. Kang, J. Am. Chem. Soc., 2022, 144,

7929–7938.

109 Z.-J. Zheng, H. Ye and Z.-P. Guo, Energy Environ. Sci., 2021,

14, 1835–1853.

110 J. Peng, W. Zhang, Q. Liu, J. Wang, S. Chou, H. Liu and

S. Dou, Adv. Mater., 2022, 34, 2108384.

111 H. Zhang, Y. Liu, J. Zhao, X. Peng, Y. Ren, X. Wei, Y. Song,

Z. Cao and Q. Wan, ChemistrySelect, 2022, 7, e202200785.

112 M. G. Moustafa and A. M. Aboraia, Ceram. Int., 2023, 49,

23068–23074.

113 S. Zheng, Z. Li, L. Chen, Y. Huang, J. Shi, S. Wang, Y. Liu,

Y. Liu, Y.-P. Cai and Q. Zheng, ACS mater. lett., 2023, 5,

1136–1144.

114 Y.-W. Song, P. Shi, B.-Q. Li, X. Chen, C.-X. Zhao,

W.-J. Chen, X.-Q. Zhang, X. Chen and Q. Zhang, Matter,

2021, 4, 253–264.

115 D. Zhu, G. Xu, M. Barnes, Y. Li, C.-P. Tseng, Z. Zhang,

J.-J. Zhang, Y. Zhu, S. Khalil, M. M. Rahman, R. Verduzco

and P. M. Ajayan, Adv. Funct. Mater., 2021, 31, 2100505.

116 B. Hu, J. Xu, Z. Fan, C. Xu, S. Han, J. Zhang, L. Ma, B. Ding,

Z. Zhuang, Q. Kang and X. Zhang, Adv. Energy Mater., 2023,

13, 2203540.

117 H. M. El-Kaderi, J. R. Hunt, J. L. Mendoza-Corte

´s,

A. P. Co

ˆte

´, R. E. Taylor, M. O’Keeﬀe and O. M. Yaghi,

Science, 2007, 316, 268–272.

118 M. E. Briggs and A. I. Cooper, Chem. Mater., 2017, 29,

149–157.

119 S. B. Kalidindi, S. Nayak, M. E. Briggs, S. Jansat,

A. P. Katsoulidis, G. J. Miller, J. E. Warren, D. Antypov,

F. Cora

`, B. Slater, M. R. Prestly, C. Martı

´-Gastaldo and

M. J. Rosseinsky, Angew. Chem., Int. Ed., 2015, 54, 221–226.

120 T. Hasell and A. I. Cooper, Nat. Rev. Mater., 2016, 1, 16053.

121 Y. Cheng, Y. Ying, S. Japip, S.-D. Jiang, T.-S. Chung,

S. Zhang and D. Zhao, Adv. Mater., 2018, 30,1802401.

122 X. Yang, Z. Ullah, J. F. Stoddart and C. T. Yavuz, Chem. Rev.,

2023, 123, 4602–4634.

123 K. Su, W. Wang, S. Du, C. Ji, M. Zhou and D. Yuan, J. Am.

Chem. Soc., 2020, 142, 18060–18072.

124 Y. Geng, T. Zhang, T. Xu, W. Mao, D. Li, K. Dai, J. Zhang

and G. Ai, Energy Storage Mater., 2022, 49, 67–76.

125 J. Ren, H. Zhu, Y. Fang, W. Li, S. Lan, S. Wei, Z. Yin,

Y. Tang, Y. Ren and Q. Liu, Carbon Neutraliz., 2023, 2,

339–377.

126 M. Chen, W. Hua, J. Xiao, J. Zhang, V. W.-H. Lau, M. Park,

G.-H. Lee, S. Lee, W. Wang, J. Peng, L. Fang, L. Zhou,

C.-K. Chang, Y. Yamauchi, S. Chou and Y.-M. Kang, J. Am.

Chem. Soc., 2021, 143, 18091–18102.

127 M. C. Orilall and U. Wiesner, Chem. Soc. Rev., 2011, 40,

520–535.

128 D. B. Mitzi, Chem. Mater., 2001, 13, 3283–3298.

129 D. P. Dubal, O. Ayyad, V. Ruiz and P. Go

´mez-Romero,

Chem. Soc. Rev., 2015, 44, 1777–1790.

130 E. Pomerantseva and Y. Gogotsi, Nat. Energy., 2017,

2, 17089.

131 P. Xiong, F. Zhang, X. Zhang, S. Wang, H. Liu, B. Sun,

J. Zhang, Y. Sun, R. Ma, Y. Bando, C. Zhou, Z. Liu, T. Sasaki

and G. Wang, Nat. Commun., 2020, 11, 3297.

132 P. Du, L. Cao, B. Zhang, C. Wang, Z. Xiao, J. Zhang,

D. Wang and X. Ou, Renew. Sustain. Energy Rev., 2021,

151, 111640.

133 T. Liu, Y. Zhao, L. Gao and J. Ni, Sci. Rep., 2015, 5, 9307.

134 F. Peng, L. Yu, S. Yuan, X.-Z. Liao, J. Wen, G. Tan, F. Feng

and Z.-F. Ma, ACS Appl. Mater. Interfaces, 2019, 11,

37685–37692.

135 B. Ni and X. Wang, Chem. Sci., 2016, 7, 3978–3991.

136 K. Mu

¨llen, Angew. Chem., Int. Ed., 2015, 54, 10040–10042.

137 I. Borukhov, D. Andelman and H. Orland, Phys. Rev. Lett.,

1997, 79, 435–438.

138 S. Kondrat and A. Kornyshev, J. Phys. Chem. C,2013, 117,

12399–12406.

139 K. Zhang, W. Liu, Y. Gao, X. Wang, Z. Chen, R. Ning,

W. Yu, R. Li, L. Li, X. Li, K. Yuan, L. Ma, N. Li, C. Shen,

W. Huang, K. Xie and K. P. Loh, Adv. Mater., 2021,

33, 2006323.

140 J. Yang, B. Yin, Y. Sun, H. Pan, W. Sun, B. Jia, S. Zhang and

T. Ma, Nano-Micro Lett., 2022, 14, 42.

141 Z. Hong, Y. Zhen, Y. Ruan, M. Kang, K. Zhou, J. M. Zhang,

Z. Huang and M. Wei, Adv. Mater., 2018, 30, 1802035.

142 W. Ye, X. Li, B. Zhang, W. Liu, Y. Cheng, X. Fan, H. Zhang,

Y. Liu, Q. Dong and M.-S. Wang, Adv. Mater., 2023,

35, 2210447.

143 H. Zhang, X. Li, J. Hou, L. Jiang and H. Wang, Chem. Soc.

Rev., 2022, 51, 2224–2254.

144 L. Wang, M. S. H. Boutilier, P. R. Kidambi, D. Jang,

N. G. Hadjiconstantinou and R. Karnik, Nat. Nanotechnol.,

2017, 12, 509–522.

145 A. R. Koltonow and J. Huang, Science, 2016, 351,

1395–1396.

146 C. L. Ritt, M. Liu, T. A. Pham, R. Epsztein, H. J. Kulik and

M. Elimelech, Sci. Adv., 2022, 8, eabl5771.

147 G. Cai, Y. Yin, D. Xia, A. A. Chen, J. Holoubek, J. Scharf,

Y. Yang, K. H. Koh, M. Li, D. M. Davies, M. Mayer,

T. H. Han, Y. S. Meng, T. A. Pascal and Z. Chen, Nat.

Commun., 2021, 12, 3395.

148 C. Cheng, G. Jiang, C. J. Garvey, Y. Wang, G. P. Simon,

J. Z. Liu and D. Li, Sci. Adv., 2016, 2, e1501272.

149 Y. Xu, L. Gao, L. Shen, Q. Liu, Y. Zhu, Q. Liu, L. Li, X. Kong,

Y. Lu and H. B. Wu, Matter, 2020, 3, 1685–1700.

150 M. Zhang, K. Guan, Y. Ji, G. Liu, W. Jin and N. Xu, Nat.

Commun., 2019, 10, 1253.

151 J. Jas

ˇı

´k, A. Fortunelli and S

ˇ. Vajda, Phys. Chem. Chem. Phys.,

2022, 24, 12083–12115.

152 Q. Zeng, L. Xu, G. Li, Q. Zhang, S. Guo, H. Lu, L. Xie,

J. Yang, J. Weng, C. Zheng and S. Huang, Adv. Funct.

Mater., 2023, 2304619.

153 S. Xin, L. Gu, N.-H. Zhao, Y.-X. Yin, L.-J. Zhou, Y.-G.

Guo and L.-J. Wan, J. Am. Chem. Soc., 2012, 134,

18510–18513.

Review Article Chem Soc Rev

Published on 04 March 2024. Downloaded by University of Wollongong on 3/8/2024 12:31:15 AM.

View Article Online

154 C. Wang, Y. Yang, X. Liu, H. Zhong, H. Xu, Z. Xu, H.

Shao and F. Ding, ACS Appl. Mater. Interfaces, 2017, 9,

13694–13702.

155 Q. Zhang, B. Yue, C. Shao, H. Shao, L. Li, X. Dong, J. Wang

and W. Yu, J. Chem. Eng, 2022, 443, 136479.

156 A. Taloni, M. Vodret, G. Costantini and S. Zapperi, Nat.

Rev. Mater, 2018, 3, 211–224.

157 J. F. Go

´mez-Corte

´s, M. L. No

´,I.Lo

´pez-Ferren

˜o, J.

Herna

´ndez-Saz, S. I. Molina, A. Chuvilin and J. M. San

Juan, Nat. Nanotechnol., 2017, 12, 790–796.

158 G. L. Gregory, H. Gao, B. Liu, X. Gao, G. J. Rees, M. Pasta,

P. G. Bruce and C. K. Williams, J. Am. Chem. Soc., 2022,

144, 17477–17486.

159 S. Rajendran, Z. Tang, A. George, A. Cannon, C. Neumann,

A. Sawas, E. Ryan, A. Turchanin and L. M. R. Arava, Adv.

Energy Mater., 2021, 11, 2100666.

160 M. Majumder, N. Chopra, R. Andrews and B. J. Hinds,

Nature, 2005, 438, 44.

161 J. Shen, G. Liu, Y. Han and W. Jin, Nat. Rev. Mater, 2021, 6,

294–312.

162 R. Epsztein, R. M. DuChanois, C. L. Ritt, A. Noy and

M. Elimelech, Nat. Nanotechnol., 2020, 15, 426–436.

163 Z. Zhu, D. Wang, Y. Tian and L. Jiang, J. Am. Chem. Soc.,

2019, 141, 8658–8669.

164 D. Pan, J. Zhang, Z. Li and M. Wu, Adv. Mater., 2010, 22,

734–738.

165 S. Levasseur, M. Me

´ne

´trier, Y. Shao-Horn, L. Gautier,

A. Audemer, G. Demazeau, A. Largeteau and C. Delmas,

Chem. Mater., 2003, 15, 348–354.

166 J.-M. Lim, D. Kim, Y.-G. Lim, M.-S. Park, Y.-J. Kim, M. Cho

and K. Cho, ChemElectroChem, 2016, 3, 943–949.

167 Z. Wang, L. Liu, L. Chen and X. Huang, Solid State Ion.,

2002, 148, 335–342.

168 F. Ning, S. Li, B. Xu and C. Ouyang, Solid State Ion., 2014,

263, 46–48.

169 G. Qi, J. Hu, M. Balogh, L. Wang, D. Darbar and W. Li,

Electrochem, 2023, 4, 21–30.

170 H. Xie, G. Hu, K. Du, Z. Peng and Y. Cao, J. Alloys Compd.,

2016, 666, 84–87.

171 H. S. Ko, J. H. Kim, J. Wang and J. D. Lee, J. Power Sources,

2017, 372, 107–115.

172 S. Lee, Y. Cho, H.-K. Song, K. T. Lee and J. Cho, Angew.

Chem., Int. Ed., 2012, 51, 8748–8752.

173 P. J. Phillips, J. Baren

˜o, Y. Li, D. P. Abraham and R. F. Klie,

Adv. Energy Mater., 2015, 5, 1501252.

174 K. Du, H. Xie, G. Hu, Z. Peng, Y. Cao and F. Yu, ACS Appl.

Mater. Interfaces, 2016, 8, 17713–17720.

175 G. Dai, H. Du, S. Wang, J. Cao, M. Yu, Y. Chen,

Y. Tang, A. Li and Y. Chen, RSC Adv., 2016, 6,

100841–100848.

176 Y. Liu, Z. Yang, J. Zhong, J. Li, R. Li, Y. Yu and F. Kang, ACS

Nano, 2019, 13, 11891–11900.

177 C. Ma, X.-L. Li, X.-Y. Yue, J. Bao, R.-J. Luo and Y.-N. Zhou,

J. Chem. Eng., 2022, 432, 134305.

178 M. Si, D. Wang, R. Zhao, D. Pan, C. Zhang, C. Yu, X. Lu,

H. Zhao and Y. Bai, Adv. Sci., 2020, 7, 1902538.

179 B. J. Hwang, R. Santhanam and C. H. Chen, J. Power

Sources, 2003, 114, 244–252.

180 W. Li and J. C. Currie, J. Electrochem. Soc., 1997, 144, 2773.

181 R. V. Chebiam, F. Prado and A. Manthiram, J. Solid State

Chem., 2002, 163, 5–9.

182 F. Wu, M. Zhang, Y. Bai, X. Wang, R. Dong and C. Wu, ACS

Appl. Mater. Interfaces, 2019, 11, 12554–12561.

183 V.-C. Ho, H. An, M. Hong, S. Lee, J. Kim, M. B. Park and

J. Mun, Energy Technol., 2021, 9, 2000800.

184 F. Schipper, M. Dixit, D. Kovacheva, M. Talianker, O. Haik,

J. Grinblat, E. M. Erickson, C. Ghanty, D. T. Major,

B. Markovsky and D. Aurbach, J. Mater. Chem. A, 2016, 4,

16073–16084.

185 N. Sun, Z. Guan, Y. Liu, Y. Cao, Q. Zhu, H. Liu, Z. Wang,

P. Zhang and B. Xu, Adv. Energy Mater., 2019, 9, 1901351.

186 Y. Zhao, J. Liu, S. Wang, R. Ji, Q. Xia, Z. Ding, W. Wei,

Y. Liu, P. Wang and D. G. Ivey, Adv. Funct. Mater., 2016, 26,

4760–4767.

187 L. Ma, L. Mao, X. Zhao, J. Lu, F. Zhang, P. Ding, L. Chen

and F. Lian, ChemElectroChem, 2017, 4, 3068–3074.

188 Q. Hu, Y. He, D. Ren, Y. Song, Y. Wu, H. Liang, J. Gao,

G. Xu, J. Cai, T. Li, H. Xu, L. Wang, Z. Chen and X. He,

Nano Energy, 2022, 96, 107123.

189 W. Li, X. Liu, H. Celio, P. Smith, A. Dolocan, M. Chi and

A. Manthiram, Adv. Energy Mater., 2018, 8, 1703154.

190 R. Va

¨li, J. Aruva

¨li, M. Ha

¨rmas, A. Ja

¨nes and E. Lust,

Batteries, 2019, 5, 56.

191 F. Xin, H. Zhou, Y. Zong, M. Zuba, Y. Chen, N. A. Chernova,

J. Bai, B. Pei, A. Goel, J. Rana, F. Wang, K. An, L. F. J. Piper,

G. Zhou and M. S. Whittingham, ACS Energy Lett., 2021, 6,

1377–1382.

192 S. Liu, X. Chen, J. Zhao, J. Su, C. Zhang, T. Huang, J. Wu

and A. Yu, J. Power Sources, 2018, 374, 149–157.

193 J. Li, M. Zhang, D. Zhang, Y. Yan and Z. Li, J. Chem. Eng.,

2020, 402, 126195.

194 C. Matei Ghimbeu, B. Zhang, A. Martinez de Yuso, B. Re

´ty

and J.-M. Tarascon, Carbon, 2019, 153, 634–647.

195 A. Gomez-Martin, F. Reissig, L. Frankenstein,

M. Heidbu

¨chel, M. Winter, T. Placke and R. Schmuch,

Adv. Energy Mater., 2022, 12, 2103045.

196 A. Windmu

¨ller, C.-L. Tsai, S. Mo

¨ller, M. Balski, Y. J. Sohn,

S. Uhlenbruck and O. Guillon, J. Power Sources, 2017, 341,

122–129.

197 A. Eftekhari, J. Power Sources, 2003, 124, 182–190.

198 S. Mukerjee, X. Q. Yang, X. Sun, S. J. Lee, J. McBreen and

Y. Ein-Eli, Electrochim. Acta, 2004, 49, 3373–3382.

199 J. Xu, Z. Han, K. Jiang, P. Bai, Y. Liang, X. Zhang, P. Wang,

S. Guo and H. Zhou, Small, 2020, 16, 1904388.

200 P.-F. Wang, Y. You, Y.-X. Yin and Y.-G. Guo, J. Mater. Chem.

A, 2016, 4, 17660–17664.

