Porous Organic Frameworks for Lithium-Metal Anodes: Design Strategies, Mechanisms, and Future Perspectives

Lithium-metal batteries (LMBs) are considered among the most promising high-performance energy storage systems because lithium metal possesses extremely high theoretical capacity and the lowest electrochemical potential among anode materials. However, their practical implementation remains severely limited by several critical challenges at the nanoscale, including uncontrolled lithium dendrite growth, unstable solid-electrolyte interphase formation, low Coulombic Efficiency, and large volume fluctuations during repeated lithium plating and stripping processes. In recent years, nanostructured porous framework materials have emerged as effective host structures and interfacial regulators for stabilizing lithium metal anodes due to their high surface areas, tunable pore architectures, and functionalizable chemical environments. In this review, we systematically summarize the recent progress in metal-organic frameworks (MOFs), covalent organic frameworks (COFs), covalent organic polymers (COPs) and other organic framework materials for lithium-metal anode applications. First, the fundamental working principles of LMBs and the major challenges associated with lithium metal anodes are discussed. Subsequently, the structural characteristics and advantages of MOFs, COFs, COPs and other framework materials are compared, followed by a detailed discussion of lithium storage mechanisms in porous frameworks, including lithium adsorption and nucleation, regulation of plating and stripping, dendrite suppression, and stabilization of the solid electrolyte interphase. Key design strategies, including hierarchical pore engineering, lithiophilic chemical functionalization, and electronic conductivity enhancement, are systematically highlighted. Representative advances in COF-based, MOF-based, and COP-based materials for lithium metal stabilization are critically summarized and compared. Finally, the remaining challenges and future research directions for porous framework materials in LMBs are discussed. This review aims to provide fundamental insights and design strategies for the rational development of advanced porous framework materials toward safe, stable, and high-energy LMBs.