Robust Pinhole-free Li₃N Solid Electrolyte Grown from Molten Lithium

Lithium metal is the ultimate anode choice for high energy density rechargeable lithium batteries. However, it suffers from inferior electrochemical performance and safety issues due to its high reactivity and the growth of lithium dendrites. It has long been desired to develop a materials coating on Li metal, which is pinhole-free, mechanically robust without fracture during Li metal deposition and stripping, and chemically stable against Li metal and liquid electrolytes, all while maintaining adequate ionic conductivity. However, such an ideal material coating has yet to be found. Here we report a novel synthesis method by reacting clean molten lithium foil directly with pure nitrogen gas to generate instantaneously a pinhole-free and ionically conductive α-Li₃N film directly bonded onto Li metal foil. The film consists of highly textured large Li₃N grains (tens of μm) with (001) crystalline planes parallel to the Li metal surface. The bonding between textured grains is strong, resulting in a mechanically robust film which does not crack even when bent to a 0.8 cm curvature radius and is found to maintain pinhole-free coverage during Li metal deposition and stripping. The measured ionic conductivity is up to 5.2 × 10^-4 S cm^-1, sufficient for maintaining regular current densities for controllable film thicknesses ranging from 2 to 30 μm. This Li₃N coating is chemically stable, isolating the reactive metallic lithium from liquid electrolyte, prevents continuous electrolyte consumption during battery cycling, and promotes dendrite-free uniform lithium plating/stripping underneath. We demonstrated Li|Li₄Ti₅O₁₂ cells with stable and flat potential profiles for 500 cycles without capacity decay or an increase in potential hysteresis.