Sulfonyl Molecules Induced Oriented Lithium Deposition for Long‐Term Lithium Metal Batteries

Dendrites growth and unstable interfacial Li + transport hinder the practical application of lithium metal batteries (LMBs). Herein, we report an active layer of 2,4,6–trihydroxy benzene sulfonyl fluorine on copper substrate that induces oriented Li + deposition and generates highly crystalline solid‐electrolyte interphase (SEI) to achieve high‐performance LMBs. The lithiophilic −SO 2 − groups of highly crystalline SEI accept the rapidly transported Li + ions and form a dense inner layer of LiF and Li 3 N, which regulate Li + plating morphology along the (110) crystal surface toward dendrite‐free Li anode. Thus, Li||Cu cells with lithiophilic SEI achieve an average deposition efficiency of 99.8 % after 700 cycles, and Li||Li cells operate well for 1100 h. Besides, Li||LiNi 0.8 Co 0.1 Mn 0.1 O 2 cells with modified SEI exhibit a capacity retention that is 14 times than that of conventional SEI. Even at −60 °C, Li||Cu cells reach stable deposition efficiency of 83.2 % after 100 cycles.