Redox-Driven Spin Transition in a Layered Battery Cathode Material

Eriko Watanabe, Wenwen Zhao, Akira Sugahara, Benoit Mortemard De Boisse, Laura Lander, Daisuke Asakura, Yohei Okamoto, Takashi Mizokawa, Masashi Okubo, Atsuo Yamada

Research output: Contribution to journalArticle

Abstract

A spin transition between high-spin (HS) and low-spin (LS) states in a solid can occur when the energies of two spin configurations intersect, which is usually caused by external perturbations such as temperature, pressure, and magnetic fields, with substantial influence to its physical and chemical properties. Here, we discover the electrochemical "redox reaction" as a new driving force to induce reversible HS-LS spin transition. Although reversible solid-state redox reaction has been thoroughly investigated as the fundamental process in battery electrode materials, coupling between redox reactions and spin transitions has not been explored. Using density functional theory calculations, we predicted the existence of redox-driven spin transition occurring exclusively for the Co 3+ /Co 2+ redox couple in layered transition-metal oxides, leading to a colossal potential hysteresis (>1 V) between the cathodic (LS Co 3+ to LS Co 2+ ) and anodic (HS Co 2+ to HS Co 3+ ) reactions. The predicted potential hysteresis associated with the spin transition of Co was experimentally verified for Na x Ti 0.5 Co 0.5 O 2 by monitoring the electrochemical potential, local coordination structure, electronic structure, and magnetic moment.

Original languageEnglish
JournalChemistry of Materials
DOIs
Publication statusPublished - 2019 Jan 1

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Redox reactions
Cathodes
Hysteresis
Magnetic moments
Oxides
Chemical properties
Electronic structure
Transition metals
Density functional theory
Physical properties
Magnetic fields
Electrodes
Monitoring
Oxidation-Reduction
Temperature

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

Cite this

Watanabe, E., Zhao, W., Sugahara, A., Mortemard De Boisse, B., Lander, L., Asakura, D., ... Yamada, A. (2019). Redox-Driven Spin Transition in a Layered Battery Cathode Material. Chemistry of Materials. https://doi.org/10.1021/acs.chemmater.8b04775

Redox-Driven Spin Transition in a Layered Battery Cathode Material. / Watanabe, Eriko; Zhao, Wenwen; Sugahara, Akira; Mortemard De Boisse, Benoit; Lander, Laura; Asakura, Daisuke; Okamoto, Yohei; Mizokawa, Takashi; Okubo, Masashi; Yamada, Atsuo.

In: Chemistry of Materials, 01.01.2019.

Research output: Contribution to journalArticle

Watanabe, E, Zhao, W, Sugahara, A, Mortemard De Boisse, B, Lander, L, Asakura, D, Okamoto, Y, Mizokawa, T, Okubo, M & Yamada, A 2019, 'Redox-Driven Spin Transition in a Layered Battery Cathode Material', Chemistry of Materials. https://doi.org/10.1021/acs.chemmater.8b04775
Watanabe E, Zhao W, Sugahara A, Mortemard De Boisse B, Lander L, Asakura D et al. Redox-Driven Spin Transition in a Layered Battery Cathode Material. Chemistry of Materials. 2019 Jan 1. https://doi.org/10.1021/acs.chemmater.8b04775
Watanabe, Eriko ; Zhao, Wenwen ; Sugahara, Akira ; Mortemard De Boisse, Benoit ; Lander, Laura ; Asakura, Daisuke ; Okamoto, Yohei ; Mizokawa, Takashi ; Okubo, Masashi ; Yamada, Atsuo. / Redox-Driven Spin Transition in a Layered Battery Cathode Material. In: Chemistry of Materials. 2019.
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