Dual-Interphase-Stabilizing Sulfolane-Based Electrolytes for High-Voltage and High-Safety Lithium Metal Batteries

High-voltage Li metal battery (HV-LMB) is one of the most promising energy storage technologies to achieve ultrahigh energy density. Nevertheless, electrolytes reported to date are difficult to simultaneously stabilize the Li metal anode and high-voltage cathode, especially without the assistance of expensive and corrosive high-concentration Li salts. Herein, a dual-interphase-stabilizing (DIS) and safe electrolyte that bypasses the high-concentration Li salt is reported. The electrolyte consists of high-flash-point sulfolane as solvent, molecular-orbital-engineered additives that enable stable B-F rich cathodic interphase, and unique C-F rich organic anodic interphase. The stable cycling of both Li metal anode and 4.75 V-LiCoO₂ cathode in the DIS electrolyte (> 500 cycles) is demonstrated. HV-LMB pouch cells of a high energy density (435 Wh kg⁻¹) can sustainably operate for more than 100 cycles. Moreover, the low cost and high thermal stability of the DIS electrolyte offer superior cost-effectiveness and safety for large-scale applications of HV-LMBs in the future.