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Dynamic Lone Pairs and Fluoride-Ion Disorder in Cubic-BaSnF 4
hal.structure.identifier | Réseau sur le stockage électrochimique de l'énergie [RS2E] | |
hal.structure.identifier | PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX [PHENIX] | |
hal.structure.identifier | Laboratoire réactivité et chimie des solides - UMR CNRS 7314 UPJV [LRCS] | |
dc.contributor.author | MERCADIER, Briséïs | |
hal.structure.identifier | University of Bath [Bath] | |
dc.contributor.author | COLES, Samuel | |
hal.structure.identifier | Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB] | |
dc.contributor.author | DUTTINE, Mathieu | |
hal.structure.identifier | Institut des Molécules et Matériaux du Mans [IMMM] | |
dc.contributor.author | LEGEIN, Christophe | |
hal.structure.identifier | Institut des Molécules et Matériaux du Mans [IMMM] | |
dc.contributor.author | BODY, Monique | |
hal.structure.identifier | Argonne National Laboratory [Lemont] [ANL] | |
dc.contributor.author | BORKIEWICZ, Olaf | |
hal.structure.identifier | Laboratoire de cristallographie et sciences des matériaux [CRISMAT] | |
dc.contributor.author | LEBEDEV, Oleg | |
hal.structure.identifier | University of Bath [Bath] | |
dc.contributor.author | MORGAN, Benjamin | |
hal.structure.identifier | Réseau sur le stockage électrochimique de l'énergie [RS2E] | |
hal.structure.identifier | Laboratoire réactivité et chimie des solides - UMR CNRS 7314 UPJV [LRCS] | |
dc.contributor.author | MASQUELIER, Christian | |
hal.structure.identifier | Réseau sur le stockage électrochimique de l'énergie [RS2E] | |
hal.structure.identifier | PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX [PHENIX] | |
dc.contributor.author | DAMBOURNET, Damien | |
dc.date.issued | 2023 | |
dc.identifier.issn | 0002-7863 | |
dc.description.abstractEn | Introducing 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.sponsorship | Laboratory of excellency for electrochemical energy storage - ANR-10-LABX-0076 | |
dc.language.iso | en | |
dc.publisher | American Chemical Society | |
dc.title.en | Dynamic Lone Pairs and Fluoride-Ion Disorder in Cubic-BaSnF 4 | |
dc.type | Article de revue | |
dc.identifier.doi | 10.1021/jacs.3c08232 | |
dc.subject.hal | Chimie | |
dc.identifier.arxiv | 10.1021/jacs.3c08232 | |
bordeaux.journal | Journal of the American Chemical Society | |
bordeaux.page | 23739–23754 | |
bordeaux.volume | 145 | |
bordeaux.issue | 43 | |
bordeaux.peerReviewed | oui | |
hal.identifier | hal-04250709 | |
hal.version | 1 | |
hal.popular | non | |
hal.audience | Internationale | |
hal.origin.link | https://hal.archives-ouvertes.fr//hal-04250709v1 | |
bordeaux.COinS | ctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Journal%20of%20the%20American%20Chemical%20Society&rft.date=2023&rft.volume=145&rft.issue=43&rft.spage=23739%E2%80%9323754&rft.epage=23739%E2%80%9323754&rft.eissn=0002-7863&rft.issn=0002-7863&rft.au=MERCADIER,%20Bris%C3%A9%C3%AFs&COLES,%20Samuel&DUTTINE,%20Mathieu&LEGEIN,%20Christophe&BODY,%20Monique&rft.genre=article |
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