201 P.-F. Wang, H.-R. Yao, X.-Y. Liu, J.-N. Zhang, L. Gu,

X.-Q. Yu, Y.-X. Yin and Y.-G. Guo, Adv. Mater., 2017,

29, 1700210.

202 S. Zheng, G. Zhong, M. J. McDonald, Z. Gong, R. Liu,

W. Wen, C. Yang and Y. Yang, J. Mater. Chem. A, 2016, 4,

9054–9062.

Chem Soc Rev Review Article

Published on 04 March 2024. Downloaded by University of Wollongong on 3/8/2024 12:31:15 AM.

View Article Online

203 Y. Zhang, N. Zhang, W. Chen, Z. Rao, J. Wu, L. Xue and

W. Zhang, Energy Technol., 2019, 7, 1900779.

204 L. Zhang, T. Yuan, L. Soule, H. Sun, Y. Pang, J. Yang and

S. Zheng, ACS Appl. Energy Mater., 2020, 3, 3770–3778.

205 Y. Shen, S. Sun, M. Yang and X. Zhao, J. Alloys Compd.,

2019, 784, 1290–1296.

206 L. Sun, Y. Xie, X.-Z. Liao, H. Wang, G. Tan, Z. Chen, Y. Ren,

J. Gim, W. Tang, Y.-S. He, K. Amine and Z.-F. Ma, Small,

2018, 14, 1704523.

207 S.-M. Oh, S.-T. Myung, J.-Y. Hwang, B. Scrosati, K. Amine

and Y.-K. Sun, Chem. Mater., 2014, 26, 6165–6171.

208 Y. You, S. Xin, H. Y. Asl, W. Li, P.-F. Wang, Y.-G. Guo and

A. Manthiram, Chem, 2018, 4, 2124–2139.

209 J.-L. Yue, Y.-N. Zhou, X. Yu, S.-M. Bak, X.-Q. Yang and

Z.-W. Fu, J. Mater. Chem. A, 2015, 3, 23261–23267.

210 C. Zhang, R. Gao, L. Zheng, Y. Hao and X. Liu, ACS Appl.

Mater. Interfaces, 2018, 10, 10819–10827.

211 M.-H. Cao, Y. Wang, Z. Shadike, J.-L. Yue, E. Hu, S.-M. Bak,

Y.-N. Zhou, X.-Q. Yang and Z.-W. Fu, J. Mater. Chem. A,

2017, 5, 5442–5448.

212 L. Mu, S. Xu, Y. Li, Y.-S. Hu, H. Li, L. Chen and X. Huang,

Adv. Mater., 2015, 27, 6928–6933.

213 C. G. Hawkins and L. Whittaker-Brooks, ACS Appl. Nano

Mater., 2018, 1, 851–859.

214 C. Vaalma, G. A. Giﬃn, D. Buchholz and S. Passerini,

J. Electrochem. Soc., 2016, 163, A1295.

215 H. Kim, J. C. Kim, S.-H. Bo, T. Shi, D.-H. Kwon and

G. Ceder, Adv. Energy Mater., 2017, 7, 1700098.

216 X. Wang, X. Xu, C. Niu, J. Meng, M. Huang, X. Liu, Z. Liu

and L. Mai, Nano Lett., 2017, 17, 544–550.

217 J. J. Ding, Y. N. Zhou, Q. Sun, X. Q. Yu, X. Q. Yang and

Z. W. Fu, Electrochim. Acta, 2013, 87, 388–393.

218 Y. Fang, X.-Y. Yu and X. W. Lou, Angew. Chem., Int. Ed.,

2017, 56, 5801–5805.

219 P. Vassilaras, X. Ma, X. Li and G. Ceder, J. Electrochem. Soc.,

2013, 160, A207.

220 N. Yabuuchi, H. Yoshida and S. Komaba, Electrochem.,

2012, 80, 716–719.

221 C.-Y. Yu, J.-S. Park, H.-G. Jung, K.-Y. Chung, D. Aurbach,

Y.-K. Sun and S.-T. Myung, Energy Environ. Sci., 2015, 8,

2019–2026.

222 D. Hamani, M. Ati, J.-M. Tarascon and P. Rozier, Electro-

chem. Commun., 2011, 13, 938–941.

223 X. Wang, P. Hu, C. Niu, J. Meng, X. Xu, X. Wei, C. Tang,

W. Luo, L. Zhou, Q. An and L. Mai, Nano Energy, 2017, 35,

71–78.

224 H. Zhang, K. Xi, K. Jiang, X. Zhang, Z. Liu, S. Guo and

H. Zhou, Chem. comm., 2019, 55, 7910–7913.

225 S. Guo, H. Yu, P. Liu, Y. Ren, T. Zhang, M. Chen,

M. Ishida and H. Zhou, Energy Environ. Sci., 2015, 8,

1237–1244.

226 Y. Wang, R. Xiao, Y.-S. Hu, M. Avdeev and L. Chen, Nat.

Commun., 2015, 6, 6954.

227 J. Xu, D. H. Lee, R. J. Cle

´ment, X. Yu, M. Leskes, A. J. Pell,

G. Pintacuda, X.-Q. Yang, C. P. Grey and Y. S. Meng, Chem.

Mater., 2014, 26, 1260–1269.

228 J. Yoshida, E. Guerin, M. Arnault,C.Constantin,B.Mortemard

de Boisse, D. Carlier, M. Guignard and C. Delmas,

J. Electrochem. Soc., 2014, 161, A1987.

229 Y. Hironaka, K. Kubota and S. Komaba, Chem. comm.,

2017, 53, 3693–3696.

230 C.-L. Liu, S.-H. Luo, H.-B. Huang, Y.-C. Zhai and Z.-W.

Wang, J. Chem. Eng., 2019, 356, 53–59.

231 H. Kim, D.-H. Seo, A. Urban, J. Lee, D.-H. Kwon, S.-H. Bo,

T. Shi, J. K. Papp, B. D. McCloskey and G. Ceder, Chem.

Mater., 2018, 30, 6532–6539.

232 L. Deng, X. Niu, G. Ma, Z. Yang, L. Zeng, Y. Zhu and L. Guo,

Adv. Funct. Mater., 2018, 28, 1800670.

233 J. U. Choi, J. Kim, J.-Y. Hwang, J. H. Jo, Y.-K. Sun and

S.-T. Myung, Nano Energy, 2019, 61, 284–294.

234 T. Deng, X. Fan, J. Chen, L. Chen, C. Luo, X. Zhou,

J. Yang, S. Zheng and C. Wang, Adv. Funct. Mater., 2018,

28, 1800219.

235 X. Zhang, Y. Yang, X. Qu, Z. Wei, G. Sun, K. Zheng, H. Yu

and F. Du, Adv. Funct. Mater., 2019, 29,1905679.

236 K. Lei, Z. Zhu, Z. Yin, P. Yan, F. Li and J. Chen, Chem, 2019,

5, 3220–3231.

237 S. Zhao, K. Yan, P. Munroe, B. Sun and G. Wang, Adv.

Energy Mater., 2019, 9, 1803757.

238 B. Peng, Y. Li, J. Gao, F. Zhang, J. Li and G. Zhang, J. Power

Sources, 2019, 437, 226913.

239 N. Naveen, W. B. Park, S. P. Singh, S. C. Han, D. Ahn,

K.-S. Sohn and M. Pyo, Small, 2018, 14, 1803495.

240 J.-Y. Hwang, J. Kim, T.-Y. Yu, S.-T. Myung and Y.-K. Sun,

Energy Environ. Sci., 2018, 11, 2821–2827.

241 N. Naveen, S. C. Han, S. P. Singh, D. Ahn, K.-S. Sohn and

M. Pyo, J. Power Sources, 2019, 430, 137–144.

242 Y. Yang, Z. Liu, L. Deng, L. Tan, X. Niu, M. M. S.

Sanad, L. Zeng, Z. Zhu and Y. Zhu, Chem. comm., 2019,

55, 14988–14991.

243 X. Niu, J. Qu, Y. Hong, L. Deng, R. Wang, M. Feng, J. Wang,

L. Zeng, Q. Zhang, L. Guo and Y. Zhu, J. Mater. Chem. A,

2021, 9, 13125–13134.

244 J. H. Jo, J.-Y. Hwang, J. U. Choi, H. J. Kim, Y.-K. Sun and

S.-T. Myung, J. Power Sources, 2019, 432, 24–29.

245 Y. Zhang, X. Niu, L. Tan, L. Deng, S. Jin, L. Zeng, H.

Xu and Y. Zhu, ACS Appl. Mater. Interfaces, 2020, 12,

9332–9340.

246 W. Li, Z. Bi, W. Zhang, J. Wang, R. Rajagopalan, Q. Wang,

D. Zhang, Z. Li, H. Wang and B. Wang, J. Mater. Chem. A,

2021, 9, 8221–8247.

247 C.-L. Liu, S.-H. Luo, H.-B. Huang, Y.-C. Zhai and Z.-W.

Wang, ChemElectroChem, 2019, 6, 2308–2315.

248 J. Weng, J. Duan, C. Sun, P. Liu, A. Li, P. Zhou and J. Zhou,

J. Chem. Eng., 2020, 392, 123649.

249 M. G. T. Nathan, N. Naveen, W. B. Park, K.-S. Sohn and

M. Pyo, J. Power Sources, 2019, 438, 226992.

250 J. U. Choi, Y. Ji Park, J. H. Jo, Y. H. Jung, D.-C.

Ahn, T.-Y. Jeon, K.-S. Lee, H. Kim, S. Lee, J. Kim and

S.-T. Myung, Energy Storage Mater, 2020, 27, 342–351.

251 P. Bai, K. Jiang, X. Zhang, J. Xu, S. Guo and H. Zhou, ACS

Appl. Mater. Interfaces, 2020, 12, 10490–10495.

Review Article Chem Soc Rev

Published on 04 March 2024. Downloaded by University of Wollongong on 3/8/2024 12:31:15 AM.

View Article Online

252 H. V. Ramasamy, B. Senthilkumar, P. Barpanda and

Y.-S. Lee, J. Chem. Eng., 2019, 368, 235–243.

253 C. Liu, S. Luo, H. Huang, Z. Wang, A. Hao, Y. Zhai and

Z. Wang, Electrochem. Commun., 2017, 82, 150–154.

254 Z. A. Ghazi, X. He, A. M. Khattak, N. A. Khan, B. Liang,

A. Iqbal, J. Wang, H. Sin, L. Li and Z. Tang, Adv. Mater.,

2017, 29, 1606817.

255 Y. Ge, X. Yan, J. Liu, X. Zhang, J. Wang, X. He, R. Wang and

H. Xie, Electrochim. Acta, 2010, 55, 5886–5890.

256 H. Liu, S.-H. Luo, S.-X. Yan, Y.-F. Wang, Q. Wang, M.-Q. Li

and Y.-H. Zhang, J. Electroanal. Chem., 2019, 850, 113434.

257 X. Li, Z. Shao, K. Liu, Q. Zhao, G. Liu and B. Xu, J. Solid

State Electrochem., 2019, 23, 465–473.

258 T. A. Wani and G. Suresh, J. Energy Storage, 2021,

44, 103307.

259 I. Seo, B. Senthilkumar, K.-H. Kim, J.-K. Kim, Y. Kim and

J.-H. Ahn, J. Power Sources, 2016, 320, 59–67.

260 M. Zhang, N. Garcia-Araez and A. L. Hector, J. Mater. Chem.

A, 2018, 6, 14483–14517.

261 Y. Xiao, P.-F. Wang, Y.-X. Yin, Y.-F. Zhu, X. Yang,

X.-D. Zhang, Y. Wang, X.-D. Guo, B.-H. Zhong and

Y.-G. Guo, Adv. Energy Mater., 2018, 8, 1800492.

262 K. Vijaya Babu, L. Seeta Devi, V. Veeraiah and K. Anand,

J. Asian Ceram. Soc., 2016, 4, 269–276.

263 Q. Ni, L. Zheng, Y. Bai, T. Liu, H. Ren, H. Xu, C. Wu and

J. Lu, ACS Energy Lett., 2020, 5, 1763–1770.

264 X. Hou, J. Liang, T. Zhang, Y. Li, S. Tang, H. Sun, J. Zhang

and H. Xie, J. Phys. Chem. C, 2017, 121, 22656–22664.

265 T. Yamada, N. Zettsu, H.-M. Kim, Y. Hagano, N. Handa,

K. Yubuta and K. Teshima, Cryst. Growth Des., 2018, 18,

6777–6785.

266 S. S. Fedotov, A. A. Kabanov, N. A. Kabanova, V. A. Blatov,

A. Zhugayevych, A. M. Abakumov, N. R. Khasanova and

E. V. Antipov, J. Phys. Chem. C, 2017, 121, 3194–3202.

267 M. Sun, G. Rousse, D. D. Corte, M. Saubane

`re, M.-L.

Doublet and J.-M. Tarascon, Chem. Mater., 2016, 28,

1607–1610.

268 C. Frayret, A. Villesuzanne, N. Spaldin, E. Bousquet,

J.-N. Chotard, N. Recham and J.-M. Tarascon, Phys. Chem.

Chem. Phys., 2010, 12, 15512–15522.

269 T. Mueller, G. Hautier, A. Jain and G. Ceder, Chem. Mater.,

2011, 23, 3854–3862.

270 W. Wen, X. Wang, S. Chen, H. Shu and X. Yang, J. Power

Sources, 2015, 281, 85–93.

271 M. H. Nasir, N. K. Janjua and J. Santoki, J. Electrochem.

Soc., 2020, 167, 130526.

272 X. Wu, Z. Gong, S. Tan and Y. Yang, J. Power Sources, 2012,

220, 122–129.

273 N. Membren

˜o, K. Park, J. B. Goodenough and

K. J. Stevenson, Chem. Mater., 2015, 27, 3332–3340.

274 Y. Liu, Z. Wu, S. Indris, W. Hua, N. P. M. Casati, A. Tayal,

M. S. D. Darma, G. Wang, Y. Liu, C. Wu, Y. Xiao, B. Zhong

and X. Guo, Nano Energy, 2021, 79, 105417.

275 M. Hadouchi, N. Yaqoob, P. Kaghazchi, M. Tang, J. Liu,

P. Sang, Y. Fu, Y. Huang and J. Ma, Energy Storage Mater.,

2021, 35, 192–202.

276 S.-M. Oh, S.-T. Myung, J. Hassoun, B. Scrosati and

Y.-K. Sun, Electrochemistry Communications, 2012, 22,

149–152.

277 Y. Liu, N. Zhang, F. Wang, X. Liu, L. Jiao and L.-Z. Fan, Adv.

Funct. Mater., 2018, 28, 1801917.

278 Y. Liu, Y. Xu, X. Han, C. Pellegrinelli, Y. Zhu, H. Zhu,

J. Wan, A. C. Chung, O. Vaaland, C. Wang and L. Hu, Nano

Lett., 2012, 12, 5664–5668.

279 G. He, W. H. Kan and A. Manthiram, Chem. Mater., 2016,

28, 682–688.

280 Y. Fang, Q. Liu, L. Xiao, Y. Rong, Y. Liu, Z. Chen, X. Ai,

Y. Cao, H. Yang, J. Xie, C. Sun, X. Zhang, B. Aoun, X. Xing,

X. Xiao and Y. Ren, Chem, 2018, 4, 1167–1180.

281 J. Kim, G. Yoon, H. Kim, Y.-U. Park and K. Kang, Chem.

Mater., 2018, 30, 3683–3689.

282 K. Saravanan, C. W. Mason, A. Rudola, K. H. Wong and

P. Balaya, Adv. Energy Mater., 2013, 3, 444–450.

283 R. Rajagopalan, B. Chen, Z. Zhang, X.-L. Wu, Y. Du,

Y.Huang,B.Li,Y.Zong,J.Wang,G.-H.Nam,M.Sindoro,

S. X. Dou, H. K. Liu and H. Zhang, Adv. Mater., 2017,

29, 1605694.

284 K. Kawai, W. Zhao, S.-I. Nishimura and A. Yamada, ACS

Appl. Energy Mater, 2018, 1, 928–931.

285 D. Wang, X. Bie, Q. Fu, D. Dixon, N. Bramnik, Y.-S. Hu,

F. Fauth, Y. Wei, H. Ehrenberg, G. Chen and F. Du, Nat.

Commun., 2017, 8, 15888.

286 W. Zhou, L. Xue, X. Lu

¨, H. Gao, Y. Li, S. Xin, G. Fu, Z. Cui,

Y. Zhu and J. B. Goodenough, Nano Lett., 2016, 16,

7836–7841.

287 H. Gao, I. D. Seymour, S. Xin, L. Xue, G. Henkelman and

J. B. Goodenough, J. Am. Chem. Soc., 2018, 140, 18192–18199.

288 H. Li, M. Xu, C. Gao, W. Zhang, Z. Zhang, Y. Lai and L. Jiao,

Energy Storage Mater., 2020, 26, 325–333.

289 C. S. Park, H. Kim, R. A. Shakoor, E. Yang, S. Y. Lim,

R. Kahraman, Y. Jung and J. W. Choi, J. Am. Chem. Soc.,

2013, 135, 2787–2792.

