Lithium Lanthanum Titanate Single Crystals: Dependence of Lithium-Ion Conductivity on Crystal Domain Orientation

Lithium lanthanum titanate La_2/3-Li₃TiO₃ (LLTO) has the potential to exhibit the highest Li-ion conductivity among oxide-based electrolytes because of the fast Li-ion diffusion derived from its crystal structure. Herein, bulk Li-ion conductivity of up to σ_bulk = 4.0 × 10^-3 S/cm at 300 K, which is approximately three to four times higher than that of LLTO polycrystals, was demonstrated using LLTO single crystals, and their dependence on crystal domain orientation was examined. A change in the activation energy, which was previously obscured because of random crystal orientation, was observed at approximately 260 K. Furthermore, electron microscopy analysis indicated that the ionic conductivity of LLTOs remained higher because the region with the highest ionic conductivity was tilted away from the ideal conduction orientation. The results reported herein provide the highest conductivity in LLTO and important insights into their crystal structures, enabling higher conductivity in novel oxide-based electrolyte design.