Regulating Non‐Equilibrium Solvation Structure in Locally Concentrated Ionic Liquid Electrolytes for Wide‐Temperature and High‐Voltage Lithium Metal Batteries

Abstract The development of high‐voltage lithium metal batteries (LMBs) encounters significant challenges due to aggressive electrode chemistry. Recently, locally concentrated ionic liquid electrolytes (LCILEs) have garnered attention for their exceptional stability with both Li anodes and high‐voltage cathodes. However, there remains a limited understanding of how diluents in LCILEs affect the thermodynamic stability of the solvation structure and transportation dynamics of Li + ions. Herein, we propose a wide‐temperature LCILEs with 1,3‐dichloropropane (DCP13) diluent to construct a non‐equilibrium solvation structure under external electric field, wherein the DCP13 diluent enters the Li + ion solvation sheath to enhance Li + ion transport and suppress oxidative side reactions at high‐nickel cathode (LiNi 0.9 Co 0.05 Mn 0.05 O 2 , NCM90). Consequently, a Li/NCM90 cell utilizing this LCILE achieves a high capacity retention of 94 % after 240 cycles at 4.3 V, also operates stably at high cut‐off voltages from 4.4 V to 4.6 V and over a wide temperature range from −20 °C to 60 °C. Additionally, an Ah‐level pouch cell with this LCILE simultaneously achieves high‐energy‐density and stable cycling, manifesting the practical feasibility. This work redefines the role of diluents in LCILEs, providing inspiration for electrolyte design in developing high‐energy‐density batteries.