Toward High‐Performance Metal–Organic‐Framework‐Based Quasi‐Solid‐State Electrolytes: Tunable Structures and Electrochemical Properties

Abstract Metal–organic frameworks (MOFs) have been reported as promising materials for electrochemical applications owing to their tunable porous structures and ion‐sieving capability. However, it remains challenging to rationally design MOF‐based electrolytes for high‐energy lithium batteries. In this work, by combining advanced characterization and modeling tools, a series of nanocrystalline MOFs is designed, and the effects of pore apertures and open metal sites on ion‐transport properties and electrochemical stability of MOF quasi‐solid‐state electrolytes are systematically studied. It isdemonstrated that MOFs with non‐redox‐active metal centers can lead to a much wider electrochemical stability window than those with redox‐active centers. Furthermore, the pore aperture of MOFs is found to be a dominating factor that determines the uptake of lithium salt and thus ionic conductivity. The ab initio molecular dynamics simulations further demonstrate that open metal sites of MOFs can facilitate the dissociation of lithium salt and immobilize anions via Lewis acid–base interaction, leading to good lithium‐ion mobility and high transference number. The MOF quasi‐solid‐state electrolyte demonstrates great battery performance with commercial LiFePO ₄ and LiCoO ₂ cathodes at 30 °C. This work provides new insights into structure–property relationships between tunable structure and electrochemical properties of MOFs that can lead to the development of advanced quasi‐solid‐state electrolytes for high‐energy lithium batteries.