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Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode

Author

Listed:
  • Benoit Mortemard de Boisse

    (School of Engineering, The University of Tokyo
    Elements Strategy Initiative for Catalysts & Batteries (ESICB), Kyoto University)

  • Guandong Liu

    (School of Engineering, The University of Tokyo)

  • Jiangtao Ma

    (School of Engineering, The University of Tokyo)

  • Shin-ichi Nishimura

    (School of Engineering, The University of Tokyo
    Elements Strategy Initiative for Catalysts & Batteries (ESICB), Kyoto University)

  • Sai-Cheong Chung

    (School of Engineering, The University of Tokyo
    Elements Strategy Initiative for Catalysts & Batteries (ESICB), Kyoto University)

  • Hisao Kiuchi

    (School of Engineering, The University of Tokyo)

  • Yoshihisa Harada

    (Institute for Solid State Physics, The University of Tokyo
    Synchrotron Radiation Research Organization, The University of Tokyo)

  • Jun Kikkawa

    (National Institute for Materials Science)

  • Yoshio Kobayashi

    (The University of Electro-Communications
    RIKEN Nishina Center for Accelerator-Based Science, RIKEN)

  • Masashi Okubo

    (School of Engineering, The University of Tokyo
    Elements Strategy Initiative for Catalysts & Batteries (ESICB), Kyoto University)

  • Atsuo Yamada

    (School of Engineering, The University of Tokyo
    Elements Strategy Initiative for Catalysts & Batteries (ESICB), Kyoto University)

Abstract

Sodium-ion batteries are attractive energy storage media owing to the abundance of sodium, but the low capacities of available cathode materials make them impractical. Sodium-excess metal oxides Na2MO3 (M: transition metal) are appealing cathode materials that may realize large capacities through additional oxygen redox reaction. However, the general strategies for enhancing the capacity of Na2MO3 are poorly established. Here using two polymorphs of Na2RuO3, we demonstrate the critical role of honeycomb-type cation ordering in Na2MO3. Ordered Na2RuO3 with honeycomb-ordered [Na1/3Ru2/3]O2 slabs delivers a capacity of 180 mAh g−1 (1.3-electron reaction), whereas disordered Na2RuO3 only delivers 135 mAh g−1 (1.0-electron reaction). We clarify that the large extra capacity of ordered Na2RuO3 is enabled by a spontaneously ordered intermediate Na1RuO3 phase with ilmenite O1 structure, which induces frontier orbital reorganization to trigger the oxygen redox reaction, unveiling a general requisite for the stable oxygen redox reaction in high-capacity Na2MO3 cathodes.

Suggested Citation

  • Benoit Mortemard de Boisse & Guandong Liu & Jiangtao Ma & Shin-ichi Nishimura & Sai-Cheong Chung & Hisao Kiuchi & Yoshihisa Harada & Jun Kikkawa & Yoshio Kobayashi & Masashi Okubo & Atsuo Yamada, 2016. "Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode," Nature Communications, Nature, vol. 7(1), pages 1-9, June.
    • Handle: RePEc:nat:natcom:v:7:y:2016:i:1:d:10.1038_ncomms11397
    DOI: 10.1038/ncomms11397
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    Cited by:

    1. Chen Cheng & Manling Ding & Tianran Yan & Kehua Dai & Jing Mao & Nian Zhang & Liang Zhang & Jinghua Guo, 2020. "Exploring the Charge Compensation Mechanism of P2-Type Na 0.6 Mg 0.3 Mn 0.7 O 2 Cathode Materials for Advanced Sodium-Ion Batteries," Energies, MDPI, vol. 13(21), pages 1-12, November.

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