Correlation between the O 2p Orbital and Redox Reaction in LiMn0.6Fe0.4PO4 Nanowires Studied by Soft X-ray Absorption

Daisuke Asakura*, Eiji Hosono, Masashi Okubo, Yusuke Nanba, Haoshen Zhou, Per Anders Glans, Jinghua Guo

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

2 Citations (Scopus)

Abstract

The changes in the electronic structure of LiMn0.6Fe0.4PO4 nanowires during discharge processes were investigated by using ex situ soft X-ray absorption spectroscopy. The Fe L-edge X-ray absorption spectrum attributes the potential plateau at 3.45 V versus Li/Li+ of the discharge curve to a reduction of Fe3+ to Fe2+. The Mn L-edge X-ray absorption spectra exhibit the Mn2+ multiplet structure throughout the discharge process, and the crystal-field splitting was slightly enhanced upon full discharge. The configuration-interaction full-multiplet calculation for the X-ray absorption spectra reveals that the charge-transfer effect from O 2p to Mn 3d orbitals should be considerably small, unlike that from the O 2p to Fe 3d orbitals. Instead, the O K-edge X-ray absorption spectrum shows a clear spectral change during the discharge process, suggesting that the hybridization of O 2p orbitals with Fe 3d orbitals contributes essentially to the reduction.

Original languageEnglish
Pages (from-to)4110-4115
Number of pages6
JournalChemPhysChem
Volume17
Issue number24
DOIs
Publication statusPublished - 2016 Dec 15
Externally publishedYes

Keywords

  • cathode materials
  • lithium-ion batteries
  • olivine
  • redox reactions
  • soft X-ray absorption spectroscopy

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Physical and Theoretical Chemistry

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