Hao Liu's research while affiliated with Tsinghua University and other places

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Publications (60)


d3ta05148j1.pdf
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June 2024

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3 Reads

Yi Liu

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chunxing li

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Jiayu Wan
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(a) The designing principles of LiETFSI and the comparison between LiFEA and LiETFSI. X‐ray single crystal structure of (b) LiFEA and (c) LiETFSI. The distance between Li1 and N1 changes from 2.069 Å in LiFEA to 4.367 Å in LiETFSI.
(a) Fitting curves of the relationship between ²³Na chemical shift and the donor number of different solvents, and the determined value of pure EC/DEC and EC/DEC‐based electrolytes with 1 M LiTFSI, LiFEA and LiETFSI respectively. (b) ²³Na NMR results of sodium salts with various anions in DMF. (c) The peak position of ²³Na NMR results with various anions. The donor number of anions increases in sequence from left to right. ¹H spectra of (d) LiFEA in FEC and (e) LiETFSI in FEC with DMSO‐d6 as reference. ¹⁹F spectra of (f) LiFEA in FEC and (g) LiETFSI in FEC with DMSO‐d6 as reference. The NMR spectra were recorded initially, after 3 days and 10 days, respectively.
A soaking experiment to validate the solubilization ability of LiETFSI and the XPS results of the SEI after being soaked in different electrolytes. (a) The C 1s and (b) O1 s XPS spectra of the SEI after being soaked in the BE or LiETFSI electrolyte. (c) The percentage of CH2CH2O− in O species and all species in the unit of O atomic number. (d) The F 1s XPS spectra of the SEI after being soaked in the BE or LiETFSI electrolyte. Schematics exhibiting the solubility of SEI species in (e) LiFEA‐based electrolyte and (f) LiETFSI‐based electrolyte.
A pulse current experiment to confirm the SEI “self‐cleaning and reconstruction mechanism. (a) Schematics of the pulse experiment, where galvanic deposition and standing‐by process were conducted alternately for 1 s and 8 s respectively. (b) Schematics of the SEI “self‐cleaning and reconstruction” process in the BE and LiETFSI electrolyte. (c) The C 1s, (d) O 1s, and (e) F 1s XPS spectra of the SEI on the surface in BE and LiETFSI electrolyte with the pulse current experiment. (f) The C 1s, (g) O 1s, and (h) F 1s XPS spectra of the SEI at a depth of 20 nm in the BE and LiETFSI electrolyte with the pulse current experiment.
(a) The Coulombic efficiency of Li plating/stripping process evaluated by Aurbach's method in Li||Cu cells with BE, advanced LiFEA, LiETFSI, and advanced LiETFSI electrolyte. (b) Nyquist plots of the Li||Li cells with the BE and advanced LiETFSI electrolyte at various temperature. (c) Arrhenius behavior of the resistance corresponding to Li⁺ transport through the SEI. (d) The morphology of deposited Li at 2 mA cm⁻² in BE electrolyte. The morphology of deposited Li at (e) 2 mA cm⁻², (f) 15 mA cm⁻² in advanced LiETFSI electrolyte. (g) The morphology of deposited Li at 15 mA cm⁻² in advanced LiFEA electrolyte.

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Rational Lithium Salt Molecule Tuning for Fast Charging/Discharging Lithium Metal Battery
Angewandte Chemie International Edition

Angewandte Chemie International Edition

The electrolytes for lithium metal batteries (LMBs) are plagued by a low Li⁺ transference number (T+) of conventional lithium salts and inability to form a stable solid electrolyte interphase (SEI). Here, we synthesized a self‐folded lithium salt, lithium 2‐[2‐(2‐methoxy ethoxy)ethoxy]ethanesulfonyl(trifluoromethanesulfonyl) imide (LiETFSI), and comparatively studied with its structure analogue, lithium 1,1,1‐trifluoro‐N‐[2‐[2‐(2‐methoxyethoxy)ethoxy)]ethyl]methanesulfonamide (LiFEA). The special anion chemistry imparts the following new characteristics: i) In both LiFEA and LiETFSI, the ethylene oxide moiety efficiently captures Li⁺, resulting in a self‐folded structure and high T+ around 0.8. ii) For LiFEA, a Li−N bond (2.069 Å) is revealed by single crystal X‐ray diffraction, indicating that the FEA anion possesses a high donor number (DN) and thus an intensive interphase “self‐cleaning” function for an ultra‐thin and compact SEI. iii) Starting from LiFEA, an electron‐withdrawing sulfone group is introduced near the N atom. The distance of Li−N is tuned from 2.069 Å in LiFEA to 4.367 Å in LiETFSI. This alteration enhances ionic separation, achieves a more balanced DN, and tunes the self‐cleaning intensity for a reinforced SEI. Consequently, the fast charging/discharging capability of LMBs is progressively improved. This rationally tuned anion chemistry reshapes the interactions among Li⁺, anions, and solvents, presenting new prospects for advanced LMBs.


