Molecular‐Locking Strategy Enables Volatile Ether Organic Electrolytes to Achieve High‐Energy Lithium Battery

Abstract High‐energy lithium (Li) metal batteries are constrained by safety and lifespan owing to the lack of suitable electrolyte solutions. Here, we report a synergy of molecular‐locking and gelation treatment by cations–bridged polyoxometalate subnanometer nanowires (SNW), which facilitates using ether‐based electrolytes for high‐energy Li metal batteries. The formed SNW‐based gel electrolyte (SNWGE) exhibits continuous three‐dimensional networks that effectively capture nonpolar ether electrolytes and promote the dissociation of Li salts, eliminating the risks of electrolyte leakage and volatilization. Homogeneous and continuous Li + fast transport channels were created in the SNWGE through intermolecular interactions, contributing to sufficient ionic conductivity (1.26 mS cm −1 ), high oxidative stability (up to 5.0 V versus Li + /Li), and good solid/cathode electrolyte interphase formation capability. The SNWGE enables the Li||LiNi 0.8 Co 0.1 Mn 0.1 O 2 cells to reach good cyclability (over 88% capacity retention after 670 cycles), excellent low‐temperature, and abuse‐tolerant properties. Notably, the cost of the SNWGE is only 28.5% of the commercial electrolyte (1 M lithium hexafluorophosphate in ethylene carbonate/dimethyl carbonate), highlighting its significant potential for industrial application. When the SNWGE is tested in Li–air batteries, a stable cycling of > 520 cycles was obtained. The electrolyte design paves a promising path for highly energetic, durable, and safe rechargeable Li metal batteries.