“Pseudo‐Charge‐Transfer Complex” Electrolyte Enables 490 Wh kg‐1 Lithium Metal Battery Operated from ‐40 °C to 80 °C

Electric vehicles and electric aircraft demand all‐climate lithium metal batteries (LMBs) with high energy density. However, the interaction mechanism between charge transfer in solvation sheath and interfacial evolution is not yet clear. Herein, we proposed a “pseudo‐charge‐transfer complex” strategy by introducing an amide polymer encapsulation matrix (APEM) to construct local charge‐transfer channels to solvents for tuning the negative charge center. Theoretical calculations and synchrotron X‐ray tomography reveal that the APEM drags out the polar solvent and promotes cation‐anion coordination in the primary solvation sheath, contributing to AGGs‐dominated interfacial solvation chemistry. The designed electrolyte improves the cyclability of Li|LiNi0.9Co0.05Mn0.05O2 up to 300 cycles at 4.6 V and high‐temperature capability at 80 °C. Even at ‐40 °C, it still delivers a high capacity of 87.9 mAh g−1 with negligible capacity decay for 160 cycles. Industrial 3Ah‐level pouch cells over 490 Wh kg‐1 exhibit 91.3% capacity retention after 100 cycles, manifesting high potential in extreme applications.