290 P. Barpanda, J. Lu, T. Ye, M. Kajiyama, S.-C. Chung,

N. Yabuuchi, S. Komaba and A. Yamada, RSC Adv., 2013,

3, 3857–3860.

291 B. Lin, S. Zhang and C. Deng, J. Mater. Chem. A, 2016, 4,

2550–2559.

292 J. Kim, I. Park, H. Kim, K.-Y. Park, Y.-U. Park and K. Kang,

Adv. Energy Mater., 2016, 6, 1502147.

293 P. Barpanda, G. Liu, M. Avdeev and A. Yamada, ChemElec-

troChem, 2014, 1, 1488–1491.

294 Y. Kee, N. Dimov, A. Staikov, P. Barpanda, Y.-C. Lu,

K. Minami and S. Okada, RSC Adv., 2015, 5, 64991–64996.

295 M. Zarrabeitia, M. Ja

´uregui, N. Sharma, J. C. Pramudita

and M. Casas-Cabanas, Chem. Mater., 2019, 31, 5152–5159.

296 H. Zhang, I. Hasa, D. Buchholz, B. Qin, D. Geiger, S. Jeong,

U. Kaiser and S. Passerini, NPG Asia Mater., 2017, 9,

e370–e370.

297 W. Fang, Z. An, J. Xu, H. Zhao and J. Zhang, RSC Adv., 2018,

8, 21224–21228.

298 T. Jin, Y. Liu, Y. Li, K. Cao, X. Wang and L. Jiao, Adv. Energy

Mater., 2017, 7, 1700087.

Chem Soc Rev Review Article

Published on 04 March 2024. Downloaded by University of Wollongong on 3/8/2024 12:31:15 AM.

View Article Online

299 J.-Z. Guo, P.-F. Wang, X.-L. Wu, X.-H. Zhang, Q. Yan,

H. Chen, J.-P. Zhang and Y.-G. Guo, Adv. Mater., 2017,

29, 1701968.

300 R. Tripathi, S. M. Wood, M. S. Islam and L. F. Nazar, Energy

Environ. Sci., 2013, 6, 2257–2264.

301 H. Zou, S. Li, X. Wu, M. J. McDonald and Y. Yang, ECS

Electrochem. Lett., 2015, 4, A53.

302 W. Pan, W. Guan, S. Liu, B. B. Xu, C. Liang, H. Pan,

M. Yan and Y. Jiang, J. Mater. Chem. A, 2019, 7,

13197–13204.

303 P. Barpanda, G. Oyama, C. D. Ling and A. Yamada, Chem.

Mater., 2014, 26, 1297–1299.

304 M. Chen, D. Cortie, Z. Hu, H. Jin, S. Wang, Q. Gu, W. Hua,

E. Wang, W. Lai, L. Chen, S.-L. Chou, X.-L. Wang and

S.-X. Dou, Adv. Energy Mater., 2018, 8, 1800944.

305 A. Gon

˜i, A. Iturrondobeitia, I. Gil de Muro, L. Lezama and

T. Rojo, J. Power Sources, 2017, 369, 95–102.

306 J. Lin, Y. Xu, J. Wang, B. Zhang, C. Wang, S. He and J. Wu,

Chem. Eng. J., 2019, 373, 78–85.

307 P. Singh, K. Shiva, H. Celio and J. B. Goodenough, Energy

Environ. Sci., 2015, 8, 3000–3005.

308 M. Law, V. Ramar and P. Balaya, J. Power Sources, 2017,

359, 277–284.

309 K. Kaliyappan and Z. Chen, Electrochim. Acta, 2018, 283,

1384–1389.

310 J. C. Treacher, S. M. Wood, M. S. Islam and E. Kendrick,

Phys. Chem. Chem. Phys., 2016, 18, 32744–32752.

311 M. Chen, W. Hua, J. Xiao, D. Cortie, W. Chen, E. Wang,

Z. Hu, Q. Gu, X. Wang, S. Indris, S.-L. Chou and S.-X. Dou,

Nat. Commun., 2019, 10, 1480.

312 J. Han, Y. Niu, S.-J. Bao, Y.-N. Yu, S.-Y. Lu and M. Xu, Chem.

Commun., 2016, 52, 11661–11664.

313 N. Recham, G. Rousse, M. T. Sougrati, J.-N. Chotard,

C. Frayret, S. Mariyappan, B. C. Melot, J.-C. Jumas and

J.-M. Tarascon, Chem. Mater., 2012, 24, 4363–4370.

314 J. Han, G.-N. Li, F. Liu, M. Wang, Y. Zhang, L. Hu, C. Dai

and M. Xu, Chem. comm., 2017, 53, 1805–1808.

315 X. Lin, J. Huang, H. Tan, J. Huang and B. Zhang, Energy

Storage Mater., 2019, 16, 97–101.

316 J. Liao, Q. Hu, B. Che, X. Ding, F. Chen and C. Chen,

J. Mater. Chem. A, 2019, 7, 15244–15251.

317 N. Imanishi, T. Morikawa, J. Kondo, Y. Takeda, O.

Yamamoto, N. Kinugasa and T. Yamagishi, J. Power

Sources, 1999, 79, 215–219.

318 L. Shen, Z. Wang and L. Chen, Chem. Eur. J., 2014, 20,

12559–12562.

319 X. Wu, M. Shao, C. Wu, J. Qian, Y. Cao, X. Ai and H. Yang,

ACS Appl. Mater. Interfaces, 2016, 8, 23706–23712.

320 Z. Zhang, M. Avdeev, H. Chen, W. Yin, W. H. Kan and

G. He, Nat. Commun., 2022, 13, 7790.

321 Y. You, X.-L. Wu, Y.-X. Yin and Y.-G. Guo, J. Mater. Chem. A,

2013, 1, 14061–14065.

322 H. Lee, Y.-I. Kim, J.-K. Park and J. W. Choi, Chem. comm.,

2012, 48, 8416–8418.

323 J. Peng, M. Ou, H. Yi, X. Sun, Y. Zhang, B. Zhang, Y. Ding,

F. Wang, S. Gu, C. A. Lo

´pez, W. Zhang, Y. Liu, J. Fang, P.

Wei,Y.Li,L.Miao,J.Jiang,C.Fang,Q.Li,M.T.Ferna

´ndez-

Dı

az,J.A.Alonso,S.ChouandJ.Han,Energy Environ. Sci.,

2021, 14, 3130–3140.

324 W. Wang, Y. Gang, Z. Hu, Z. Yan, W. Li, Y. Li, Q.-F. Gu,

Z. Wang, S.-L. Chou, H.-K. Liu and S.-X. Dou, Nat. Com-

mun., 2020, 11, 980.

325 J. Peng, W. Zhang, J. Wang, L. Li, W. Lai, Q. Yang,

B. Zhang, X. Li, Y. Du, H. Liu, J. Wang, Z. Cheng,

L. Wang, S. Wang, J. Wang, S. Chou, H. Liu and S. Dou,

Adv. Energy Mater., 2021, 11, 2102356.

326 Y. Shang, X. Li, J. Song, S. Huang, Z. Yang, Z. J. Xu and

H. Y. Yang, Chem, 2020, 6, 1804–1818.

327 Y. Liu, Y. Qiao, W. Zhang, Z. Li, X. Ji, L. Miao, L. Yuan,

X. Hu and Y. Huang, Nano Energy, 2015, 12, 386–393.

328 Y. Tang, W. Zhang, L. Xue, X. Ding, T. Wang, X. Liu,

J. Liu, X. Li and Y. Huang, J. Mater. Chem. A, 2016, 4,

6036–6041.

329 S. Qiao, S. Dong, L. Yuan, T. Li, M. Ma, Y. Wu, Y. Hu, T. Qu

and S. Chong, J. Alloys Compd., 2023, 950, 169903.

330 A. Eftekhari, J. Power Sources, 2004, 126, 221–228.

331 X. Bie, K. Kubota, T. Hosaka, K. Chihara and S. Komaba,

J. Mater. Chem. A, 2017, 5,4325–4330.

332 L. Deng, J. Qu, X. Niu, J. Liu, J. Zhang, Y. Hong, M. Feng,

J. Wang, M. Hu, L. Zeng, Q. Zhang, L. Guo and Y. Zhu, Nat.

Commun., 2021, 12, 2167.

333 S. Chong, Y. Chen, Y. Zheng, Q. Tan, C. Shu, Y. Liu and

Z. Guo, J. Mater. Chem. A, 2017, 5, 22465–22471.

334 P. Padigi, J. Thiebes, M. Swan, G. Goncher, D. Evans and

R. Solanki, Electrochim. Acta, 2015, 166, 32–39.

335 Y.-h Zhu, Y.-b Yin, X. Yang, T. Sun, S. Wang, Y.-s Jiang,

J.-m Yan and X.-b Zhang, Angew. Chem., Int. Ed., 2017, 56,

7881–7885.

336 L. Xue, Y. Li, H. Gao, W. Zhou, X. Lu

¨, W. Kaveevivitchai,

A. Manthiram and J. B. Goodenough, J. Am. Chem. Soc.,

2017, 139, 2164–2167.

337 X. Jiang, T. Zhang, L. Yang, G. Li and J. Y. Lee, ChemElec-

troChem, 2017, 4, 2237–2242.

338 Z. Shadike, D.-R. Shi, W. Tian, M.-H. Cao, S.-F. Yang,

J. Chen and Z.-W. Fu, J. Mater. Chem. A, 2017, 5, 6393–6398.

339 X. Wu, Z. Jian, Z. Li and X. Ji, Electrochem. Commun., 2017,

77, 54–57.

340 G. He and L. F. Nazar, ACS Energy Lett., 2017, 2, 1122–1127.

341 X. Han, C. Chang, L. Yuan, T. Sun and J. Sun, Adv. Mater.,

2007, 19, 1616–1621.

342 A. Molina, N. Patil, E. Ventosa, M. Liras, J. Palma and

R. Marcilla, Adv. Funct. Mater., 2020, 30, 1908074.

343 Z. Ouyang, D. Tranca, Y. Zhao, Z. Chen, X. Fu, J. Zhu,

G. Zhai, C. Ke, E. Kymakis and X. Zhuang, ACS Appl. Mater.

Interfaces, 2021, 13, 9064–9073.

344 M. G. Mohamed, S. U. Sharma, C.-H. Yang, M. M. Samy,

A. A. K. Mohammed, S. V. Chaganti, J.-T. Lee and S. Wei-

Kuo, ACS Appl. Energy Mater., 2021, 4, 14628–14639.

345 Z. Chen, W. Li, Y. Dai, N. Xu, C. Su, J. Liu and C. Zhang,

Electrochim. Acta, 2018, 286, 187–194.

346 C. Zhang, X. Yang, W. Ren, Y. Wang, F. Su and J.-X. Jiang,

J. Power Sources, 2016, 317, 49–56.

Review Article Chem Soc Rev

Published on 04 March 2024. Downloaded by University of Wollongong on 3/8/2024 12:31:15 AM.

View Article Online

347 K. S. Weeraratne, A. A. Alzharani and H. M. El-Kaderi, ACS

Appl. Mater. Interfaces, 2019, 11, 23520–23526.

348 K. Sakaushi, E. Hosono, G. Nickerl, T. Gemming, H. Zhou,

S. Kaskel and J. Eckert, Nat. Commun., 2013, 4, 1485.

349 K. Li, Y. Wang, B. Gao, X. Lv, Z. Si and H.-G. Wang,

J. Colloid Interface Sci., 2021, 601, 446–453.

350 B. Tian, J. Zheng, C. Zhao, C. Liu, C. Su, W. Tang,

X. Li and G.-H. Ning, J. Mater. Chem. A, 2019, 7,

9997–10003.

351 R. R. Kapaev, I. S. Zhidkov, E. Z. Kurmaev, K. J. Stevenson

and P. A. Troshin, J. Mater. Chem. A, 2019, 7, 22596–22603.

352 Z. Luo, L. Liu, J. Ning, K. Lei, Y. Lu, F. Li and J. Chen,

Angew. Chem., Int. Ed., 2018, 57, 9443–9446.

353 M. Wu, Y. Zhao, B. Sun, Z. Sun, C. Li, Y. Han, L. Xu, Z. Ge,

Y. Ren, M. Zhang, Q. Zhang, Y. Lu, W. Wang, Y. Ma and

Y. Chen, Nano Energy, 2020, 70, 104498.

354 K. Nakashima, T. Shimizu, Y. Kamakura, A. Hinokimoto,

Y. Kitagawa, H. Yoshikawa and D. Tanaka, Chem. Sci.,

2020, 11, 37–43.

355 R. Shi, L. Liu, Y. Lu, C. Wang, Y. Li, L. Li, Z. Yan and

J. Chen, Nat. Commun., 2020, 11, 178.

356 J. Duan, W. Wang, D. Zou, J. Liu, N. Li, J. Weng, L.-P. Xu,

Y. Guan, Y. Zhang and P. Zhou, ACS Appl. Mater. Interfaces,

2022, 14, 31234–31244.

357 J. Lee, H. Lim, J. Park, M.-S. Kim, J.-W. Jung, J. Kim and

I.-D. Kim, Adv. Energy Mater, 2023, 13, 2300442.

358 G. Fe

´rey, F. Millange, M. Morcrette, C. Serre, M.-L. Doublet,

J.-M. Grene

`che and J.-M. Tarascon, Angew. Chem., Int. Ed.,

2007, 46, 3259–3263.

359 T. L. A. Nguyen, R. Demir-Cakan, T. Devic, M. Morcrette,

T. Ahnfeldt, P. Auban-Senzier, N. Stock, A.-M. Goncalves,

Y. Filinchuk, J.-M. Tarascon and G. Fe

´rey, Inorg. Chem.,

2010, 49, 7135–7143.

360 B. Tian, G.-H. Ning, Q. Gao, L.-M. Tan, W. Tang, Z. Chen,

C. Su and K. P. Loh, ACS Appl. Mater. Interfaces, 2016, 8,

31067–31075.

361 S. Zheng, Y. Chen, Y. Xu, F. Yi, Y. Zhu, Y. Liu, J. Yang and

C. Wang, ACS Nano, 2013, 7, 10995–11003.

362 Z. Li, X. Li, Y. Liao, X. Li and W. Li, J. Power Sources,2016,

334, 23–30.

363 Y. Liu, L. Si, X. Zhou, X. Liu, Y. Xu, J. Bao and Z. Dai,

J. Mater. Chem. A, 2014, 2, 17735–17739.

364 Y. Yan, M. Shi, Y. Wei, C. Zhao, M. Carnie, R. Yang and

Y. Xu, J. Alloys Compd., 2018, 738, 16–24.

365 Z. Li, L. Yuan, Z. Yi, Y. Sun, Y. Liu, Y. Jiang, Y. Shen, Y. Xin,

Z. Zhang and Y. Huang, Adv. Energy Mater., 2014,

4, 1301473.

366 M. H. Aboonasr Shiraz, H. Zhu, Y. Liu, X. Sun and J. Liu,

J. Power Sources, 2019, 438, 227059.

367 Q. Guo, S. Li, X. Liu, H. Lu, X. Chang, H. Zhang, X. Zhu,

Q. Xia, C. Yan and H. Xia, Adv. Sci., 2020, 7, 1903246.

368 D. Zhao, S. Jiang, S. Yu, J. Ren, Z. Zhang, S. Liu,

X. Liu, Z. Wang, Y. Wu and Y. Zhang, Carbon, 2023, 201,

864–870.

369 Q. Guo, S. Sun, K.-I. Kim, H. Zhang, X. Liu, C. Yan and

H. Xia, Carbon Energy, 2021, 3, 440–448.

370 D. Zhao, S. Ge-Zhang, Z. Zhang, H. Tang, Y. Xu, F. Gao,

X. Xu, S. Liu, J. Zhou, Z. Wang, Y. Wu, X. Liu and Y. Zhang,

ACS Appl. Mater. Interfaces, 2022, 14, 54662–54669.

371 P. Xiong, X. Han, X. Zhao, P. Bai, Y. Liu, J. Sun and Y. Xu,

ACS Nano, 2019, 13, 2536–2543.

372 X. Han, M. Wang, J. Yu and S. Wang, Mater. Adv., 2022, 3,

1652–1659.

373 Y. Xiao, Y. Miao, S. Wan, Y.-K. Sun and S. Chen, Small,

2022, 18, 2202582.

374 H.-S. Zhao, Y.-L. Qi, K. Liang, W.-K. Zhu, H.-B. Wu, J.-B. Li

and Y.-R. Ren, Rare Met., 2022, 41, 1284–1293.

375 M. Nazarian-Samani, M. Nazarian-Samani, S. Haghighat-

Shishavan and K.-B. Kim, Energy Storage Mater., 2021, 36,

229–241.

376 Z. Wang, H. Shi, S. Yang, Z. Cai, H. Lu, L. Jia, M. Hu, H. He

and K. Zhou, J. Alloys Compd., 2021, 888, 161553.

