中国物理B ›› 2025, Vol. 34 ›› Issue (6): 66103-066103.doi: 10.1088/1674-1056/adc671

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Deciphering the capacity degradation mechanism in lithium manganese oxide batteries

Lin Wang(王琳)1,3, Shijie Li(李世杰)2,†, Na Li(李娜)2, and Wei-Li Song(宋维力)1,‡   

  1. 1 Institute of Advanced Structure Technology, Beijing Institute of Technology, Beijing 100081, China;
    2 State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing 100083, China;
    3 Tianjin Lishen Battery Joint-Stock Co., Ltd., Tianjin 300384, China
  • 收稿日期:2024-09-05 修回日期:2025-03-25 接受日期:2025-03-28 出版日期:2025-05-16 发布日期:2025-06-16
  • 通讯作者: Shijie Li, Wei-Li Song E-mail:sli@ustb.edu.cn;weilis@bit.edu.cn
  • 基金资助:
    Project supported by the National Natural Science Foundation of China (Grant Nos. 52074036 and 52404313) and the Beijing Institute of Technology Teli Young Fellow Program.

Deciphering the capacity degradation mechanism in lithium manganese oxide batteries

Lin Wang(王琳)1,3, Shijie Li(李世杰)2,†, Na Li(李娜)2, and Wei-Li Song(宋维力)1,‡   

  1. 1 Institute of Advanced Structure Technology, Beijing Institute of Technology, Beijing 100081, China;
    2 State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing 100083, China;
    3 Tianjin Lishen Battery Joint-Stock Co., Ltd., Tianjin 300384, China
  • Received:2024-09-05 Revised:2025-03-25 Accepted:2025-03-28 Online:2025-05-16 Published:2025-06-16
  • Contact: Shijie Li, Wei-Li Song E-mail:sli@ustb.edu.cn;weilis@bit.edu.cn
  • Supported by:
    Project supported by the National Natural Science Foundation of China (Grant Nos. 52074036 and 52404313) and the Beijing Institute of Technology Teli Young Fellow Program.

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摘要： Spinel lithium manganese oxide (LiMn$_{2}$O$_{4}$, LMO) emerges as a promising cathode material for future stationary energy storage applications due to its high voltage, safety, cost-effectiveness, and electrochemical performance. However, LMO suffers from rapid capacity degradation caused by the Jahn-Teller effect, Mn dissolution and side reactions. The mechanism remains unclear and even contradictory across various studies, impeding the advancement of high-performance LMO and its widespread utilization. In this study, 14 Ah commercial-level LMO batteries were manufactured and assessed. The mechanism of capacity attenuation in cycle-aged cells at room temperature (RT, 25 $^\circ$C) and high temperature (HT, 55 $^\circ$C) storage cells was systematically investigated through the application of electrochemical quantitative methods. The results indicate specific capacity losses of approximately 6.26% and 2.55% for the cathodes in RT cycle-aged cells and HT storage cells, respectively, in comparison to fresh cells. These values are lower than the 12.54% and 6.99% capacity losses observed in RT cycle-aged cells and HT storage cells. While RT cycle-aging and HT storage conditions do not lead to irreversible capacity loss on the anode side. The results suggest that the primary causes of irreversible capacity degradation are not located on the cathode or anode. Nevertheless, significant polarization arises from the continuous growth of the solid electrolyte interphase (SEI), believed to be catalyzed by Mn deposited on the anode, which is considered harmful. This study elucidates that inhibiting the dissolution of Mn from the cathode, facilitating its transport in the electrolyte, promoting its deposition on the anode, and catalyzing the decomposition of the electrolyte are crucial factors for enhancing the performance of LMO batteries.

关键词: cathode materials, commercial-level lithium manganese oxide (LMO) batteries, Mn deposition

Abstract: Spinel lithium manganese oxide (LiMn$_{2}$O$_{4}$, LMO) emerges as a promising cathode material for future stationary energy storage applications due to its high voltage, safety, cost-effectiveness, and electrochemical performance. However, LMO suffers from rapid capacity degradation caused by the Jahn-Teller effect, Mn dissolution and side reactions. The mechanism remains unclear and even contradictory across various studies, impeding the advancement of high-performance LMO and its widespread utilization. In this study, 14 Ah commercial-level LMO batteries were manufactured and assessed. The mechanism of capacity attenuation in cycle-aged cells at room temperature (RT, 25 $^\circ$C) and high temperature (HT, 55 $^\circ$C) storage cells was systematically investigated through the application of electrochemical quantitative methods. The results indicate specific capacity losses of approximately 6.26% and 2.55% for the cathodes in RT cycle-aged cells and HT storage cells, respectively, in comparison to fresh cells. These values are lower than the 12.54% and 6.99% capacity losses observed in RT cycle-aged cells and HT storage cells. While RT cycle-aging and HT storage conditions do not lead to irreversible capacity loss on the anode side. The results suggest that the primary causes of irreversible capacity degradation are not located on the cathode or anode. Nevertheless, significant polarization arises from the continuous growth of the solid electrolyte interphase (SEI), believed to be catalyzed by Mn deposited on the anode, which is considered harmful. This study elucidates that inhibiting the dissolution of Mn from the cathode, facilitating its transport in the electrolyte, promoting its deposition on the anode, and catalyzing the decomposition of the electrolyte are crucial factors for enhancing the performance of LMO batteries.

Key words: cathode materials, commercial-level lithium manganese oxide (LMO) batteries, Mn deposition

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)