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In situ X-ray absorption fine structure studies of amorphous and crystalline polyoxovanadate cluster cathodes for lithium batteries

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Abstract

Amorphous and crystalline MetfV10 electrodes for lithium ion batteries were prepared by mixing MetfV10 with different binders: polyvinylidenefluoride (PVDF) or polytetrafluoroethylene (PTFE). The amorphous MetfV10 cathode demonstrates a higher specific capacity than the crystalline cathode. The reaction mechanism was studied using in situ X-ray absorption fine structure (XAFS) and impedance measurements. The X-ray absorption near-edge structure (XANES) results exhibited a 10-electron reduction per the formula of MetfV10 during discharge, resulting in a large capacity. Extended X-ray absorption fine structure (EXAFS) analyses suggested a slight expansion in the molecular size of MetfV10. The impedance measurements reveal that an increase of discharge capacities for the amorphous cathode is due to lower resistance than in the crystalline cathode. This study presents a rational selection of amorphous or crystalline cathode materials for high power and high energy density lithium batteries.

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Acknowledgements

The synchrotron radiation experiments were performed at the Japan Atomic Energy Agency (JAEA) beamline BL14B1 in SPring-8 with the approval of JASRI (Proposal Nos. 2015B3615, 2016B3634, and 2017A3634). They were also performed under the Shared Use Program of JAEA Facilities (Proposal Nos. 2015B-E10, 2016B-E02, and 2017A-E01), with the approval of the Nanotechnology Platform project supported by the Ministry of Education, Culture, Sports, Science and Technology (Proposal Nos. A-15-AE-0032, A-16-AE-0015, and A-17-AE-0001).

Funding

This work was financially supported by JSPS KAKENHI Grant Nos. 17H03048, JP16KT0062, JP15K13769, JP15H00935, and JP26288034 for H.Y. This work was also supported by the JSPS Core-to-Core Program A-Advanced Research Networks. Financial support of the Research Grant of Tokuyama Science Foundation and the Grant for Basic Science Research Projects of the Sumitomo foundation.

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Authors and Affiliations

  1. School of Material and Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou, 450002, China

    Heng Wang

  2. School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo, 669-1337, Japan

    Jin Isobe & Hirofumi Yoshikawa

  3. Quantum Beam Science Center, Japan Atomic Energy Agency, Sayo-gun, Hyogo, 679-5148, Japan

    Daiju Matsumura

Authors
  1. Heng Wang
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  2. Jin Isobe
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  3. Daiju Matsumura
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  4. Hirofumi Yoshikawa
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Correspondence to Hirofumi Yoshikawa.

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Wang, H., Isobe, J., Matsumura, D. et al. In situ X-ray absorption fine structure studies of amorphous and crystalline polyoxovanadate cluster cathodes for lithium batteries. J Solid State Electrochem 22, 2067–2071 (2018). https://doi.org/10.1007/s10008-018-3920-4

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  • DOI: https://doi.org/10.1007/s10008-018-3920-4

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