Multiorbital bond formation for stable oxygen-redox reaction in battery electrodes

Takaaki Sudayama, Kazuki Uehara, Takahiro Mukai, Daisuke Asakura, Xiang Mei Shi, Akihisa Tsuchimoto, Benoit Mortemard De Boisse, Tatau Shimada, Eriko Watanabe, Yoshihisa Harada, Masanobu Nakayama, Masashi Okubo, Atsuo Yamada*

*この研究の対応する著者

研究成果: Article査読

16 被引用数 (Scopus)

抄録

High-energy-density batteries have been a long-standing target toward sustainability, but the energy density of state-of-the-art lithium-ion batteries is limited in part by the small capacity of the positive electrode materials. Although employing the additional oxygen-redox reaction of Li-excess transition-metal oxides is an attractive approach to increase the capacity, an atomic-level understanding of the reaction mechanism has not been established so far. Here, using bulk-sensitive resonant inelastic X-ray scattering spectroscopy combined with ab initio computations, we demonstrate the presence of a localized oxygen 2p orbital weakly hybridized with transition metal t2g orbitals that was theoretically predicted to play a key role in oxygen-redox reactions. After oxygen oxidation, the hole in the oxygen 2p orbital is stabilized by the generation of either a (σ + π) multiorbital bond through strong π back-donation or peroxide O22- through oxygen dimerization. The multiorbital bond formation with σ-accepting and π-donating transition metals can thus lead to reversible oxygen-redox reaction.

本文言語English
ページ(範囲)1492-1500
ページ数9
ジャーナルEnergy and Environmental Science
13
5
DOI
出版ステータスPublished - 2020
外部発表はい

ASJC Scopus subject areas

  • 環境化学
  • 再生可能エネルギー、持続可能性、環境
  • 原子力エネルギーおよび原子力工学
  • 汚染

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