Catalytic Chemistry Derived Artificial Solid Electrolyte Interphase for Stable Lithium Metal Anodes Working at 20 mAcm−2 and 20 mAhcm−2

A stable solid electrolyte interphase (SEI) layer is crucial for lithium metal anode (LMA) to survive in long‐term cycling. However, chaotic structures and chemical inhomogeneity of natural SEI make LMA suffering from exasperating dendrite growth and severe electrode pulverization, which hinder the practical application of LMAs. Here, we design a catalyst‐derived artificial SEI layer with an ordered polyamide‐lithium hydroxide (PA‐LiOH) bi‐phase structure to modulate ion transport and enable dendrite‐free Li deposition. The PA‐LiOH layer can substantially suppress the volume changes of LMA during Li plating/stripping cycles, as well as alleviate the parasitic reactions between LMA and electrolyte. The optimized LMAs demonstrate excellent stability in Li plating/stripping cycles for over 1000 hours at an ultra‐high current density of 20 mA cm−2 in Li||Li symmetric cells. A high coulombic efficiency up to 99.2 % in Li half cells in additive‐free electrolytes is achieved even after 500 cycles at a current density of 1 mA cm−2 with a capacity of 1 mAh cm−2.