Grafting Polyethyleneimine–Poly(ethylene glycol) Gel onto a Heat-Resistant Polyimide Nanofiber Separator for Improving Lithium-Ion Transporting Ability in Lithium-Ion Batteries

To improve the lithium-ion transporting ability in lithium-ion batteries, a high-performance polyimide-based lithium-ion battery separator (PI-mod) was prepared by chemically grafting poly(ethylene glycol) (PEG) onto the surface of a heat-resistant polyimide nanofiber matrix with the assistance of amino-rich polyethyleneimine (PEI). The resulted PEI-PEG polymer coating exhibited unique gel-like properties with an electrolyte uptake rate of 168%, an area resistance as low as 2.60 Ω·cm², and an ionic conductivity up to 2.33 mS·cm^-1, which are 3.5, 0.10, and 12.3 times that of the commercial separator Celgard 2320, respectively. Meanwhile, the heat-resistant polyimide skeleton can effectively avoid thermal shrinkage of the modified separator even after 200 °C treatment for 0.5 h, which ensures the safety of the battery working under extreme conditions. The modified PI separator possessed a high electrochemical stability window of 4.5 V. Compared with the batteries from the commercial separator Celgard 2320 and the pure polyimide matrix, the assembled coin cell with the PI-mod separator showed much better rate capabilities and capacity retention due to the high electrolyte affinity of the PEI-PEG polymer coating. The developed strategy of using the electrolyte-swollen polymer to modify the thermal-resistant separator network provides an efficient way for establishing high-power lithium-ion batteries with good safety performance.