Three-Dimensional Interpenetrated Metal–Organic Frameworks for Stabilizing Lithium Metal Interfaces: Structural Engineering of Ion Flux and Interfacial Dynamics

Rechargeable lithium metal batteries (LMBs) are hindered by uncontrolled dendrite growth and interfacial instability driven by erratic ion migration and unstable electrochemical dynamics at the anode interface. In this study, a multifunctional three-dimensional interpenetrating Co-DPBB metal-organic framework (MOF) coating as an artificial solid electrolyte interphase was introduced to homogenize ion migration and expedite transport behaviors across the electrode-electrolyte interface. Through synergistic density functional theory (DFT) calculations and comprehensive <i>in situ</i>/<i>ex situ</i> characterizations, the relationship of orchestrated lithium-ion desolvation kinetics, charge transfer efficiency, and deposition topography with Co-DPBB's nanoarchitectural channels and lithiophilic anchoring moieties were decoupled. Co-DPBB-modified electrodes exhibit exceptional electrochemical performance, with reduced polarization, extended cycle life (>8000 h), and stable lithium deposition. This work introduces a transformative interfacial engineering approach, laying the groundwork for high-energy-density LMBs.