Abstract The interfacial instability of graphite anodes at high temperatures critically undermines the safety and fast‐charging capability of lithium‐ion batteries. To overcome this challenge, trimethylsilyl‐2,2‐difluoro‐2‐fluorosulfonylacetate (TD) is proposed as a multifunctional electrolyte additive that significantly enhances anode performance through synergistic adjacent element induction and solvation‐weakening effects. The sulfur atom in TD's sulfonyl group induces an adjacent‐element effect, catalyzing the transformation of PF 6 − derivatives into stable LiF and Li 3 PO 4 species. Simultaneously, TD self‐decomposition forms a robust, multi‐layered solid electrolyte interphase (SEI), comprising both organic ((TMS) 2 O) and inorganic (Li 2 S, Li 2 SO 4 ) components, thereby substantially improving thermal stability. Furthermore, TD weakens Li⁺–solvent interactions, notably by decreasing the coordination number of fluoroethylene carbonate (FEC), which enhances interfacial kinetics and stability. Consequently, graphite anodes employing TD‐modified electrolytes exhibit remarkable fast‐charging performance, achieving 300 mAh·g −1 at 10C and 60 °C, along with superior cyclability. NCM811/graphite pouch cells retain 87.8% capacity after 200 cycles at 60 °C, while cylindrical cells at full state of charge display reduced self‐discharge across various temperatures. This work presents a novel electrolyte design strategy based on synergistic molecular effects, offering critical insights for developing advanced LIBs suited for extreme operating conditions.
Pan et al. (Wed,) studied this question.