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Comprehensive investigation of the Na3V2(PO4)2F3–NaV2(PO4)2F3 system by operando high resolution synchrotron x-ray diffraction

hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
hal.structure.identifierInstitut Laue-Langevin [ILL]
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.authorBIANCHINI, Matteo
hal.structure.identifierEuropean Synchrotron Radiation Facility [ESRF]
dc.contributor.authorFAUTH, François
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorBRISSET, N.
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorWEILL, François
hal.structure.identifierInstitut Laue-Langevin [ILL]
dc.contributor.authorSUARD, Emmanuelle
hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
hal.structure.identifierAdvanced Lithium Energy Storage Systems - ALISTORE-ERI [ALISTORE-ERI]
hal.structure.identifierLaboratoire réactivité et chimie des solides - UMR CNRS 7314 UPJV [LRCS]
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.issued2015
dc.identifier.issn0897-4756
dc.description.abstractEnNa3V2(PO4)2F3 is a positive electrode material for Na-ion batteries which is attracting strong interest due to its high capacity, rate capability, and long-term cycling stability. The sodium extraction mechanism from this material has been always described in the literature as a straightforward solid solution, but several hints point toward a more complicated phase diagram. In this work we performed high angular resolution synchrotron radiation diffraction measurements, realized operando on sodium batteries upon charge. We reveal an extremely interesting phase diagram, created by the successive crystallization of four intermediate phases before the end composition NaV2(PO4)2F3 is reached. Only one of these phases undergoes a solid solution reaction, in the interval between 1.8 and 1.3 Na per formula unit. The ability to resolve weak Bragg reflections allowed us to reveal differences in terms of symmetry among the phases, to determine their previously unknown space groups, and to correlate them with sodium (dis)ordering in the structure. Rietveld refinements enabled us to follow fine structural modifications in great detail. Intermediate identified phases are not simply described by their unit cell parameters, but bond-length variations can be tracked, as well as polyhedral distortions and site occupancy factors for mobile sodium ions. For NaV2(PO4)2F3 a full crystal structure determination was also carried out for the first time directly from operando measurements, assigning it to the Cmc21 space group and revealing two vanadium environments: V3+ and V5+. Our study demonstrates that improved angular resolution and high intensity diffraction data are key parameters for direct observation of fine reaction pathways in electrode materials and that the obtained insight is crucial for the understanding of (de)intercalation mechanisms in Na-ion batteries.
dc.description.sponsorshipBatteries à ions sodium pour des robots télécommandés - ANR-13-DESC-0001
dc.description.sponsorshipLaboratory of excellency for electrochemical energy storage - ANR-10-LABX-0076
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.title.enComprehensive investigation of the Na3V2(PO4)2F3–NaV2(PO4)2F3 system by operando high resolution synchrotron x-ray diffraction
dc.typeArticle de revue
dc.identifier.doi10.1021/acs.chemmater.5b00361
dc.subject.halChimie/Matériaux
bordeaux.journalChemistry of Materials
bordeaux.page3009-3020
bordeaux.volume27
bordeaux.issue8
bordeaux.peerReviewedoui
hal.identifierhal-01233162
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-01233162v1
bordeaux.COinSctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Chemistry%20of%20Materials&rft.date=2015&rft.volume=27&rft.issue=8&rft.spage=3009-3020&rft.epage=3009-3020&rft.eissn=0897-4756&rft.issn=0897-4756&rft.au=BIANCHINI,%20Matteo&FAUTH,%20Fran%C3%A7ois&BRISSET,%20N.&WEILL,%20Fran%C3%A7ois&SUARD,%20Emmanuelle&rft.genre=article


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