377 Y. Zhang, M. Zhang, Y. Liu, H. Zhu, L. Wang, Y. Liu,

M. Xue, B. Li and X. Tao, Electrochim. Acta, 2020,

330, 135299.

378 C. M. Park and H. J. Sohn, Adv. Mater., 2007, 19,

2465–2468.

379 C. Xia, Y. Zhou, D. B. Velusamy, A. A. Farah, P. Li, Q. Jiang,

I. N. Odeh, Z. Wang, X. Zhang and H. N. Alshareef, Nano

Lett.,2018, 18, 1506–1515.

380 U. Chothe, C. Ugale, M. Kulkarni and B. Kale, Crystals,

2021, 11, 660.

381 Z. Hu, Q. Liu, W. Sun, W. Li, Z. Tao, S.-L. Chou, J.

Chen and S.-X. Dou, Inorganic Chemistry Frontiers, 2016,

3, 532–535.

382 R. Zhou, H. Wang, J. Chang, C. Yu, H. Dai, Q. Chen,

J. Zhou, H. Yu, G. Sun and W. Huang, ACS Appl. Mater.

Interfaces, 2021, 13, 17459–17466.

383 F. Wang, Y. Li, X. Liang, Y. Liu, Q. Chen and M. Chen,

Mater. Chem. Phys., 2022, 278, 125681.

384 P. Lian, Y. Dong, Z.-S. Wu, S. Zheng, X. Wang, W. Sen,

C. Sun, J. Qin, X. Shi and X. Bao, Nano Energy, 2017, 40,

1–8.

385 P. A. Maughan, L. Bouscarrat, V. R. Seymour, S. Shao,

S. J. Haigh, R. Dawson, N. Tapia-Ruiz and N. Bimbo,

Nanoscale Adv., 2021, 3, 3145–3158.

386 S. Kajiyama, L. Szabova, K. Sodeyama, H. Iinuma,

R. Morita, K. Gotoh, Y. Tateyama, M. Okubo and

A. Yamada, ACS Nano, 2016, 10, 3334–3341.

387 Y. Xie, Y. Dall’Agnese, M. Naguib, Y. Gogotsi, M. W.

Barsoum, H. L. Zhuang and P. R. C. Kent, ACS Nano,

2014, 8, 9606–9615.

388 X. Wang, S. Kajiyama, H. Iinuma, E. Hosono, S. Oro,

I. Moriguchi, M. Okubo and A. Yamada, Nat. Commun.,

2015, 6, 6544.

389 Y. Dall’Agnese, P.-L. Taberna, Y. Gogotsi and P. Simon,

J. Phys. Chem. Lett., 2015, 6, 2305–2309.

390 S. Imtiaz, J. Zhang, Z. A. Zafar, S. N. Ji, T. Z. Huang,

J. A. Anderson, Z. L. Zhang and Y. H. Huang, Science

China-Materials, 2016, 59, 389–407.

391 Z. Lu, C.-T. Yip, L. Wang, H. Huang and L. Zhou, Chem-

PlusChem, 2012, 77, 991–1000.

Chem Soc Rev Review Article

Published on 04 March 2024. Downloaded by University of Wollongong on 3/8/2024 12:31:15 AM.

View Article Online

392 K. Su, T. Jin, C. H. Zhang, R. Wang, S. Yuan, N. W. Li and

L. Yu, J. Chem. Eng., 2022, 450, 138049.

393 J. Han, I. Johnson, Z. Lu, A. Kudo and M. Chen, Nano Lett.,

2021, 21, 6504–6510.

394 L. Zhong, W. Zhang, S. Sun, L. Zhao, W. Jian, X. He,

Z. Xing, Z. Shi, Y. Chen, H. N. Alshareef and X. Qiu, Adv.

Funct. Mater., 2023, 33, 2211872.

395 J. Wu, X. Zhang, Z. Li, C. Yang, W. Zhong, W. Li, C. Zhang,

N. Yang, Q. Zhang and X. Li, Adv. Funct. Mater., 2020,

30, 2004348.

396 N. Xiao, X. Zhang, C. Liu, Y. Wang, H. Li and J. Qiu,

Carbon, 2019, 147, 574–581.

397 D. Yoon, J. Hwang, W. Chang and J. Kim, ACS Appl. Mater.

Interfaces, 2018, 10, 569–581.

398 J. Yang, X. Wang, W. Dai, X. Lian, X. Cui, W. Zhang,

K. Zhang, M. Lin, R. Zou, K. P. Loh, Q.-H. Yang and

W. Chen, Nano-Micro Lett., 2021, 13, 98.

399 S. Zhang, W. Huang, P. Hu, C. Huang, C. Shang, C.

Zhang, R. Yang and G. Cui, J. Mater. Chem. A, 2015, 3,

1896–1901.

400 T. Yang, C. Zhang, W. Ma, X. Gao, C. Yan, F. Wang and

J.-X. Jiang, Solid State Ion., 2020, 347, 115247.

401 C. Zhang, Y. Qiao, P. Xiong, W. Ma, P. Bai, X. Wang, Q. Li,

J. Zhao, Y. Xu, Y. Chen, J. H. Zeng, F. Wang, Y. Xu and

J.-X. Jiang, ACS Nano, 2019, 13, 745–754.

402 S.-Y. Li, W.-H. Li, X.-L. Wu, Y. Tian, J. Yue and G. Zhu,

Chem. Sci., 2019, 10, 7695–7701.

403 Y. Han, P. Qi, X. Feng, S. Li, X. Fu, H. Li, Y. Chen, J. Zhou,

X. Li and B. Wang, ACS Appl. Mater. Interfaces, 2015, 7,

2178–2182.

404 C. Yan, H. Zhao, J. Li, H. Jin, L. Liu, W. Wu, J. Wang, Y. Lei

and S. Wang, Small, 2020, 16, 1907141.

405 W. Li, S. Hu, X. Luo, Z. Li, X. Sun, M. Li, F. Liu and Y. Yu,

Adv. Mater., 2017, 29, 1605820.

406 S. Yao, J. Cui, J. Huang, J.-Q. Huang, W. G. Chong, L. Qin,

Y.-W. Mai and J.-K. Kim, Adv. Energy Mater, 2018,

8, 1702267.

407 S.-A. He, Q. Liu, Z. Cui, K. Xu, R. Zou, W. Luo and M. Zhu,

Small, 2022, 18, 2105866.

408 J. Xiao, Z. Cai, T. Muhmood, X. Hu, S. Lin and X. Hu, Small,

2022, 18, 2106930.

409 Y. Liu, S. Sun, Y. Wang, C. Wang, Q.-C. Wang, J. Han and

R. Guo, J. Power Sources, 2022, 549, 232087.

410 L. Wu, L. Wang, X. Cheng, M. Ma, Y. Wu, X. Wu,

H. Yang, Y. Yu and C. He, Nano Res., 2022, 15,

2147–2156.

411 Z. Yan, Z. Sun, A. Li, H. Liu, Z. Guo, L. Zhao, J. Feng and

L. Qian, J. Chem. Eng., 2022, 429, 132249.

412 W. Li, H. Li, Z. Lu, L. Gan, L. Ke, T. Zhai and H. Zhou,

Energy Environ. Sci., 2015, 8, 3629–3636.

413 L. Z. Wenchao Bi, Jian Chen, Ruixue Tian, Hao Huang and

Man Yao, Acta Chim, 2022, 80, 756–764.

414 F. Song, R. Zhang, X. Zhang, J. Qin and R. Liu, Energy Fuels,

2020, 34, 13032–13037.

415 Y.-N. Zhang, Y. Zhou, J. Su, Y.-F. Long, X.-Y. Lv, H.-X. Kuai

and Y.-X. Wen, Appl. Surf. Sci., 2022, 585, 152763.

416 Y. Zhao, T. Sun, Q. Yin, J. Zhang, S. Zhang, J. Luo, H. Yan,

L. Zheng, J. Han and M. Wei, J. Mater. Chem. A, 2019, 7,

15371–15377.

417 P. Lian, X. Zhu, S. Liang, Z. Li, W. Yang and H. Wang,

Electrochim. Acta, 2010, 55, 3909–3914.

418 Y. Sun, J. Tang, K. Zhang, J. Yuan, J. Li, D.-M. Zhu,

K. Ozawa and L.-C. Qin, Nanoscale, 2017, 9, 2585–2595.

419 G. Ma, K. Huang, J.-S. Ma, Z. Ju, Z. Xing and Q.-C. Zhuang,

J. Mater. Chem. A, 2017, 5, 7854–7861.

420 Z. Chen, Y. Liu, Y. Zhang, F. Shen, G. Yang, L. Wang,

X. Zhang, Y. He, L. Luo and S. Deng, Mater. Lett., 2018, 229,

134–137.

421 Z.-L. Xu, G. Yoon, K.-Y. Park, H. Park, O. Tamwattana,

S. Joo Kim, W. M. Seong and K. Kang, Nat. Commun., 2019,

10, 2598.

422 Y. Wen, K. He, Y. Zhu, F. Han, Y. Xu, I. Matsuda,

Y. Ishii, J. Cumings and C. Wang, Nat. Commun., 2014,

5, 4033.

423 M. G. Kim, S. Lee and J. Cho, J. Electrochem. Soc., 2009,

156, A89.

424 F. Han, C. Zhang, J. Yang, G. Ma, K. He and X. Li, J. Mater.

Chem. A, 2016, 4, 12781–12789.

425 Y. Kim, H. Hwang, C. S. Yoon, M. G. Kim and J. Cho, Adv.

Mater., 2007, 19, 92–96.

426 Q. Zhang, P. Man, B. He, C. Li, Q. Li, Z. Pan, Z. Wang,

J. Yang, Z. Wang, Z. Zhou, X. Lu, Z. Niu, Y. Yao and L. Wei,

Nano Energy, 2020, 67, 104212.

427 P. Senguttuvan, G. Rousse, V. Seznec, J.-M. Tarascon and

M. R. Palacı

´n, Chem. Mater., 2011, 23, 4109–4111.

428 T. Yuan, Z. Tan, C. Ma, J. Yang, Z.-F. Ma and S. Zheng, Adv.

Energy Mater., 2017, 7, 1601625.

429 E. Griﬃn, L. Mogg, G.-P. Hao, G. Kalon, C. Bacaksiz,

G. Lopez-Polin, T. Zhou, V. Guarochico, J. Cai and

C. Neumann, ACS Nano, 2020, 14, 7280–7286.

430 J. Chmiola, C. Largeot, P. L. Taberna, P. Simon and

Y. Gogotsi, Angew. Chem., Int. Ed., 2008, 47, 3392–3395.

431 C. Lu, C. Hu, C. L. Ritt, X. Hua, J. Sun, H. Xia, Y. Liu,

D.-W. Li, B. Ma and M. Elimelech, J. Am. Chem. Soc., 2021,

143, 14242–14252.

432 Y. Li, X. Jin, X. Yan, X. Ai, X. Yang, Z.-J. Zheng, K. Huang,

G. Zhao, Y. Yang, M. Wu and K.-G. Zhou, Nano Res, 2023,

16, 10913–10921.

433 H. X. Yang, Z. K. Liu, Y. Wang, N. W. Li and L. Yu, Adv.

Funct. Mater., 2023, 33, 2209837.

434 X. Li, H. Zhang, P. Wang, J. Hou, J. Lu, C. D. Easton,

X. Zhang, M. R. Hill, A. W. Thornton and J. Z. Liu, Nat.

Commun., 2019, 10, 2490.

435 Z. Chang, H. Yang, X. Zhu, P. He and H. Zhou, Nat.

Commun., 2022, 13, 1510.

436 L. Du, B. Zhang, W. Deng, Y. Cheng, L. Xu and L. Mai, Adv.

Energy Mater., 2022, 12, 2200501.

437 W. He, D. Li, S. Guo, Y. Xiao, W. Gong, Q. Zeng, Y. Ouyang,

X. Li, H. Deng and C. Tan, Energy Storage Mater., 2022, 47,

271–278.

438 G. S. MacGlashan, Y. G. Andreev and P. G. Bruce, Nature,

1999, 398, 792–794.

Review Article Chem Soc Rev

Published on 04 March 2024. Downloaded by University of Wollongong on 3/8/2024 12:31:15 AM.

View Article Online

439 C. Yang, Q. Wu, W. Xie, X. Zhang, A. Brozena, J. Zheng,

M. N. Garaga, B. H. Ko, Y. Mao and S. He, Nature, 2021,

598, 590–596.

440 Q. Zeng, J. Wang, X. Li, Y. Ouyang, W. He, D. Li, S. Guo,

Y. Xiao, H. Deng, W. Gong, Q. Zhang and S. Huang, ACS

Energy Lett., 2021, 6, 2434–2441.

441 A. Hu, Z. Sun, Q. Hou, J. Duan, C. Li, W. Dou, J. Fan,

M. Zheng and Q. Dong, Small, 2022, 18, 2205571.

442 Y. Kato, S. Hori, T. Saito, K. Suzuki, M. Hirayama,

A. Mitsui, M. Yonemura, H. Iba and R. Kanno, Nat. Energy.,

2016, 1, 1–7.

443 J. A. Dawson, P. Canepa, T. Famprikis, C. Masquelier and

M. S. Islam, J. Am. Chem. Soc., 2018, 140, 362–368.

444 G. Redhammer, D. Rettenwander, S. Pristat, E. Dashjav,

C. Kumar, D. Topa and F. Tietz, Solid State Sci., 2016, 60,

99–107.

445 G. Yang, C. Chanthad, H. Oh, I. A. Ayhan and Q. Wang,

J. Mater. Chem. A, 2017, 5, 18012–18019.

446 M. F. Majid, H. F. Mohd Zaid, C. F. Kait, A. Ahmad and

K. Jumbri, Nanomaterials, 2022, 12(7), 1076.

447 T. Zhou, Y. Zhao, J. W. Choi and A. Coskun, Angew. Chem.,

Int. Ed., 2021, 60, 22791–22796.

448 D.-J. Yoo, K. J. Kim and J. W. Choi, Adv. Energy Mater.,

2018, 8, 1702744.

449 W. Lei, C. Zhang, R. Qiao, M. Ravivarma, H. Chen,

F. B. Ajdari, M. Salavati-Niasari and J. Song, ACS Appl.

Energy Mater., 2023, 6, 4363–4371.

450 Z. Wang, H. Zhou, C. Meng, L. Zhang, Y. Cai and A. Yuan,

ChemElectroChem, 2020, 7, 2660–2664.

451 E. M. Miner, S. S. Park and M. Dinca

˘,J. Am. Chem. Soc.,

2019, 141, 4422–4427.

452 T. Wang, X. Zhang, N. Yuan and C. Sun, J. Chem. Eng.,

2023, 451, 138819.

453 B. M. Wiers, M.-L. Foo, N. P. Balsara and J. R. Long, J. Am.

Chem. Soc., 2011, 133, 14522–14525.

454 T. Zhao, W. Kou, Y. Zhang, W. Wu, W. Li and J. Wang,

J. Power Sources, 2023, 554, 232349.

455 L. Liu and C. Sun, ChemElectroChem, 2020, 7,707–715.

456 K. Fujie, R. Ikeda, K. Otsubo, T. Yamada and H. Kitagawa,

Chem. Mater., 2015, 27, 7355–7361.

457 Z. Wang, R. Tan, H. Wang, L. Yang, J. Hu, H. Chen and

F. Pan, Adv. Mater., 2018, 30, 1704436.

458 K. Wang, L. Yang, Z. Wang, Y. Zhao, Z. Wang, L. Han,

Y. Song and F. Pan, Chem. comm., 2018, 54, 13060–13063.

459 Z. Liu, Z. Hu, X. Jiang, X. Wang, Z. Li, Z. Chen, Y. Zhang

and S. Zhang, Small, 2022, 18, 2203011.

460 Z. Wang, Z. Wang, L. Yang, H. Wang, Y. Song, L. Han,

K. Yang, J. Hu, H. Chen and F. Pan, Nano Energy, 2018, 49,

580–587.

461 R. Zettl and I. Hanzu, Front. energy res., 2021, 9, 714698.

462 T. Jiang, P. He, G. Wang, Y. Shen, C.-W. Nan and L.-Z. Fan,

Adv. Energy Mater., 2020, 10, 1903376.

463 W. Lu, M. Xue and C. Zhang, Energy Storage Mater., 2021,

39, 108–129.

464 S. Liu, W. Liu, D. Ba, Y. Zhao, Y. Ye, Y. Li and J. Liu, Adv.

Mater., 2023, 35, 2110423.

465 W. Liu, D. Lin, J. Sun, G. Zhou and Y. Cui, ACS Nano, 2016,

10, 11407–11413.

466 Y. Zhu, J. Cao, H. Chen, Q. Yu and B. Li, J. Mater. Chem. A,

2019, 7, 6832–6839.

467 K. He, C. Chen, R. Fan, C. Liu, C. Liao, Y. Xu, J. Tang and

R. K. Y. Li, Compos. Sci. Technol., 2019, 175, 28–34.

468 K. West, B. Zachau-Christiansen, T. Jacobsen, E. Hiort-

Lorenzen and S. Skaarup, Br. Polym. J., 1988, 20, 243–246.

