Figure - available from: Advanced Materials
This content is subject to copyright. Terms and conditions apply.
![a,b) Schematic diagrams of Li nucleation and subsequent deposition process based on the self‐healing electrostatic shield mechanism (a), and on a GF‐modified Cu foil electrode (b). c,d) Schemes of Li ion distribution under the function of Lorentz force (c), and ultrasonic waves (d). a) Reproduced with permission.[⁹⁵] Copyright 2013, American Chemical Society. b) Reproduced with permission.[⁹⁶] Copyright 2016, Wiley‐VCH. c) Reproduced with permission.[⁹⁹] Copyright 2019, Wiley‐VCH. d) Reproduced with permission.[¹⁰⁰] Copyright 2020, Wiley‐VCH.](publication/348513801/figure/fig14/AS:11431281173003044@1688732392570/a-b-Schematic-diagrams-of-Li-nucleation-and-subsequent-deposition-process-based-on-the.png)
a,b) Schematic diagrams of Li nucleation and subsequent deposition process based on the self‐healing electrostatic shield mechanism (a), and on a GF‐modified Cu foil electrode (b). c,d) Schemes of Li ion distribution under the function of Lorentz force (c), and ultrasonic waves (d). a) Reproduced with permission.[⁹⁵] Copyright 2013, American Chemical Society. b) Reproduced with permission.[⁹⁶] Copyright 2016, Wiley‐VCH. c) Reproduced with permission.[⁹⁹] Copyright 2019, Wiley‐VCH. d) Reproduced with permission.[¹⁰⁰] Copyright 2020, Wiley‐VCH.
Source publication
Lithium (Li) metal is one of the most promising alternative anode materials of next‐generation high‐energy‐density batteries demanded for advanced energy storage in the coming fourth industrial revolution. Nevertheless, disordered Li deposition easily causes short lifespan and safety concerns and thus severely hinders the practical applications of...
Similar publications
Crystallography modulation of zinc (Zn) metal anode is promising to promote Zn reversibility in aqueous electrolytes, but efficiently constructing Zn with specific crystallographic texture remains challenging. Herein, we report a current‐controlled electrodeposition strategy to texture the Zn electrodeposits in conventional aqueous electrolytes. Us...
Citations
... Although the considerable success achieved in stabilizing SEI to a certain extent at low areal capacities (<2 mAh cm −2 ), deposition morphologies under high areal capacity (≥4 mAh cm −2 ) are filaments, nanorods, columns or chunks 15 , and tend to pack up into loose and porous structure during the growth process, which not only leads to severe side reactions between Li metal and electrolytes due to the large specific surface area, but also results in huge volume expansion during repeated cycles 16,17 . The main reason for this phenomenon is that the reactivity of Li metal with electrolytes is not effectively suppressed, that is the preferred orientation of Li plating is not fundamentally regulated, which is tightly related to the deposition morphology 18 . Thus, forming a dense deposition morphology under high areal capacity (≥4 mAh cm −2 ) is much essential and still highly challenging, which is beneficial for realizing the goal of high-energy-density LMBs. ...
The advancement of Li-metal batteries is significantly impeded by the presence of unstable solid electrolyte interphase and Li dendrites upon cycling. Herein, we present an innovative approach to address these issues through the synergetic regulation of solid electrolyte interphase mechanics and Li crystallography using yttrium fluoride/polymethyl methacrylate composite layer. Specifically, we demonstrate the in-situ generation of Y-doped lithium metal through the reaction of composite layer with Li metal, which reduces the surface energy of the (200) plane, and tunes the preferential crystallographic orientation to (200) plane from conventional (110) plane during Li plating. These changes effectively passivate Li metal, thereby significantly reducing undesired side reactions between Li and electrolytes by 4 times. Meanwhile, the composite layer with suitable modulus (~1.02 GPa) can enhance mechanical stability and maintain structural stability of SEI. Consequently, a 4.2 Ah pouch cell with high energy density of 468 Wh kg⁻¹ and remarkable capacity stability of 0.08% decay/cycle is demonstrated under harsh condition, such as high-areal-capacity cathode (6 mAh cm⁻²), lean electrolyte (1.98 g Ah⁻¹), and high current density (3 mA cm⁻²). Our findings highlight the potential of reactive composite layer as a promising strategy for the development of stable Li-metal batteries.
