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Correlation between the O 2p Orbital and Redox Reaction in LiMn 0.6 Fe 0.4 PO 4 Nanowires Studied by Soft X‐ray Absorption
Author(s) -
Asakura Daisuke,
Hosono Eiji,
Okubo Masashi,
Nanba Yusuke,
Zhou Haoshen,
Glans PerAnders,
Guo Jinghua
Publication year - 2016
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201600952
Subject(s) - absorption spectroscopy , atomic orbital , absorption (acoustics) , chemistry , x ray absorption spectroscopy , molecular orbital , absorption edge , electronic structure , atomic physics , analytical chemistry (journal) , materials science , electron , computational chemistry , physics , optics , molecule , optoelectronics , organic chemistry , chromatography , quantum mechanics , band gap , composite material
The changes in the electronic structure of LiMn 0.6 Fe 0.4 PO 4 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 Fe 3+ to Fe 2+ . The Mn L ‐edge X‐ray absorption spectra exhibit the Mn 2+ 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.