Density-Functional-Theory Modeling of Cation Diffusion in Bulk La 1 - x Sr x MnO 3 ± δ ( x = 0.0 – 0.25 ) for Solid-Oxide Fuel-Cell Cathodes
In this work, the A - and B -site cation migration pathways involving defect complexes in bulk La 1-x Sr x MnO 3±δ (LSM) at x = 0.0-0.25 are investigated based on density-functional-theory modeling for solid-oxide fuel-cell (SOFC) cathode applications. We propose a dominant A -site cation migration mechanism which involves an A -site cation (e.g., La$x\atop{A}$) V A "' of a V A "' -V B "' cluster, where La$x\atop{A}$, V A "' and V B "' are La 3+ , A-site vacancy, and B-site vacancy in bulk LSM, respectively, and V A "' -V B "' is the first nearest-neighbor V A "' and V B "' pair. This hop exhibits an approximately 1.6-eV migration barrier as compared to approximately 2.9 eV of the La$x\atop{A}$ hop into a V A "'. This decrease in the cation migration barrier is attributed to the presence of the V B "' relieving the electrostatic repulsion and steric constraints to the migrating A-site cations in the transition-state image configurations.