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Research Article

A highly ionic transference number eutectogel hybrid electrolytes based on spontaneous coupling inhibitor for solid-state lithium metal batteries

Linnan Bi1,2, Xiongbang Wei1,2, Yuhong Qiu1,2, Yaochen Song1,2, Xin Long1,2, Zhi Chen1,2, Sizhe Wang2,3( ), Jiaxuan Liao1,2( )
School of Materials and Energy, University of Electronic Science and Technology of China, Chengdu 611731, China
The Yangtze Delta Region Institute (Quzhou), University of Electronic Science and Technology of China, Quzhou 324000, China
School of Materials Science and Engineering, Shaanxi Key Laboratory of Green Preparation and Functionalization for Inorganic Materials, Shaanxi University of Science & Technology, Xi’an 710021, China
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Graphical Abstract

Based on the garnet ceramic doping, a deep understanding of the Li+ conduction mechanism and the interaction between Li6.4La3Zr1.4Ta0.6O12 (LLZTO) and poly(vinylidene fluoride-chlorotrifluoroethylene) (P(VDF-CTFE)) polymer in the composite solid electrolyte, a high lithium ion migration number and lithiophilic solid electrolyte material were designed.

Abstract

Polymer-based solid electrolytes have been extensively studied for solid-state lithium metal batteries to achieve high energy density and reliable security. But, its practical application is severely limited by low ionic conductivity and slow Li+ transference. Herein, based on the “binary electrolytes” of poly(vinylidene fluoride-chlorotrifluoroethylene) (P(VDF-CTFE)) and lithium salt (LiTFSI), a kind of eutectogel hybrid electrolytes (EHEs) with high Li+ transference number was developed via tuning the spontaneous coupling of charge and vacated space generated by Li-cation diffusion utilizing the Li6.4La3Zr1.4Ta0.6O12 (LLZTO) dopant. LLZTO doping promotes the dissociation of lithium salt, increases Li+ carrier density, and boosts ion jumping and the coordination/decoupling reactions of Li+. As a result, the optimized EHEs-10% possess a high Li-transference number of 0.86 and a high Li+ conductivity of 3.2 × 10–4 S·cm–1 at room temperature. Moreover, the prepared EHEs-10% composite solid electrolyte presents excellent lithiumphilic and compatibility, and can be tested stably for 1,200 h at 0.3 mA·cm–2 with assembled lithium symmetric batteries. Likewise, the EHEs-10% films match well with high-loading LiFePO4 and LiCoO2 cathodes (> 10 mg·cm–2) and exhibit remarkable interface stability. Particularly, the LiFePO4//EHEs-10%//Li and LiCoO2//EHEs-10%//Li cells deliver high rate performance of 118 mAh·g–1 at 1 C and 93.7 mAh·g–1 at 2 C with coulombic efficiency of 99.3% and 98.1%, respectively. This work provides an in-depth understanding and new insights into our design for polymer electrolytes with fast Li+ diffusion.

Keywords

poly(vinylidene fluoride-chlorotrifluoroethylene) (P(VDF-CTFE))Li6.4La3Zr1.4Ta0.6O12 (LLZTO)ionic transference numberseutectic solvent composite electrolytessolid state lithium metal battery

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Nano Research
Volume 16 Issue 1,
January 2023
Pages 1717-1725
DOI: 10.1007/s12274-022-4759-7
Cite this article:
Bi L, Wei X, Qiu Y, et al. A highly ionic transference number eutectogel hybrid electrolytes based on spontaneous coupling inhibitor for solid-state lithium metal batteries. Nano Research, 2023, 16(1): 1717-1725. https://doi.org/10.1007/s12274-022-4759-7
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Received: 21 April 2022
Revised: 07 June 2022
Accepted: 11 July 2022
Published: 04 August 2022
© Tsinghua University Press 2022
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