Highly Conductive Imidazolate Covalent Organic Frameworks with Ether Chains as Solid Electrolytes for Lithium Metal Batteries

Abstract Poly(ethylene oxide) (PEO)‐based electrolytes are often used for Li + conduction as they can dissociate the Li salts efficiently. However, high entanglement of the chains and lack of pathways for rapid ion diffusion limit their applications in advanced batteries. Recent developments in ionic covalent organic frameworks (iCOFs) showed that their highly ordered structures provide efficient pathways for Li + transport, solving the limitations of traditional PEO‐based electrolytes. Here, we present imidazolate COFs, PI‐TMEFB‐COFs, having methoxyethoxy chains, synthesized by Debus–Radziszewski multicomponent reactions and their ionized form, Li + @PI‐TMEFB‐COFs, showing a high Li + conductivity of 8.81 mS cm −1 and a transference number of 0.974. The mechanism for such excellent electrochemical properties is that methoxyethoxy chains dissociate LiClO 4 , making free Li + , then those Li + are transported through the imidazolate COFs’ pores. The synthesized Li + @PI‐TMEFB‐COFs formed a stable interface with Li metal. Thus, employing Li + @PI‐TMEFB‐COFs as the solid electrolyte to assemble LiFePO 4 batteries showed an initial discharge capacity of 119.2 mAh g −1 at 0.5 C, and 82.0 % capacity and 99.9 % Coulombic efficiency were maintained after 400 cycles. These results show that iCOFs with ether chains synthesized via multicomponent reactions can create a new chapter for making solid electrolytes for advanced rechargeable batteries.