469 J. Serra Moreno, M. Armand, M. B. Berman, S. G.

Greenbaum, B. Scrosati and S. Panero, J. Power Sources,

2014, 248, 695–702.

470 X. Qi, Q. Ma, L. Liu, Y.-S. Hu, H. Li, Z. Zhou, X. Huang and

L. Chen, ChemElectroChem, 2016, 3, 1741–1745.

471 A. Bitner-Michalska, G. M. Nolis, G. Z

˙ukowska, A.

Zalewska, M. Poterała, T. Trzeciak, M. Dranka, M. Kalita,

P. Jankowski, L. Niedzicki, J. Zachara, M. Marcinek and

W. Wieczorek, Sci. Rep., 2017, 7, 40036.

472 C. V. Subba Reddy, A. P. Jin, Q. Y. Zhu, L. Q. Mai and

W. Chen, Eur. Phys. J. E, 2006, 19, 471–476.

473 P. B. Bhargav, V. M. Mohan, A. K. Sharma and

V. V. R. N. Rao, J. Appl. Polym. Sci., 2008, 108, 510–517.

474 H. Gao, S. Xin, L. Xue and J. B. Goodenough, Chem, 2018,

4, 833–844.

475 S. Song, H. M. Duong, A. M. Korsunsky, N. Hu and L. Lu,

Sci. Rep, 2016, 6, 32330.

476 Q. Ma, M. Guin, S. Naqash, C.-L. Tsai, F. Tietz and

O. Guillon, Chem. Mater., 2016, 28, 4821–4828.

477 X. Chi, Y. Liang, F. Hao, Y. Zhang, J. Whiteley, H. Dong,

P. Hu, S. Lee and Y. Yao, Angew. Chem., Int. Ed., 2018, 57,

2630–2634.

478 N. Tanibata, K. Noi, A. Hayashi and M. Tatsumisago, RSC

Adv., 2014, 4, 17120–17123.

479 Z. Yu, S.-L. Shang, J.-H. Seo, D. Wang, X. Luo, Q. Huang,

S. Chen, J. Lu, X. Li, Z.-K. Liu and D. Wang, Adv. Mater.,

2017, 29, 1605561.

480 I.-H. Chu, C. S. Kompella, H. Nguyen, Z. Zhu, S. Hy,

Z. Deng, Y. S. Meng and S. P. Ong, Sci. Rep., 2016, 6, 33733.

481 L. Zhang, K. Yang, J. Mi, L. Lu, L. Zhao, L. Wang, Y. Li and

H. Zeng, Adv. Energy Mater., 2015, 5, 1501294.

482 T. J. Udovic, M. Matsuo, W. S. Tang, H. Wu, V. Stavila,

A. V. Soloninin, R. V. Skoryunov, O. A. Babanova,

A. V. Skripov, J. J. Rush, A. Unemoto, H. Takamura and

S.-I. Orimo, Adv. Mater, 2014, 26, 7622–7626.

483 L. Duche

ˆne, R. S. Ku

¨hnel, D. Rentsch, A. Remhof,

H. Hagemann and C. Battaglia, Chem. comm., 2017, 53,

4195–4198.

484 Z. Zhang, Q. Zhang, C. Ren, F. Luo, Q. Ma, Y.-S. Hu,

Z. Zhou, H. Li, X. Huang and L. Chen, J. Mater. Chem. A,

2016, 4, 15823–15828.

485 S. Li, M. Jiang, Y. Xie, H. Xu, J. Jia and J. Li, Adv. Mater.,

2018, 30, e1706375.

486 A. Chandra, Ind. J. Phys., 2016, 90, 759–765.

487 P. Kesharwani, D. K. Sahu, M. Sahu, T. B. Sahu and

R. C. Agrawal, Ionics, 2017, 23, 2823–2827.

488 J. Siva Kumar, M. Jaipal Reddy and U. V. Subba Rao,

J. Mater. Sci., 2006, 41,6171–6173.

Chem Soc Rev Review Article

Published on 04 March 2024. Downloaded by University of Wollongong on 3/8/2024 12:31:15 AM.

View Article Online

489 C. Zhao, L. Liu, X. Qi, Y. Lu, F. Wu, J. Zhao, Y. Yu, Y.-S. Hu

and L. Chen, Adv. Energy Mater, 2018, 8, 1703012.

490 P. Kesharwani, D. K. Sahu, Y. K. Mahipal and

R. C. Agrawal, Mater. Chem. Phys., 2017, 193, 524–531.

491 H. Yuan, H. Li, T. Zhang, G. Li, T. He, F. Du and S. Feng,

J. Mater. Chem. A, 2018, 6, 8413–8418.

492 Z. Li, L. Wang, Y. Liu, M. Yu, B. Liu, Y. Men, Z. Sun, W. Hu

and G. Zhu, Small, 2023, 2302818.

493 K. Shen, Z. Wang, X. Bi, Y. Ying, D. Zhang, C. Jin, G. Hou,

H. Cao, L. Wu, G. Zheng, Y. Tang, X. Tao and J. Lu, Adv.

Energy Mater, 2019, 9, 1900260.

494 Z. Lu, H. Yang, Y. Guo, P. He, S. Wu, Q.-H. Yang and

H. Zhou, Angew. Chem., Int. Ed., 2022, 61, e202206340.

495 R. Tan, A. Wang, R. Malpass-Evans, R. Williams, E. W.

Zhao,T.Liu,C.Ye,X.Zhou,B.P.Darwich,Z.Fan,L.Turcani,

E.Jackson,L.Chen,S.Y.Chong,T.Li,K.E.Jelfs,A.I.Cooper,

N.P.Brandon,C.P.Grey,N.B.McKeownandQ.Song,Nat.

Mater., 2020, 19, 195–202.

496 J. C. Barbosa, D. M. Correia, A. Fidalgo-Marijuan, R.

Gonçalves, S. Ferdov, V. de Zea Bermudez, S. Lanceros-

Mendez and C. M. Costa, ACS Appl. Mater. Interfaces, 2023,

15, 32301–32312.

497 H. Jamal, F. Khan, S. Hyun, S. W. Min and J. H. Kim,

J. Mater. Chem. A, 2021, 9, 4126–4137.

498 H. Jamal, F. Khan, H.-R. Si and J. H. Kim, J. Mater. Chem. A,

2021, 9, 27304–27319.

499 Y.Feng,Y.Li,J.Lin,H.Wu,L.Zhu,X.Zhang,L.Zhang,

C.-F.Sun,M.WuandY.Wang,Nat. Commun., 2023, 14, 3639.

500 T. Kim, S. Hyeok Ahn, Y.-Y. Song, B. Jin Park, C. Lee,

A. Choi, M.-H. Kim, D.-H. Seo, S.-K. Jung and H.-W. Lee,

Angew. Chem., Int. Ed., 2023, e202309852.

501 A. Hayashi, K. Noi, A. Sakuda and M. Tatsumisago, Nat.

Commun., 2012, 3, 856.

502 R. Schlem, A. Banik, M. Eckardt, M. Zobel and W. G. Zeier,

ACS Appl. Energy Mater., 2020, 3, 10164–10173.

503 T. Fuchs, S. P. Culver, P. Till and W. G. Zeier, ACS Energy

Lett., 2020, 5, 146–151.

504 E. A. Wu, S. Banerjee, H. Tang, P. M. Richardson,

J.-M. Doux, J. Qi, Z. Zhu, A. Grenier, Y. Li, E. Zhao,

G. Deysher, E. Sebti, H. Nguyen, R. Stephens, G. Verbist,

K. W. Chapman, R. J. Cle

´ment, A. Banerjee, Y. S. Meng and

S. P. Ong, Nat. Commun., 2021, 12, 1256.

505 J. Shao, H. Ao, L. Qin, J. Elgin, C. E. Moore, Y. Khalifa,

S. Zhang and Y. Wu, Adv. Mater., 2023, 2306809.

506 D. Sarkar, A. Bhattacharya, J. Meyer, A. M. Kirchberger,

V. Mishra, T. Nilges and V. K. Michaelis, J. Am. Chem. Soc.,

2023, 145, 19727–19745.

507 Y. Li, Z. Deng, J. Peng, J. Gu, E. Chen, Y. Yu, J. Wu, X. Li,

J. Luo, Y. Huang, Y. Xu, Z. Gao, C. Fang, J. Zhu, Q. Li,

J. Han and Y. Huang, ACS Appl. Mater. Interfaces, 2018, 10,

15760–15766.

508 Y. Cheng, X. Liu, Y. Guo, G. Dong, X. Hu, H. Zhang, X. Xiao,

Q. Liu, L. Xu and L. Mai, Adv. Mater., 2023, 2303226.

509 J.-H. Lee, H. Lee, J. Lee, T. W. Kang, J. H. Park, J.-H. Shin,

H. Lee, D. Majhi, S. U. Lee and J.-H. Kim, ACS Nano, 2023,

17, 17372–17382.

510 L. Du, B. Zhang, C. Yang, L. Cui, L. Mai and L. Xu, Energy

Storage Mater., 2023, 61, 102914.

511 R. Xu, Y. Kang, W. Zhang, B. Pan and X. Zhang, Nat.

Commun., 2023, 14, 4907.

512 X. Wang, Y. Luo, H. Wang, C. Wu, Z. Zhang and J. Li,

J. Electroanal. Chem., 2021, 897, 115564.

513 H. Sun, G. Zhu, Y. Zhu, M. C. Lin, H. Chen, Y. Y. Li,

W. H. Hung, B. Zhou, X. Wang, Y. Bai, M. Gu, C. L. Huang,

H. C. Tai, X. Xu, M. Angell, J. J. Shyue and H. Dai, Adv.

Mater., 2020, e2001741, DOI: 10.1002/adma.202001741.

514 Y. Zang, F. Pei, J. Huang, Z. Fu, G. Xu and X. Fang, Adv.

Energy Mater., 2018, 8, 1802052.

515 Z. Jin, K. Xie and X. Hong, RSC Adv., 2013, 3, 8889–8898.

516 Y. Suharto, Y. Lee, J.-S. Yu, W. Choi and K. J. Kim, J. Power

Sources, 2018, 376, 184–190.

517 S. Bai, X. Liu, K. Zhu, S. Wu and H. Zhou, Nat. Energy.,

2016, 1, 16094.

518 H. Kwon, H.-J. Choi, J.-K. Jang, J. Lee, J. Jung, W. Lee,

Y. Roh, J. Baek, D. J. Shin, J.-H. Lee, N.-S. Choi, Y. S. Meng

and H.-T. Kim, Nat. Commun., 2023, 14, 4047.

519 C. Yin, Z. Li, D. Zhao, J. Yang, Y. Zhang, Y. Du and

Y. Wang, ACS Nano, 2022, 16, 14178–14187.

520 H. Zhang, C. Lin, X. Hu, B. Zhu and D. Yu, ACS Appl. Mater.

Interfaces, 2018, 10, 12708–12715.

521 C. Ye, A. Wang, C. Breakwell, R. Tan, C. Grazia Bezzu, E.

Hunter-Sellars, D. R. Williams, N. P. Brandon, P. A. A.

Klusener, A. R. Kucernak, K. E. Jelfs, N. B. McKeown and

Q. Song, Nat. Commun., 2022, 13, 3184.

522 C. Qi, L. Xu, J. Wang, H. Li, C. Zhao, L. Wang and T. Liu,

ACS Sustainable Chem. Eng., 2020, 8, 12968–12975.

523 A. Wang, R. Tan, D. Liu, J. Lu, X. Wei, A. Alvarez-Fernandez,

C.Ye,C.Breakwell,S.Guldin,A.R.Kucernak,K.E.Jelfs,

N. P. Brandon, N. B. McKeown and Q. Song, Adv. Mater.,

2023, 35, 2210098.

524 Y. Huai, J. Gao, Z. Deng and J. Suo, Ionics, 2010, 16,

603–611.

525 J. H. Lee, J. Manuel, H. Choi, W. H. Park and J.-H. Ahn,

Polymer, 2015, 68, 335–343.

526 S. Janakiraman, A. Surendran, S. Ghosh, S. Anandhan and

A. Venimadhav, Solid State Ion., 2016, 292, 130–135.

527 S. Janakiraman, M. Khalifa, R. Biswal, S. Ghosh,

S. Anandhan and A. Venimadhav, J. Power Sources, 2020,

460, 228060.

528 H. Fei, Y. Liu, Y. An, X. Xu, J. Zhang, B. Xi, S. Xiong and

J. Feng, J. Power Sources, 2019, 433, 226697.

529 H. Fei, Y. Liu, Y. An, X. Xu, G. Zeng, Y. Tian, L. Ci, B. Xi,

S. Xiong and J. Feng, J. Power Sources, 2018, 399, 294–298.

530 T. C. Mendes, X. Zhang, Y. Wu, P. C. Howlett, M. Forsyth

and D. R. Macfarlane, ACS Sustain. Chem. Eng., 2019, 7,

3722–3726.

531 S. Chen, J. Zheng, L. Yu, X. Ren, M. H. Engelhard, C. Niu,

H. Lee, W. Xu, J. Xiao, J. Liu and J.-G. Zhang, Joule, 2018, 2,

1548–1558.

532 H. Yang, J. Bright, B. Chen, P. Zheng, X. Gao, B. Liu,

S. Kasani, X. Zhang and N. Wu, J. Mater. Chem. A, 2020,

8, 7261–7272.

Review Article Chem Soc Rev

Published on 04 March 2024. Downloaded by University of Wollongong on 3/8/2024 12:31:15 AM.

View Article Online

533 X. Chen, Y. Xie, Y. Ling, J. Zhao, Y. Xu, Y. Tong, S. Li and

Y. Wang, Mater. Des., 2020, 192, 108760.

534 B. Zhou, Y. H. Jo, R. Wang, D. He, X. Zhou, X. Xie and

Z. Xue, J. Mater. Chem. A, 2019, 7, 10354–10362.

535 Z. Li, T. Chen and Y. Liao, Ionics, 2015, 21, 2763–2770.

536 R. Subramani, Y.-H. Tseng, Y.-L. Lee, C.-C. Chiu, S.-S. Hou

and H. Teng, J. Mater. Chem. A, 2019, 7, 12244–12252.

537 X. Ren, L. Zou, X. Cao, M. H. Engelhard, W. Liu, S. D.

Burton, H. Lee, C. Niu, B. E. Matthews, Z. Zhu, C. Wang,

B. W. Arey, J. Xiao, J. Liu, J.-G. Zhang and W. Xu, Joule,

2019, 3, 1662–1676.

538 H. Li, Y.-M. Chen, X.-T. Ma, J.-L. Shi, B.-K. Zhu and

L.-P. Zhu, J. Membr. Sci., 2011, 379, 397–402.

539 H.-L. Guo, H. Sun, Z.-L. Jiang, C.-S. Luo, M.-Y. Gao,

M.-H. Wei, J.-Y. Hu, W.-K. Shi, J.-Y. Cheng and H.-J.

Zhou, J. Mater. Sci., 2019, 54, 4874–4883.

540 G. Fu, M. D. Soucek and T. Kyu, Solid State Ion., 2018, 320,

310–315.

541 P. Shi, T. Li, R. Zhang, X. Shen, X. B. Cheng, R. Xu,

J. Q. Huang, X. R. Chen, H. Liu and Q. Zhang, Adv. Mater.,

2019, 31, e1807131.

542 P. Chen, J. Shen, T. Wang, M. Dai, C. Si, J. Xie, M. Li,

X. Cong and X. Sun, J. Power Sources, 2018, 400, 325–332.

543 T. Song, C. Wang and C.-S. Lee, Carbon Neutraliz., 2022, 1,

68–92.

544 K. Mizushima, P. C. Jones, P. J. Wiseman and J. B.

Goodenough, Mater. Res. Bull., 1980, 15, 783–789.

545 I. Bezza, E. Luais, F. Ghamouss, M. Zaghrioui, F. Tran-van

and J. Sakai, J. Alloys Compd., 2019, 805, 19–25.

546 H. Arai, S. Okada, Y. Sakurai and J.-I. Yamaki, Solid State

Ion., 1997, 95, 275–282.

547 S.-H. Wu and M.-T. Yu, J. Power Sources, 2007, 165,

660–665.

548 Y. Sakurai, H. Arai, S. Okada and J.-I. Yamaki, J. Power

Sources, 1997, 68, 711–715.

549 J. Molenda, C. Delmas and P. Hagenmuller, Solid State

Ion., 1983, 9–10,431–435.

550 A. Eftekhari, Z. Jian and X. Ji, ACS Appl. Mater. Interfaces,

2017, 9, 4404–4419.

551 J. Li, H. Hu, J. Wang and Y. Xiao, Carbon Neutraliz, 2022, 1,

96–116.

552 J. Su, Y. Pei, Z. Yang and X. Wang, RSC Adv., 2015, 5,

27229–27234.

553 B. Hu, F. Geng, C. Zhao, B. Doumert, J. Tre

´bosc, O. Lafon,

C. Li, M. Shen and B. Hu, ACS Appl. Mater. Interfaces, 2020,

12, 41485–41494.

