Preparation and characterization of chemically stable polymer electrolyte membranes by radiation-induced graft copolymerization of four monomers into ETFE films

Chen, J.; Asano, Masaharu; Yamaki, Tetsuya; Yoshida, Masaru

To develop a highly chemically stable polymer electrolyte membrane for application in a direct methanol fuel cell (DMFC), four styrene derivative monomers, m,p-methylstyrene (MeSt), p-tert-butylstyrene (tBuSt), divinylbenzene (DVB) and bis(p,p-vinyl phenyl) ethane (BVPE) were graft copolymerized into poly(ethylene-co-tetrafluoroethylene) (ETFE) films followed by sulfonation and hydrolysis. The latter two monomers were used as crosslinkers. The graft copolymerization was carried out by the -ray preirradiation method. The influence of the preirradiation dose and the grafting kinetics were investigated in detail. Sulfonation of the grafted ETFE films was performed in a chlorosulfonic acid solution, by which the sulfonation ratio reached about 90%. The newly obtained membrane possesses significantly higher chemical stability than the traditional styrene/DVB-grafted membrane and six times lower methanol permeability compared to the Nafion 112 membrane. Therefore, this study reveals the possibility of the developed inexpensive four monomers-grafted membranes, which could provide an attractive alternative as a substitute for the expensive Nafion membranes for DMFC applications.