Catalytic Growth of Ionic Conductive Lithium Nitride Nanowire Array for Dendrite‐Free Lithium Metal Anode

Abstract The development of an artificial solid‐electrolyte interphase (SEI) has been recognized as the most efficient strategy to overcome the safety concerns associated with the lithium metal anode (LMA). Inorganic‐rich SEIs on the LMA are crucial for suppressing Li dendrites. Among the prevalent SEI inorganic compounds observed for LMA, lithium nitride (Li₃N) is often found in the SEIs of high‐performance LMA. Herein, the Li₃N nanowire array is successfully synthesized and the catalytic base‐growth mechanism is thoroughly investigated. The fast ionic conductor Li₃N nanowires act as pillars to control the nucleation and growth of lithium metal along the vertical direction of the nanowire by bottom‐up self‐lubrication, which fundamentally prevents the dendrite growth. The Li₃N is characterized by abundant lithiophilic nucleation sites, which effectively reduces the local current density, and facilitates homogeneous Li⁺ flux. Symmetric cells utilizing the Li₃N@Li anode have demonstrated excellent stability, featuring uniform deposition without dendrite formation. Additionally, high‐capacity retentions of 98% at 0.5 C after 400 cycles and impressive high‐rate performance at 31.1 mA cm⁻² have been realized in high‐loading Li₃N@Li||LFP cells. The universal preparation of the Li₃N nanowires with various precursors and substrates is further explored, which is expected to be applied in solid‐state batteries and hydrogen storage.