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Dynamic Lone Pairs and Fluoride-Ion Disorder in Cubic-BaSnF 4

hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
hal.structure.identifierPHysicochimie des Electrolytes et Nanosystèmes InterfaciauX [PHENIX]
hal.structure.identifierLaboratoire réactivité et chimie des solides - UMR CNRS 7314 UPJV [LRCS]
dc.contributor.authorMERCADIER, Briséïs
hal.structure.identifierUniversity of Bath [Bath]
dc.contributor.authorCOLES, Samuel
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorDUTTINE, Mathieu
hal.structure.identifierInstitut des Molécules et Matériaux du Mans [IMMM]
dc.contributor.authorLEGEIN, Christophe
hal.structure.identifierInstitut des Molécules et Matériaux du Mans [IMMM]
dc.contributor.authorBODY, Monique
hal.structure.identifierArgonne National Laboratory [Lemont] [ANL]
dc.contributor.authorBORKIEWICZ, Olaf
hal.structure.identifierLaboratoire de cristallographie et sciences des matériaux [CRISMAT]
dc.contributor.authorLEBEDEV, Oleg
hal.structure.identifierUniversity of Bath [Bath]
dc.contributor.authorMORGAN, Benjamin
hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
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.identifierPHysicochimie des Electrolytes et Nanosystèmes InterfaciauX [PHENIX]
dc.contributor.authorDAMBOURNET, Damien
dc.date.issued2023
dc.identifier.issn0002-7863
dc.description.abstractEnIntroducing compositional or structural disorder within crystalline solid electrolytes is a common strategy for increasing their ionic conductivity. (M,Sn)F2 fluorites have previously been proposed to exhibit two forms of disorder within their cationic host frameworks: occupational disorder from randomly distributed M and Sn cations and orientational disorder from Sn(II) stereoactive lone pairs. Here, we characterize the structure and fluoride-ion dynamics of cubic BaSnF4, using a combination of experimental and computational techniques.Rietveld refinement of the X-ray diffraction (XRD) data confirms an average fluorite structure with {Ba,Sn} cation disorder, and the 119Sn Mössbauer spectrum demonstrates the presence of stereoactive Sn(II) lone pairs. X-ray total-scattering PDF analysis and ab initio molecular dynamics simulations reveal a complex local structure with a high degree of intrinsic fluoride ion disorder, where 1/3 of fluoride ions occupy octahedral “interstitial” sites: this fluoride-ion disorder is a consequence of repulsion between Sn lone pairs and fluoride ions that destabilizes Sn-coordinated tetrahedral fluoride-ion sites. Variable-temperature 19F NMR experiments and analysis of our molecular dynamics simulations reveal highly inhomogeneous fluoride-ion dynamics, with fluoride ions in Sn-rich local environments significantly more mobile than those in Ba-rich environments. Our simulations also reveal dynamical reorientation of the Sn lone pairs that is biased by the local cation configuration and coupled to the local fluoride-ion dynamics. We end by discussing the effect of host-framework disorder on long-range diffusion pathways in cubic BaSnF4.
dc.description.sponsorshipLaboratory of excellency for electrochemical energy storage - ANR-10-LABX-0076
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.title.enDynamic Lone Pairs and Fluoride-Ion Disorder in Cubic-BaSnF 4
dc.typeArticle de revue
dc.identifier.doi10.1021/jacs.3c08232
dc.subject.halChimie
dc.identifier.arxiv10.1021/jacs.3c08232
bordeaux.journalJournal of the American Chemical Society
bordeaux.page23739–23754
bordeaux.volume145
bordeaux.issue43
bordeaux.peerReviewedoui
hal.identifierhal-04250709
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-04250709v1
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