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A combined operando synchrotron X-ray absorption spectroscopy and first-principles density functional theory study to unravel the vanadium reedox paradox in the Na3V2(PO4)2F3–Na3V2(PO4)2FO2 compositions

hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
hal.structure.identifierLaboratoire réactivité et chimie des solides - UMR CNRS 7314 [LRCS]
hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
dc.contributor.authorNGUYEN, Long H. B.
hal.structure.identifierSynchrotron SOLEIL [SSOLEIL]
dc.contributor.authorIADECOLA, Antonella
hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
dc.contributor.authorBELIN, Stéphanie
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
hal.structure.identifierAdvanced Lithium Energy Storage Systems - ALISTORE-ERI [ALISTORE-ERI]
dc.contributor.authorOLCHOWKA, Jacob
hal.structure.identifierLaboratoire réactivité et chimie des solides - UMR CNRS 7314 [LRCS]
hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
hal.structure.identifierAdvanced Lithium Energy Storage Systems - ALISTORE-ERI [ALISTORE-ERI]
dc.contributor.authorMASQUELIER, Christian
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
hal.structure.identifierAdvanced Lithium Energy Storage Systems - ALISTORE-ERI [ALISTORE-ERI]
dc.contributor.authorCARLIER, Dany
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
hal.structure.identifierAdvanced Lithium Energy Storage Systems - ALISTORE-ERI [ALISTORE-ERI]
dc.contributor.authorCROGUENNEC, Laurence
dc.date.issued2020
dc.identifier.issn1932-7447
dc.description.abstractEnThe 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.
dc.description.sponsorshipSpectromètre EXAFS Rapide pour Cinétiques Chimiques - ANR-10-EQPX-0045
dc.description.sponsorshipLaboratory of excellency for electrochemical energy storage - ANR-10-LABX-0076
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.title.enA combined operando synchrotron X-ray absorption spectroscopy and first-principles density functional theory study to unravel the vanadium reedox paradox in the Na3V2(PO4)2F3–Na3V2(PO4)2FO2 compositions
dc.typeArticle de revue
dc.identifier.doi10.1021/acs.jpcc.0c06967
dc.subject.halChimie/Matériaux
bordeaux.journalJournal of Physical Chemistry C
bordeaux.page23511–23522
bordeaux.volume124
bordeaux.issue43
bordeaux.peerReviewedoui
hal.identifierhal-02978467
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-02978467v1
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