Correlation between the O2p Orbital and Redox Reaction in LiMn0.6Fe0.4PO4 Nanowires Studied by Soft X-ray Absorption

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 chargetransfer effect from O2p to Mn3d orbitals should be considerably small, unlike that from the O2p to Fe3d orbitals. Instead, the O K-edge X-ray absorption spectrum shows a clear spectral change during the discharge process, suggesting that the hybridization of O2p orbitals with Fe3d orbitals contributes essentially to the reduction.