Recent Advances in Lithium Metal Anodes with Liquid Electrolytes: Interfacial Interaction‐Driven Assembly for Dendrite Suppression and Long‐Term Stability

ABSTRACT The direct use of lithium (Li) metal as an anode provides a promising route toward next‐generation batteries with ultrahigh energy density. However, its practical realization remains severely constrained by safety and stability issues arising from uncontrolled Li dendrite growth and unstable solid–electrolyte interphases. To overcome these challenges, various strategies have been developed, including the construction of artificial interphases, lithiophilic surface modification of current collectors or separators, and the fabrication of 3D porous current collectors. These approaches are primarily designed to mitigate Li‐ion concentration polarization and homogenize interfacial energy distribution, thereby suppressing dendritic deposition. Conventional methods, however, often rely on slurry coating of lithiophilic materials, which introduces inactive binders and thick layers. In contrast, layer‐by‐layer (LbL) assembly driven by interfacial interactions has recently emerged as a powerful alternative, enabling molecular‐level control over film composition and architecture. This strategy allows the formation of ultrathin and binder‐free coatings that simultaneously enhance electronic conductivity, electrochemical stability, and energy density. This perspective reviews recent advances in the fabrication of high‐performance Li metal anodes and demonstrates how interfacial interaction–mediated LbL assembly can serve as a transformative approach for realizing dendrite‐free, durable Li metal anodes and high‐energy‐density batteries with superior interfacial and cycling stability.