Crystal Structure of Garnet-Related Li-Ion Conductor Li(7–3x)Ga(x)La(3)Zr(2)O(12): Fast Li-Ion Conduction Caused by a Different Cubic Modification?

[Image: see text] Li-oxide garnets such as Li(7)La(3)Zr(2)O(12) (LLZO) are among the most promising candidates for solid-state electrolytes to be used in next-generation Li-ion batteries. The garnet-structured cubic modification of LLZO, showing space group Ia-3d, has to be stabilized with supervalent cations. LLZO stabilized with Ga(3+) shows superior properties compared to LLZO stabilized with similar cations; however, the reason for this behavior is still unknown. In this study, a comprehensive structural characterization of Ga-stabilized LLZO is performed by means of single-crystal X-ray diffraction. Coarse-grained samples with crystal sizes of several hundred micrometers are obtained by solid-state reaction. Single-crystal X-ray diffraction results show that Li(7–3x)Ga(x)La(3)Zr(2)O(12) with x > 0.07 crystallizes in the acentric cubic space group I-43d. This is the first definite record of this cubic modification for LLZO materials and might explain the superior electrochemical performance of Ga-stabilized LLZO compared to its Al-stabilized counterpart. The phase transition seems to be caused by the site preference of Ga(3+). (7)Li NMR spectroscopy indicates an additional Li-ion diffusion process for LLZO with space group I-43d compared to space group Ia-3d. Despite all efforts undertaken to reveal structure–property relationships for this class of materials, this study highlights the potential for new discoveries.