Binding FSI− to Construct a Self‐Healing SEI Film for Li‐Metal Batteries by In situ Crosslinking Vinyl Ionic Liquid

Abstract The solid electrolyte interphase (SEI) membrane on the Li metal anode tends to breakdown and undergo reconstruction during operation, causing Li metal batteries to experience accelerated decay. Notably, an SEI membrane with self‐healing characteristics can help considerably in stabilizing the Li‐electrolyte interface; however, uniformly fixing the repairing agent onto the anode remains a challenging task. By leveraging the noteworthy film‐forming attributes of bis(fluorosulfonyl)imide (FSI − ) anions and the photopolymerization property of the vinyl group, the ionic liquid 1‐vinyl‐3‐methylimidazolium bis(fluorosulfonyl)imide (VMI‐FSI) was crosslinked with polyethylene oxide (PEO) in this study to form a self‐healing film fixing FSI − groups as the repairing agent. When they encounter lithium metal, the FSI − groups are chemically decomposed into LiF & Li 3 N, which assist forming SEI membrane on lithium sheet and repairing SEI membrane in the cracks lacerated by lithium dendrite. Furthermore, the FSI − anions exchanged from film are electrochemically decomposed to generate inorganic salts to strengthen the SEI membrane. Benefiting from the self‐healing behavior of the film, Li/LiCoO 2 cells with the loading of 16.3 mg cm −2 exhibit the initial discharge capacities of 183.0 mAh ⋅ g −1 and are stably operated for 500 cycles with the retention rates of 81.4 % and the average coulombic efficiency of 99.97 %, operated between 3.0–4.5 V vs. Li + /Li. This study presents a new design approach for self‐healing Li metal anodes and durable lithium metal battery.