Special Adsorption Additive Enabling Robust Interphases for Thermal‐Resilient Lithium Metal Batteries

Abstract Thermal instability and interphase degradation limit the safety and durability of energy storage systems. To overcome these issues, an advanced carbonate‐based electrolyte is designed by introducing 2,5‐dichlorothiophene (DCT) as a multifunctional additive. The dynamic interphase by DCT at cathode surface not only blocks solvent molecules from cathode for suppressing side reactions under high temperature, but also promotes Li + accumulation via its chlorine‐induced electron‐withdrawing effect to boost Li + migration; thereby synergistically enhancing interphase transport kinetics and thermal resilience. Simultaneously, DCT shows preferentially coordinating capability with Li + , and thus weakening Li + ‐solvent interactions and facilitating the formation of a robust solid electrolyte interphase on Li anode. This synergistic strategy, integrating interfacial self‐assembly and solvation structure regulation, enables Li/LiFePO 4 (LFP) cells with DCT‐assisted electrolyte achieve outstanding electrochemical performance, i.e., 86.4% capacity retention after 600 cycles at 1 C with a low N/P ratio of 5.3, 80.4% after 500 cycles at 5 C, and 91.3% after 150 cycles at 60 °C. Furthermore, this advanced electrolyte system supports over 1500 hours of stable Li plating/stripping at 1 mA cm −2 in Li/Li cell, and over 450 cycles under 60 °C in Li/Cu cell. This work opens a new avenue to high‐temperature‐tolerant, fast‐charging energy storage systems by stabilizing the electrode/electrolyte interphase.