Hydrophilicity/porous structure-tuned, SiO2/polyetherimide-coated polyimide nonwoven porous substrates for reinforced composite proton exchange membranes.

Porous substrate-reinforced composite proton exchange membranes have drawn considerable attention due to their promising application to polymer electrolyte membrane fuel cells (PEMFCs). In the present study, we develop silica (SiO(2)) nanoparticles/polyetherimide (PEI) binders-coated polyimide (PI) nonwoven porous substrates (referred to as "S-PI substrates") for reinforced composite membranes. The properties of S-PI substrates, which crucially affect the performance of resulting reinforced composite membranes, are significantly improved by controlling the hygroscopic SiO(2) particle size. The 40 nm S-PI substrate (herein, 40 nm SiO(2) particles are employed) shows the stronger hydrophilicity and highly porous structure than the 530 nm S-PI substrate due to the larger specific surface area of 40 nm SiO(2) particles. Based on the comprehensive understanding of the S-PI substrates, the structures and performances of the S-PI substrates-reinforced composite membranes are elucidated. In comparison with the 530 nm S-PI substrate, the hydrophilicity/porous structure-tuned 40 nm S-PI substrate enables the impregnation of a large amount of a perfluorosulfonic acid ionomer (Nafion), which thus contributes to the improved proton conductivity of the reinforced Nafion composite membrane. Meanwhile, the reinforced Nafion composite membranes effectively mitigate the steep decline of proton conductivity with time at low humidity conditions, as compared to the pristine Nafion membrane. This intriguing finding is further discussed by considering the unusual features of the S-PI substrates and the state of water in the reinforced Nafion composite membranes.