Stability of Garnet-Type Li7La3Zr2O12-Based Ceramics for All-Solid-State Batteries

Al and Nb-doped Li₇ La₃ Zr₂O₁₂ (LLZO) and W-doped LLZO lithium ion conducting electrolyte samples were prepared and their H₂O stability was investigated. The LLZO samples were exposed to 50% humidified air for 48 h. After H₂O exposure, a cubic to tetragonal transformation occurred and acquired SEM images exhibited the presence of reaction phases at the grain boundaries of Al and Nb-LLZO. As a result, the lithium ion conductivity significantly decreased after H₂O exposure. On the contrary, W-LLZO showed good stability against H₂O. Although the cubic to tetragonal transformation was also observed in H₂O-exposed W-LLZO, the decrease in lithium ion conductivity was found to be modest. No morphological changes of the W-LLZO samples were confirmed in the H₂O-exposed W-LLZO samples.