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Effects of Partial Substitution of Mo6+ by Cr6+ and W6+ on the Crystal Structure of the Fast Oxide-Ion Conductor La2Mo2O9

Abstract : The crystal structure of the solid solutions La2Mo2-yCryO9 (y≤0.5) and La2Mo2-yWyO9 (y≤1.4) has been studied using X-ray and neutron powder diffraction. These two series of lanthanum molybdates, which belong to the LAMOX family of fast oxide-ion conductors, exhibit a different structural behavior depending on the substituting element. The Cr series follows a regular Vegard-type evolution of crystallographic parameters. However, the behavior of theWseries is different, the lattice constant varying in a nonlinear fashion with substitution level, resulting in a smaller cell volume for higher tungsten contents, despite the larger ionic radius of tungsten. Two main structural effects are evidenced: a variation in the distribution of ligands around tungsten, made apparent through the changing balance of oxygen O2 and O3 site occupancies along the series, and a nonlinear evolution of interatomic distances and angles involving the O1 oxygen site. An alternative structural description, based on [O1La3Mo] antitetrahedra, is proposed in order to better account for the transport properties of these materials.
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https://hal-univ-lemans.archives-ouvertes.fr/hal-02133790
Contributeur : Gwenaël Corbel <>
Soumis le : dimanche 19 mai 2019 - 22:04:28
Dernière modification le : samedi 3 août 2019 - 01:14:06

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Gwenaël Corbel, Y. Laligant, F. Goutenoire, E. Suard, P. Lacorre. Effects of Partial Substitution of Mo6+ by Cr6+ and W6+ on the Crystal Structure of the Fast Oxide-Ion Conductor La2Mo2O9. Chemistry of Materials, American Chemical Society, 2005, 17 (18), pp.4678-4684. ⟨10.1021/cm0501214⟩. ⟨hal-02133790⟩

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