Abstract
The room temperature crystal structure of the fast oxygen ion conductor Bi4(V0.85Co0.15)2O11−δ(BICOVOX.15) was refined within the average tetragonal unit cell from single-crystal neutron diffraction data. The unit cell dimensions areaT=3.929(2) Å andcT=15.476(9) Å in space groupI4/mmmwithZ=1. The conventionalRwfactor is 0.067. The structure consists of intergrowth, along the c-axis, of alternating (Bi2O2)2+sheets and (VO3.5□0.5)2−oxygen-deficient perovskite-like layers. The compound, which exhibits a high ionic conductivity at moderate temperatures, undergoes a phase transition around 780 K between the disordered high-temperatureγ-phase and the lower temperatureγ′-phase, showing a modulated superstructure. Oxygen vacancies are localized in the perovskite-like layers, oxygen stoichiometry is derived, and oxygen diffusion paths are proposed for theγ′-phase at room temperature.
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