Insight into Design of Improved Oxide Ion Conductors: Dynamics and Conduction Mechanisms in the Bi(0.913)V(0.087)O(1.587) Solid Electrolyte

[Image: see text] Extensive quasielastic neutron scattering measurements have been used to directly observe oxide ion dynamics on the nanosecond time scale in bismuth vanadate with formula Bi(0.913)V(0.087)O(1.587), which exhibits remarkable oxide ion conductivity at low temperatures. This is the longest time scale neutron scattering study of any fluorite-type solid electrolyte, and it represents only the second case of oxide ion dynamics in any material observed on a nanosecond time scale by quasielastic neutron scattering. Ab initio molecular dynamics simulations reveal two mechanisms that contribute to the oxide ion dynamics in the material: a slower diffusion process through the Bi–O sublattice and a faster process which corresponds to more localized dynamics of the oxide ions within the VO(x) coordination spheres. The length of the trajectories simulated and the validation of the simulations by neutron scattering experiments provide for the first time a quantitative insight into the relative contributions of the two processes to the oxide ion conduction in this exceptional solid electrolyte, which can be used to derive design principles for the preparation of related oxide ion conductors with even better properties.