Fast Li-Ion-Conducting Garnet-Related Li_7-3xFe_xLa₃Zr₂O₁₂ with Uncommon I4-3d Structure

Fast Li-ion-conducting Li oxide garnets receive a great deal of attention as they are suitable candidates for solid-state Li electrolytes. It was recently shown that Ga-stabilized Li₇La₃Zr₂O₁₂ crystallizes in the acentric cubic space group I4-3d. This structure can be derived by a symmetry reduction of the garnet-type Ia3-d structure, which is the most commonly found space group of Li oxide garnets and garnets in general. In this study, single-crystal X-ray diffraction confirms the presence of space group I4-3d also for Li_7-3xFe_xLa₃Zr₂O₁₂. The crystal structure was characterized by X-ray powder diffraction, single-crystal X-ray diffraction, neutron powder diffraction, and Mößbauer spectroscopy. The crystal-chemical behavior of Fe³⁺ in Li₇La₃Zr₂O₁₂ is very similar to that of Ga³⁺. The symmetry reduction seems to be initiated by the ordering of Fe³⁺ onto the tetrahedral Li1 (12a) site of space group I4-3d. Electrochemical impedance spectroscopy measurements showed a Li-ion bulk conductivity of up to 1.38 × 10^-3 S cm^-1 at room temperature, which is among the highest values reported for this group of materials.