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First-cycle voltage hysteresis in Li-rich 3d cathodes associated with molecular O2 trapped in the bulk

Author

Listed:
  • Robert A. House

    (University of Oxford
    University of Oxford
    The Henry Royce Institute
    The Faraday Institution)

  • Gregory J. Rees

    (University of Oxford
    University of Oxford
    The Henry Royce Institute
    The Faraday Institution)

  • Miguel A. Pérez-Osorio

    (University of Oxford
    University of Oxford
    The Henry Royce Institute
    The Faraday Institution)

  • John-Joseph Marie

    (University of Oxford
    University of Oxford
    The Henry Royce Institute
    The Faraday Institution)

  • Edouard Boivin

    (University of Oxford
    University of Oxford
    The Henry Royce Institute)

  • Alex W. Robertson

    (University of Oxford
    University of Oxford
    The Henry Royce Institute)

  • Abhishek Nag

    (Diamond Light Source)

  • Mirian Garcia-Fernandez

    (Diamond Light Source)

  • Ke-Jin Zhou

    (Diamond Light Source)

  • Peter G. Bruce

    (University of Oxford
    University of Oxford
    The Henry Royce Institute
    The Faraday Institution)

Abstract

Li-rich cathode materials are potential candidates for next-generation Li-ion batteries. However, they exhibit a large voltage hysteresis on the first charge/discharge cycle, which involves a substantial (up to 1 V) loss of voltage and therefore energy density. For Na cathodes, for example Na0.75[Li0.25Mn0.75]O2, voltage hysteresis can be explained by the formation of molecular O2 trapped in voids within the particles. Here we show that this is also the case for Li1.2Ni0.13Co0.13Mn0.54O2. Resonant inelastic X-ray scattering and 17O magic angle spinning NMR spectroscopy show that molecular O2, rather than O22−, forms within the particles on the oxidation of O2− at 4.6 V versus Li+/Li on charge. These O2 molecules are reduced back to O2− on discharge, but at the lower voltage of 3.75 V, which explains the voltage hysteresis in Li-rich cathodes. 17O magic angle spinning NMR spectroscopy indicates a quantity of bulk O2 consistent with the O-redox charge capacity minus the small quantity of O2 loss from the surface. The implication is that O2, trapped in the bulk and lost from the surface, can explain O-redox.

Suggested Citation

  • Robert A. House & Gregory J. Rees & Miguel A. Pérez-Osorio & John-Joseph Marie & Edouard Boivin & Alex W. Robertson & Abhishek Nag & Mirian Garcia-Fernandez & Ke-Jin Zhou & Peter G. Bruce, 2020. "First-cycle voltage hysteresis in Li-rich 3d cathodes associated with molecular O2 trapped in the bulk," Nature Energy, Nature, vol. 5(10), pages 777-785, October.
  • Handle: RePEc:nat:natene:v:5:y:2020:i:10:d:10.1038_s41560-020-00697-2
    DOI: 10.1038/s41560-020-00697-2
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    Citations

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    Cited by:

    1. Kit McColl & Robert A. House & Gregory J. Rees & Alexander G. Squires & Samuel W. Coles & Peter G. Bruce & Benjamin J. Morgan & M. Saiful Islam, 2022. "Transition metal migration and O2 formation underpin voltage hysteresis in oxygen-redox disordered rocksalt cathodes," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
    2. Chuanlai Liu & Franz Roters & Dierk Raabe, 2024. "Role of grain-level chemo-mechanics in composite cathode degradation of solid-state lithium batteries," Nature Communications, Nature, vol. 15(1), pages 1-18, December.
    3. 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.
    4. Qi Liang & Peirong Li & Yue Zhao & Supeng Chen & Jixiang Yin & Yingchun Lyu & Qiang Li & Qinghao Li, 2023. "Investigation on the Origin of Sluggish Anionic Redox Kinetics in Cation-Disordered Cathode," Energies, MDPI, vol. 16(18), pages 1-12, September.
    5. Qingyuan Li & De Ning & Deniz Wong & Ke An & Yuxin Tang & Dong Zhou & Götz Schuck & Zhenhua Chen & Nian Zhang & Xiangfeng Liu, 2022. "Improving the oxygen redox reversibility of Li-rich battery cathode materials via Coulombic repulsive interactions strategy," Nature Communications, Nature, vol. 13(1), pages 1-13, December.
    6. Jun-Hyuk Song & Seungju Yu & Byunghoon Kim & Donggun Eum & Jiung Cho & Ho-Young Jang & Sung-O Park & Jaekyun Yoo & Youngmin Ko & Kyeongsu Lee & Myeong Hwan Lee & Byungwook Kang & Kisuk Kang, 2023. "Slab gliding, a hidden factor that induces irreversibility and redox asymmetry of lithium-rich layered oxide cathodes," Nature Communications, Nature, vol. 14(1), pages 1-10, December.

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