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Investigation on the Origin of Sluggish Anionic Redox Kinetics in Cation-Disordered Cathode

Author

Listed:
  • Qi Liang

    (College of Physics, Center for Marine Observation and Communications, Qingdao University, Qingdao 266071, China)

  • Peirong Li

    (College of Physics, Center for Marine Observation and Communications, Qingdao University, Qingdao 266071, China)

  • Yue Zhao

    (College of Physics, Center for Marine Observation and Communications, Qingdao University, Qingdao 266071, China)

  • Supeng Chen

    (College of Physics, Center for Marine Observation and Communications, Qingdao University, Qingdao 266071, China)

  • Jixiang Yin

    (College of Physics, Center for Marine Observation and Communications, Qingdao University, Qingdao 266071, China)

  • Yingchun Lyu

    (Materials Genome Institute, Shanghai University, Shanghai 200444, China)

  • Qiang Li

    (College of Physics, Center for Marine Observation and Communications, Qingdao University, Qingdao 266071, China)

  • Qinghao Li

    (College of Physics, Center for Marine Observation and Communications, Qingdao University, Qingdao 266071, China)

Abstract

Cation-disordered rock salt (DRX) cathodes exhibit high specific capacity due to the simultaneous use of anionic and cationic redox reactions. However, DRX systems face severe challenges that limit their practical applications; a most important challenge is their poor rate performance. In this work, the structure and morphology of Li 1.17 Ti 0.58 Ni 0.25 O 2 (LTNO) were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), etc. In combination with various electrochemical characterizations, we found that the sluggish kinetics of anionic redox within LTNO can be the key reason for the inferior rate performance. By sample relaxation at moderate temperature and X-ray absorption near edge structure (XANES), the ligand-to-metal charge transfer process is verified to occur between O and Ni and exhibits a prolonged characteristic time of 113.8 min. This time-consuming charge transfer process is verified to be the very fundamental origin of the slow kinetics of oxygen oxidation and reduction. This claim is further supported by the galvanostatic intermittent titration technique (GITT) at different temperatures. These findings provide essential guidance for understanding and further optimizing cathodes with anion redox reactions not only in the context of DRX cathodes but also conventional Li-rich cathodes.

Suggested Citation

  • 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.
    • Handle: RePEc:gam:jeners:v:16:y:2023:i:18:p:6740-:d:1244536
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    References listed on IDEAS

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