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Entropy-increased LiMn2O4-based positive electrodes for fast-charging lithium metal batteries

Author

Listed:
  • Weihao Zeng

    (Wuhan University of Technology)

  • Fanjie Xia

    (Wuhan University of Technology)

  • Juan Wang

    (Wuhan University of Technology)

  • Jinlong Yang

    (Shenzhen University)

  • Haoyang Peng

    (Wuhan University of Technology)

  • Wei Shu

    (Wuhan University of Technology)

  • Quan Li

    (Wuhan University of Technology)

  • Hong Wang

    (Wuhan University of Technology)

  • Guan Wang

    (Wuhan University of Technology)

  • Shichun Mu

    (Wuhan University of Technology)

  • Jinsong Wu

    (Wuhan University of Technology)

Abstract

Fast-charging, non-aqueous lithium-based batteries are desired for practical applications. In this regard, LiMn2O4 is considered an appealing positive electrode active material because of its favourable ionic diffusivity due to the presence of three-dimensional Li-ion diffusion channels. However, LiMn2O4 exhibits inadequate rate capabilities and rapid structural degradation at high currents. To circumvent these issues, here we introduce quintuple low-valence cations to increase the entropy of LiMn2O4. As a result, the entropy-increased LiMn2O4-based material, i.e., LiMn1.9Cu0.02Mg0.02Fe0.02Zn0.02Ni0.02O4, when tested in non-aqueous lithium metal coin cell configuration, enable 1000 cell cycles at 1.48 A g−1 (corresponding to a cell charging time of 4 minutes) and 25°C with a discharge capacity retention of about 80%. We demonstrate that the increased entropy in LiMn2O4 leads to an increase in the disordering of dopant cations and a contracted local structure, where the enlarged LiO4 space and enhanced Mn-O covalency improve the Li-ion transport and stabilize the diffusion channels. We also prove that stress caused by cycling at a high cell state of charge is relieved through elastic deformation via a solid-solution transition, thus avoiding structural degradation upon prolonged cycling.

Suggested Citation

  • Weihao Zeng & Fanjie Xia & Juan Wang & Jinlong Yang & Haoyang Peng & Wei Shu & Quan Li & Hong Wang & Guan Wang & Shichun Mu & Jinsong Wu, 2024. "Entropy-increased LiMn2O4-based positive electrodes for fast-charging lithium metal batteries," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
  • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-51168-1
    DOI: 10.1038/s41467-024-51168-1
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    1. Rui Zhang & Chunyang Wang & Peichao Zou & Ruoqian Lin & Lu Ma & Liang Yin & Tianyi Li & Wenqian Xu & Hao Jia & Qiuyan Li & Sami Sainio & Kim Kisslinger & Stephen E. Trask & Steven N. Ehrlich & Yang Ya, 2022. "Compositionally complex doping for zero-strain zero-cobalt layered cathodes," Nature, Nature, vol. 610(7930), pages 67-73, October.
    2. Yayuan Liu & Yangying Zhu & Yi Cui, 2019. "Challenges and opportunities towards fast-charging battery materials," Nature Energy, Nature, vol. 4(7), pages 540-550, July.
    3. Tongchao Liu & Alvin Dai & Jun Lu & Yifei Yuan & Yinguo Xiao & Lei Yu & Matthew Li & Jihyeon Gim & Lu Ma & Jiajie Liu & Chun Zhan & Luxi Li & Jiaxin Zheng & Yang Ren & Tianpin Wu & Reza Shahbazian-Yas, 2019. "Correlation between manganese dissolution and dynamic phase stability in spinel-based lithium-ion battery," Nature Communications, Nature, vol. 10(1), pages 1-11, December.
    4. Rui Wang & Xin Chen & Zhongyuan Huang & Jinlong Yang & Fusheng Liu & Mihai Chu & Tongchao Liu & Chaoqi Wang & Weiming Zhu & Shuankui Li & Shunning Li & Jiaxin Zheng & Jie Chen & Lunhua He & Lei Jin & , 2021. "Twin boundary defect engineering improves lithium-ion diffusion for fast-charging spinel cathode materials," Nature Communications, Nature, vol. 12(1), pages 1-10, December.
    5. Michael M. Thackeray & Khalil Amine, 2021. "LiMn2O4 spinel and substituted cathodes," Nature Energy, Nature, vol. 6(5), pages 566-566, May.
    6. Zhen-Feng Huang & Shibo Xi & Jiajia Song & Shuo Dou & Xiaogang Li & Yonghua Du & Caozheng Diao & Zhichuan J. Xu & Xin Wang, 2021. "Tuning of lattice oxygen reactivity and scaling relation to construct better oxygen evolution electrocatalyst," Nature Communications, Nature, vol. 12(1), pages 1-9, December.
    7. Haodong Liu & Zhuoying Zhu & Qizhang Yan & Sicen Yu & Xin He & Yan Chen & Rui Zhang & Lu Ma & Tongchao Liu & Matthew Li & Ruoqian Lin & Yiming Chen & Yejing Li & Xing Xing & Yoonjung Choi & Lucy Gao &, 2020. "A disordered rock salt anode for fast-charging lithium-ion batteries," Nature, Nature, vol. 585(7823), pages 63-67, September.
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