554 S. Yun, S. Muhammad, J. Choi, W. Lee, J. Yu, H. Lee,

Y. Lee and W.-S. Yoon, ACS Energy Lett, 2022, 7, 3989–3996.

555 X. Zhang, X. Yang, G. Sun, S. Yao, Y. Xie, W. Zhang, C. Liu,

X. Wang, R. Yang, X. Jin, Z. X. Shen, H. J. Fan and F. Du,

Adv. Funct. Mater., 2022, 32, 2204318.

556 Z. Lu and J. R. Dahn, J. Electrochem. Soc., 2001, 148,

A1225.

557 N. Yabuuchi, M. Kajiyama, J. Iwatate, H. Nishikawa, S.

Hitomi, R. Okuyama, R. Usui, Y. Yamada and S. Komaba,

Nat. Mater., 2012, 11, 512–517.

558 X. Wang, G. Liu, T. Iwao, M. Okubo and A. Yamada, J. Phys.

Chem. C, 2014, 118, 2970–2976.

559 T. Ohzuku and Y. Makimura, Chem. Lett, 2001, 30, 642–643.

560 H.-J. Noh, S. Youn, C. S. Yoon and Y.-K. Sun, J. Power

Sources, 2013, 233, 121–130.

561 C. Zhao, F. Ding, Y. Lu, L. Chen and Y.-S. Hu, Angew.

Chem., Int. Ed., 2020, 59, 264–269.

562 T. Chen, W. Liu, Y. Zhuo, H. Hu, M. Zhu, R. Cai, X. Chen,

J. Yan and K. Liu, J. Energy Chem., 2020, 43, 148–154.

563 Y. Zheng, J. Li, S. Ji, K. S. Hui, S. Wang, H. Xu, K. Wang,

D. A. Dinh, C. Zha, Z. Shao and K. N. Hui, Small, 2023,

15, 2302160.

564 T. Jin, H. Li, K. Zhu, P.-F. Wang, P. Liu and L. Jiao, Chem.

Soc. Rev., 2020, 49, 2342–2377.

565 B. Senthilkumar, C. Murugesan, L. Sharma, S. Lochab and

P. Barpanda, Small Methods, 2019, 3, 1800253.

566 S. K. Sapra, J. Pati, P. K. Dwivedi, S. Basu, J.-K. Chang and

R. S. Dhaka, Wiley Interdiscip. Rev.: Energy Environ., 2021,

10, e400.

567 S.-J. Lim, D.-W. Han, D.-H. Nam, K.-S. Hong, J.-Y. Eom,

W.-H. Ryu and H.-S. Kwon, J. Mater. Chem. A, 2014, 2,

19623–19632.

568 W. Shen, H. Li, Z. Guo, Z. Li, Q. Xu, H. Liu and Y. Wang,

RSC Adv., 2016, 6, 71581–71588.

569 L. Li, Y. Qin, S. Zhang, H. Zhao, J. Zhao, X. Li, J. Zhao,

H. Wu, Y. Su and S. Ding, J. Power Sources, 2023,

576, 233226.

570 J.-Z. Guo, H.-X. Zhang, Z.-Y. Gu, M. Du, H.-Y. Lu

¨,

X.-X. Zhao, J.-L. Yang, W.-H. Li, S. Kang, W. Zou and

X.-L. Wu, Adv. Funct. Mater., 2022, 32, 2209482.

571 M. Chen, L. Chen, Z. Hu, Q. Liu, B. Zhang, Y. Hu, Q. Gu,

J.-L. Wang, L.-Z. Wang, X. Guo, S.-L. Chou and S.-X. Dou,

Adv. Mater., 2017, 29, 1605535.

572 A. Chiring and P. Senguttuvan, Bull. Mater. Sci., 2020,

43, 306.

573 C.-T. Chu, A. Mondal, N. V. Kosova and J.-Y. Lin, Appl. Surf.

Sci., 2020, 530, 147169.

574 M. M. Thackeray and K. Amine, Nat. Energy., 2021, 6, 566.

575 Q. Zhong, A. Bonakdarpour, M. Zhang, Y. Gao and

J. R. Dahn, J. Electrochem. Soc., 1997, 144, 205.

576 W. Zhu, A. Li, Z. Wang, J. Yang and Y. Xu, Small, 2021,

17, 2006424.

577 A. Indra, T. Song and U. Paik, Adv. Mater., 2018,

30, 1705146.

578 Y. He, B. Li, M. O’Keeﬀe and B. Chen, Chem. Soc. Rev.,

2014, 43, 5618–5656.

579 Z. Peng, X. Yi, Z. Liu, J. Shang and D. Wang, ACS Appl.

Mater. Interfaces, 2016, 8, 14578–14585.

580 B. Huang, Y. Liu, Z. Lu, M. Shen, J. Zhou, J. Ren, X. Li and

S. Liao, ACS Sustain. Chem. Eng., 2019, 7, 16659–16667.

581 Y. Ma, Y. Ma, S. L. Dreyer, Q. Wang, K. Wang, D.

Goonetilleke, A. Omar, D. Mikhailova, H. Hahn, B.

Breitung and T. Brezesinski, Adv. Mater., 2021, 33,

2101342.

582 K. Wada, K. Sakaushi, S. Sasaki and H. Nishihara, Angew.

Chem., Int. Ed., 2018, 57, 8886–8890.

Chem Soc Rev Review Article

Published on 04 March 2024. Downloaded by University of Wollongong on 3/8/2024 12:31:15 AM.

View Article Online

583 Q. Jiang, P. Xiong, J. Liu, Z. Xie, Q. Wang, X.-Q. Yang,

E. Hu, Y. Cao, J. Sun, Y. Xu and L. Chen, Angew. Chem., Int.

Ed., 2020, 59, 5273–5277.

584 A. P. Co

ˆte

´, A. I. Benin, N. W. Ockwig, M. O’Keeﬀe,

A. J. Matzger and O. M. Yaghi, Science, 2005, 310,

1166–1170.

585 S. Wang, Q. Wang, P. Shao, Y. Han, X. Gao, L. Ma, S. Yuan,

X. Ma, J. Zhou, X. Feng and B. Wang, J. Am. Chem. Soc.,

2017, 139, 4258–4261.

586 H. Li, M. Tang, Y. Wu, Y. Chen, S. Zhu, B. Wang, C. Jiang,

E. Wang and C. Wang, J. Phys. Chem. Lett., 2018, 9,

3205–3211.

587 C. Zhu, G. Fang, J. Zhou, J. Guo, Z. Wang, C. Wang, J. Li,

Y. Tang and S. Liang, J. Mater. Chem. A, 2018, 6, 9677–9683.

588 J.-S. M. Lee and A. I. Cooper, Chem. Rev., 2020, 120,

2171–2214.

589 Y. Liu, G. He, H. Jiang, I. P. Parkin, P. R. Shearing and

D. J. L. Brett, Adv. Funct. Mater., 2021, 31, 2010445.

590 K. W. Nam, S. Kim, S. Lee, M. Salama, I. Shterenberg,

Y. Gofer, J.-S. Kim, E. Yang, C. S. Park, J.-S. Kim, S.-S. Lee,

W.-S. Chang, S.-G. Doo, Y. N. Jo, Y. Jung, D. Aurbach and

J. W. Choi, Nano Lett., 2015, 15, 4071–4079.

591 H. Li, H. Yang, Z. Sun, Y. Shi, H.-M. Cheng and F. Li, Nano

Energy, 2019, 56, 100–108.

592 M. A. Pope and I. A. Aksay, Adv. Energy Mater, 2015,

5, 1500124.

593 W.-P. Wang, J. Zhang, J. Chou, Y.-X. Yin, Y. You, S. Xin and

Y.-G. Guo, Adv. Energy Mater., 2021, 11, 2000791.

594 C. Fu, M. B. Oviedo, Y. Zhu, A. von Wald Cresce,

K. Xu, G. Li, M. E. Itkis, R. C. Haddon, M. Chi, Y. Han,

B. M. Wong and J. Guo, ACS Nano, 2018, 12, 9775–9784.

595 W. C. Du, J. Zhang, Y. X. Yin, Y. G. Guo and L. J. Wan, Asian

J. Chem., 2016, 11, 2690–2694.

596 C. Wu, Y. Lei, L. Simonelli, D. Tonti, A. Black, X. Lu,

W. H. Lai, X. Cai, Y. X. Wang, Q. Gu, S. L. Chou,

H. K. Liu, G. Wang and S. X. Dou, Adv. Mater., 2022,

34, e2108363.

597 D. Su, M. Cortie, H. Fan and G. Wang, Adv. Mater., 2017,

29, 1700587.

598 S. Xin, Y.-X. Yin, Y.-G. Guo and L.-J. Wan, Adv. Mater., 2014,

26,1261–1265.

599 P. V. C. Medeiros, S. Marks, J. M. Wynn, A. Vasylenko,

Q. M. Ramasse, D. Quigley, J. Sloan and A. J. Morris, ACS

Nano, 2017, 11, 6178–6185.

600 W.-C. Du, J. Zhang, Y.-X. Yin, Y.-G. Guo and L.-J. Wan,

Chem. Asian J., 2016, 11, 2690–2694.

601 A. Kwade, W. Haselrieder, R. Leithoﬀ, A. Modlinger,

F. Dietrich and K. Droeder, Nat. Energy, 2018, 3,

290–300.

602 F. Xiao, H. Wang, J. Xu, W. Yang, X. Yang, D. Y. W. Yu and

A. L. Rogach, Adv. Energy Mater., 2021, 11, 2100989.

603 C. Ye, Y. Jiao, D. Chao, T. Ling, J. Shan, B. Zhang, Q. Gu,

K. Davey, H. Wang and S.-Z. Qiao, Adv. Mater., 2020,

32, 1907557.

604 C. Wu, Y. Lei, L. Simonelli, D. Tonti, A. Black, C. Marini,

X. Lu, W.-H. Lai, X. Cai, Y.-X. Wang, Q. Gu, S.-L. Chou,

H.-K. Liu, G. Wang and S.-X. Dou, Adv. Mater., 2022,

34, 2205634.

605 J. Kim, J. H. Kim and K. Ariga, Joule, 2017, 1, 739–768.

606 H. Kim, J. Lee, H. Ahn, O. Kim and M. J. Park, Nat.

Commun., 2015, 6, 7278.

607 L. F. Zhao, Z. Hu, W. H. Lai, Y. Tao, J. Peng, Z. C. Miao,

Y. X. Wang, S. L. Chou, H. K. Liu and S. X. Dou, Adv. Energy

Mater., 2021, 11, 2002704.

608 Y. Li, Y. Lu, Q. Meng, A. C. S. Jensen, Q. Zhang, Q. Zhang,

Y. Tong, Y. Qi, L. Gu, M.-M. Titirici and Y.-S. Hu, Adv.

Energy Mater., 2019, 9, 1902852.

609 D. Li, X. Ren, Q. Ai, Q. Sun, L. Zhu, Y. Liu, Z. Liang,

R. Peng, P. Si, J. Lou, J. Feng and L. Ci, Adv. Energy Mater.,

2018, 8, 1802386.

610 X. Yao, Y. Ke, W. Ren, X. Wang, F. Xiong, W. Yang, M. Qin,

Q. Li and L. Mai, Adv. Energy Mater, 2019, 9, 1803260.

611 J. An, H. Y. Zhang, L. Qi, G. X. Li and Y. L. Li, Angew. Chem.,

Int. Ed., 2022, 134, e202113313.

612 W. Liu, H. Zhang, W. Ye, B. Xiao, Z. Sun, Y. Cheng and

M.-S. Wang, Small, 2023, 19, 2300605.

613 Y. Zheng, Y. Lu, X. Qi, Y. Wang, L. Mu, Y. Li, Q. Ma,

J. Li and Y.-S. Hu, Energy Storage Mater., 2019, 18,

269–279.

614 H. Wang, J.-L. Lan, H. Yuan, S. Luo, Y. Huang, Y. Yu, Q. Cai

and X. Yang, Appl. Surf. Sci., 2020, 518,146221.

615 C. Yang, X. Sun, X. Zhang, J. Li, J. Ma, Y. Li, L. Xu, S. Liu,

J. Yang, S. Fang, Q. Li, X. Yang, F. Pan, J. Lu and D. Yu,

Carbon, 2021, 176, 242–252.

616 C. Yang, X. Zhang, J. Li, J. Ma, L. Xu, J. Yang, S. Liu,

S. Fang, Y. Li, X. Sun, X. Yang, F. Pan, J. Lu and D. Yu,

Electrochim. Acta, 2020, 346, 136244.

617 Y. C. Lee and S. C. Jung, Nanoscale Adv., 2022, 4,

5378–5391.

618 L. Zhao, T. Tang, W. Chen, X. Feng and L. Mi, Green Energy

Environ, 2018, 3, 277–285.

619 J. Yang, X. Xiao, W. Gong, L. Zhao, G. Li, K. Jiang, R. Ma,

M. H. Rummeli, F. Li, T. Sasaki and F. Geng, Angew. Chem.,

Int. Ed., 2019, 58, 8740–8745.

620 L. Zhang, Y. Pan, Y. Chen, M. Li, P. Liu, C. Wang, P. Wang

and H. Lu, Chem. comm., 2019, 55, 4258–4261.

621 B. Wang, E. H. Ang, Y. Yang, Y. Zhang, H. Geng, M. Ye and

C. C. Li, Adv. Funct. Mater., 2020, 30, 2001708.

622 Y. Wang, M. Liu, Z. Wang, Q. Gu, B. Liu, C. Zhao, J. Zhang,

S. Xu, M. Lu, H. Li and B. Zhang, J. Energy Chem., 2022, 68,

306–313.

623 C. Xue, Y. Zhang, Z. Nie, C. Du, J. Zhang and J. Zhang,

Electrochim. Acta, 2023, 444, 142021.

624 L. Xu, X. Chen, W. Guo, L. Zeng, T. Yang, P. Xiong,

Q. Chen, J. Zhang, M. Wei and Q. Qian, Nanoscale, 2021,

13, 5033–5044.

625 J. Liao, Q. Hu, J. Mu, F. Chen, X. He, F. Chen, Z. Wen and

C. Chen, Chem. comm., 2020, 56, 8392–8395.

626 H. Zhang, Y. Geng, J. Huang, Z. Wang, K. Du and H. Li,

Energy Environ. Sci., 2023, 16, 889–951.

627 W. Zhang, H. Zuo, Z. Cheng, Y. Shi, Z. Guo, N. Meng,

A. Thomas and Y. Liao, Adv. Mater., 2022, 34, 2104952.

Review Article Chem Soc Rev

Published on 04 March 2024. Downloaded by University of Wollongong on 3/8/2024 12:31:15 AM.

View Article Online

628 L. Zhong, J. Li, C. Liu, L. Fang, Z. Yuan, D. Yu and X. Chen,

Adv. Funct. Mater., 2023, 33, 2215133.

629 L. Meng, S. Ren, C. Ma, Y. Yu, Y. Lou, D. Zhang and Z. Shi,

Chem. comm., 2019, 55, 9491–9494.

630 X. Zhang, F. Wu, X. Lv, L. Xu, R. Huang, R. Chen and L. Li,

Adv. Mater., 2022, 34, 2204370.

631 S. Qiao, Q. Zhou, M. Ma, H. K. Liu, S. X. Dou and S. Chong,

ACS Nano, 2023, 17(12), 11220–11252.

632 C. Yan, C. Lv, Y. Zhu, G. Chen, J. Sun and G. Yu, Adv.

Mater., 2017, 29, 1703909.

633 C. Park, Y. H. Kim, H. Lee, H. S. Kang, T. Kim, S. W. Lee,

K. Lee, K.-B. Kim and C. Park, Adv. Energy Mater., 2021,

11, 2003243.

634 H. Li, S. Hao, Z. Tian, Z. Zhao and X. Wang, Electrochim.

Acta, 2019, 321, 134624.

635 W. Zhang, W. Li and X. Zhou, Batter. Supercaps, 2020, 3,

439–449.

636 Y. Xi, D. Yang, H. Lou, Y. Gong, C. Yi, G. Lyu, W. Han,

F. Kong and X. Qiu, Ind. Crops Prod., 2021, 161, 113179.

637 M. Peng, K. Shin, L. Jiang, Y. Jin, K. Zeng, X. Zhou and

Y. Tang, Angew. Chem., Int. Ed., 2022, 61, e202206770.

638 Y. Qiuran, F. Qining, P. Jian, C. Shulei, L. Huakun and

W. Jiazhao, Microstructures, 2023, 3, 2023013.

639 W. Xueting, W. Yunchuang, W. Meichao, F. Ruopian, Y. Xi

and W. Da-Wei, Microstructures, 2022, 2, 2022016.

640 Q. Ai, Q. Fang, J. Liang, X. Xu, T. Zhai, G. Gao, H. Guo,

G. Han, L. Ci and J. Lou, Nano Energy, 2020, 72, 104657.

641 Z. Yan, L. Zhao, Y. Wang, Z. Zhu and S. L. Chou, Adv. Funct.

Mater., 2022, 32, 2205622.

