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Redox paradox of vanadium in Tavorite LiVPO4F1-yOy

hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
hal.structure.identifierLaboratoire réactivité et chimie des solides - UMR CNRS 7314 UPJV [LRCS]
hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
dc.contributor.authorBOIVIN, Edouard
hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
dc.contributor.authorIADECOLA, Antonella
hal.structure.identifierALBA Synchrotron light source [Barcelone]
dc.contributor.authorFAUTH, François
hal.structure.identifierLaboratoire réactivité et chimie des solides - UMR CNRS 7314 UPJV [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.authorCHOTARD, Jean-Noël
hal.structure.identifierLaboratoire réactivité et chimie des solides - UMR CNRS 7314 UPJV [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.authorCROGUENNEC, Laurence
dc.date.issued2019
dc.identifier.issn0897-4756
dc.description.abstractEnVanadyl-type defects in vanadium oxy-fluoride phosphates confer interesting properties to these materials as positive electrodes in Li-ion or Na-ion batteries. The influence of defect concentration on the phase diagram and redox mechanisms in LiVPO4F1–yOy tavorite phases has been investigated by combining operando synchrotron X-ray powder diffraction (SXRPD) and X-ray absorption spectroscopy (XAS). Operando X-ray absorption near edge structure (XANES) reveals the activation of the V4+═O/V5+═O redox couple during the first step of the charge, and then upon further Li+ extraction the activation of the V3+/V4+ redox couple in fluorine-rich environments. This result, although surprising, is in full agreement with the operating voltages of the end-member phases, as LixVIII,IVPO4F operates at a higher voltage than LixVIV,VPO4O. The unexpected succession of these redox couples is observed for the first time in the same material. The small volume changes undergone by the materials upon electrochemical operation were proposed to be at the origin of the better performance observed for the mixed valence samples: “freezing” of the framework is observed all along the activation of the V4+═O/V5+═O redox couple in a solid-solution-type domain.
dc.description.sponsorshipLaboratory of excellency for electrochemical energy storage - ANR-10-LABX-0076
dc.description.sponsorshipDevelopment of New High Voltage Positive Electrodes for Sustainable Li-Ion Batteries - ANR-12-PRGE-0005
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.title.enRedox paradox of vanadium in Tavorite LiVPO4F1-yOy
dc.typeArticle de revue
dc.identifier.doi10.1021/acs.chemmater.9b01987
dc.subject.halChimie/Matériaux
dc.subject.halChimie/Chimie inorganique
bordeaux.journalChemistry of Materials
bordeaux.page7367-7376
bordeaux.volume31
bordeaux.issue18
bordeaux.peerReviewedoui
hal.identifierhal-02298423
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-02298423v1
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