Density Functional Theory Modeling of Cation Diffusion in Bulk Lanthanum Manganite and Tetragonal Zirconia for Solid Oxide Fuel Cell Applications
Authors: Lee Yueh-Lin , Duan Yuhua , Morgan Dane , Sorescu Dan , Abernathy Harry , Hackett Gregory A 
Published: February 2022

Cation diffusion in perovskites such as La1-xSrxMnO3±δ (LSM) and fluorites such as Yttria Stabilized Zirconia (YSZ) plays a key role in controlling performance and long-term stability of solid oxide fuel cells (SOFCs) and of the corresponding electrode/electrolyte interfaces. For point defects based cation migration mechanisms, discrepancies between experimental studies and atomistic modeling results are generally observed when trying to identify the apparent activation energies of the cation diffusivities. In particular, computational modeling of the simple point defect migration generally overestimates the apparent activation energies by several eVs [1-3] relative to experimental results. Despite the existence of few proposed defect cluster pathways in the SOFC literature, the corresponding energetics based on atomistic level modeling is quite limited. As a result, outstanding questions related to the influence of the local bonding environment of the material upon the activation energies of cation diffusion and upon the energetics of the defect cluster carriers are still open.

In this presentation, density functional theory (DFT) calculations of the cation diffusion involving mechanisms beyond the isolated point defect migration mechanism are discussed in connection to SOFC applications. The barriers of the cations, cation vacancy clusters, and cation impurities migration as well as their corresponding saddle point configurations in bulk LaMnO3±δ (LMO) and tetragonal ZrO2 are investigated. For cation vacancy migration in both LaMnO3 and tetragonal ZrO2 systems, it was revealed that significant reduction in the barriers of 1~3 eV takes place when there exists an additional nearest neighbor vacancy or a nearest neighbor vacancy pair bound to the original cation vacancy transport carrier (i.e., partially or fully bound Schottky defects). Such a significant reduction in the migration barriers of isolated cation vacancy migration due to the presence of an additional nearest neighbor vacancy or a vacancy pair invokes the need to examine other possible defect cluster diffusion mechanisms that exhibit attractive or weakly repulsive interactions between point defects. For example, our recent studies [1,3] suggest that the presence of a nearest neighbor B-site cation vacancy in bulk LMO decreases the electrostatic repulsion and steric constraints to the migrating A-site cations in the transition state configurations, leading to a more active A-site cation diffusion with apparent activation energies in good agreement with the experimental measurements. An analogous scenario is also observed for the Lanthanide impurity migration (via a cation vacancy related mechanism) in tetragonal ZrO2, where the migration barriers of partial and full Schottky bound defects are about 1.5 and 2.4 eV lower than those of simple cation vacancy migration (about 3 eV). By considering the attractive interactions of -1.0 and -1.4 eV for the partial (VZr-VO) and full (VO-VZr-VO) bound Schottky defects along with the separated Schottky defect formation energies of 4~5 eV (in a 288-atom ZrO2 supercells), it follows that cation impurity diffusion via partially and fully bonded Schottky defects could be more active than the cation vacancy migration of the separated Schottky defects in tetragonal ZrO2. Finally, the trends in the migration barriers of the defect cluster mechanisms among several types of cation impurities relevant for SOFC applications in LMO and tetragonal ZrO2 will be also discussed.

References:

Y.-L. Lee, Y. Duan, D. Morgan, D. C. Sorescu, H. Abernathy, and G. Hackett, “Density-Functional-Theory Modeling of Cation Diffusion in Bulk La1−xSrxMnO3±δ (x=0.0–0.25) for Solid-Oxide Fuel-Cell Cathodes”,
Physical Review Applied, 8, 044001 (2017).

B. Puchala, Y.-L. Lee, and D. Morgan, A-Site Diffusion in La1−xSrxMnO3: Ab Initio and Kinetic Monte Carlo Calculations, Journal of The Electrochemical Society, 160 (8) F877-F882 (2013).

Y.-L. Lee, Y. Duan, D. Morgan, D. C. Sorescu, H. Abernathy, and G. Hackett, “Density Functional Theory Modeling of A-site Cation Diffusion in Bulk LaMnO3±δ for Solid Oxide Fuel Cell Cathodes”, ECS Transactions, 78(1)2797-2806 (2017).