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

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_0.8Co_0.1Mn_0.1O₂ 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.