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All-solid-state Li-ion batteries with metallic Li anodes and solid electrolytes could offer superior energy density and safety over conventional Li-ion batteries. However, compared with organic liquid electrolytes, the low conductivity of solid electrolytes and large electrolyte/electrode interfacial resistance impede their practical application. Garnet-type Li-ion conducting oxides are among the most promising electrolytes for all-solid-state Li-ion batteries. In this work, the large-radius Rb is doped at the La site of cubic Li 6.10 Ga 0.30 La 3 Zr 2 O 12 o enhance the Li-ion conductivity for the first time. The Li 6.20 Ga 0.30 La 2.95 Rb 0.05 Zr 2 O 12 electrolyte exhibits a Li-ion conductivity of 1.62 mS cm -1 at room temperature, which is the highest conductivity reported until now. All-solid-state Li-ion batteries are constructed from the electrolyte, metallic Li anode, and LiFePO 4 active cathode. The addition of Li(CF 3 SO 2 ) 2 N electrolytic salt in the cathode effectively reduces the interfacial resistance, allowing for a high initial discharge capacity of 152 mAh g -1 and good cycling stability with 110 mAh g -1 retained after 20 cycles at a charge/discharge rate of 0.05 C at 60 °C.

Garnet-Type Fast Li-Ion Conductors with High Ionic Conductivities for All-Solid-State Batteries