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A tough, resilient, and fluorinated solid-electrolyte interphase stabilizing lithium metal in carbonate electrolytes

坚韧、弹性的氟化固体电解质界面稳定碳酸酯电解 质中的锂金属

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Abstract

The unstable interface between lithium metal anodes and carbonate-based electrolytes is a key challenge limiting the cycling lifespan of high-energy lithium metal batteries. Here, a resilient artificial solid electrolyte interphase (RASEI) was designed by regulating poly(hexafluorobutyl acrylate) (PHFBA) matrix with the benzene-containing bisphenol A ethoxylate dimethacrylate (BAED) crosslinker to address this issue. The rigid BAED molecule can finely tune the flexible PHFBA matrix, enabling superior resilience from 600% elongation to 90% compression with a high Young’s modulus of over 2 MPa. RASEI with these characteristics can accommodate large volume changes of lithium metal and ensure the intimate contact between the lithium metal and the RASEI during battery operation. Consequently, it facilitated homogeneous lithium deposition while mitigating parasitic side reactions. Thanks to the tough and resilient nature of the fluorinated RASEI, the long-term cycling of Li∣∣Li symmetric cells can be achieved for over 500 h at 1 mA cm−2 and 1 mAh cm−2. The following post-mortem of cycled Li metal reveals that Li dendrite growth is effectively inhibited. Furthermore, the NCM811 pouch cell with a high cathode loading of 20 mg cm−2 exhibits a capacity retention of over 85% after 200 cycles at 1 C.

摘要

锂金属负极和碳酸酯类电解液之间不稳定的界面是限制高比能 锂金属电池循环寿命的关键挑战. 本文使用含苯环的双酚A乙氧基化物 二甲基丙烯酸酯(BAED)交联剂调节聚(丙烯酸六氟丁酯)(PHFBA), 设 计了一种弹性人造固体电解质中间相(RASEI)来解决这个问题. 刚性 BAED分子可以对柔性PHBA基体进行调控, 实现从600%伸长率到90% 压缩率的卓越回弹性, 并具有超过2 MPa的高杨氏模量. RASEI可以适 应锂金属较大的体积变化, 并确保电池运行过程中锂金属与RASEI之 间的紧密接触, 促进均匀的锂沉积并减少副反应. 因此, 经过RASEI修 饰的Li∣∣Li对称电池可以在1 mA cm−2和1 mAh cm−2下实现超过500小 时的长期循环. 对循环后锂金属进行测试分析表明锂枝晶的生长得到 了有效的抑制. 此外, 搭配20 mg cm−2高阴极负载的NCM811软包电池 在1 C下, 经过200次循环后容量保持率超过85%.

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Acknowledgements

This work was supported by National Key R&D Program of China (2023YFB2503801), the National Natural Science Foundation of China (Grant Nos. 52302253, and 5202780089), the Key Program of the National Natural Science Foundation of China (Grant No. 52231009), the Fundamental Research Funds for the Central Universities (HUST: 2172020kfyXJJS089), Key R&D Program of Hubei Province (2023BAB028). The authors thank the Analytical and Testing Centre of HUST and the State Key Laboratory of Materials Processing and Die & Mold Technology of HUST for XRD and SEM measurements. The authors thank the Neware Technology Limited for the electrochemical testing. Thanks to eceshi (www.eceshi.com) for FTIR.

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Authors and Affiliations

  1. State Key Laboratory of Material Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan, 430074, China

    Jia Kong  (孔佳), Tianyi Hou  (侯添壹), Ting Shi  (石婷), Jianbo Li  (李剑波), Xin Deng  (邓鑫), Yunhui Huang  (黄云辉) & Henghui Xu  (许恒辉)

  2. School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan, 430074, China

    Dinggen Li  (李顶根)

Authors
  1. Jia Kong  (孔佳)
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  2. Tianyi Hou  (侯添壹)
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  3. Ting Shi  (石婷)
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  4. Jianbo Li  (李剑波)
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  5. Xin Deng  (邓鑫)
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  6. Dinggen Li  (李顶根)
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  7. Yunhui Huang  (黄云辉)
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  8. Henghui Xu  (许恒辉)
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Contributions

Author contributions Kong J and Hou T conceived the project. Kong J designed the experiments and collected all data, Deng X, Li J helped with the characterization and data analysis. Kong J wrote the paper with support from Shi T, Hou T. Li D, Xu H and Huang Y provided critical feedback and helped shape the manuscript.

Corresponding authors

Correspondence to Dinggen Li  (李顶根), Yunhui Huang  (黄云辉) or Henghui Xu  (许恒辉).

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Conflict of interest The authors declare no conflict of interest.

Additional information

Supplementary information Experimental details and supporting data are available in the online version of the paper.

Jia Kong is currently a Master degree candidate at the School of Materials Science and Engineering, Huazhong University of Science and Technology. His current research mainly focuses on lithium metal batteries.

Henghui Xu received his PhD at Huazhong University of Science and Technology (HUST) in 2015, followed by a five-year postdoctoral research at The University of Texas at Austin. He is now a Professor of materials science in HUST working on solid-state batteries.

Yunhui Huang received his BS, MS, and PhD degrees from Peking University. From 2002 to 2004, he worked as an associate professor at Fudan University. He then worked with Prof. John B. Goodenough at the University of Texas at Austin for more than three years. In 2008, he became a chair professor of materials science at Huazhong University of Science and Technology. His research group works on rechargeable batteries and electrode materials.

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Kong, J., Hou, T., Shi, T. et al. A tough, resilient, and fluorinated solid-electrolyte interphase stabilizing lithium metal in carbonate electrolytes. Sci. China Mater. 67, 1403–1411 (2024). https://doi.org/10.1007/s40843-024-2914-x

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  • DOI: https://doi.org/10.1007/s40843-024-2914-x

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