Fluorine grafted gel polymer electrolyte by in situ construction for high-voltage lithium metal batteries

Gel polymer electrolytes (GPEs) are promising candidates for next generation lithium metal batteries (LMBs) due to their reassuring safety and high ionic conductivity at room temperature. However, they are still plagued by incompatible interfaces and poor compatibility with Ni-rich cathodes, imposing great restrictions on the scalability of high-voltage cathodes. To overcome these problems, a GPE with a polyacrylonitrile porous membrane, together with 2,2,3,4,4,4-hexafluorobutyl acrylate grafted pentaerythritol tetraacrylate, is fabricated via in-situ thermal polymerization. By virtue of the effective transport channels provided by PAN and PETEA molecules, our GPE exhibits both a high lithium-ion transference number and a high ionic conductivity of 0.87 and 4.06 × 10−3 S cm−1, respectively at 30 °C. Moreover, the GPE ensures a high electrochemical window, stable at potentials up to 5.35 V, enabling the application of LiNi0.8Co0.1Mn0.1O2 (NCM811) cathodes. Due to the uniform cathode electrolyte interface (CEI) formed by our GPE on the surface of NCM811, the assembled NCM811|GPE|Li batteries present an excellent cycling life of 300 cycles in the voltage range of 3 ∼ 4.5 V with a capacity retention of 84% at 2C. Our study provides a novel strategy for constructing fast Li+ transport channels and stable CEI membranes in LMBs operating at high voltages.