Fast-ion conduction and local environments in BIMEVOX

Abstract

The energy landscape of the fast-ion conductor Bi 4 V 2 O 11 is studied using density functional theory. There are a large number of energy minima, dominated by low-lying thermally accessible configurations in which there are equal numbers of oxygen vacancies in each vanadium–oxygen layer, a range of vanadium coordinations and a large variation in Bi–O and V–O distances. By dividing local minima in the energy landscape into sets of configurations, we then examine diffusion in each different layer using ab initio molecular dynamics. These simulations show that the diffusion mechanism mainly takes place in the 〈110〉 directions in the vanadium layers, involving the cooperative motion of the oxide ions between the O(2) and O(3) sites in these layers, but not O(1) in the Bi–O layers, in agreement with experiment. O(1) vacancies in the Bi–O layers are readily filled by the migration of oxygens from the V–O layers. The calculated ionic conductivity is in reasonable agreement with the experiment. We compare ion conduction in δ-Bi 4 V 2 O 11 with that in δ-Bi 2 O 3 . This article is part of the Theo Murphy meeting issue ‘Understanding fast-ion conduction in solid electrolytes’.