... Usually, this SEI layer is unstable and governs the transport of Li + , further influencing the morphologies of Li deposits and generating a series of issues during cycling process ( Figure S1, Supporting Information), finally resulting in battery failure. [16,17] Recently, some innovative approaches have been developed to remove the SEI film, including chemical treatment, [18,19] electrochemical polishing, [20] and physical polishing. [21] Impressively, Baek et al. reported a nearly perfect lattice match between the Li metal foil and Li deposits by removing the SEI film through chemical polishing process. ...
... Generally speaking, for commercial Li metal composed of different crystal grains, its surface has many protrusions, [3,59] where Li + can be preferentially deposited due to the tip effect of the electric field during the electroplating process. [16] Zooming into the microscopic level, undesirable intercrystalline reactions, nonuniform and disordered SEI film can promote the formation and continuous growth of Li dendrites, finally resulting in the failure of battery ( Figure S45, Supporting Information). As a sharp comparison, polished Li(110) and Li(200) with a flat and shiny surface can fundamentally alleviate the formation of Li dendrites during cycling process due to the formation of a uniform and disordered SEI film on the surface of Li metal ( Figure 6K,L). ...
A formidable challenge to achieve the practical applications of rechargeable lithium (Li) metal batteries (RLMBs) is to suppress the uncontrollable growth of Li dendrites. One of the most effective solutions is to fabricate Li metal anodes with specific crystal plane, but still lack of a simple and high‐efficient approach. Herein, a facile and controllable way for the scalable customization of polished Li metal anodes with highly preferred (110) and (200) crystallographic orientation (donating as polished Li(110) and polished Li(200), respectively) by regulating the times of accumulative roll bonding, is reported. According to the inherent characteristics of polished Li(110)/Li(200), the influence of Li atomic structure on the electrochemical performance of RLMBs is deeply elucidated by combining theoretical calculations with relative experimental proofs. In particular, a polished Li(110) crystal plane is demonstrated to induce Li⁺ uniform deposition, promoting the formation of flat and dense Li deposits. Impressively, the polished Li(110)||LiFePO4 full cells exhibit unprecedented cycling stability with 10 000 cycles at 10 C almost without capacity degradation, indicating the great potential application prospect of such textured Li metal. More valuably, this work provides an important reference for low‐cost, continued, and large‐scale production of Li metal anodes with highly preferred crystal orientation through roll‐to‐roll manufacturability.
... 16,20 These issues adversely affect the rate performance and safety of batteries due to sluggish and uneven Li + transport, incomplete charging-discharging, and local overcharging. [21][22][23] Furthermore, polyolefin separators show poor thermal stability, with melting points of 135°C and 165°C for PE and PP, respectively. Consequently, the separators shrink at high temperatures, leading to short circuit and making the batteries unsafe for use. ...
... 41,85,86 First, due to the poor electrolyte wettability, disconnected pores, and uneven pore distribution of polyolefin separators, sluggish and ununiform Li + transportation occurs, leading to unsatisfactory high-rate performance, failure, and safety concerns of the batteries. 21,22 Additionally, the poor heat resistance of polyolefin separators also gives rise to many safety issues. 87,88 Moreover, traditional dry and wet processes of polyolefin separators usually have limitations of poor material applicability, complex procedures, and expensive equipment, imposing performance limitations on separators and preventing their application in high-end battery markets like highenergy LIBs with LiMO 2 cathodes and Li-S batteries. ...
