NGUYEN, Long H. B.; IADECOLA, Antonella; BELIN, Stéphanie; OLCHOWKA, Jacob; MASQUELIER, Christian; CARLIER, Dany; CROGUENNEC, Laurence

doi:10.1021/acs.jpcc.0c06967

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NGUYEN, Long H. B.
Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
Laboratoire réactivité et chimie des solides - UMR CNRS 7314 UPJV [LRCS]
Réseau sur le stockage électrochimique de l'énergie [RS2E]

IADECOLA, Antonella
Synchrotron SOLEIL [SSOLEIL]

BELIN, Stéphanie
Réseau sur le stockage électrochimique de l'énergie [RS2E]

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Article de revue

Ce document a été publié dans

Journal of Physical Chemistry C. 2020, vol. 124, n° 43, p. 23511–23522

American Chemical Society

Résumé en anglais

The redox processes involved in the Na+ deintercalation from Na3V2(PO4)2F3, Na3V2(PO4)2F2O, and Na3V2(PO4)2F1.5O1.5 are investigated operando by synchrotron X-ray absorption spectroscopy at the vanadium K-edge. A continuous evolution in the pre-edge and edge regions is observed for the three compositions, which is in good agreement with a progressive oxidation of vanadium. In the oxygen-substituted compositions, Na3V2(PO4)2F2O and Na3V2(PO4)2F1.5O1.5, the F–V3+O4–F and F–V4+O4═O redox centers coexist and can be simultaneously activated owing to the reverse inductive effect promoted by the presence of highly covalent vanadyl bonds on V4+ sites. Principal component analysis of the dataset collected operando for the three compositions is performed. It reveals that three independent spectra, corresponding to different charge orderings on vanadium sites at different states of charge, are required to describe these three systems. Furthermore, the extended X-ray absorption fine structure analysis of the principal components is performed in order to gain insightful information on the evolution of the vanadium local environment upon cycling. By the use of first-principles density functional theory calculations, we demonstrate that the potential step observed in all Na2V2(PO4)2F3–yOy compositions is related to a charge ordering on vanadium sites with a preferential oxidation of vanadium ions in the same bioctahedra.< Réduire

DOI

http://dx.doi.org/10.1021/acs.jpcc.0c06967

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Spectromètre EXAFS Rapide pour Cinétiques Chimiques - ANR-10-EQPX-0045
Laboratory of excellency for electrochemical energy storage - ANR-10-LABX-0076

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Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB) - UMR 5026