TY - JOUR
T1 - Mastering the Copolymerization Behavior of Ethyl Cyanoacrylate as Gel Polymer Electrolyte for Lithium-metal Battery Application
AU - Min, Weixing
AU - Li, Lengwan
AU - Wang, Mingli
AU - Ma, Shuaijiang
AU - Feng, Hao
AU - Wang, Weirong
AU - Ding, Hang
AU - Cheng, Tianhui
AU - Li, Zhenxi
AU - Saito, Tomonori
AU - Yang, Huabin
AU - Cao, Peng Fei
N1 - Publisher Copyright:
© 2025 Wiley-VCH GmbH.
PY - 2025
Y1 - 2025
N2 - 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).
AB - 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).
KW - Copolymerization Behavior
KW - ECA-based Copolymer
KW - Gel Polymer Electrolyte
KW - High Voltage Cathode
KW - Lithium Metal Batteries
UR - http://www.scopus.com/inward/record.url?scp=85215535346&partnerID=8YFLogxK
U2 - 10.1002/anie.202422510
DO - 10.1002/anie.202422510
M3 - Article
AN - SCOPUS:85215535346
SN - 1433-7851
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
ER -