LAUSR

Abstract Garnet-type electrolytes with high ionic conductivity and chemical stability against lithium metal show promise as solid-state electrolytes for lithium-ion batteries. However, a high concentration of pores and grain boundaries in air-processed polycrystalline electrolytes makes them prone to dendrite formation and reaction with atmospheric moisture, leading to electrochemical and mechanical instability. In this work, we illustrate that abnormal grain growth, an often-avoided phenomenon in conventional ceramic processing, can be employed as a unique approach to obtain extraordinarily large oligo crystals for minimal grain boundaries. Here we report a straightforward approach to develop a robust Ga-doped garnet, Li6.25Ga0.25La3Zr2O12 (LGLZO) electrolyte with conventional solid-state sintering in air. By preparing nanopowders without agglomeration through ball milling and freeze drying, we can control the microstructure of air-sintered electrolytes for desirable properties of a high density (98% of theoretical density) and an average grain size of 460 µm. The robust air-processed LGLZO electrolytes demonstrate high ionic conductivity, stability in air, and mechanical robustness relative to other garnet electrolytes offering promise as cost- and performance-competitive solid-state electrolytes for safe lithium-ion batteries.