Clarifying the local structure of dopants in garnet solid-state electrolytes for lithium-ion batteries

The high Li-ion conductivity and wide electrochemical stability of Li-rich garnets (Li7La3Zr2O12) make them one of the leading solid electrolyte candidates for solid-state batteries. Dopants such as Al and Ga are typically used to enable stabilisation of the high Li+ ion-conductive cubic phase at room temperature. Although numerous studies exist that have characterized the electrochemical properties, structure, and lithium diffusion in Al- and Ga-LLZO, the local structure and site occupancy of dopants in these compounds are not well understood. Two broad 27Al or 69,71Ga resonances are often observed with chemical shifts consistent with tetrahedrally coordinated Al/Ga in the magic angle spinning nuclear magnetic resonance (MAS-NMR) spectra of both Al- and Ga-LLZO, which have been assigned to either Al and/or Ga occupying 24d and 96h/48g sites in the LLZO lattice or to the different Al/Ga configurations that arise from different arrangements of Li around these dopants. In this work, we unambiguously show that the side products γ-LiAlO2 and LiGaO2 lead to the high frequency resonance observed by NMR spectroscopy and that both Al and Ga only occupy the 24d site in the LLZO lattice. Furthermore, it was observed that the excess Li often used during synthesis leads to the formation of these side-products by consuming the Al/Ga dopants. In addition, the consumption of Al/Ga dopants lead to the tetragonal phase formation commonly observed in the literature even after careful mixing of precursors. The side-products can exist even after sintering, thus controlling the Al/Ga content in the LLZO lattice, substantially influencing the lithium-ion conductivity in LLZO as measured here by electrochemical impedance spectroscopy.