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Origin of Vanadium Site Sequential Oxidation in KxVPO4F1–yOy

hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
hal.structure.identifierInstitut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier [ICGM]
hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
dc.contributor.authorWERNERT, Romain
hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
dc.contributor.authorIADECOLA, Antonella
hal.structure.identifierInstitut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier [ICGM]
hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
hal.structure.identifierAdvanced Lithium Energy Storage Systems - ALISTORE-ERI [ALISTORE-ERI]
dc.contributor.authorSTIEVANO, Lorenzo
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.issued2023
dc.identifier.issn0897-4756
dc.description.abstractEnM-ion batteries (M = Li, Na, K ...) positive electrode materials most often operate through the reversible oxidation of transition-metal ions. In complex materials involving many transition metals or many redox centers, understanding the sequence in which they participate to the reaction is not trivial but is often necessary to explain the electrochemical properties. Mixed anion vanadium phosphates, such as KVPO4F0.5O0.5, are known to contain two different redox entities that are V3+O4F2 and V3+O5F “ionic” entities on the one hand and {V4+═O}O5 and {V4+═O}O4F “covalent” vanadyl-type units on the other hand. However, their participation to the redox mechanism occurring during the charge of this material has never been studied. Here, we use V K-edge X-ray absorption spectroscopy to unveil the redox mechanism of KVPO4F1–yOy (y = 0, 0.5, 1), performing data analysis via a chemometric approach. With XAS being very sensitive to the oxidation state and bond length, it was found that the ionic V3+–F units oxidize at a lower potential than the covalent {V4+═O} ones, which is surprising considering the high electronegativity of fluoride anions but is consistent with the redox potential observed for KVPO4F and KVOPO4. Further, ab initio calculations and ex situ X-ray diffraction analyses allowed an atomistic description of the redox mechanism with the sequential oxidation of the cis V site before the trans V site in KVPO4F upon charge. Finally, the complete atomically resolved redox mechanism of KVPO4F0.5O0.5 is proposed.
dc.description.sponsorshipVers des batteries innovantes K-ion - ANR-19-CE05-0026
dc.description.sponsorshipLaboratory of excellency for electrochemical energy storage - ANR-10-LABX-0076
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.subject.enElectrodes
dc.subject.enMaterials
dc.subject.enOxidation
dc.subject.enRedox reactions
dc.subject.enVanadium
dc.title.enOrigin of Vanadium Site Sequential Oxidation in KxVPO4F1–yOy
dc.typeArticle de revue
dc.identifier.doi10.1021/acs.chemmater.2c03132
dc.subject.halChimie/Matériaux
bordeaux.journalChemistry of Materials
bordeaux.page617-627
bordeaux.volume35
bordeaux.issue2
bordeaux.peerReviewedoui
hal.identifierhal-03925593
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-03925593v1
bordeaux.COinSctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Chemistry%20of%20Materials&rft.date=2023&rft.volume=35&rft.issue=2&rft.spage=617-627&rft.epage=617-627&rft.eissn=0897-4756&rft.issn=0897-4756&rft.au=WERNERT,%20Romain&IADECOLA,%20Antonella&STIEVANO,%20Lorenzo&CARLIER,%20Dany&CROGUENNEC,%20Laurence&rft.genre=article


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