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Electrochemical and Solid State Letters, Vol.9, No.9, A415-A417, 2006
Electronic structure of the electrochemically delithiated Li-1-xFePO4 electrodes investigated by PK-edge X-ray absorption spectroscopy
P K-edge X-ray absorption spectroscopy (XAS) has been carried out to investigate the electronic structure of the electrochemically delithiated Li1-xFePO4 for Li rechargeable batteries. The gradual shift of main edge features to higher energy side showed that P-O bonds become less covalent during delithiation due to the more covalent Fe3+-O bonds via the inductive effect. A principal component analysis of P K-edge XAS spectra of the electrochemically delithiated Li1-xFePO4 reveals that this set of spectra can be well represented by two primary components, in good agreement with a first-order phase transition involving the LiFePO4 and FePO4 phases. From the observation of pre-edge peaks, it is concluded that electrochemical delithiation of Li1-xFePO4 results in the hybridization of P 3p states with the Fe 3d states. (c) 2006 The Electrochemical Society.