642 H. Sun, G. Zhu, X. Xu, M. Liao, Y. Y. Li, M. Angell, M. Gu,

Y. Zhu, W. H. Hung, J. Li, Y. Kuang, Y. Meng, M. C. Lin,

H. Peng and H. Dai, Nat. Commun., 2019, 10, 3302.

643 H. Duan, Y. You, G. Wang, X. Ou, J. Wen, Q. Huang, P. Lyu,

Y. Liang, Q. Li, J. Huang, Y.-X. Wang, H.-K. Liu, S. X. Dou

and W.-H. Lai, Nano-Micro Lett., 2024, 16, 78.

644 L. Zhao, Y. Tao, W. H. Lai, Z. Hu, J. Peng, Y. Lei, Y. Cao,

S. L. Chou, Y. X. Wang, H. K. Liu and S. X. Dou, Adv. Funct.

Mater., 2024, 34, 2302026.

645 L. F. Zhao, Z. Hu, Z. Y. Huang, Y. Tao, W. H. Lai, A. L. Zhao,

Q. N. Liu, J. Peng, Y. J. Lei, Y. X. Wang, Y. L. Cao, C. Wu,

S. L. Chou, H. K. Liu and S. X. Dou, Adv. Energy Mater.,

2022, 12, 2200990.

646 X. Li, Y. Tian, L. Shen, Z. Qu, T. Ma, F. Sun, X. Liu,

C. Zhang, J. Shen, X. Li, L. Gao, S. Xiao, T. Liu, Y. Liu

and Y. Lu, Adv. Funct. Mater., 2021, 31, 2009718.

647 J. Yun, B.-K. Park, E.-S. Won, S. H. Choi, H. C. Kang,

J. H. Kim, M.-S. Park and J.-W. Lee, ACS Energy Lett.,

2020, 5, 3108–3114.

648 D. Chen, S. Huang, L. Zhong, S. Wang, M. Xiao, D. Han

and Y. Meng, Adv. Funct. Mater., 2020, 30, 1907717.

649 J. He, A. Bhargav and A. Manthiram, Angew. Chem., Int. Ed.,

2022, 61, e202116586.

650 M. Chen, Q. Liu, S. W. Wang, E. Wang, X. Guo and

S. L. Chou, Adv. Energy Mater, 2019, 9, 1803609.

651 J. He, A. Bhargav and A. Manthiram, Angew. Chem., Int. Ed.,

2022, 61, e202116586.

652 S. Zhou, W. Chen, J. Shi, G. Li, F. Pei, S. Liu, W. Ye, L.

Xiao, M.-S. Wang, D. Wang, Y. Qiao, L. Huang, G.-L. Xu,

H.-G. Liao, J.-F. Chen, K. Amine and S.-G. Sun, Energy

Environ. Sci., 2022, 15, 196–205.

653 H. R. Shin, J. Yun, G. H. Eom, J. Moon, J. H. Kim, M.-S.

Park, J.-W. Lee and S. X. Dou, Nano Energy, 2022, 95, 106999.

654 S. A. Han, H. Qutaish, J.-W. Lee, M.-S. Park and J. H. Kim,

EcoMat, 2023, 5, e12283.

655 H. R. Shin, S. Kim, J. Park, J. H. Kim, M.-S. Park and

J.-W. Lee, Energy Storage Mater., 2023, 56, 515–523.

656 J. Kim, J. Lee, J. Yun, S. H. Choi, S. A. Han, J. Moon,

J. H. Kim, J.-W. Lee and M.-S. Park, Adv. Funct. Mater.,

2020, 30, 1910538.

657 R. Zhao, J. Yang, X. Han, Y. Wang, Q. Ni, Z. Hu, C. Wu and

Y. Bai, Adv. Energy Mater., 2023, 13, 2203542.

658 H. Liu, Q. Ye, D. Lei, Z. Hou, W. Hua, Y. Huyan, N. Li,

C. Wei, F. Kang and J.-G. Wang, Energy Environ. Sci., 2023,

16, 1610–1619.

659 L. Yuan, J. Hao, C.-C. Kao, C. Wu, H.-K. Liu, S.-X. Dou and

S.-Z. Qiao, Energy Environ. Sci., 2021, 14, 5669–5689.

660 K. Amin, N. Ashraf, L. Mao, C. F. J. Faul and Z. Wei, Nano

Energy, 2021, 85, 105958.

661 Y. Sun, J. Tang, K. Zhang, X. Yu, J. Yuan, D.-M. Zhu,

K. Ozawa and L.-C. Qin, RSC Adv.,2021, 11, 34152–34159.

662 Y. Yang, C. Zhang, Z. Mei, Y. Sun, Q. An, Q. Jing, G. Zhao

and H. Guo, Nano Res., 2023, 16(7), 9289–9298.

663 B. Zhou, A. Hu, X. Zeng, M. He, R. Li, C. Zhao, Z. Yan,

Y. Pan, J. Chen, Y. Fan, M. Liu and J. Long, J. Chem. Eng.,

2022, 450, 137921.

664 S. You, D.-S. Liu, M. Ye, Y. Zhang, Y. Tang, X. Liu and

C. Chao Li, J. Chem. Eng, 2023, 454, 139907.

665 P. Jaumaux, J. Wu, D. Shanmukaraj, Y. Wang, D. Zhou,

B. Sun, F. Kang, B. Li, M. Armand and G. Wang, Adv. Funct.

Mater., 2021, 31, 2008644.

666 Q. Zhao, S. Stalin, C.-Z. Zhao and L. A. Archer, Nat. Rev.

Mater., 2020, 5, 229–252.

667 J. Lu, P. Jaumaux, T. Wang, C. Wang and G. Wang, J. Mater.

Chem. A, 2021, 9, 24175–24194.

668 Y. S. Meng, V. Srinivasan and K. Xu, Science, 2022,

378, eabq3750.

669 J. Li, J. K. Park, R. B. Moore and L. A. Madsen, Nat. Mater.,

2011, 10, 507–511.

670 Q. Wen, D. Yan, F. Liu, M. Wang, Y. Ling, P. Wang,

P. Kluth, D. Schauries, C. Trautmann and P. Apel, Adv.

Funct. Mater., 2016, 26, 5796–5803.

671 C. L. Ritt, M. Liu, T. A. Pham, R. Epsztein, H. J. Kulik and

M. Elimelech, Sci. Adv., 2022, 8, eabl5771.

672 H. Khani, S. Kalami and J. B. Goodenough, Sustainable

Energy Fuels, 2020, 4, 177–189.

673 H. Zou, Y. Wang, X. Li, P. Ding, H. Guo and F. Li, J. Membr.

Sci., 2023, 685, 121939.

674 D.-D. Han, Z.-Y. Wang, G.-L. Pan and X.-P. Gao, ACS Appl.

Mater. Interfaces, 2019, 11, 18427–18435.

675 Z. Wu, Y. Yi, F. Hai, X. Tian, S. Zheng, J. Guo, W. Tang,

W. Hua and M. Li, ACS Appl. Mater. Interfaces, 2023, 15,

22065–22074.

Chem Soc Rev Review Article

Published on 04 March 2024. Downloaded by University of Wollongong on 3/8/2024 12:31:15 AM.

View Article Online

676 J.Y.Jung,S.A.Han,H.-S.Kim,J.H.Suh,J.-S.Yu,W.Cho,

M.-S. Park and J. H. Kim, ACS Nano, 2023, 17, 15931–15941.

677 Z. Li, L. Wang, Y. Liu, M. Yu, B. Liu, Y. Men, Z. Sun, W. Hu

and G. Zhu, Small, 2023, 19, 2302818.

678 Z. Guo, Y. Zhang, Y. Dong, J. Li, S. Li, P. Shao, X. Feng and

B. Wang, J. Am. Chem. Soc., 2019, 141, 1923–1927.

679 S. Lascaud, M. Perrier, A. Vallee, S. Besner, J. Prud’homme

and M. Armand, Macromol., 1994, 27, 7469–7477.

680 W. Gorecki, M. Jeannin, E. Belorizky, C. Roux and

M. Armand, J. Condens. Matter Phys., 1995, 7, 6823.

681 Z. Stoeva, I. Martin-Litas, E. Staunton, Y. G. Andreev and

P. G. Bruce, J. Am. Chem. Soc., 2003, 125, 4619–4626.

682 Y. Nikodimos, W. N. Su and B. J. Hwang, Adv. Energy

Mater., 2023, 13, 2202854.

683 W. Zhao, J. Yi, P. He and H. Zhou, Electrochem. Energy Rev.,

2019, 2, 574–605.

684 S. Yu, J. Noh, B. Kim, J.-H. Song, K. Oh, J. Yoo, S. Lee,

S.-O. Park, W. Kim, B. Kang, D. Kil and K. Kang, Science,

2023, 382, 573–579.

685 B. Zhang, R. Tan, L. Yang, J. Zheng, K. Zhang, S. Mo, Z. Lin

and F. Pan, Energy Storage Mater, 2018, 10, 139–159.

686 X. Feng, H. Fang, N. Wu, P. Liu, P. Jena, J. Nanda and

D. Mitlin, Joule, 2022, 6, 543–587.

687 X. Yu and A. Manthiram, Energy Environ. Sci., 2018, 11,

527–543.

688 Y. Huang, B. Shao and F. Han, Curr. Opin. Electrochem.,

2022, 33, 100933.

689 S. Lou, F. Zhang, C. Fu, M. Chen, Y. Ma, G. Yin and

J. Wang, Adv. Mater., 2021, 33, 2000721.

690 Y. Huang, L. Zhao, L. Li, M. Xie, F. Wu and R. Chen, Adv.

Mater., 2019, 31, 1808393.

691 N. Ohta, K. Takada, L. Zhang, R. Ma, M. Osada and

T. Sasaki, Adv. Mater., 2006, 18, 2226–2229.

692 Y. Li, W. Zhou, X. Chen, X. Lu

¨, Z. Cui, S. Xin, L. Xue, Q. Jia

and J. B. Goodenough, Proc. Natl. Acad. Sci. U. S. A., 2016,

113, 13313–13317.

693 K. Yamamoto, R. Yoshida, T. Sato, H. Matsumoto, H.

Kurobe, T. Hamanaka, T. Kato, Y. Iriyama and T.

Hirayama, J. Power Sources, 2014, 266, 414–421.

694 S. Bai, B. Kim, C. Kim, O. Tamwattana, H. Park, J. Kim, D. Lee

and K. Kang, Nat. Nanotechnol., 2021, 16,77–84.

695 H. Wu, D. Zhuo, D. Kong and Y. Cui, Nat. Commun., 2014,

5, 5193.

696 M. F. Lagadec, R. Zahn and V. Wood, Nat. Energy., 2019, 4,

16–25.

697 J. Pu, J. Li, K. Zhang, T. Zhang, C. Li, H. Ma, J. Zhu,

P. V. Braun, J. Lu and H. Zhang, Nat. Commun., 2019, 10,

1896.

698 Z. Liu, Y. Jiang, Q. Hu, S. Guo, L. Yu, Q. Li, Q. Liu and

X. Hu, Energy Environ. Mater., 2021, 4, 336–362.

699 L. Zhang, X. Li, M. Yang and W. Chen, Energy Storage

Mater., 2021, 41, 522–545.

700 W. Zhang, Z. Tu, J. Qian, S. Choudhury, L. A. Archer and

Y. Lu, Small, 2018, 14, 1703001.

701 P. Sun, K. Wang and H. Zhu, Adv. Mater., 2016, 28,

2287–2310.

702 Y. Cao, C. Liu, M. Wang, H. Yang, S. Liu, H. Wang, Z. Yang,

F. Pan, Z. Jiang and J. Sun, Energy Storage Mater, 2020, 29,

207–215.

703 J. Xu, H. Zhang, F. Yu, Y. Cao, M. Liao, X. Dong and

Y. Wang, Angew. Chem., Int. Ed., 2022, 61, e202211933.

704 K. Mullapudi, R. Addou, C. L. Dezelah, D. F. Moser,

R. K. Kanjolia, J. H. Woodruﬀ and J. F. ConleyJr., Chem.

Mater., 2023, 35, 4649–4659.

705 Z. Zhao, W. Chen, S. Impeng, M. Li, R. Wang, Y. Liu,

L. Zhang, L. Dong, J. Unruangsri, C. Peng, C. Wang,

S. Namuangruk, S.-Y. Lee, Y. Wang, H. Lu and J. Guo,

J. Mater. Chem. A, 2020, 8, 3459–3467.

706 J. Li, C. Jiao, J. Zhu, L. Zhong, T. Kang, S. Aslam, J. Wang,

S. Zhao and Y. Qiu, J. Energy Chem., 2021, 57, 469–476.

707 C. Kisielowski, B. Freitag, M. Bischoﬀ, H. van Lin, S. Lazar,

G. Knippels, P. Tiemeijer, M. van der Stam, S. von Harrach,

M. Stekelenburg, M. Haider, S. Uhlemann, H. Mu

¨ller,

P. Hartel, B. Kabius, D. Miller, I. Petrov, E. A. Olson,

T. Donchev, E. A. Kenik, A. R. Lupini, J. Bentley, S. J.

Pennycook, I. M. Anderson, A. M. Minor, A. K. Schmid,

T. Duden, V. Radmilovic, Q. M. Ramasse, M. Watanabe,

R. Erni, E. A. Stach, P. Denes and U. Dahmen, Microsc.

Microanal., 2008, 14, 469–477.

708 S. I. Wright, M. M. Nowell and D. P. Field, Microsc.

Microanal.,2011, 17, 316–329.

709 Y. Li, Y. Li, A. Pei, K. Yan, Y. Sun, C.-L. Wu, L.-M. Joubert,

R. Chin, A. L. Koh, Y. Yu, J. Perrino, B. Butz, S. Chu and

Y. Cui, Science, 2017, 358, 506–510.

710 X. Wang, Y. Li and Y. S. Meng, Joule, 2018, 2, 2225–2234.

711 S. Dolabella, A. Borzı

`, A. Dommann and A. Neels, Small

Methods, 2022, 6, 2100932.

712 Y. Umena, K. Kawakami, J.-R. Shen and N. Kamiya, Nature,

2011, 473, 55–60.

713 Y. Fukuda, Y. Hirano, K. Kusaka, T. Inoue and T. Tamada,

Proc. Natl. Acad. Sci. U. S. A., 2020, 117, 4071–4077.

714 S. Mahapatra, L. Li, J. F. Schultz and N. Jiang, J. Chem.

Phys., 2020, 153, 010902.

715 Z. Wu, W. Kong Pang, L. Chen, B. Johannessen and Z. Guo,

Batter. Supercaps, 2021, 4, 1547–1566.

716 J. Kim, D. Lee, C. Nam, J. Chung, B. Koo, N. Kim and J. Lim,

J. Electron. Spectrosc. Relat. Phenom., 2023, 266, 147337.

717 Y. Yan, C. Cheng, L. Zhang, Y. Li and J. Lu, Adv. Energy

Mater., 2019, 9, 1900148.

718 Y. S. Meng and M. E. Arroyo-de Dompablo, Energy Environ.

Sci., 2009, 2, 589–609.

719 S. Bai, Y. Sun, J. Yi, Y. He, Y. Qiao and H. Zhou, Joule, 2018,

2, 2117–2132.

720 L. Wang, F. Zhou, Y. S. Meng and G. Ceder, Phys. Rev. B,

2007, 76, 165435.

721 T. Lombardo, M. Duquesnoy, H. El-Bouysidy, F. Åre

´n, A.

Gallo-Bueno, P. B. Jørgensen, A. Bhowmik, A. Demortie

`re,

E. Ayerbe, F. Alcaide, M. Reynaud, J. Carrasco, A. Grimaud,

C. Zhang, T. Vegge, P. Johansson and A. A. Franco, Chem.

Rev., 2022, 122, 10899–10969.

722 Y. Xiao, Y. Wang, S.-H. Bo, J. C. Kim, L. J. Miara and

G. Ceder, Nat. Rev. Mater., 2020, 5, 105–126.

Review Article Chem Soc Rev

Published on 04 March 2024. Downloaded by University of Wollongong on 3/8/2024 12:31:15 AM.

View Article Online

723 H.-K. Tian, R. Jalem, B. Gao, Y. Yamamoto, S. Muto,

M. Sakakura, Y. Iriyama and Y. Tateyama, ACS Appl. Mater.

Interfaces, 2020, 12, 54752–54762.

724 Z. Sun, K. Xi, J. Chen, A. Abdelkader, M.-Y. Li, Y. Qin,

Y. Lin, Q. Jiang, Y.-Q. Su, R. Vasant Kumar and S. Ding,

Nat. Commun., 2022, 13, 3209.

725Y.Gao,T.Rojas,K.Wang,S.Liu,D.Wang,T.Chen,H.

Wang,A.T.NgoandD.Wang,Nat. Energy., 2020, 5, 534–542.

726 Z. Yan, L. Zhao, Y. Wang, Z. Zhu and S.-L. Chou, Adv. Funct.

Mater., 2022, 32, 2205622.

727 H. Ye, M. Li, T. Liu, Y. Li and J. Lu, ACS Energy Lett., 2020,

5, 2234–2245.

