An Inorganic‐Rich SEI Layer by the Catalyzed Reduction of LiNO3 Enabled by Surface‐Abundant Hydrogen Bonding for Stable Lithium Metal Batteries

Lithium (Li) metal anodes (LMAs) are promising anode candidates for realizing high-energy-density batteries. However, the formation of unstable solid electrolyte interphase (SEI) layers on Li metal is harmful for stable Li cycling; hence, enhancing the physical/chemical properties of SEI layers is important for stabilizing LMAs. Herein, thiourea (TU, CH₄ N₂ S) is introduced as a new catalyzing agent for LiNO₃ reduction to form robust inorganic-rich SEI layers containing abundant Li₃ N. Due to the unique molecular structure of TU, the TU molecules adsorb on the Cu electrode by forming CuS bond and simultaneously form hydrogen bonding with other hydrogen bonds accepting species such as NO₃ ^- and TFSI^- through its NH bonds, leading to their catalyzed reduction and hence the formation of inorganic-rich SEI layer with abundant Li₃ N, LiF, and Li₂ S/Li₂ S₂ . Particularly, this TU-modified SEI layer shows a lower film resistance and better uniformity compared to the electrochemically and naturally formed SEI layers, enabling planar Li growth without any other material treatments and hence improving the cyclic stability in Li/Cu half-cells and Li@Cu/LiFePO₄ full-cells.