Materials with high oxygen ion conductivity and low electronic conductivity are required for electrolytes in solid oxide fuel cells (SOFC) and high-temperature electrolysis (SOEC). A potential candidate for the electrolytes, which separate oxidation and reduction processes, is rare-earth doped ceria. The prediction of the ionic conductivity of the electrolytes and a better understanding of the underlying atomistic mechanisms provide an important contribution to the future of sustainable and efficient energy conversion and storage. The central aim of this paper is the detailed investigation of the relationship between defect interactions at the microscopic level and the macroscopic oxygen ion conductivity in the bulk of doped ceria. By combining ab initio density functional theory (DFT) with Kinetic Monte Carlo (KMC) simulations, the oxygen ion conductivity is predicted as a function of the doping concentration. Migration barriers are analyzed for energy contributions, which are caused by the interactions of dopants and vacancies with the migrating oxygen vacancy. We clearly distinguish between energy contributions that are either uniform for forward and backward jumps or favor one migration direction over the reverse direction. If the presence of a dopant changes the migration energy identically for forward and backward jumps, the resulting energy contribution is referred to as blocking. If the change in migration energy due to doping is different for forward and backward jumps of a specific ionic configuration, the resulting energy contributions are referred to as trapping. The influence of both effects on the ionic conductivity is analyzed: blocking determines the dopant fraction where the ionic conductivity exhibits the maximum. Trapping limits the maximum ionic conductivity value. In this way, a deeper understanding of the underlying mechanisms determining the influence of dopants on the ionic conductivity is obtained and the ionic conductivity is predicted more accurately. The detailed results and insights obtained here for doped ceria can be generalized and applied to other ion conductors that are important for SOFCs and SOECs as well as solid state batteries.

We investigate the dopant distribution and its influence on the oxygen ion conductivity of ceria doped with rare earth oxides by combining density functional theory and Monte Carlo simulations. We calculate the association energies of dopant pairs, oxygen vacancy pairs and between dopant ions and oxygen vacancies by means of DFT + U including finite size corrections. The cation coordination numbers from ensuing Metropolis Monte Carlo simulations show remarkable agreement with experimental data. Combining Metropolis and Kinetic Monte Carlo simulations we find a distinct dependence of the ionic conductivity on the dopant distribution and predict long term degradation of electrolytes based on doped ceria.

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