Defect‐Free Metal–Organic Framework Membrane for Precise Ion/Solvent Separation toward Highly Stable Magnesium Metal Anode

Metallic magnesium batteries are promising candidates beyond lithium-ion batteries; however, a passive interfacial layer because of the electro-reduction of solvents on Mg surfaces usually leads to ultrahigh overpotential for the reversible Mg chemistry. Inspired by the excellent separation effect of permselective metal-organic framework (MOF) at angstrom scale, a large-area and defect-free MOF membrane directly on Mg surfaces is here constructed. In this process, the electrochemical deprotonation of ligand can be facilitated to afford the self-correcting of intercrystalline voids until a seamless membrane formed, which can eliminate nonselective intercrystalline diffusion of electrolyte and realize selective Mg2+ transport but precisely separate the solvent molecules from the MOF channels. Compared with the continuous solvent reduction on bare Mg anode, the as-constructed MOF membrane is demonstrated to significantly stabilize the Mg electrode via suppressing the permeation of solvents, hence contributing to a low-overpotential plating/stripping in conventional electrolytes. The concept is demonstrated that membrane separation can serve as solid-electrolyte interphase, which would be widely applicable to other energy-storage systems.