Janus Quasi-Solid Electrolyte Membranes with Asymmetric Porous Structure for High-Performance Lithium-Metal Batteries

doi:10.1007/s40820-024-01325-4

Abstract

Abstract:

Quasi-solid electrolytes (QSEs) based on nanoporous materials are promising candidates to construct high-performance Li-metal batteries (LMBs). However, simultaneously boosting the ionic conductivity (σ) and lithium-ion transference number (t₊) of liquid electrolyte confined in porous matrix remains challenging. Herein, we report a novel Janus MOFLi/MSLi QSEs with asymmetric porous structure to inherit the benefits of both mesoporous and microporous hosts. This Janus QSE composed of mesoporous silica and microporous MOF exhibits a neat Li⁺ conductivity of 1.5 × 10^-4 S cm⁻¹ with t₊ of 0.71. A partially de-solvated structure and preference distribution of Li⁺ near the Lewis base O atoms were depicted by MD simulations. Meanwhile, the nanoporous structure enabled efficient ion flux regulation, promoting the homogenous deposition of Li⁺. When incorporated in Li||Cu cells, the MOFLi/MSLi QSEs demonstrated a high Coulombic efficiency of 98.1%, surpassing that of liquid electrolytes (96.3%). Additionally, NCM 622||Li batteries equipped with MOFLi/MSLi QSEs exhibited promising rate performance and could operate stably for over 200 cycles at 1 C. These results highlight the potential of Janus MOFLi/MSLi QSEs as promising candidates for next-generation LMBs.

Key words: Metal-organic frameworks, Mesoporous silicas, Quasi-solid electrolytes, Janus structure, Lithium-metal battery

Zerui Chen, Wei Zhao, Qian Liu, Yifei Xu, Qinghe Wang, Jinmin Lin, Hao Bin Wu. Janus Quasi-Solid Electrolyte Membranes with Asymmetric Porous Structure for High-Performance Lithium-Metal Batteries[J]. Nano-Micro Letters, 2024, 16(1): 114-.

Zerui Chen, Wei Zhao, Qian Liu, Yifei Xu, Qinghe Wang, Jinmin Lin, Hao Bin Wu. [J]. Nano-Micro Letters, 2024, 16(1): 114-.

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URL: https://www.qk.sjtu.edu.cn/nml/EN/10.1007/s40820-024-01325-4

https://www.qk.sjtu.edu.cn/nml/EN/Y2024/V16/I1/114

Figures/Tables 5

Scheme 1 Schematic illustration of the Janus MSLi/MOFLi QSEs with an asymmetric porous structure

Fig. 1 Structure characterization and electrochemical properties of MOF and MS particles. SEM image of a MOF particles and b MS particles. c PXRD patterns of the as-synthesized MOF and MS particles. d Pore size and pore volume of MOF and MS. e Corresponding Arrhenius plots of the ionic conductivity of LE in PE membrane (LE@PE, MOFLi QSEs, MSLi QSEs and MOFLi/MSLi QSEs. f Ionic conductivity corresponding to Li⁺ and TFSI⁻ of different samples based on EIS plots and t₊ measurement. g-i SEM image and corresponding energy dispersive spectrometry (EDS) mapping of Janus MOF/MS membrane

Fig. 2 Molecular dynamic (MD simulations of different electrolytes. The final snap of the models and the distribution of Li⁺ during the whole simulation procedure of a MOFLi, b MSLi, and c LEs. Radial distribution function (RDF) and Raman spectra of d, g MOFLi, e, h MSLi and f, i LEs

Fig. 3 Finite element method (FEM) simulations of different types of electrolytes. Ion flux distribution when employing a LEs in PE membrane, b MSLi QSEs and c MOFLi QSEs. Simulation of the deposition of Li⁺ at a local current density of d 5 mA cm⁻², e 2 mA cm⁻², and f 1 mA cm⁻². g-i The morphology of the deposited Li under a current density of 0.5 mA cm⁻² and a capacity of 5 mAh cm.⁻²

Fig. 4 Half cells and full batteries performance. a Average CE of Li||Cu cells using PE membrane and MOFLi/MSLi QSEs at a current density of 0.5 mA cm⁻². The morphology of the deposited Li with a depositing capacity of 2 mAh cm⁻² on Cu when using b PE membrane and c MOFLi/MSLi QSEs. The inset images were the optical picture of the deposited Li. d Cycle performance of Li||thin Li symmetric cells at a current density of 0.5 mA cm⁻². e-f Rate performance of NCM 622|MOFLi/MSLi|Li batteries and the corresponding voltage profile. g Cycling performance of NCM 622||Li batteries at 1 C. h Cycling performance of pouch cell with high mass loading cathode. The inset was the safety illustration of pouch cell with MOF/MS electrolyte under abuse use

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