Interfacial Interaction‐Engineered Dual Lithiophilic Ultrathin Interlayers for Dendrite‐Suppressed Lithium Metal Textile Anodes

Lithium (Li) metal, known for its exceptional theoretical capacity and low redox potential, represents a promising anode material for next‐generation Li‐based batteries. However, its practical implementation is often compromised by uncontrolled dendritic Li growth during cycling, leading to safety hazards and accelerated degradation. In this study, we present a novel dual‐interface engineering strategy aimed at mitigating Li dendrite formation through the incorporation of ultrathin lithiophilic interlayers on both the electrode (∼44 nm) and separator (∼2 nm). We utilize a Ni‐electroplated textile as a conductive host, onto which lithiophilic Ag nanoparticles and amine‐based molecular linkers are uniformly assembled via a ligand‐exchange‐mediated approach, resulting in an ultrathin lithiophilic interlayer. Simultaneously, the separator is modified through a hydrogen‐bonding‐driven assembly of NH 2 ‐functionalized poly(ethylene imine) and COOH‐functionalized poly(acrylic acid), forming a ∼2 nm interlayer that redistributes Li + flux. This synergistic interfacial design enables symmetric cells to operate stably for over 2200 h at 1 mA cm − 2 /1 mAh cm − 2 , while lithium iron phosphate‐based full cells retain approximately 72% capacity after 5000 cycles at 1 C. Our findings underscore dual‐interface engineering as an effective and scalable approach for the development of safe and durable Li metal batteries.