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Fluorinated polycarbonate-based solid electrolyte plasticized using succinonitrile for 4.5 V lithium metal batteries

丁二腈增塑氟化聚碳酸酯基固态电解质用于4.5 V高压锂金属电池

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Abstract

Solid polymer electrolytes (SPEs) are a great promising choice for energy storage owing to their enhanced safety compared to liquid electrolytes. However, challenges such as the decomposition under the high voltage, low room-temperature ionic conductivity and poor room-temperature cycling performance have hindered the practical application of SPEs. In this study, SNSPE-40, a novel fluorinated polycarbonate-based electrolyte was prepared by the in-situ polymerization of 2,2,2-trifluoroethyl acrylate and 4-vinyl-1,3-dioxolan-2-one; succinonitrile was added to the electrolyte as a plasticizer. Notably, SNSPE-40 exhibits a high ionic conductivity of 1.33 mS cm−1 and wide electrochemical window of 5.4 V (vs. Li/Li+) at 25°C. Due to the LiF-rich solid electrolyte interphase (SEI), the Li∣SNSPE-40∣Li symmetric cell remained stable for 2000 h at 0.1 mA cm−2. Finally, the Li∣SNSPE-40∣LiNi0.9Co0.05Mn0.05O2 cell, with a cut-off voltage of 4.5 V, displayed good cycling stability at 0.5 C (1 C = 220 mA g−1) and 26°C (57.4% capacity retention after 300 cycles). The Li∣SNSPE-40∣LiCoO2 cell displayed a long-cycling ability with a capacity retention of 54.9% for 250 cycles at 1 C (1 C = 200 mA g−1) under the same voltage and temperature conditions. This new solid polymer electrolyte shows great potential for the application in high-voltage solid-state lithium metal batteries.

摘要

与液态电解质相比, 聚合物电解质(SPEs)具有更高的安全性, 在储能领域具有广阔的应用前景. 但是其高压下易分解、室温离子电导率低、室温循环性能差等问题阻碍了SPEs的应用. 本研究以丙烯酸三氟乙酯和碳酸乙烯亚乙酯为原料, 丁二腈为增塑剂, 原位聚合制备了氟化聚碳酸酯基固态电解质SNSPE-40. SNSPE-40在25°C条件下离子电导率高达1.33 mS cm−1, 电化学窗口达到5.4 V. 得益于富含氟化锂的SEI层的形成, Li∣SNSPE-40∣Li电池以0.1 mA cm−2电流密度稳定循环了2000 h. 在4.5 V截止电压和室温条件下, Li∣SNSPE-40∣LiNi0.9Co0.05Mn0.05O2电池实现了0.5C(1 C=220 mA g−1)倍率300圈的稳定循环(57.4 % 容量保持率). Li∣SNSPE - 40∣LiCoO2 电池实现了1C(1C=200 mA g−1)倍率250圈的长循环(54.9%容量保持率). 这种新型固态电解质在高压固态锂金属电池中表现出巨大应用潜力.

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Acknowledgements

This work was financially supported by the National Key R&D Program of China (No. 2022YFB3805702), the National Natural Science Foundation of China (No. 52130303 and 52327802), and Jiangsu Key Laboratory of Electrochemical Energy Storage Technologies (No. EEST20214).

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Authors and Affiliations

  1. School of Materials Science and Engineering, Tianjin University, Tianjin, 300072, China

    Jinxu Sun  (孙锦旭), Yong Wang  (王勇), Yu Li  (李瑀) & Wei Feng  (封伟)

  2. Institute of Advanced Technology and Equipment, Beijing University of Chemical Technology, Beijing, 100029, China

    Yu Li  (李瑀)

  3. Key Laboratory of Advanced Ceramics and Machining Technology Ministry of Education, Tianjin, 300072, China

    Wei Feng  (封伟)

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  1. Jinxu Sun  (孙锦旭)
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  2. Yong Wang  (王勇)
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  3. Yu Li  (李瑀)
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  4. Wei Feng  (封伟)
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Contributions

Author contributions Sun J designed the experiments, conducted the characterization and wrote the original draft; Wang Y helped with sample fabrication and processing; Li Y performed data analysis and writing-reviewing; Feng W conceived and supervised the project. All authors participated in the discussion of the manuscript.

Corresponding authors

Correspondence to Yu Li  (李瑀) or Wei Feng  (封伟).

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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.

Jinxu Sun is now pursuing MS degree at the School of Materials Science and Engineering, Tianjin University. His research focuses on energy materials in lithium secondary batteries.

Yong Wang is currently pursuing a PhD degree at the School of Materials Science and Engineering, Tianjin University. His research focuses on solid polymer electrolytes for lithium metal batteries.

Yu Li is a professor at the Institute of Advanced Technology and Equipment, Beijing University of Chemical Technology. He obtained his PhD degree from Tianjin University in 2011 and had worked as a postdoctoral research fellow at Tianjin University from 2011 to 2014. His current research is focused on conductive polymers and nano energy storage materials.

Wei Feng is a professor at the School of Materials Science and Engineering, Tianjin University. He obtained his PhD degree from the Xi’an Jiaotong University (China) in 2000. Then, he worked at Osaka University and Tsinghua University as a JSPS fellow and postdoctoral researcher, respectively. In 2004, he became a full professor at Tianjin University. His research interests include photoresponsive organic molecules and their derivatives, thermal conductive and high-strength carbon-based composites, and new fluorinated carbon materials and functional polymers.

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Supporting Information: Fluorinated polycarbonate-based solid electrolyte plasticized using succinonitrile for 4.5 V lithium metal batteries

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Sun, J., Wang, Y., Li, Y. et al. Fluorinated polycarbonate-based solid electrolyte plasticized using succinonitrile for 4.5 V lithium metal batteries. Sci. China Mater. 67, 1393–1402 (2024). https://doi.org/10.1007/s40843-024-2904-2

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