Infinite dilution in doped ceria and high activation energies

Abstract

Oxygen ion diffusion determines the performance of materials in energy conversion, energy storage and catalysis. For nominally pure cerium oxide, experiments measure high activation enthalpies while calculations predict low activation enthalpies. Moreover, for doped oxides, e.g. doped ceria, experiments show a high activation enthalpy for both pure ceria and for high dopant fractions, leading to a minimum in activation enthalpy for small dopant fractions. While for high dopant fractions the increase in activation enthalpy is correlated with the association of oxygen vacancies and dopant ions, which are both created by doping, the minimum in activation enthalpy is assumed in the literature to be related to the maximum in ionic conductivity at similar dopant fractions. In this study, density functional theory (DFT) calculations and Kinetic Monte Carlo (KMC) simulations are combined in order to calculate the ionic conductivity and activation enthalpy in doped oxides. We show that the experimental ionic conductivity and activation energy in nominally pure cerium oxide is dominated by impurities. We resolve the discrepancy between activation enthalpies of nominally pure oxides in experiments as opposed to calculations. This will lead to a more comprehensive understanding of the oxygen ion conductivity and its underlying atomistic mechanisms. Moreover, such a focus will be of great benefit to the future development of sustainable and efficient materials.