In Situ Construction of an Ultra-Stable Conductive Composite Interface for High-Voltage All-Solid-State Lithium Metal Batteries.

The garnet electrolyte presents poor wettability with Li metal, resulting in an extremely large interfacial impedance and drastic growth of Li dendrites. Herein, a novel ultra-stable conductive composite interface (CCI) consisting of Liy Sn alloy and Li3 N is constructed in situ between Li6.4 La3 Zr1.4 Ta0.6 O12 (LLZTO) pellet and Li metal by a conversion reaction of SnNx with Li metal at 300 °C. The Liy Sn alloy as a continuous and robust bridge between LLZTO and Li metal can effectively reduce the LLZTO/Li interfacial resistance from 4468.0 Ω to 164.8 Ω. Meanwhile, the Li3 N as a fast Li-ion channel can efficiently transfer Li ions and give their uniform distribution at the LLZTO/Li interface. Therefore, the Li/LLZTO@CCI/Li symmetric battery stably cycles for 1200 h without short circuit, and the all-solid-state high-voltage Li/LLZTO@CCI/LiNi0.5 Co0.2 Mn0.3 O2 battery achieves a specific capacity of 161.4 mAh g-1 at 0.25 C with a capacity retention rate of 92.6 % and coulombic efficiency of 100.0 % after 200 cycles at 25 °C.