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Highly crystalline vinylene-linked covalent organic frameworks enhanced solid polycarbonate electrolyte for dendrite-free solid lithium metal batteries

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Abstract

The development of solid-state electrolytes (SSEs) with high ionic conductivity, outstanding electrochemical window, and promising mechanical strength is a key factor in realizing the commercialization of high energy density solid-state lithium metal batteries (LMBs). Covalent organic frameworks (COFs) are a functional crystalline material with highly customizable molecular networks and one-dimensional channel structures, thus showing great potential applications in SSEs. Herein, we design flexible COF-poly(vinyl ethylene carbonate) (PVEC) (abbreviated as COF-PVEC) composite electrolyte films with excellent ionic conductivity and high mechanical strength, enabling dendrite-free and long-term running solid-state LMBs. Owing to the lithium-philic triazine and carbon-carbon double bonds groups in the COF skeleton, the obtained flexible COF-PVEC shows high ionic conductivity up to 1.11 × 10−4 S·cm−1 at 40 °C, and enlarged electrochemical window up to 4.6 V (vs. Li+/Li) compared with pure PVEC electrolyte. At the same time, the lithium dendrites are efficiently inhibited after discharge-charging cycles, due to the improved Young’s modulus (150 MPa) and ordered channels of COF. Using the various features of COF-PVEC, we assembled a solid-state full battery with LiFePO4 cathode, which showed superior rate capacity (151.8, 146.2, 139.2, 128.1, 113.7, and 100.8 mAh·g−1 at 0.1, 0.2, 0.5, 1, 1.5, and 2 C, respectively) and excellent long-term cycling stability (over 400 cycles at 1 C). We believe that the COF-based composite electrolyte can become one of the most promising high-performance SSEs for solid-state LMBs.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 22022510, 51873039, and 21374106), and the National Key Research and Development Program of China (No. 2018YFD0400700).

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Author notes

  1. Kaige Zhang and Chaoqun Niu contributed equally to this work.

Authors and Affiliations

  1. School of Materials and Engineering, Zhengzhou University, Zhengzhou, 450001, China

    Kaige Zhang & Li Zhang

  2. School of Engineering, Westlake University, Hangzhou, 310024, China

    Kaige Zhang, Chaoqun Niu & Yuxi Xu

  3. School of Materials Science and Engineering, Shanghai University, Shanghai, 201800, China

    Chengbing Yu

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  1. Kaige Zhang
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  2. Chaoqun Niu
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  3. Chengbing Yu
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  4. Li Zhang
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Correspondence to Chengbing Yu, Li Zhang or Yuxi Xu.

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Highly crystalline vinylene-linked covalent organic frameworks enhanced solid polycarbonate electrolyte for dendrite-free solid lithium metal batteries

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Zhang, K., Niu, C., Yu, C. et al. Highly crystalline vinylene-linked covalent organic frameworks enhanced solid polycarbonate electrolyte for dendrite-free solid lithium metal batteries. Nano Res. 15, 8083–8090 (2022). https://doi.org/10.1007/s12274-022-4480-6

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