Due to the limitations of the raw materials and processes involved, polyolefin separators used in commercial lithium‐ion batteries (LIBs) have gradually failed to meet the increasing requirements of high‐end batteries in terms of energy density, power density, and safety. Hence, it is very important to develop next‐generation separators for advanced lithium (Li)‐based rechargeable batteries including LIBs and Li–S batteries. Nonwoven nanofiber membranes fabricated via electrospinning technology are highly attractive candidates for high‐end separators due to their simple processes, low‐cost equipment, controllable microporous structure, wide material applicability, and availability of multiple functions. In this review, the electrospinning technologies for separators are reviewed in terms of devices, process and environment, and polymer solution systems. Furthermore, strategies toward the improvement of electrospun separators in advanced LIBs and Li–S batteries are presented in terms of the compositions and the structure of nanofibers and separators. Finally, the challenges and prospects of electrospun separators in both academia and industry are proposed. We anticipate that these systematic discussions can provide information in terms of commercial applications of electrospun separators and offer new perspectives for the design of functional electrospun separators for advanced Li‐based batteries.
... However, studies have delineated that conventional carbonate electrolytes may not be apt for lithium metal batteries, as they readily undergo reactions with lithium metal anodes, engendering unstable solid-electrolyte interphases (SEIs) [5][6][7]. Unstable SEIs lead to uncontrolled lithium dendrite growth and limited Coulombic efficiency during repeated plating/stripping processes, which remain key challenges limiting their practical application [8][9][10]. ...
The unstable interface between lithium metal anodes and carbonate-based electrolytes is a key challenge limiting the cycling lifespan of high-energy lithium metal batteries. Here, a resilient artificial solid electrolyte interphase (RASEI) was designed by regulating poly(hexafluorobutyl acrylate) (PHFBA) matrix with the benzene-containing bisphenol A ethoxylate dimethacrylate (BAED) crosslinker to address this issue. The rigid BAED molecule can finely tune the flexible PHFBA matrix, enabling superior resilience from 600% elongation to 90% compression with a high Young’s modulus of over 2 MPa. RASEI with these characteristics can accommodate large volume changes of lithium metal and ensure the intimate contact between the lithium metal and the RASEI during battery operation. Consequently, it facilitated homogeneous lithium deposition while mitigating parasitic side reactions. Thanks to the tough and resilient nature of the fluorinated RASEI, the long-term cycling of Li∣∣Li symmetric cells can be achieved for over 500 h at 1 mA cm−2 and 1 mAh cm−2. The following post-mortem of cycled Li metal reveals that Li dendrite growth is effectively inhibited. Furthermore, the NCM811 pouch cell with a high cathode loading of 20 mg cm−2 exhibits a capacity retention of over 85% after 200 cycles at 1 C.
... However, the utilization of commercial metallic foam (e.g., copper, nickel) as 3D current collectors, with natural lithiophobic features, demonstrates uneven lithium deposition [36]. It has been suggested that introducing lithiophilic materials can improve the lithiophilicity of 3D current collectors, thus inducing uniform Li-ion flux and lithium deposition in the pore structure [37][38][39]. ...
Constructing three-dimensional (3D) current collectors is an effective strategy to solve the hindrance of the development of lithium metal anodes (LMAs). However, the excessive mass of the metallic scaffold structure leads to a decrease in energy density. Herein, lithiophilic graphene aerogels comprising reduced graphene oxide aerogels and silver nanowires (rGO-AgNW) are synthesized through chemical reduction and freeze-drying techniques. The rGO aerogels with large specific surface areas effectively mitigate local current density and delay the formation of lithium dendrites, and the lithiophilic silver nanowires can provide sites for the uniform deposition of lithium. The rGO-AgNW/Li symmetric cell presents a stable cycle of about 2000 h at 1 mA cm−2. When coupled with the LiFePO4 cathode, the assembled full cells exhibit outstanding cycle stability and rate performance. Lightweight rGO-AgNW aerogels, as the host for lithium metal, can significantly improve the energy density of lithium metal anodes.
