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Towards reversible high-voltage multi-electron reactions in alkali-ion batteries using vanadium phosphate positive electrode materials

hal.structure.identifierLaboratoire réactivité et chimie des solides - UMR CNRS 7314 UPJV [LRCS]
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.authorBOIVIN, Edouard
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.issued2021-03
dc.identifier.issn1420-3049
dc.description.abstractEnVanadium phosphate positive electrode materials attract great interest in the field of Alkali-ion (Li, Na and K-ion) batteries due to their ability to store several electrons per transition metal. These multi-electron reactions (from V2+ to V5+) combined with the high voltage of corresponding redox couples (e.g., 4.0 V vs. for V3+/V4+ in Na3V2(PO4)2F3) could allow the achievement the 1 kWh/kg milestone at the positive electrode level in Alkali-ion batteries. However, a massive divergence in the voltage reported for the V3+/V4+ and V4+/V5+ redox couples as a function of crystal structure is noticed. Moreover, vanadium phosphates that operate at high V3+/V4+ voltages are usually unable to reversibly exchange several electrons in a narrow enough voltage range. Here, through the review of redox mechanisms and structural evolutions upon electrochemical operation of selected widely studied materials, we identify the crystallographic origin of this trend: the distribution of PO4 groups around vanadium octahedra, that allows or prevents the formation of the vanadyl distortion (O…V4+=O or O…V5+=O). While the vanadyl entity massively lowers the voltage of the V3+/V4+ and V4+/V5+ couples, it considerably improves the reversibility of these redox reactions. Therefore, anionic substitutions, mainly O2− by F−, have been identified as a strategy allowing for combining the beneficial effect of the vanadyl distortion on the reversibility with the high voltage of vanadium redox couples in fluorine rich environments.
dc.description.sponsorshipLaboratory of excellency for electrochemical energy storage - ANR-10-LABX-0076
dc.language.isoen
dc.publisherMDPI
dc.subject.enbatteries
dc.subject.enpositive electrode
dc.subject.envanadium phosphates
dc.subject.encovalent vanadyl bond
dc.subject.enmixed anion
dc.title.enTowards reversible high-voltage multi-electron reactions in alkali-ion batteries using vanadium phosphate positive electrode materials
dc.typeArticle de revue
dc.identifier.doi10.3390/molecules26051428
dc.subject.halChimie/Matériaux
bordeaux.journalMolecules
bordeaux.page1428 (22 p.)
bordeaux.volume26
bordeaux.issue5
bordeaux.peerReviewedoui
hal.identifierhal-03196199
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-03196199v1
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