Trifunctional Synergy of Host‐Catalysis‐Interface Engineering for Ultrastable Lithium Metal Batteries

ABSTRACT Utilizing ultrathin lithium metal batteries (LMBs) is highly promising for next‐generation energy storage, offering exceptional energy density and enhanced safety. However, their widespread adoption is severely hindered by poor Li plating/stripping reversibility and unstable electrode/electrolyte interfaces. In this study, an architectured current collector (CC) is designed by integrating a three‐dimensional (3D) conductive host co‐functionalized with single‐atomic Zn sites and Ag nano‐clusters (Zn 1 ‐Ag n @CP) dual active sites in conjunction with a prelithiation protocol. Advanced in situ/operando characterizations combined with density functional theory (DFT) calculations reveal that single‐atom Zn and Ag clusters effectively modulate charge distribution within the CP matrix, thereby promoting uniform Li‐ion flux and fast reaction kinetics. Specifically, Zn 1 ‐Ag n @CP induces the formation of an inorganic‐rich solid‐electrolyte interphase (SEI) that suppresses dendrite growth, while the Ag clusters catalyze solvent decomposition to generate a compact cathode‐electrolyte interphase (CEI) that limits transition metal (TM) ion migration and reinforces cathode structural stability. Consequently, the well‐orchestrated Zn 1 ‐Ag n @CP achieves reversible Li deposition with a high Coulombic efficiency (CE) of 99.91% over 900 cycles. When paired with a LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathode, the system retains substantial reversible capacity after 1000 cycles at 5 C with a high CE of 99.58%, highlighting the efficacy of the integrated “host‐catalysis‐interface” synergistic strategy for high‐rate LMBs.