... The results imply that the faster capacity decay may originate from the un-protected Li, which may have resulted in the exhaustion of liquid electrolyte. 60,61 It can be concluded that modification on the S cathode can alleviate capacity loss in the early stage, while protecting Li anode can prevent the capacity diving in the later stage. Therefore, simultaneously modifying the S cathode and Li anode can further improve the cycling performance of Li-S batteries. ...
Lithium–sulfur (Li–S) batteries have been considered as one of the most promising candidates for high energy-density batteries due to their high theoretical capacity (1675 mA h g⁻¹). However, the cycling performance is not satisfactory due to the “shuttle effect” of polysulfide and the growth of Li dendrites. In this study, imidazole-based poly(ionic liquid) (PIL) is synthesized. Using PIL in Li–S batteries, we realize the goal of achieving two benefits with one action. The cross-linked PIL (c-PIL) is used to modify the S cathode, and the shuttling of polysulfides is effectively inhibited due to the strong adsorption capability. Density functional theory (DFT) calculations indicate that the strong van der Waals and electrostatic interaction promote the adsorption of polysulfides. PIL, as an artificial solid electrolyte interface layer, is coated on the Li anode to prevent the corrosion of liquid electrolyte and homogenize Li⁺ flux. The results of DFT and X-ray photoelectron spectroscopy indicate that the N containing imidazole in PIL can be reduced by active Li to form a Li3N rich layer on the interface. The Li3N containing interfacial layer can promote dendrite-free Li deposition beneath the PIL coating layer. By functionalizing the S cathode and Li anode, the PIL@Li‖c-PIL@S batteries show much improved cycling stability and C-rate performance. The results manifest that our strategy of modification of the cathode and anode electrodes is effective, which is sure to promote the development of advanced Li–S batteries.
... Disadvantageous states of nuclei, with shortened incubation period, out-plane growth orientation, uneven distribution, etc., would induce the later growth of Li toward 1D dendritic whiskers, which is thermodynamically difficult to suppress. [3,10] Therefore, the early state of Li nuclei that are not yet in the growth period is pivotal, which is determined by the transport kinetics of Li + ions from the electrolyte to the negative electrode and the thermodynamic reaction at the interface. Comprehending how these processes impact the nucleation process of Li and direct the formation of early Li nuclei is imperative in achieving advantageous physicochemical characteristics, which would guide the design principles, allowing for beneficial nucleation distribution, a survivable electrochemical environment, favorable growth orientations, and ultimately enhanced safety and extended cycle life in Li-metal batteries. ...
Lithium (Li) metal has emerged as a viable alternative anode material to address the current energy density shortfalls in Li batteries. However, its integration into widespread implementation remains somewhat constrained due to the substandard reversibility issues and safety concerns arising from erratic Li deposition. To effectively tackle these obstacles, considerable endeavors have been exerted to modulate the morphology of Li deposition. Nevertheless, it is exceedingly challenging for Li nuclei that tend to dendritic growth thermodynamically to transform into dense Li morphologies during their growth process. Therefore, it is crucial to understand what influences the formation process of Li nuclei and how to improve the state of Li nuclei. Herein, Li nucleation mechanisms involving mass transport across the solid electrolyte interface from electrolyte to electrode and electrode interfacial reactions are elucidated. Inspired by the understanding of Li nucleation, the corresponding design principles, including enhancing and homogenizing mass transport, stabilizing solid electrolyte interface film, and regulating surface interaction/selection, are summarized for optimizing Li nucleation and further inducing dendrite‐free Li deposition. In light of the competition among these design principles, a perspective on the existing challenges and opportunities for further promoting the application of Li metal batteries is proposed.
... However, the effects of O 2− and OH − on Zn dendrite formation are not well-explored in ZIB. [22] In this work, the first principles simulation was performed to gain an in-depth understanding of the effects of O 2− and OH − on the formation of Zn dendrite. The calculated diffusion ...
