中国物理B ›› 2023, Vol. 32 ›› Issue (5): 56101-056101.doi: 10.1088/1674-1056/acb919

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Zr-doping stabilizes spinel LiMn2O4 as a low cost long cycle life cathode for lithium ion batteries

Xiang-Gong Zhang(张祥功)1, Wei Wu(吴伟)2, Si-Si Zhou(周思思)1,†, Fei Huang(黄飞)2, Shi-Hao Xu(许诗浩)2, Liang Yin(尹良)2,3,‡, Wei Yang(杨伟)2,§, and Hong Li(李泓)2,3   

  1. 1 Wuhan Institute of Marine Electric Propulsion, Wuhan 430064, China;
    2 Tianmu Lake Institute of Advanced Energy Storage Technologies Co., Ltd., Liyang 213300, China;
    3 Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
  • 收稿日期:2022-12-30 修回日期:2023-01-30 接受日期:2023-02-06 出版日期:2023-04-21 发布日期:2023-05-05
  • 通讯作者: Si-Si Zhou, Liang Yin, Wei Yang E-mail:zhousisi18@126.com;lyin@iphy.ac.cn;billwyang@163.com
  • 基金资助:
    Project supported by research on high power flexible battery in all sea depth (Grant No. 2020-XXXX-XX-246-00).

Zr-doping stabilizes spinel LiMn2O4 as a low cost long cycle life cathode for lithium ion batteries

Xiang-Gong Zhang(张祥功)1, Wei Wu(吴伟)2, Si-Si Zhou(周思思)1,†, Fei Huang(黄飞)2, Shi-Hao Xu(许诗浩)2, Liang Yin(尹良)2,3,‡, Wei Yang(杨伟)2,§, and Hong Li(李泓)2,3   

  1. 1 Wuhan Institute of Marine Electric Propulsion, Wuhan 430064, China;
    2 Tianmu Lake Institute of Advanced Energy Storage Technologies Co., Ltd., Liyang 213300, China;
    3 Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
  • Received:2022-12-30 Revised:2023-01-30 Accepted:2023-02-06 Online:2023-04-21 Published:2023-05-05
  • Contact: Si-Si Zhou, Liang Yin, Wei Yang E-mail:zhousisi18@126.com;lyin@iphy.ac.cn;billwyang@163.com
  • Supported by:
    Project supported by research on high power flexible battery in all sea depth (Grant No. 2020-XXXX-XX-246-00).

摘要: The present commercial spinel LiMn$_{2}$O$_{4}$ delivers only 90 mAh/g-115 mAh/g, far lower than the theoretical specific capacity. It degrades fast caused by the Jahn-Teller effect, Mn dissolution and related side reactions that consume Li inventory. In this work, Zr doping is employed to improve the structural stability and electrochemical performance of spinel LiMn$_{2}$O$_{4}$. Li$_{1.06}$Mn$_{1.94-x}$Zr$_{x}$O$_{4}$ ($x = 0$, 0.01, 0.02, 0.04) have been successfully synthesized by a simple solid-state reaction method and evaluated as cathode for lithium ion batteries (LIB). Li$_{1.06}$Mn$_{1.92}$Zr$_{0.02}$O$_{4}$ is superior cathode material with a high capacity of 122 mAh/g at 1-C rate; long cycle stability, 98.39% retention after 100 cycles at 1-C rate, excellent high rate performance 107.1 mAh/g at 10-C rate, and high temperature performance 97.39% retention after 60 cycles. These are thought to be related to Zr doping effectively stabilizing the spinel LiMn$_{2}$O$_{4}$, by forming stronger Zr-O bonds in the octahedron, suppressing the Jahn-Teller effect, thus improving electrochemical performance.

关键词: lithium battery, cathode, LiMn2O4, cycle life

Abstract: The present commercial spinel LiMn$_{2}$O$_{4}$ delivers only 90 mAh/g-115 mAh/g, far lower than the theoretical specific capacity. It degrades fast caused by the Jahn-Teller effect, Mn dissolution and related side reactions that consume Li inventory. In this work, Zr doping is employed to improve the structural stability and electrochemical performance of spinel LiMn$_{2}$O$_{4}$. Li$_{1.06}$Mn$_{1.94-x}$Zr$_{x}$O$_{4}$ ($x = 0$, 0.01, 0.02, 0.04) have been successfully synthesized by a simple solid-state reaction method and evaluated as cathode for lithium ion batteries (LIB). Li$_{1.06}$Mn$_{1.92}$Zr$_{0.02}$O$_{4}$ is superior cathode material with a high capacity of 122 mAh/g at 1-C rate; long cycle stability, 98.39% retention after 100 cycles at 1-C rate, excellent high rate performance 107.1 mAh/g at 10-C rate, and high temperature performance 97.39% retention after 60 cycles. These are thought to be related to Zr doping effectively stabilizing the spinel LiMn$_{2}$O$_{4}$, by forming stronger Zr-O bonds in the octahedron, suppressing the Jahn-Teller effect, thus improving electrochemical performance.

Key words: lithium battery, cathode, LiMn2O4, cycle life

中图分类号:  (Structure of bulk crystals)

  • 61.50.-f
61.66.Fn (Inorganic compounds) 82.47.Aa (Lithium-ion batteries) 82.45.Fk (Electrodes)