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Highly reversible oxygen redox in layered compounds enabled by surface polyanions

Author

Listed:
  • Qing Chen

    (Harbin Institute of Technology
    The University of Texas at Austin)

  • Yi Pei

    (Harbin Institute of Technology)

  • Houwen Chen

    (Chongqing University)

  • Yan Song

    (Harbin Institute of Technology (Weihai))

  • Liang Zhen

    (Harbin Institute of Technology
    Harbin Institute of Technology (Shenzhen))

  • Cheng-Yan Xu

    (Harbin Institute of Technology
    Harbin Institute of Technology (Shenzhen))

  • Penghao Xiao

    (The University of Texas at Austin
    Lawrence Livermore National Laboratory)

  • Graeme Henkelman

    (The University of Texas at Austin)

Abstract

Oxygen-anion redox in lithium-rich layered oxides can boost the capacity of lithium-ion battery cathodes. However, the over-oxidation of oxygen at highly charged states aggravates irreversible structure changes and deteriorates cycle performance. Here, we investigate the mechanism of surface degradation caused by oxygen oxidation and the kinetics of surface reconstruction. Considering Li2MnO3, we show through density functional theory calculations that a high energy orbital (lO2p’) at under-coordinated surface oxygen prefers over-oxidation over bulk oxygen, and that surface oxygen release is then kinetically favored during charging. We use a simple strategy of turning under-coordinated surface oxygen into polyanionic (SO4)2−, and show that these groups stabilize the surface of Li2MnO3 by depressing gas release and side reactions with the electrolyte. Experimental validation on Li1.2Ni0.2Mn0.6O2 shows that sulfur deposition enhances stability of the cathode with 99.0% capacity remaining (194 mA h g−1) after 100 cycles at 1 C. Our work reveals a promising surface treatment to address the instability of highly charged layered cathode materials.

Suggested Citation

  • Qing Chen & Yi Pei & Houwen Chen & Yan Song & Liang Zhen & Cheng-Yan Xu & Penghao Xiao & Graeme Henkelman, 2020. "Highly reversible oxygen redox in layered compounds enabled by surface polyanions," Nature Communications, Nature, vol. 11(1), pages 1-12, December.
    • Handle: RePEc:nat:natcom:v:11:y:2020:i:1:d:10.1038_s41467-020-17126-3
    DOI: 10.1038/s41467-020-17126-3
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    Cited by:

    1. Shuo Sun & Zhen Han & Wei Liu & Qiuying Xia & Liang Xue & Xincheng Lei & Teng Zhai & Dong Su & Hui Xia, 2023. "Lattice pinning in MoO3 via coherent interface with stabilized Li+ intercalation," Nature Communications, Nature, vol. 14(1), pages 1-13, December.
    2. Yi Pei & Qing Chen & Meiyu Wang & Pengjun Zhang & Qingyong Ren & Jingkai Qin & Penghao Xiao & Li Song & Yu Chen & Wen Yin & Xin Tong & Liang Zhen & Peng Wang & Cheng-Yan Xu, 2022. "A medium-entropy transition metal oxide cathode for high-capacity lithium metal batteries," Nature Communications, Nature, vol. 13(1), pages 1-13, December.

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