Aqueous zinc ion batteries (ZIBs) exhibit great potential for next‐generation energy storage devices. However, significant challenges exist, including the uncontrollable formation of Zn dendrite and side reactions during zinc stripping and plating. The mechanism of Zn dendrite nucleation has yet to be fully understood. In this work, the first principles simulations are used to investigate the Zn dendrite formation process. The unintentionally adsorbed O²⁻ and OH⁻ ions are the inducing factors for Zn dendrite nucleation and growth on the Zn (0001) plane due to significantly increased Zn diffusion barriers. A top‐down method is demonstrated to suppress the dendrite using delaminated V2CTx to capture O²⁻ and OH⁻ ions thanks to reduced Zn diffusion barriers. The experimental results revealed significantly suppressed Zn dendrite nucleation and growth, resulting in a layer‐by‐layer deposit/stripping of Zn. Based on the electrochemical evaluations, the V2CTx‐coated Zn composite delivers a high coulombic efficiency of 99.3% at 1.0 mAh cm⁻². Furthermore, the full cell achieves excellent cyclic performance of 93.6% capacity retention after 2000 cycles at 1 A g⁻¹. This strategy has broad scalability and can be widely applied in designing metallic anodes for rechargeable batteries.
... After 300 h of stable plating/stripping, the overpotential gradually rose with the number of cycles, reaching a cutoff voltage of about 750 h of cycles (Fig. S9a). The failure of Li//Li symmetrical batteries in such a short time is primarily due to lithium dendrite overgrowth, including the rapid consumption of electrolytes and lithium metals, the emergence of side reactions, and the increase in polarization reactions [42]. After the introduction of a TCCNT layer on the surface of the common separator, the assembled Li//Li symmetric cell showed a very stable lithium plating/stripping process, with a low overpotential below 25 mV even after 1000 cycles ( Fig. 4a and Fig. S9b), indicating that the TCCNT interlayer can effectively regulate lithium deposition and suppress lithium dendrite overgrowth. ...
Polysulfide shuttle and lithium dendrite growth severely limit the practical application of lithium−sulfur batteries (LSBs); however, a rational design of a separator can achieve the effect of two birds with one stone. Herein, nitrogen-doped carbon nanotubes with dispersed TiN/CoO particles (TCCNT) were designed and applied as a separator modification layer for LSBs. The porous structure of TCCNT can confine the diffusion of soluble polysulfides by physical adsorption first, and then the TiN/CoO particles carried on its surface/inside can not only further anchor the polysulfides via chemisorption but also act as a catalyst to facilitate their conversion. Meanwhile, the good lithophilicity of TiN was beneficial to homogenizing the Li+ fluxes, guiding a uniform deposition of lithium and realizing a stable cycle of the lithium symmetric battery for up to 2000 h at 5 mA cm−2. Ascribed to the rational layout of the TCCNT layer that allows maximization of the synergistic effect between various material components, an LSB equipped with a modified separator displayed satisfactory electrochemical performance in both cases of conventional and high sulfur loadings, demonstrating its practical application potential.
... Since the discovery of lithium dendrites, much effort has been invested in studying the growth mechanism of lithium dendrites and inhibiting dendrite growth. Many well-known reaction models have been established, greatly motivating the advancement of alkali metal batteries [122][123][124]. Meanwhile, many strategies have been proposed to inhibit dendrite growth and can be subdivided into electrode structure engineering, metal−electrolyte interfacial engineering and electrolyte optimization [125,126]. ...
Bismuth (Bi) has been prompted many investigations into the development of next-generation energy storage systems on account of its unique physicochemical properties. Although there are still some challenges, the application of metallic Bi-based materials in the field of energy storage still has good prospects. Herein, we systematically review the application and development of metallic Bi-based anode in lithium ion batteries and beyond-lithium ion batteries. The reaction mechanism, modification methodologies and their relationship with electrochemical performance are discussed in detail. Additionally, owing to the unique physicochemical properties of Bi and Bi-based alloys, some innovative investigations of metallic Bi-based materials in alkali metal anode modification and sulfur cathodes are systematically summarized for the first time. Following the obtained insights, the main unsolved challenges and research directions are pointed out on the research trend and potential applications of the Bi-based materials in various energy storage fields in the future.
