Interface‐Engineered All‐Solid‐State Li‐Ion Batteries Based on Garnet‐Type Fast Li+ Conductors

All‐solid‐state Li‐ion batteries based on Li 7 La 3 Zr 2 O 12 (LLZO) garnet structures require novel electrode assembly strategies to guarantee a proper Li + transfer at the electrode–electrolyte interfaces. Here, first stable cell performances are reported for Li‐garnet, c‐Li 6.25 Al 0.25 La 3 Zr 2 O 12 , all‐solid‐state batteries running safely with a full ceramics setup, exemplified with the anode material Li 4 Ti 5 O 12 . Novel strategies to design an enhanced Li + transfer at the electrode–electrolyte interface using an interface‐engineered all‐solid‐state battery cell based on a porous garnet electrolyte interface structure, in which the electrode material is intimately embedded, are presented. The results presented here show for the first time that all‐solid‐state Li‐ion batteries with LLZO electrolytes can be reversibly charge–discharge cycled also in the low potential ranges (≈1.5 V) for combinations with a ceramic anode material. Through a model experiment, the interface between the electrode and electrolyte constituents is systematically modified revealing that the interface engineering helps to improve delivered capacities and cycling properties of the all‐solid‐state Li‐ion batteries based on garnet‐type cubic LLZO structures.