Lithium metal is an attractive anode for next‐generation high‐energy batteries, but its practical use is plagued by dendrite growth and parasitic reactions, which are particularly severe in Li‐air cells operated in ambient air. A simple in situ solution‐conversion strategy is employed to construct an artificial protective layer (APL) on Li through immersion of Li foil in a 0.05 m AgOTf/DME solution. Density functional theory reveals spontaneous Ag + reduction, yielding an Ag‐containing organic–inorganic hybrid interphase with a LiF/Ag‐rich inner inorganic layer and a compliant ‐CF 3 ‐containing organic layer. This architecture endows Li with enhanced lithiophilicity, a markedly reduced Li + transport activation energy (12.63 vs 52.74 kJ mol −1 for bare Li), and strong tolerance toward H 2 O/O 2 , suppressing LiOH/Li 2 CO 3 formation after air exposure. Consequently, APL@Li delivers nearly 100% Coulombic efficiency for >400 cycles in Li||Cu cells and stable plating/stripping for over 2000 h in symmetric cells. APL@Li||LFP full cells exhibit excellent rate capability and ultra‐long cycling over 4000 cycles at 1 C, while ambient‐air Li‐air cells achieve ultrahigh discharge capacity (>14 000 mAh g −1 based on Pt/C cathode) and >300 stable cycles, highlighting a practical and scalable route to air‐tolerant Li metal anodes.
Li et al. (Thu,) studied this question.