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Exploring the Sm1-xCaxFe3-x tysonite solid solution as a solid-state electrolyte : relationship between structural features and F- ionic conductivity

hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorDIEUDONNÉ, Belto
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
hal.structure.identifierInstitut des Molécules et Matériaux du Mans [IMMM]
dc.contributor.authorCHABLE, Johann
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorMAUVY, Fabrice
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorFOURCADE, Sébastien
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorDURAND, Etienne
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorLEBRAUD, Éric
hal.structure.identifierInstitut des Molécules et Matériaux du Mans [IMMM]
dc.contributor.authorLEBLANC, Marc
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.identifierInstitut des Molécules et Matériaux du Mans [IMMM]
dc.contributor.authorMAISONNEUVE, Vincent
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorDEMOURGUES, Alain
dc.date.issued2015
dc.identifier.issn1932-7447
dc.description.abstractEnPure tysonite Sm1–xCaxF3–x solid solutions for 0.05 ≤ x ≤ 0.17 have been prepared by the solid-state route. For the first time, the partial Sm1–xCaxF3–x solid solution is investigated on the basis of structural features and ionic conductivity measurements. Powder X-ray diffraction Rietveld refinements show an unexpected decrease of the hexagonal unit cell volume related to the creation of fluorine vacancies. The local environment of F1, which is mainly responsible for the ionic conductivity, changes with the Ca content: the distortion of the F1(Sm,Ca)4 tetrahedral site decreases with the Ca content. Fluoride ion exchanges have been qualitatively probed on two Sm1–xCaxF3–x (x = 0.05 and x = 0.15) samples thanks to 19F magic angle spinning NMR experiments at various spinning frequencies and temperatures. At room temperature, the ionic conductivity decreases exponentially with the Ca content and the activation energy increases monotonously with the Ca content. The highest conductivity is found for the lowest Ca content or the smallest fluorine vacancy content stabilized in the Sm1–xCaxF3–x tysonite network corresponding to Sm0.95Ca0.05F2.95 (10–4 S·cm–1, Ea = 0.36 eV at room temperature). For this composition, the largest dispersions of F2–(Sm,Ca) and F3–(Sm,Ca) distances as well as (Sm,Ca)–F1–(Sm,Ca) angles are observed. The buckling of F2/F3 sheets around the z = 1/4 coordinate for low Ca content affects the large F1 tetrahedral site with the strongest distortion. The higher the buckling effect into the F2/F3 sheets, the higher the F1 local site distortion and the higher the ionic mobility and conductivity.
dc.description.sponsorshipBatteries tout solide à ions fluorure - ANR-12-PRGE-0009
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.subject.enAnions
dc.subject.enSolutions
dc.subject.enFluorine
dc.subject.enIonic conductivity
dc.subject.enNuclear magnetic resonance spectroscopy
dc.title.enExploring the Sm1-xCaxFe3-x tysonite solid solution as a solid-state electrolyte : relationship between structural features and F- ionic conductivity
dc.typeArticle de revue
dc.identifier.doi10.1021/acs.jpcc.5b05016
dc.subject.halChimie/Matériaux
bordeaux.journalJournal of Physical Chemistry C
bordeaux.page25170–25179
bordeaux.volume119
bordeaux.issue45
bordeaux.peerReviewedoui
hal.identifierhal-01232331
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-01232331v1
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