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Modulating composite polymer electrolyte by lithium closo-borohydride achieves highly stable solid-state battery at 25°C

闭式硼氢化锂基聚合物复合电解质实现25°C下固态 锂电池的高稳定循环

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Abstract

Rational composite design is highly important for the development of high-performance composite polymer electrolytes (CPEs) for solid-state lithium (Li) metal batteries. In this work, Li closo-borohydride, Li2B12H12, is introduced to poly(vinylidene fluoride)-Li-bis-(trifluoromethanesulfonyl) imide (PVDF-LiTFSI) with a bound N-methyl pyrrolidone plasticizer to form a novel CPE. This CPE shows superb Li+ conduction properties, as evidenced by its conductivity of 1.43 × 10−4 S cm−1 and Li+ transference number of 0.34 at 25°C. Density functional theory calculations reveal that Li2B12H12, which features electron-deficient multicenter bonds, can facilitate the dissociation of LiTFSI and enhance the immobilization of TFSI to improve the Li+ conduction properties of the CPE. Moreover, the fabricated CPE exhibits excellent electrochemical, thermal, and mechanical stability. The addition of Li2B12H12 can help form a protective layer at the anode/electrolyte interface, thereby preventing unwanted reactions. The above benefits of the fabricated CPE contribute to the high compatibility of the electrode. Symmetric Li cells can be stably cycled at 0.2 mA cm−2 for over 1200 h, and Li∥LiFePO4 cells can deliver a reversible specific capacity of 140 mA h g−1 after 200 cycles at 1 C at 25°C with a capacity retention of 98%.

摘要

合理的成分设计是固态锂电池用高性能复合电解质开发的重要 策略. 本文将闭式硼氢化锂Li2B12H12引入到含非游离态N-甲基吡咯烷 酮塑化剂的聚偏二氟乙烯-双三氟甲基磺酰亚胺锂(PVDF-LiTFSI)中, 制成新型复合聚合物电解质. 该电解质在25°C时具有1.43 × 10−4 S cm−1 的电导率和0.34的锂离子迁移数, 显示出优异的导锂性能. 密度泛函理 论计算表明, 具有缺电子多中心键的Li2B12H12可以促进LiTFSI的解离和 TFSI−的固定, 是锂离子导电性能改善的主要原因. 此外, 该电解质还具 有出色的电化学、热力学和机械稳定性. Li2B12H12的添加有助于在负 极/电解质界面形成保护性中间相, 阻止副反应的进一步发生. 由于上 述优势, 该电解质具有很高的电极兼容性, 如锂对称电池可以在 0.2mAcm−2下稳定循环1200多个小时, Li∥LiFePO4电池在1 C和25°C的 条件下经200个循环仍可以保持140 mA h g−1的可逆比容量, 容量保持 率为98%.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (51971146 and 51971147), the Major Program for the Scientific Research Innovation Plan of Shanghai Education Commission (2019-01-07-00-07-E00015), Shanghai Outstanding Academic Leaders Plan, Guangxi Key Laboratory of Information Materials (Guilin University of Electronic Technology, 201017-K), Shanghai Rising-Star Program (20QA1407100), and the General Program of Natural Science Foundation of Shanghai (20ZR1438400).

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Authors and Affiliations

  1. School of Materials Science and Engineering, University of Shanghai for Science and Technology, Shanghai, 200093, China

    Kepan Bao  (保克畔), Yuepeng Pang  (庞越鹏), Junhe Yang  (杨俊和) & Shiyou Zheng  (郑时有)

  2. Department of Materials Science, Fudan University, Shanghai, 200433, China

    Dalin Sun  (孙大林) & Fang Fang  (方方)

Authors
  1. Kepan Bao  (保克畔)
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  2. Yuepeng Pang  (庞越鹏)
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  4. Dalin Sun  (孙大林)
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  5. Fang Fang  (方方)
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  6. Shiyou Zheng  (郑时有)
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Contributions

Pang Y and Zheng S proposed the idea; Bao K conducted the experiments; Bao K and Fang F performed the data analysis; Bao K and Pang Y wrote the paper with support from Yang J and Zheng S; Pang Y and Sun D contributed to the theoretical analysis. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Yuepeng Pang  (庞越鹏), Fang Fang  (方方) or Shiyou Zheng  (郑时有).

Additional information

Kepan Bao received his BS degree from the School of Energy and Environmental Engineering at the University of Science and Technology Beijing in 2018. Currently, he is an MS student at the School of Materials Science and Engineering, University of Shanghai for Science and Technology. His research focuses on composite solid electrolytes for solid-state batteries.

Yuepeng Pang received his PhD degree from the Department of Materials Science and Engineering at Zhejiang University in 2014. He is currently an associate professor at the School of Materials Science and Engineering, University of Shanghai for Science and Technology. His current research mainly focuses on hydride materials for solid-state batteries.

Fang Fang received his PhD degree from the Department of Materials Science at Fudan University in 2009. He is currently a professor at the Department of Materials Science, Fudan University. His current research interests focus on high-performance hydrogen storage materials and key materials for solid-state batteries.

Shiyou Zheng received his BS, MS, and PhD degrees from Sichuan University, Zhejiang University, and Fudan University, respectively. He became a visiting researcher at the National Institute of Standards and Technology and the University of Maryland and is currently a professor at the University of Shanghai for Science and Technology. His research interests include new energy materials for batteries, supercapacitors, and hydrogen storage. He was selected as a “Young and Middle-aged Experts with Outstanding Experts” by the New Century Talents Project in 2019.

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The authors declare that they have no conflict of interest.

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Modulating composite polymer electrolyte by lithium closo-borohydride achieves highly stable solid-state battery at 25°C

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Bao, K., Pang, Y., Yang, J. et al. Modulating composite polymer electrolyte by lithium closo-borohydride achieves highly stable solid-state battery at 25°C. Sci. China Mater. 65, 95–104 (2022). https://doi.org/10.1007/s40843-021-1740-7

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