Ao Du, Juan Zhang, Pan Xu, Yajie Li, Kangwoo Yi, Zhen-Zhen Shen, Huilin Ge, Guangwen Zhang, Chaohui Zhang, Yuhao Wang, Chen‐Zi Zhao, Mengyang Xu, Yulin Jie, Rui Wen, Shuhong Jiao, Siqi Shi, Qiang Zhang, Chunpeng Yang, Yu‐Guo Guo
Lithium metal anodes, with a theoretical capacity of up to 3860 mAh·g−1, are regarded as the cornerstone for developing next-generation high-energy-density batteries. However, several key challenges hinder their practical applications, including dendrite formation, unstable solid electrolyte interphase (SEI), side reactions with electrolytes, and associated safety risks. This review systematically explores the mechanisms of lithium nucleation, growth, and stripping in both liquid and solid-state battery systems, analyzing critical theoretical concepts like heterogeneous nucleation thermodynamics, surface diffusion kinetics, space charge effects, and SEI-induced nucleation, which are crucial for understanding the genesis of dendrite growth. Additionally, the review discusses the electrochemical-mechanical coupling failures that lead to SEI degradation and the formation of dead lithium. For liquid systems, the review proposes strategies to mitigate dendrite formation and SEI instability, which include electrolyte optimization, artificial SEI design, and electrode framework design. In solidstate batteries, the review offers a granular analysis of the interface challenges associated with polymer, sulfide, and halide electrolytes and summarizes different solutions for different solid-state electrolytes. Meanwhile, the review emphasizes the importance of advanced characterization techniques and computational modeling in understanding and regulating the interface between lithium metal and electrolytes. Looking ahead, the review highlights future research directions that emphasize the integration of cross-disciplinary approaches to tackle these interconnected challenges. By addressing these issues, the path will be clear for the rapid commercialization and widespread application of lithium metal batteries, bringing us closer to realizing stable, high-energy-density batteries that can satisfy the escalating demands of modern energy storage applications across various industries.