Sustaining Surface Lithiophilicity of Ultrathin Li‐Alloy Coating Layers on Current Collector for Zero‐Excess Li‐Metal Batteries

Abstract Zero‐excess Li‐metal batteries (ZE‐LMBs) have emerged as the ultimate battery platform, offering an exceptionally high energy density. However, the absence of Li‐hosting materials results in uncontrolled dendritic Li deposition on the Cu current collector, leading to chronic loss of Li inventory and severe electrolyte decomposition, limiting its full utilization upon cycling. This study presents the application of ultrathin (≈50 nm) coatings comprising six metallic layers (Cu, Ag, Au, Pt, W, and Fe) on Cu substrates in order to provide insights into the design of Li‐depositing current collectors for stable ZE‐LMB operation. In contrast to non‐alloy Cu, W, and Fe coatings, Ag, Au, and Pt coatings can enhance surface lithiophilicity, effectively suppressing Li dendrite growth, thereby improving Li reversibility. Considering the distinct Li‐alloying behaviors, particularly solid‐solution and/or intermetallic phase formation, Pt‐coated Cu current collectors maintain surface lithiophilicity over repeated Li plating/stripping cycles by preserving the original coating layer, thereby attaining better cycling performance of ZE‐LMBs. This highlights the importance of selecting suitable Li‐alloy metals to sustain surface lithiophilicity throughout cycling to regulate dendrite‐less Li plating and improve the electrochemical stability of ZE‐LMBs.