Electrophilically Trapping Water for Preventing Polymerization of Cyclic Ether Towards Low‐Temperature Li Metal Battery

Abstract Cyclic ether, such as 1,3‐dioxolane (DOL), are promising solvent for low‐temperature electrolytes because of the low freezing point. Their use in electrolytes, however, is severely limited since it easily polymerizes in the presence of lithium inorganic salts. The trace water plays a key role via providing the source (proton) for chain initiation, which has, unfortunately, been neglected in most cases. In this work, we present an electrophile, trimethylsilyl isocyanate (Si−NCO), as the water scavenger, which eliminates moisture by a nucleophilic addition reaction. Si−NCO allows DOL to maintain liquid over a wide temperature range even in high‐concentration electrolyte. Electrolyte with Si−NCO additive shows promising low‐temperature performance. Our finding expands the use of cyclic ether solvents in the presence of inorganic salts and highlights a large space for unexplored design of water scavenger with electrophilic feature for low‐temperature electrolytes.