Changes in electronic structure upon lithium insertion into Fe2(SO4)3 and Fe2(MoO4)3 investigated by X-ray absorption spectroscopy |
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Authors: | Shirakawa Junichi Nakayama Masanobu Wakihara Masataka Uchimoto Yoshiharu |
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Affiliation: | Department of Applied Chemistry, Tokyo Institute of Technology, Tokyo 152-8552, Japan. |
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Abstract: | Changes in electronic structure upon electrochemical lithium insertion into two iron compounds, namely, rhombohedral Fe2(SO4)3 with a NASICON-type structure and monoclinic Fe2(MoO4)3, were investigated using X-ray absorption spectroscopy (XAS). Fe K-edge and L(III)- and L(II)-edge XAS revealed that the rearrangement of Fe d electrons or rehybridization of Fe d-O p bonding took place accompanied by the reduction of Fe ions upon Li insertion for both samples and that a larger change in spectra was observed in Fe2(SO4)3. In addition, the changes in the electronic structure of the polyanion units XO4(2-) (X = S or Mo) after Li insertion were also investigated by O K-edge and S K-edge or Mo L(III)-edge XAS. The results indicated that the electronic structure around oxygen markedly changed in Fe2(MoO4)3, while no significant change was observed in Fe2(SO4)3. |
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