Pathway of in situ polymerization of 1,3-dioxolane in LiPF6 electrolyte on Li metal anode

Although the lithium metal battery has been considered to be one of most promising candidates facilitate high-density energy storage, practical applications anodes are significantly hindered by its high reactivity. Electrolytes based on 1,3-dioxolane (DOL) have demonstrated effective electrolytes that can suppress side reactions, but underlying mechanism is still far from clear. In this work, we carried out multi-scale simulations combine density functional theory (DFT) and reactive force field (ReaxFF) investigate initial reactions 1.0 M LiPF6 salt in DOL with Li anode. Our simulation results reveal PF6? anions either fully decompose via reduction reaction when they directly contact anode or convert PF5 stay bulk. While decomposition products (F? Px?) contribute formation inorganic part solid electrolyte interphase (SEI), latter serve as an initiator polymerization DOL. Such provides unexpected protective effect resembles polymer formed situ. The kinetically favorable pathway then distinguished hybrid DFT calculations, which confirms plays important role activating ring for further polymerization. insights revealed work should help expedite rational design provide SEI stabilize