Mn 2p resonant X-ray emission clarifies the redox reaction and charge-transfer effects in LiMn2O4

Daisuke Asakura*, Yusuke Nanba, Eiji Hosono, Masashi Okubo, Hideharu Niwa, Hisao Kiuchi, Jun Miyawaki, Yoshihisa Harada

*この研究の対応する著者

研究成果: Article査読

4 被引用数 (Scopus)

抄録

High-energy-resolution soft X-ray emission spectroscopy (XES) was applied to understand the changes in the electronic structure of LiMn2O4 upon Li-ion extraction/insertion. Mn 2p-3d-2p resonant XES spectra were analyzed by configuration-interaction full-multiplet (CIFM) calculations, which reproduced both dd and charge-transfer (CT) excitations. From the resonant XES spectra it is found that Mn3+ and Mn4+ coexist in the initial state, while this changes into Mn4+ in the charged-state. For the discharged-state, the Mn3+ component appears again although the dd excitations are slightly modified from those for the initial state. Furthermore, negative CT energy is expected for the Mn4+ configuration, which suggests very strong hybridization between the Mn 3d and O 2p orbitals. The large difference in the CT effect between the Mn4+ and Mn3+ states should give mechanical stress to the Mn-O bond during charge-discharge cycling, leading to capacity fading.

本文言語English
ページ(範囲)18363-18369
ページ数7
ジャーナルPhysical Chemistry Chemical Physics
21
33
DOI
出版ステータスPublished - 2019
外部発表はい

ASJC Scopus subject areas

  • 物理学および天文学(全般)
  • 物理化学および理論化学

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