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Tawse, Dylan
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article
Variable Temperature Neutron Diffraction Study of the Oxide Ion Conductor Ba3VWO8.5
Abstract
Ba3VWO8.5 is an oxide ion conductor with a bulk conductivity of 5.0 x 10-5 S cm-1 at 600 °C. Ba3VWO8.5 is anomalous to the other Ba3M’M’’O8.5 (M’ = Nb; M’’= Mo, W) oxide ionic conductors, as it exhibits cation order with vanadium and tungsten on the M1 site only. Here we report a variable temperature neutron diffraction study of Ba3VWO8.5 that demonstrates cation order is retained up to 800 °C. We show for the first time that the structural rearrangements reported for hexagonal perovskite derivatives Ba3M’M’’O8.5 are dictated by water absorption. The significant water uptake in Ba3M’M’’O8.5 (M’ = Nb; M’’= Mo, W) arises due to the flexibility of the crystal structure, whereby upon absorption of water, a fraction of the transition metal cations moves from the M1 site to the octahedral M2 site. The results presented here demonstrate that the presence of 50% V5+ on the M1 site, which has a strong preference for tetrahedral geometry, is enough to disrupt the flexibility of the cation sublattice resulting in the ordering of the cations exclusively on the M1 site and no significant water absorption.