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Stabilizing lattice oxygen redox in layered sodium transition metal oxide through spin singlet state

Author

Listed:
  • Xuelong Wang

    (Brookhaven National Laboratory
    Chinese Academy of Sciences)

  • Liang Yin

    (Chinese Academy of Sciences
    Argonne National Laboratory)

  • Arthur Ronne

    (Brookhaven National Laboratory
    Stony Brook University)

  • Yiman Zhang

    (Oak Ridge National Laboratory)

  • Zilin Hu

    (Chinese Academy of Sciences)

  • Sha Tan

    (Brookhaven National Laboratory)

  • Qinchao Wang

    (Brookhaven National Laboratory)

  • Bohang Song

    (Oak Ridge National Laboratory)

  • Mengya Li

    (Oak Ridge National Laboratory)

  • Xiaohui Rong

    (Chinese Academy of Sciences)

  • Saul Lapidus

    (Argonne National Laboratory)

  • Shize Yang

    (Yale University)

  • Enyuan Hu

    (Brookhaven National Laboratory)

  • Jue Liu

    (Oak Ridge National Laboratory)

Abstract

Reversible lattice oxygen redox reactions offer the potential to enhance energy density and lower battery cathode costs. However, their widespread adoption faces obstacles like substantial voltage hysteresis and poor stability. The current research addresses these challenges by achieving a non-hysteresis, long-term stable oxygen redox reaction in the P3-type Na2/3Cu1/3Mn2/3O2. Here we show this is accomplished by forming spin singlet states during charge and discharge. Detailed analysis, including in-situ X-ray diffraction, shows highly reversible structural changes during cycling. In addition, local CuO6 Jahn-Teller distortions persist throughout, with dynamic Cu-O bond length variations. In-situ hard X-ray absorption and ex-situ soft X-ray absorption study, along with density function theory calculations, reveal two distinct charge compensation mechanisms at approximately 3.66 V and 3.99 V plateaus. Notably, we observe a Zhang-Rice-like singlet state during 3.99 V charging, offering an alternative charge compensation mechanism to stabilize the active oxygen redox reaction.

Suggested Citation

  • Xuelong Wang & Liang Yin & Arthur Ronne & Yiman Zhang & Zilin Hu & Sha Tan & Qinchao Wang & Bohang Song & Mengya Li & Xiaohui Rong & Saul Lapidus & Shize Yang & Enyuan Hu & Jue Liu, 2023. "Stabilizing lattice oxygen redox in layered sodium transition metal oxide through spin singlet state," Nature Communications, Nature, vol. 14(1), pages 1-13, December.
    • Handle: RePEc:nat:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-43031-6
    DOI: 10.1038/s41467-023-43031-6
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    References listed on IDEAS

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