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Abstract

Metal fluorides with 3D open structures, pyrochlore (pyr) or hexagonal tungsten bronze (HTB), are promising materials as positive electrodes for rechargeable batteries or catalysts. Herein, we have developed a two-step synthesis procedure to obtain new anhydrous mixed-metal-cation fluorides crystallizing in the pyrochlore structure. The first step consists of preparing mixed-metal ammonium fluorides (NH4)M2+Fe3+F6 (M = Mn, Fe, Co Ni) using different synthesis strategies. For M = Mn, three allotropic varieties of (NH4)Mn2+Fe3+F6 are obtained; two phases adopt the expected pyrochlore network with either the cubic Fm(3)m or the orthorhombic Pnma space group, and the third phase exhibits a 3D network with narrow pseudotriangular cavities. Fe-57 Mossbauer spectrometry indicates that the crystal structures are governed by the Fe3+/Mn2+ cationic order or disorder. The second step is a topotactic oxidation of pyr-(NH4)(M2+Fe3+F6) under a molecular F-2 flow. To better understand the reaction mechanism, the topotactic oxidation was followed by thermogravimetry, XRD, FTIR, and Mossbauer spectrometry. The successful synthesis of the first anhydrous pyr-M0.53+Fe0.5F3 provides a new route to prepare anhydrous mixed-metal fluorides pyrochlore with empty cavities of the open framework.

Authors

Lemoine, Kevin;  Moury, Romain;  Durand, Etienne;  Arroyo-de Dompablo, Elena;  Moran, Emilio;  Leblanc, Marc;  Hemon-Ribaud, Annie;  Greneche, Jean-Marc;  Galven, Cyrille;  Gunes, Veyis;  Lhoste, Jerome;  Maisonneuve, Vincent

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