Durable Lithium Metal Anodes Enabled by {110}‐Textured Epitaxy on a LiF@Ag Commensurate Heterostructure

Abstract Lithium metal anodes (LMAs) hold great promise for high‐energy storage, but their practical application is hindered by challenges such as Li dendrite growth and unstable solid electrolyte interphase. Designing heteroepitaxial substrates to guide {110}‐textured Li growth is a promising strategy to suppress dendrite formation and parasitic reactions. LiF and Ag are potential candidates owing to their low lattice mismatch with Li, whilst the former lacks sufficient lithiophilicity and the latter suffers from Li‐Ag alloying. A LiF@Ag commensurate heterostructure composed of Ag nanoparticles (NPs) uniformly grown on 2D LiF layers is hence proposed, where the composition pinning effect prevents Li‐Ag alloying and stabilizes the lithiophilic Ag NPs upon Li plating. Meanwhile, Ag contributes to a significantly reduced Li adatom diffusion barrier compared with LiF, providing a synergistic effect of low lattice mismatch and improved interfacial dynamics to promote Li heteroepitaxy. Ultra‐dense and dendrite‐free Li heteroepitaxial deposition with prominent {110} texture is achieved, which enables improved coulombic efficiency, enhanced high‐rate capability, and prolonged cycle life in Li metal full cells with a low negative‐to‐positive ratio. The results demonstrate that constructing commensurate heterostructures offers a new synergistic strategy to regulate both deposition thermodynamics and kinetics toward high‐performance {110}‐textured LMAs.