“Pseudo‐Charge‐Transfer Complex” Electrolyte Enables 490 Wh Kg ⁻¹ Lithium Metal Battery Operated From −40 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 the 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|LiNi_0.9Co_0.05Mn_0.05O₂ 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 3 Ah-level pouch cells over 490 Wh kg^-1 exhibit 91.3% capacity retention after 100 cycles, manifesting high potential in extreme applications.