Phase evolution,structure, and electrochemical performance of Al-, Ga- and Ta- substituted Li7La3Zr2O12 ceramic electrolytes by a modified wet chemical route

Garnet-type Li₇La₃Zr₂O₁₂ (LLZO) is one of the most promising solid-state electrolytes (SSEs) for advanced solid-state lithium batteries (SSLBs). In this work, Li_6.25Al_0.25La₃Zr₂O₁₂, Li_6.4Ga_0.2La₃Zr₂O₁₂, and Li_6.4La₃Zr_1.4Ta_0.6O₁₂ ceramics are prepared by a modified wet chemical route. The composition of the black mixtures derived from the precursors is ascertained. The phase evolution and structural properties from the ceramic mother powders to the final ceramic electrolytes are discussed in detail. The characteristic of cubic LLZO with the space group I-43d arises in the Li_6.4Ga_0.2La₃Zr₂O₁₂ ceramic electrolyte pellet after the secondary higher-temperature (1200 °C) sintering. The Rietveld refinement reveals the roles of Al³⁺ substitution at the Li⁺ sites and Ta⁵⁺ substitution at the Zr⁴⁺ sites to adjust crystal structure. In addition, the electrochemical performance of the ceramic pellets is also investigated. Remarkably, the Li_6.4La₃Zr_1.4Ta_0.6O₁₂ ceramic electrolyte has the most outstanding electrochemical performance, showing the high ionic conductivity of 6.88 × 10^?4 S cm^?1 (25 °C), the low activation energy of 0.42 eV and an extremely low electronic conductivity of 1.77 × 10^?8 S cm^?1 (25 °C). Overall, it is supposed that this work may help to achieve high-quality modified LLZO ceramic electrolytes, especially using the wet chemical strategy.