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Electronic structure of Li2Fe1−xMnxP2O7 for lithium-ion battery studied by resonant photoemission spectroscopy

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, , Citation Koji Horiba et al 2014 J. Phys.: Conf. Ser. 502 012004 DOI 10.1088/1742-6596/502/1/012004

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1 Department of Applied Chemistry, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-8656, Japan

2 Synchrotron Radiation Research Organization, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-8656, Japan

3 Photon Factory, Institute of Materials Structure Science, High Energy Accelerator Research Organization, 1-1 Oho, Tsukuba, Ibaraki 305-0801, Japan

4 Precursory Research for Embryonic Science and Technology, Japan Science and Technology Agency, Gobancho Building, 7, Gobancho, Chiyodaku, Tokyo 102-0076 Japan

5 Department of Chemical System Engineering, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-8656, Japan

6 Present address: Photon Factory, Institute of Materials Structure Science, High Energy Accelerator Research Organization, 1-1 Oho, Tsukuba, Ibaraki 305-0801, Japan

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1742-6596/502/1/012004

Abstract

In order to clarify changes in the electronic structures, especially Fe partial density of states (DOS), of Li2Fe1−xMnxP2O7 with Mn substitution, we have performed x-ray absorption spectroscopy and resonant photoemission spectroscopy (RPES) experiments for Li2Fe1−xMnxP2O7. Using RPES teqniques, we have succeeded in extracting the Fe2+ partial DOS. We have found the systematic shift to higher binding energy and broadening of Fe 3d t2g down-spin states accompanying with the Mn substitution. The peak shift of the Fe 3d t2g down-spin states is matched very well to the change of Fe3+/Fe2+ redox potential, suggesting that the origin of high Fe3+/Fe2+ redox potential in Li2Fe1−xMnxP2O7 is the shift of the Fe 3d t2g down-spin states to the higher binding energy with Mn substitution.

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10.1088/1742-6596/502/1/012004