The Li metal anode has been spotlighted for large-scale battery systems such as electric vehicles (EVs) and energy storage systems (ESSs) because of its high theoretical energy density and lowest potential. However, the Li metal anode still has the several challenging issues like Li dendrite growth and many side reactions. Our strategy to this problem is to utilize Li metal powder (LMP), which has superior advantages in reducing local current and utilizing slurry-based coating process for wide-width electrodes. Nevertheless, the spherical shape of LMP with the imperfect protection layer can be lost during the long-term cycling, which leads to dead particles formation and ununiform Li distribution.

In this work, we present a LMP electrode having pre-planted nitrates (LN-LMP). The LiNO₃ additive in the LMP electrode can chemically replace the native layer with the uniform Li₃N-rich passivation layer on the surface during the simple slurry mixing process. Furthermore, residual LiNO₃ was continuously released toward electrolyte, thereby repairing the SEI during cycling. As a result, the 20 µm‐thick LN‐LMP electrodes exhibited the robust cycling performances compared to control cells with conventional LMPs and LiNO₃‐containing electrolytes.