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Probing the thermal effects of voltage hysteresis in anionic redox-based lithium-rich cathodes using isothermal calorimetry

Author

Listed:
  • Gaurav Assat

    (Collège de France
    FR CNRS 3459
    Sorbonne University)

  • Stephen L. Glazier

    (Dalhousie University)

  • Charles Delacourt

    (FR CNRS 3459
    Université de Picardie Jules Verne)

  • Jean-Marie Tarascon

    (Collège de France
    FR CNRS 3459
    Sorbonne University)

Abstract

The commercialization of high-energy batteries with lithium-rich cathode materials exhibiting combined cationic/anionic redox processes awaits the elimination of certain practical bottlenecks. Among these, large voltage hysteresis remains the most obscure from a fundamental thermochemical perspective. Here, we study this issue by directly measuring, via isothermal calorimetry, the heat generated by Li/Li2Ru0.75Sn0.25O3 (Li/LRSO) cells during various cycling conditions, with LRSO being a ‘model’ Li-rich layered cathode. We show how this heat thermodynamically relates to the lost electrical work that is crucial for practical applications. We further reveal that anionic redox on charging and discharging adopts different metastable paths having non-identical enthalpy potentials, such that the overall Li content no longer remains the unique reaction coordinate, unlike in fully path-reversible cationic redox. We elucidate how quasi-static voltage hysteresis is related to heat dissipated due to non-equilibrium entropy production. Overall, this study establishes the great benefits of isothermal calorimetry for enabling energy-efficient electrode materials in next-generation batteries.

Suggested Citation

  • Gaurav Assat & Stephen L. Glazier & Charles Delacourt & Jean-Marie Tarascon, 2019. "Probing the thermal effects of voltage hysteresis in anionic redox-based lithium-rich cathodes using isothermal calorimetry," Nature Energy, Nature, vol. 4(8), pages 647-656, August.
    • Handle: RePEc:nat:natene:v:4:y:2019:i:8:d:10.1038_s41560-019-0410-6
    DOI: 10.1038/s41560-019-0410-6
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    Cited by:

    1. 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.
    2. Shunsuke Sasaki & Souvik Giri & Simon J. Cassidy & Sunita Dey & Maria Batuk & Daphne Vandemeulebroucke & Giannantonio Cibin & Ronald I. Smith & Philip Holdship & Clare P. Grey & Joke Hadermann & Simon, 2023. "Anion redox as a means to derive layered manganese oxychalcogenides with exotic intergrowth structures," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    3. 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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