Toward Highly Stable Lithium Metal Anodes: Nucleation Chemistry, Interfacial Engineering, and Structural Design

ABSTRACT Lithium metal anodes (LMAs), with ultrahigh theoretical capacity and extremely low electrochemical potentials, are key enablers for next‐generation high‐energy‐density batteries (LMBs). However, their practical deployment remains severely impeded by nonuniform Li nucleation, dendritic growth, drastic volume fluctuation, parasitic side reactions, and solid electrolyte interphase (SEI) instability. This review provides a comprehensive, mechanism‐oriented overview of recent advances in stabilizing LMAs. We first summarize fundamental thermodynamic and kinetic principles underlying Li nucleation and growth, establishing the theoretical basis for understanding deposition heterogeneity and interfacial failure. Representative strategies in interfacial engineering and host architecture design are then discussed, emphasizing how these approaches regulate Li + flux, guide uniform deposition, suppress dendrites, and accommodate volume changes. Furthermore, we highlight advanced characterization techniques and multiscale simulations for probing the dynamic evolution of Li metal and its interphase, providing critical insight into structure‐property relationships and failure mechanisms. Additionally, key challenges toward practical LMBs, including realistic full‐cell evaluation, scalable manufacturing, and data‐driven research paradigms, are critically discussed. Finally, perspectives are offered on integrating materials design, mechanistic understanding, advanced diagnostics, and intelligent methodologies to accelerate the transition of LMAs from fundamental research to practical applications, providing a comprehensive blueprint for developing safe and high‐energy‐density LMBs.