Solid-State Transformations of Active Materials in the Pores of Sulfurized-Polyacrylonitrile Fiber Membranes via Nucleophilic Reactions for High-Loading and Free-Standing Lithium–Sulfur Battery Cathodes

March 2024

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10 Reads

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1 Citation

Advanced Fiber Materials

Sulfurized polyacrylonitrile (SPAN) has emerged as an excellent cathode material for lithium–sulfur batteries (LiSBs), and it addresses the shuttle effect through a solid‒solid reaction. However, the actual sulfur loadings in SPAN often remain below 40 wt%. Due to the susceptibility of polysulfides-to-nucleophilic reactions with electrolytes, achieving physical encapsulation of elemental sulfur is a challenging task. In this study, a free-standing cathode material with a high sulfur/selenium (S/Se) loading of 55 wt% was fabricated by introducing SeSx into the unique lotus root-like pores of porous SeSxPAN nanofiber membranes by electrospinning and a two-step heat treatment. Insoluble compounds were formed due to nucleophilic interactions between lithium polyselenosulfides (LiSeSx) and the electrolyte, which potently blocked the existing lotus root-like pores and facilitated the creation of a thin cathode–electrolyte interphase on the fiber surface. This dual functionality of LiSeSx safeguarded the active material embedded within the porous structure. The SeS15PAN cathode exhibited remarkable cycling stability with almost no degradation after 200 cycles at 0.2 C, along with a high discharge capacity of 580 mAh/g. This approach presents a solution for addressing the insufficient sulfur content in SPAN.


Rational Lithium Salt Molecule Tuning for Fast Charging/Discharging Lithium Metal Battery

March 2024

·

10 Reads

Angewandte Chemie

The electrolytes for lithium metal batteries (LMBs) are plagued by a low Li+ transference number (T+) of conventional lithium salts and inability to form a stable solid electrolyte interphase (SEI). Here, we synthesized a self‐folded lithium salt, lithium 2‐[2‐(2‐methoxyethoxy)ethoxy]ethanesulfonyl(trifluoromethanesulfonyl) imide (LiETFSI), and comparatively studied with its structure analogue, lithium 1,1,1‐trifluoro‐N‐[2‐[2‐(2‐methoxyethoxy)ethoxy)]ethyl]methanesulfonamide (LiFEA). The special anion chemistry imparts the following new characteristics: i) In both LiFEA and LiETFSI, the ethylene oxide moiety efficiently captures Li+, resulting in a self‐folded structure and high T+ around 0.8. ii) For LiFEA, a Li‐N bond (2.069 Å) is revealed by single crystal X‐ray diffraction, indicating that the FEA anion possesses a high donor number (DN) and thus the intensive interphase “self‐cleaning” function for an ultra‐thin and compact SEI. iii) Starting from LiFEA, an electron‐withdrawing sulfone group is introduced near the N atom. The distance of Li‐N is tuned from 2.069 Å in LiFEA to 4.367 Å in LiETFSI. This alteration enhances ionic separation, achieves a more balanced DN, and tunes the self‐cleaning intensity for a reinforced SEI. Consequently, the fast charging/discharging capability of LMBs is progressively improved. This rationally tuned anion chemistry reshapes the interactions among Li+, anions, and solvents, presenting new prospects for advanced LMBs.







Citations (27)


... Kai Liu's team designed asymmetric trihaloaromatic lithium salts for solid polymer electrolytes to promote the formation of SEI film enriched with LiF and LiBr, thereby improving interface stability (Figure 6 b). [120] The incorporation of LiF and LiBr in the SEI film was found to significantly enhance Young's modulus and surface energy, thereby promoting the homogenization of Li + flux. Moreover, the presence of LiBr effectively reduces the diffusion barrier for Li + within the SEI film. ...

Reference:

Solid Electrolyte Interphase on Lithium Metal Anodes
Asymmetric Trihalogenated Aromatic Lithium Salt Induced Lithium Halide Rich Interface for Stable Cycling of All-Solid-State Lithium Batteries
  • Citing Article
  • October 2023

ACS Nano

... Upon cycling, the O spectrum collected at the Li/LPS-0.05SnO 2 interface additionally shows a Li 2 O peak at 526.6 eV. The presence of Li 2 O in the interphase would modulate interfacial lithium deposition behaviors and maintain the stability of the SSE/Li interphase, thus inhibiting lithium dendrite formation within the SSE [46,47] . The initial S spectrum of LPS-0.05SnO 2 is ascribed to non-bridging sulfur Li-S-P and bridging sulfur P-S-P. ...

Fluorinated Carbamate-Based Electrolyte Enables Anion-Dominated Solid Electrolyte Interphase for Highly Reversible Li Metal Anode
  • Citing Article
  • August 2023

ACS Nano

... where V cell and C full are the average working voltage and the reversible capacity of the full cell, respectively, m total is the total weight based on the sum of current collector, cathode, anode, separator and electrolyte. The weight of the packing cell bag is excluded from the specific energy calculation due to our limited size of cell 42,43 . To assess the overcharge-safety, the pouch cells were charged from the open circuit voltage to 9 V at a scan rate of 20 mV s -1 , and the infrared thermography images of the pouch cells were captured using a FLIR ONE PRO. ...

