Gallium-Doping Effects on Structure, Lithium-Conduction, and Thermochemical Stability of Li7-3xGaxLa3Zr2O12 Garnet-Type Electrolytes

One of the most promising electrolytes for all-solid-state lithium batteries is Li₇La₃Zr₂O₁₂. Previously, their thermodynamic stability, Li-ion conductivity, and structural features induced by Ga-doping have not been empirically determined or correlated. Here, their interplay was examined for Li_7−3xGa_xLa₃Zr₂O₁₂ with target xGa=0, 0.25, 0.50, 0.75, and 1.00 atoms per formula unit (apfu). Formation enthalpies, obtained with calorimetry and found to be exothermic at all compositions, linearly decreased in stability with increased xGa. At dilute xGa substitution, the formation enthalpy curve shifted stepwise endothermically, and the conductivity increased to a maximum, coinciding with 0.529 Ga apfu. This correlated with percolation threshold analysis (0.558 Ga apfu). Further substitution (0.787 Ga apfu) produced a large decrease in the stability and conductivity due to a large increase in point defects and blocked Li-migration pathways. At xGa=1.140 apfu, a small exothermic shift was related to defect cluster organization extending the Li hopping distance and decreased Li-ion conductivity.