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

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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 mA·hg−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.

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Acknowledgements

This work was supported by the International Cooperation Projects of Sichuan Provincial Department of Science and Technology (No. 2021YFH0126) and Quzhou Science and Technology Bureau Project (No. 2021D006), and the Fundamental Research Funds for the Central Universities (No. A030202063008029). The China Postdoctoral Science Foundation (Nos. 2021T140433, 2020M683408) and the Natural Science Foundation of Shaanxi Province (No. 2021JQ-538). The authors would like to thank Qian Fu from shiyanjia Lab (https://www.shiyanjia.com) for support of XPS analysis.

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Authors and Affiliations

  1. School of Materials and Energy, University of Electronic Science and Technology of China, Chengdu, 611731, China

    Linnan Bi, Xiongbang Wei, Yuhong Qiu, Yaochen Song, Xin Long, Zhi Chen & Jiaxuan Liao

  2. The Yangtze Delta Region Institute (Quzhou), University of Electronic Science and Technology of China, Quzhou, 324000, China

    Linnan Bi, Xiongbang Wei, Yuhong Qiu, Yaochen Song, Xin Long, Zhi Chen, Sizhe Wang & Jiaxuan Liao

  3. 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

    Sizhe Wang

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  1. Linnan Bi
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Correspondence to Sizhe Wang or Jiaxuan Liao.

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

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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 Res. 16, 1717–1725 (2023). https://doi.org/10.1007/s12274-022-4759-7

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