Metal-Organic Frameworks for Stabilizing Zinc Metal Anodes in Aqueous Batteries: Structure-Interface-Performance Relationships: A Critical Review.

Abstract

Aqueous zinc-ion batteries (ZIBs), with intrinsic advantages such as environmental friendliness, cost-effectiveness, and high theoretical capacity, have emerged as promising candidates for energy storage systems. However, the zinc anode in ZIBs faces several challenges, including dendrite formation, the hydrogen evolution reaction, corrosion, and surface passivation. These processes are strongly coupled rather than independent failure modes. To address these challenges, functional-material-based strategies involving electrode architecture, interface engineering, separator modification, and electrolyte regulation have been developed to improve the reversibility of the Zn metal anode. This review summarizes a structure-interface-performance framework for understanding MOF-enabled stabilization of Zn metal anodes. Four implementation routes are systematically examined and compared: MOF protective coatings, MOF-based three-dimensional hosts, MOF-modified separators, and MOF-containing liquid, gel, or solid-state electrolytes. Particular attention is paid to the relationships between pore aperture, framework chemistry, zincophilic sites, conductivity, mechanical integrity and five major interfacial functions: homogeneous nucleation, selective deposition, zincophilic regulation, accelerating Zn2+ desolvation, and interfacial shielding against water and detrimental anions. Representative studies are critically assessed by considering the trade-offs between ion selectivity and ionic conductivity, interfacial protection and transport resistance, and long-duration laboratory cycling and practical Zn utilization, allowing to develop predictive design principles for MOF-enabled aqueous Zn metal batteries.