Mastering the Copolymerization Behavior of Ethyl Cyanoacrylate as Gel Polymer Electrolyte for Lithium‐metal Battery Application

Polymers with strong electron‐withdrawing groups (e.g., cyano‐containing polymers) are attractive for a wide range of applications due to their high dielectric constant and outstanding electrochemical stability. However, the polymerization of such monomers is difficult to control with trace of water affording instant reactions, and copolymerization with other monomers without using strong acid is even more challenging. The present study demonstrates a facile approach enabling efficient and controllable copolymerization of ethyl cyanoacrylate (ECA) without adding undesired additives, achieving mechanically robust and high ion‐conduction gel polymer electrolyte (GPE) for safe and long cycle‐life lithium‐metal batteries (LMBs). The incorporated dual‐lithium salts, i.e., lithium difluoro(oxalato)borate (LiDFOB) and lithium bis(trifluoromethanesulphonyl)imide (LiTFSI) not only facilitate radical polymerization of ECA monomers by suppressing their anionic polymerization, but also promote the formation of high‐ionic conducting GPE. The incorporated methyl methacrylate (MMA) monomer accelerates the radical polymerization of ECA (confirmed by DFT calculations), achieving controlled copolymerization of ECA‐based copolymers. The mechanically robust polymer network made by the ECA copolymer enables LMBs with both LFP cathodes and high‐voltage LCO cathodes (4.5 V) operatable at different temperatures with ultra‐long cycle life at 1 C (capacity retention of 81.1% and 83.8%, respectively, over 1000 cycles).