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V^IV disproportionation upon sodium extraction from Na3V2(PO4)2F3 observed by operando x-ray absorption spectroscopy and solid-state NMR

hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
hal.structure.identifierLaboratoire réactivité et chimie des solides - UMR CNRS 7314 [LRCS]
dc.contributor.authorBROUX, Thibault
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
dc.contributor.authorBAMINE, Tahya
hal.structure.identifierALBA Synchrotron light source [Barcelone]
dc.contributor.authorSIMONELLI, Laura
hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
hal.structure.identifierInstitut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier [ICGM]
hal.structure.identifierAdvanced Lithium Energy Storage Systems - ALISTORE-ERI [ALISTORE-ERI]
dc.contributor.authorSTIEVANO, Lorenzo
hal.structure.identifierALBA Synchrotron light source [Barcelone]
dc.contributor.authorFAUTH, François
hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
hal.structure.identifierAdvanced Lithium Energy Storage Systems - ALISTORE-ERI [ALISTORE-ERI]
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorMÉNÉTRIER, Michel
hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorCARLIER, Dany
hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
hal.structure.identifierLaboratoire réactivité et chimie des solides - UMR CNRS 7314 [LRCS]
hal.structure.identifierAdvanced Lithium Energy Storage Systems - ALISTORE-ERI [ALISTORE-ERI]
dc.contributor.authorMASQUELIER, Christian
hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
hal.structure.identifierAdvanced Lithium Energy Storage Systems - ALISTORE-ERI [ALISTORE-ERI]
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorCROGUENNEC, Laurence
dc.date.issued2017
dc.identifier.issn1932-7447
dc.description.abstractEnAmong the series of polyanionic positive electrodes for sodium-ion batteries having the general formula Na3V2(PO4)2F3–yOy (0 ≤ y ≤ 2), the composition Na3V2(PO4)2F3 (y = 0) has the highest theoretical energy that offers competitive electrochemical performances compared to sodium transition metal oxides. Recently, the structural phase diagram from Na3V2(PO4)2F3 to Na1V2(PO4)2F3 has been thoroughly investigated by operando synchrotron X-ray diffraction revealing an unexpected structural feature for the end member composition. In fact, the crystal structure of Na1V2(PO4)2F3 has two very different vanadium environments within each bioctahedron that suggests a charge disproportionation of two VIV into VIII and VV. This work shows an operando X-ray absorption spectroscopy at vanadium K edge during the electrochemical extraction of Na+ in order to monitor the redox processes involved in this compound. The large data set provided by this experiment has been processed by the principal component analysis combined with multivariate curve resolution. The results suggest that the bioctahedra have to be considered as the basic structural unit. The peculiar geometry of this material combined with the mixed vanadium valence, directly investigated here along the reaction, seems to allow original electronic configurations. In particular, the two vanadium sites into the basic bioctahedra unit evolve from VIII–VIII to VIII–VIV and to a final VIII–VIV configuration. These observations are completed with 51V NMR sensitive to diamagnetic V^V.
dc.description.sponsorshipLaboratory of excellency for electrochemical energy storage - ANR-10-LABX-0076
dc.description.sponsorshipBatteries à ions sodium pour des robots télécommandés
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.title.enV^IV disproportionation upon sodium extraction from Na3V2(PO4)2F3 observed by operando x-ray absorption spectroscopy and solid-state NMR
dc.typeArticle de revue
dc.identifier.doi10.1021/acs.jpcc.6b11413
dc.subject.halChimie/Chimie inorganique
dc.subject.halChimie/Matériaux
dc.description.sponsorshipEuropeNa-Ion bAttery Demonstration for Electric Storage
bordeaux.journalJournal of Physical Chemistry C
bordeaux.page4103-4111
bordeaux.volume121
bordeaux.issue8
bordeaux.peerReviewedoui
hal.identifierhal-01481123
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-01481123v1
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