Insight into Design of Improved Oxide Ion Conductors: Dynamics and Conduction Mechanisms in the Bi0.913V0.087O1.587 Solid Electrolyte

Abstract

Extensive quasielastic neutron scattering measurements have been used to directly observe oxide ion dynamics on the nanosecond timescale in bismuth vanadate with formula Bi0.913V0.087O1.587, which exhibits remarkable oxide ion conductivity at low temperatures. This is the longest timescale 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 timescale 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 localised dynamics of the oxide ions within the VOx 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.