728 Y. Kim, N. J. Dudney, M. Chi, S. K. Martha, J. Nanda,

G. M. Veith and C. Liang, J. Electrochem. Soc., 2013,

160, A3113.

729 S. Rajendran, A. George, Z. Tang, C. Neumann, A. Turchanin

andL.M.R.Arava,Small, 2023, 19, 2303625.

730 B. Campbell, R. Ionescu, Z. Favors, C. S. Ozkan and

M. Ozkan, Sci. Rep., 2015, 5, 14575.

731 A. Karatrantos and Q. Cai, Phys. Chem. Chem. Phys., 2016,

18, 30761–30769.

732 S. Sun, Z. Han, W. Liu, Q. Xia, L. Xue, X. Lei, T. Zhai, D. Su

and H. Xia, Nat. Commun., 2023, 14, 6662.

733 Q. Li, Y. Qiao, S. Guo, K. Jiang, Q. Li, J. Wu and H. Zhou,

Joule, 2018, 2, 1134–1145.

734 Y.-J. Lei, H.-L. Yang, Y. Liang, H.-W. Liu, B. Zhang,

L. Wang, W.-H. Lai, Y.-X. Wang, H.-K. Liu and S.-X. Dou,

Adv. Energy Mater., 2022, 12, 2202523.

735 N. An-Giang, V. Rakesh, N. D. Pravin and P. Chan-Jin,

Energy Materials, 2023, 3, 300030.

736 R. Ding, Y. Huang, G. Li, Q. Liao, T. Wei, Y. Liu, Y. Huang

and H. He, Front. Chem., 2020, 8, 607504.

737 R. J. Cle

´ment, P. G. Bruce and C. P. Grey, J. Electrochem.

Soc., 2015, 162, A2589.

Chem Soc Rev Review Article

Published on 04 March 2024. Downloaded by University of Wollongong on 3/8/2024 12:31:15 AM.

View Article Online

Elucidating the role of embedding dispersed cobalt sites in nitrogen-doped carbon frameworks in Si-based anodes for stable and superior storage

Article

Jun 2024

Interfacial Spinel Local Interlocking Strategy Toward Structural Integrity in P3 Oxide Cathodes

Article

Full-text available

May 2024
ACS NANO

Lithium-Ion Charged Polymer Channels Flattening Lithium Metal Anode

Article

Full-text available

Jan 2024

The concentration difference in the near-surface region of lithium metal is the main cause of lithium dendrite growth. Resolving this issue will be key to achieving high-performance lithium metal batteries (LMBs). Herein, we construct a lithium nitrate (LiNO3)-implanted electroactive β phase polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) crystalline polymorph layer (PHL). The electronegatively charged polymer chains attain lithium ions on the surface to form lithium-ion charged channels. These channels act as reservoirs to sustainably release Li ions to recompense the ionic flux of electrolytes, decreasing the growth of lithium dendrites. The stretched molecular channels can also accelerate the transport of Li ions. The combined effects enable a high Coulombic efficiency of 97.0% for 250 cycles in lithium (Li)||copper (Cu) cell and a stable symmetric plating/stripping behavior over 2000 h at 3 mA cm⁻² with ultrahigh Li utilization of 50%. Furthermore, the full cell coupled with PHL-Cu@Li anode and LiFePO4 cathode exhibits long-term cycle stability with high-capacity retention of 95.9% after 900 cycles. Impressively, the full cell paired with LiNi0.87Co0.1Mn0.03O2 maintains a discharge capacity of 170.0 mAh g⁻¹ with a capacity retention of 84.3% after 100 cycles even under harsh condition of ultralow N/P ratio of 0.83. This facile strategy will widen the potential application of LiNO3 in ester-based electrolyte for practical high-voltage LMBs. Supplementary Information The online version contains supplementary material available at 10.1007/s40820-023-01300-5.

Lattice pinning in MoO3 via coherent interface with stabilized Li intercalation

Article

Full-text available

Oct 2023

Large lattice expansion/contraction with Li⁺ intercalation/deintercalation of electrode active materials results in severe structural degradation to electrodes and can negatively impact the cycle life of solid-state lithium-based batteries. In case of the layered orthorhombic MoO3 (α-MoO3), its large lattice variation along the b axis during Li⁺ insertion/extraction induces irreversible phase transition and structural degradation, leading to undesirable cycle life. Herein, we propose a lattice pinning strategy to construct a coherent interface between α-MoO3 and η-Mo4O11 with epitaxial intergrowth structure. Owing to the minimal lattice change of η-Mo4O11 during Li⁺ insertion/extraction, η-Mo4O11 domains serve as pin centers that can effectively suppress the lattice expansion of α-MoO3, evidenced by the noticeably decreased lattice expansion from about 16% to 2% along the b direction. The designed α-MoO3/η-Mo4O11 intergrown heterostructure enables robust structural stability during cycling (about 81% capacity retention after 3000 cycles at a specific current of 2 A g⁻¹ and 298 ± 2 K) by harnessing the merits of epitaxial stabilization and the pinning effect. Finally, benefiting from the stable positive electrode–solid electrolyte interface, a highly durable and flexible all-solid-state thin-film lithium microbattery is further demonstrated. This work advances the fundamental understanding of the unstable structure evolution for α-MoO3, and may offer a rational strategy to develop highly stable electrode materials for advanced batteries.

Design and Synthesis of Cubic K3-2x Bax SbSe4 Solid Electrolytes for K-O2 Batteries

Article

Full-text available

Oct 2023
ADV MATER

Developing K‐ion conducting solid‐state electrolytes (SSEs) plays a critical role in the safe implementation of potassium batteries. In this work, we report a chalcogenide‐based potassium ion SSEs, K 3 SbSe 4 , which adopts a trigonal structure at room temperature. Single‐crystal structural analysis reveals a trigonal‐to‐cubic phase transition at the low temperature of 50°C, which is the lowest among similar compounds and thus provides easy access to the cubic phase. The substitution of barium for potassium in K 3 SbSe 4 leads to the creation of potassium vacancies, expansion of lattice parameters, and a transformation from a trigonal phase to a cubic phase. As a result, the maximum conductivity of K 3‐2x Ba x SbSe 4 reaches around 0.1 mS/cm at 40°C for K 2.2 Ba 0.4 SbSe 4 , which is over two orders of magnitude higher than that of undoped K 3 SbSe 4 . This novel SSE is successfully employed in a K‐O 2 battery operating at room temperature where a polymer‐laminated K 2.2 Ba 0.4 SbSe 4 pellet serves as a separator between the oxygen cathode and the potassium metal anode. Effective protection of the K metal anode against corrosion caused by O 2 has been demonstrated. This article is protected by copyright. All rights reserved

Monodispersed Sub‐1 nm Inorganic Cluster Chains in Polymers for Solid Electrolytes with Enhanced Li‐Ion Transport

Article

Full-text available

Oct 2023
ADV MATER

The organic‐inorganic interfaces can enhance Li+ transport in composite solid‐state electrolytes (CSEs) due to the strong interface interactions. However, Li+ non‐conductive areas in CSEs with inert fillers will hinder the construction of efficient Li+ transport channels. Herein, CSEs with fully active Li+ conductive networks are proposed to improve Li+ transport by composing sub‐1 nm inorganic cluster chains and organic polymer chains. The inorganic cluster chains are monodispersed in polymer matrix by a brief mixed‐solvent strategy, their sub‐1 nm diameter and ultrafine dispersion state eliminate Li+ non‐conductive areas in the interior of inert fillers and filler‐agglomeration, respectively, providing rich surface areas for interface interactions. Therefore, the three‐dimensional networks connected by the monodispersed cluster chains finally construct homogeneous, large‐scale, continuous Li+ fast transport channels. Furthermore, a conjecture about 1D oriented distribution of organic polymer chains along the inorganic cluster chains is proposed to optimize Li+ pathways. Consequently, the as‐obtained CSEs possess high ionic conductivity at room temperature (0.52 mS cm−1), high Li+ transference number (0.62), and more mobile Li+ (50.7%). The assembled LiFePO4/Li cell delivers excellent stability of 1000 cycles at 0.5 C and 700 cycles at 1 C. This research provides a new strategy for enhancing Li+ transport by efficient interfaces. This article is protected by copyright. All rights reserved

Two-dimensional MXene membranes with biomimetic sub-nanochannels for enhanced cation sieving

Article

Full-text available

Aug 2023

Membranes with high ion permeability and selectivity are of considerable interest for sustainable water treatment, resource extraction and energy storage. Herein, inspired by K⁺ channel of streptomyces A (KcsA K⁺), we have constructed cation sieving membranes using MXene nanosheets and Ethylenediaminetetraacetic acid (EDTA) molecules as building blocks. Numerous negatively charged oxygen atoms of EDTA molecules and 6.0 Å two-dimensional (2D) sub-nanochannel of MXene nanosheets enable biomimetic channel size, chemical groups and tunable charge density for the resulting membranes. The membranes show the capability to recognize monovalent/divalent cations, achieving excellent K⁺/Mg²⁺ selectivity of 121.2 using mixed salt solution as the feed, which outperforms other reported membranes under similar testing conditions and transcends the current upper limit. Characterization and simulations indicate that the cation recognition effect of EDTA and partial dehydration effects play critical roles in cations selective sieving and increasing the local charge density within the sub-nanochannel significantly improves cation selectivity. Our findings provide a theoretical basis for ions transport in sub-nanochannels and an alternative strategy for design ions separation membranes.

Enhancement of the ionic conductivity of a composite polymer electrolyte via surface functionalization of SSZ-13 zeolite for all-solid- state Li-metal batteries †

Article

Nov 2020

To mitigate the safety issues of liquid electrolyte-based Li-ion batteries, there is a growing interest in the development of solid-state electrolyte (SSE) based Li-metal batteries. Regrettably, most SSEs have low ionic conductivity (s), which significantly lowers the performance of the Li-metal batteries. However, a composite polymer electrolyte (CPE) offers a higher s value, which still needs to be improved for a reliable Li-metal battery. Here, a superior CPE (MZ-CPE) was synthesized using modified SSZ-13 (M-SSZ-13) as a ceramic filler. Polyethylene oxide (PEO) and lithium bis-(trifluoromethanesulfonyl)imide (LiTFSI) were used as the substrate and Li-salt, respectively. Due to the upgraded and hydrophobic surface of M-SSZ-13, the dispersion of the Li-salt in PEO is significantly improved. Thus, the value of s was greatly enhanced, which helps to make better interfacial contact with the electrodes. The MZ-CPE electrolyte with 5 wt% M-SSZ-13 (5% MZ-CPE) provided an outstanding s value of 5.34 Â 10 À2 S cm À1 (@ 70 C) along with a Li-ion transference number of 0.85. Besides, the obtained discharge specific capacities were 154 and 194 mA h g À1 using LiFePO 4 and LiNiCoAlO 2 cathodes, respectively at the discharge current density of 0.1C. For LiFePO 4 cathode, the capacity retention was 94.1% after 80 cycles @ 60 C. These results indicate that hydrophobic zeolite containing composite polymer electrolytes could be a potential alternative for solid-state Li-metal batteries.

Design of a trigonal halide superionic conductor by regulating cation order-disorder

Article

Nov 2023

Lithium-metal-halides have emerged as a class of solid electrolytes that can deliver superionic conductivity comparable to that of state-of-the-art sulfide electrolytes, as well as electrochemical stability that is suitable for high-voltage (>4 volt) operations. We show that the superionic conduction in a trigonal halide, such as Li 3 MCl 6 [where metal (M) is Y or Er], is governed by the in-plane lithium percolation paths and stacking interlayer distance. These two factors are inversely correlated with each other by the partial occupancy of M, serving as both a diffusion inhibitor and pillar for maintaining interlayer distance. These findings suggest that a critical range or ordering of M exists in trigonal halides, and we showcase the achievement of high ionic conductivity by adjusting the simple M ratio (per Cl or Li). We provide general design criteria for superionic trigonal halide electrolytes.

Unraveling Sodium-Ion Dynamics in Honeycomb-Layered Na2MgxZn2-xTeO6 Solid Electrolytes with Solid-State NMR

Article

Aug 2023
J AM CHEM SOC

All-solid-state sodium-ion batteries (SIBs) have the potential to offer large-scale, safe, cost-effective, and sustainable energy storage solutions by supplementing the industry-leading lithium-ion batteries. However, for the enhanced bulk properties of SIB components (e.g., solid electrolytes), a comprehensive understanding of their atomic-scale structure and the dynamic behavior of sodium (Na) ions is essential. Here, we utilize a robust multinuclear (23Na, 125Te, 25Mg, and 67Zn) magnetic resonance approach to explore a novel Mg/Zn homogeneously mixed-cation honeycomb-layered oxide Na2MgxZn2-xTeO6 solid solution series. These new intermediate compounds exhibit tailorable bulk Na-ion conductivity (σ) with the highest σ = 0.14 × 10-4 S cm-1 for Na2MgZnTeO6 at room temperature suitable for SIB solid electrolyte applications as observed by powder electrochemical impedance spectroscopy (EIS). A combination of powder X-ray diffraction (XRD), energy-dispersive X-ray (EDX) spectroscopy, and field emission scanning electron microscopy (FESEM) reveals highly crystalline phase-pure compounds in the P6322 space group. We show that the Mg/Zn disorder is random within the honeycomb layers using 125Te nuclear magnetic resonance (NMR) and resolve multiple Na sites using two-dimensional (triple-quantum magic-angle spinning (3QMAS)) 23Na NMR. The medium-range disorder in the honeycomb layer is revealed through the combination of 25Mg and 67Zn NMR, complemented by electronic structure calculations using density functional theory (DFT). Furthermore, we expose very fast local Na-ion hopping processes (hopping rate, 1/τNMR = 0.83 × 109 Hz) by using a laser to achieve variable high-temperature (∼860 K) 23Na NMR, which are sensitive to different Mg/Zn ratios. The Na2MgZnTeO6 with maximum Mg/Zn disorder displays the highest short-range Na-ion dynamics among all of the solid solution members.

Multicomponent Covalent Organic Framework Solid Electrolyte Allowing Effective Li-Ion Dissociation and Diffusion for All-Solid-State Batteries

Article

Aug 2023
ACS NANO

Organic solid electrolytes compatible with all-solid-state Li metal batteries (LMBs) are essential to ensuring battery safety, high energy density, and long-term cycling performance. However, it remains a challenge to develop an approach to provide organic solid electrolytes with capabilities for the facile dissociation of strong Li-ion pairs and fast transport of ionic components. Herein, a diethylene glycol-modified pyridinium covalent organic framework (DEG-PMCOF) with a well-defined periodic structure is prepared as a multicomponent solid electrolyte with a cationic moiety of high polarity, an additional flexible ion-transporter, and an ordered ionic channel for all-solid-state LMBs. The DEG-containing pyridinium groups of DEG-PMCOF allow a lower dissociation energy of Li salts and a smaller energy barrier of Li-ion transport, leading to high ion conductivity (1.71 × 10-4 S cm-1) and a large Li-ion transfer number (0.61) at room temperature in the solid electrolyte. The DEG-PMCOF solid electrolyte exhibits a wide electrochemical stability window and effectively suppresses the formation of Li dendrites and dead Li in all-solid-state LMBs. Molecular dynamics and density functional theory simulations provide insights into the mechanisms for the enhanced Li-ion transport driven by the integrated diffusion process based on hopping motion, vehicle motion, and free diffusion of DEG-PMCOF. The all-solid-state LMB assembled with a DEG-PMCOF solid electrolyte displays a high specific capacity with a retention of 99% and an outstanding Coulombic efficiency of 99% at various C-rates during long-term cycling. This DEG-PMCOF approach can offer an effective route to design various solid-state Li batteries.

High-Performance Lithium-Sulfur Batteries via Molecular Complexation

Article

Aug 2023
J AM CHEM SOC

Beyond lithium-ion technologies, lithium-sulfur batteries stand out because of their multielectron redox reactions and high theoretical specific energy (2500 Wh kg-1). However, the intrinsic irreversible transformation of soluble lithium polysulfides to solid short-chain sulfur species (Li2S2 and Li2S) and the associated large volume change of electrode materials significantly impair the long-term stability of the battery. Here we present a liquid sulfur electrode consisting of lithium thiophosphate complexes dissolved in organic solvents that enable the bonding and storage of discharge reaction products without precipitation. Insights garnered from coupled spectroscopic and density functional theory studies guide the complex molecular design, complexation mechanism, and associated electrochemical reaction mechanism. With the novel complexes as cathode materials, high specific capacity (1425 mAh g-1 at 0.2 C) and excellent cycling stability (80% retention after 400 cycles at 0.5 C) are achieved at room temperature. Moreover, the highly reversible all-liquid electrochemical conversion enables excellent low-temperature battery operability (>400 mAh g-1 at -40 °C and >200 mAh g-1 at -60 °C). This work opens new avenues to design and tailor the sulfur electrode for enhanced electrochemical performance across a wide operating temperature range.

Electrochemical coupling in subnanometer pores/channels for rechargeable batteries

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