Defect structure of quenched γ-BICOVOX by combined X-ray and neutron powder diffraction

A detailed investigation of the defect structure of the Co doped BIMEVOX solid electrolyte, Bi₂V_{1 ? x}Co_xO_{5.5 ? 3x/2} (x = 0.1 and x = 0.2), quenched from high temperature, has been carried out using X-ray and neutron powder diffraction data measured at room temperature. The structure is built up from alternating layers of Bi₂O₂]_n²ⁿ⁺ and V_{1 ? x}Co_xO_{3.5 ? 3x/2}]_n^2n? with disorder limited to the vanadate layer. The ideal V/Co co-ordination is octahedral with corner sharing of equatorial oxygens. The refinements show that the true structure is distorted, with disorder in both apical and equatorial oxygens and oxygen vacancies concentrated in the equatorial positions. Detailed analysis of the oxygen site occupancies reveals two main types of V/Co co-ordination viz. distorted octahedral and distorted tetrahedral. The majority of the sites in both compositions are tetrahedral.