Revealing the Interplay of Local Environments and Ionic Transport in Perovskite Solid Electrolytes

Solid-state ionic conduction is significantly influenced by bottleneck sizes, which impede ion diffusion within solid lattices. Using aberration-corrected scanning transmission electron microscopy and multislice electron ptychography, we directly observed that increased La occupancy in the perovskite solid electrolyte Li_0.5La_0.5TiO₃ correlates with reduced bottleneck sizes formed by four oxygen atoms connecting neighboring A-site cages. This correlation was also confirmed in local aperiodic regions, where smaller bottleneck sizes due to increased La occupancies affect the directionality and dimensionality of the Li⁺ ion conductivity. Furthermore, while prior studies have focused on averaged Li⁺ ion diffusion across different bottleneck areas or chemical environments, by devising a molecular dynamics (MD)-based methodology, we quantify the diffusivity of Li⁺ ions through specific bottleneck regions. Atomistic simulations, including nudged elastic band calculations and this MD-based methodology, revealed that larger bottleneck sizes correlate with smaller local migration barriers and higher local diffusivity. This study elucidates the relationship among local chemistry, lattice structure, and Li⁺ ion transport, providing insights for the design of advanced oxide solid electrolytes.