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Issue 39, 2018
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Phosphorus anionic redox activity revealed by operando P K-edge X-ray absorption spectroscopy on diphosphonate-based conversion materials in Li-ion batteries

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Abstract

When cycling diphosphonate-based organic–inorganic hybrid materials as negative battery electrodes, specific charges exceeding the maximum for a metal redox reaction are recorded. Classical explanations are electrolyte reduction and solid electrolyte interphase (SEI) oxidation. Using operando X-ray absorption spectroscopy (XAS) at the P K-edge experiment, we demonstrate an additional contribution of reversible ligand co-cycling based on the P-atoms of the diphosphonate ligands, upon delithiation occurring during the first potential plateau, which matches perfectly to previous investigations using Fe K-edge XAS. We thus investigate experimentally an anionic redox process in situ. Thereby we could demonstrate a possible methodology to measure P K-edge XANES on Li-ion battery active materials under operando conditions, which could be applied to verify the predicted P co-cycling of other conversion-type negative electrode materials.

Graphical abstract: Phosphorus anionic redox activity revealed by operando P K-edge X-ray absorption spectroscopy on diphosphonate-based conversion materials in Li-ion batteries

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Publication details

The article was received on 16 Feb 2018, accepted on 19 Apr 2018 and first published on 19 Apr 2018


Article type: Communication
DOI: 10.1039/C8CC01350K
Chem. Commun., 2018,54, 4939-4942

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    Phosphorus anionic redox activity revealed by operando P K-edge X-ray absorption spectroscopy on diphosphonate-based conversion materials in Li-ion batteries

    S. Schmidt, S. Sallard, C. Borca, T. Huthwelker, P. Novák and C. Villevieille, Chem. Commun., 2018, 54, 4939
    DOI: 10.1039/C8CC01350K

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