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.