Reduced Energy Barrier for Li+ Transport Across Grain Boundaries with Amorphous Domains in LLZO Thin Films.

The high-resistive grain boundaries are the bottleneck for Li+ transport in Li7La3Zr2O12 (LLZO) solid electrolytes. Herein, high-conductive LLZO thin films with cubic phase and amorphous domains between crystalline grains are prepared, via annealing the repetitive LLZO/Li2CO3/Ga2O3 multi-nanolayers at 600 °C for 2 h. The amorphous domains may provide additional vacant sites for Li+, and thus relax the accumulation of Li+ at grain boundaries. The significantly improved ionic conductivity across grain boundaries demonstrates that the high energy barrier for Li+ migration caused by space charge layer is effectively reduced. Benefiting from the Li+ transport paths with low energy barriers, the presented LLZO thin film exhibits a cutting-edge value of ionic conductivity as high as 6.36 × 10-4 S/cm, which is promising for applications in thin film lithium batteries.