Tuning the Li+ Solvation Structure by a "Bulky Coordinating" Strategy Enables Nonflammable Electrolyte for Ultrahigh Voltage Lithium Metal Batteries
  • Citing Article
  • May 2023

ACS Nano

... Compared with traditional nanomaterials such as metal nanomaterials, lipid nanoparticles, polymer nanoparticles, and carbon nanomaterials, biomass materials have good reproducibility and biocompatibility, and their development value far exceeds that of other materials (Lugoloobi et al. 2021;Liu et al. 2023a). As representatives of biomass materials, cellulose nanocrystals (CNCs) and polydopamine (PDA) have received extensive attention in the biomedical field for their strong hydrophilicity, good biocompatibility, and ability to be prepared in large quantities (Long et al. 2021;Cui et al. 2023;Liu et al. 2022). It is reported that the morphology, proper aspect ratio, and rigid backbone of the materials affect the cellular uptake, while the rod-like structure of CNCs can enhance cellular internalization and improve transfection efficiency Gratton et al. 2008;Lin et al. 2015). ...

A highly therapeutic and selective delivery system for curcumin based on nanocellulose and folic acid

Cellulose

... However, their activities still fell short compared to those of carbon catalysts and commercial Pt/C catalysts, and the current record for a half-wave potential is 0.75 V vs. RHE. This limited activity was attributed to the poor electron conductivity of the frameworks and the weak binding of O 2 and other oxygen-containing intermediates 51 . Thus, developing electronic conductive frameworks with strong polar sites holds promise for constructing highly active metal-free ORR catalysts [52][53][54][55][56][57] . ...

A Fluorinated Covalent Organic Framework with Accelerated Oxygen Transfer Nanochannels for High‐Performance Zinc–Air Batteries

... The NiS NPs' wrapping around porous carbon may be the cause of this. As a result, the carbon diffraction peaks are obscured by the strong characteristic peaks of NiS, suggesting a strong chemical bond between NiS NPs and AC (Zhu et al. 2021;Liu et al. 2023). In addition, the lack of any extra peaks resulting from impurities demonstrates the high purity of the NiS NPs-AC nanocomposite. ...

Enhanced sodium storage performance by improving the utilization of NiS through electrode membrane 3D hierarchical porous structure
  • Citing Article
  • November 2022

Colloids and Surfaces A Physicochemical and Engineering Aspects

... The TRPS material provides high electronic conductivity, high thermal sensitivity (rapid response in less than 1 s at 70°C), and excellent electrochemical stability for LIBs. Jia et al. 186 developed a smart thermally responsive current collector by combining the shape memory polymer (EPON cross-linking network), which could be pulled up to restore the original shape and pierce the cover Cu layer with a circuit disconnection when the temperature exceeded its shape memory triggering temperature (Fig. 12d, 90°C, i.e., self-shutdown). ...

Early Braking of Overwarmed Lithium-Ion Batteries by Shape-Memorized Current Collectors
  • Citing Article
  • November 2022

Nano Letters

... As a result, the distance between friction layers can be left uncontrolled, resulting in better energy conversion. The most widely used polymer matrices for MXene-reinforced nanofibers are PLA [93][94][95], PVA [88,90], PVDF [89,96] and CA [97]. Zhang et al. reported the preparation of endogenous TENG by electrospinning PLA fiber films with the addition of MXene as filler. ...

MXene/Multiwalled Carbon Nanotube/Polymer Hybrids for Tribopiezoelectric Nanogenerators
  • Citing Article
  • September 2022

ACS Applied Nano Materials

... Among them, the compounds such as vanadium nitride (VN) [11], titanium dioxide (TiO 2 ) [12], cobalt phosphide (CoP) [13], etc., provided with promoted chemical affinity of LiPS and efficient utilization of the active material. Furthermore, increased interaction of LiPS with carbon and metal compounds led to improved conductivity, buffering volumetric changes of sulfur and enhanced kinetics of RedOx reactions in Li-S cells afterwards [15,16]. ...

Flexible NiCo2S4-Hollow Carbon Nanofibers Electrocatalytic Membrane as an Advanced Interlayer for Lithium-Sulfur Batteries
  • Citing Article
  • May 2022

Colloids and Surfaces A Physicochemical and Engineering Aspects

... In contrast to conventional flat displays, foldable and flexible displays offer a range of form factors for implementing flexible electronics [1][2][3] . As the outermost layer of these displays, developing a foldable and flexible cover window is crucial to replace the conventional rigid cover glass 1,[3][4][5] . ...

Highly Foldable, Super-Sensitive, and Transparent Nanocellulose/Ceramic/Polymer Cover Windows for Flexible OLED Displays
  • Citing Article
  • March 2022

ACS Applied Materials & Interfaces