Highly Conductive Garnet-Type Electrolytes: Access to Li_6.5La₃Zr_1.5Ta_0.5O₁₂ Prepared by Molten Salt and Solid-State Methods

Tantalum-doped garnet (Li_6.5La₃Zr_1.5Ta_0.5O₁₂, LLZTO) is a promising candidate to act as a solid electrolyte in all-solid-state batteries owing to both its high Li⁺ conductivity and its relatively high robustness against the Li metal. Synthesizing LLZTO using conventional solid-state reaction (SSR) requires, however, high calcination temperature (>1000 °C) and long milling steps, thereby increasing the processing time. Here, we report on a facile synthesis route to prepare LLZTO using a molten salt method (MSS) at lower reaction temperatures and shorter durations (900 °C, 5 h). Additionally, a thorough analysis on the properties, i.e., morphology, phase purity, and particle size distribution of the LLZTO powders, is presented. LLZTO pellets, either prepared by the MSS or the SSR method, that were sintered in a Pt crucible showed Li⁺ ion conductivities of up to 0.6 and 0.5 mS cm^-1, respectively. The corresponding activation energy values are 0.37 and 0.38 eV, respectively. The relative densities of the samples reached values of approximately 96%. For comparison, LLZTO pellets sintered in alumina crucibles or with γ-Al₂O₃ as sintering aid revealed lower ionic conductivities and relative densities with abnormal grain growth. We attribute these observations to the formation of Al-rich phases near the grain boundary regions and to a lower Li content in the final garnet phase. The MSS method seems to be a highly attractive and an alternative synthetic approach to SSR route for the preparation of highly conducting LLZTO-type ceramics.