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Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

Author

Listed:
  • Naoaki Yabuuchi

    (Tokyo Denki University)

  • Masanobu Nakayama

    (Frontier Research Institute for Materials Science, Nagoya Institute of Technology, Gokiso-cho, Showa-ku
    Japan Science and Technology Agency (JST))

  • Mitsue Takeuchi

    (Tokyo University of Science)

  • Shinichi Komaba

    (Tokyo University of Science)

  • Yu Hashimoto

    (Frontier Research Institute for Materials Science, Nagoya Institute of Technology, Gokiso-cho, Showa-ku)

  • Takahiro Mukai

    (Frontier Research Institute for Materials Science, Nagoya Institute of Technology, Gokiso-cho, Showa-ku)

  • Hiromasa Shiiba

    (Frontier Research Institute for Materials Science, Nagoya Institute of Technology, Gokiso-cho, Showa-ku)

  • Kei Sato

    (Tokyo Denki University)

  • Yuki Kobayashi

    (Tokyo Denki University)

  • Aiko Nakao

    (Bio-engineering Lab.)

  • Masao Yonemura

    (Institute of Materials Structure Science (IMSS), High Energy Accelerator Research Organization (KEK)
    Sokendai (The Graduate University for Advanced Studies))

  • Keisuke Yamanaka

    (SR Center, Ritsumeikan University)

  • Kei Mitsuhara

    (SR Center, Ritsumeikan University)

  • Toshiaki Ohta

    (SR Center, Ritsumeikan University)

Abstract

Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g−1 based on solid-state redox reaction of oxide ions.

Suggested Citation

  • Naoaki Yabuuchi & Masanobu Nakayama & Mitsue Takeuchi & Shinichi Komaba & Yu Hashimoto & Takahiro Mukai & Hiromasa Shiiba & Kei Sato & Yuki Kobayashi & Aiko Nakao & Masao Yonemura & Keisuke Yamanaka &, 2016. "Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries," Nature Communications, Nature, vol. 7(1), pages 1-10, December.
    • Handle: RePEc:nat:natcom:v:7:y:2016:i:1:d:10.1038_ncomms13814
    DOI: 10.1038/ncomms13814
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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.

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