Preparation and analysis of new proton conducting membranes for fuel cells

A range of potential new fuel cell membranes were prepared by inserting zirconium phosphate (ZrP) into divinylbenzene (DVB) crosslinked, sulfonated, polystyrene grafted poly(ethylene-alt-tetrafluoroethylene) and poly(vinyl difluoride) membranes using an ion exchange procedure. In short, the preformed membranes are called ETFE-g-PSSA and PVdF-g-PSSA. The ETFE based membranes represented various degrees of grafting (DOG) and degrees of sulfonation (DOS) whereas all of the PVdF based membranes had a DOG of app. 30% and a DOS of app. 90%. The ion exchange capacity (IEC) values of the ETFE based starting materials were in the range 0.5–2, and those of the PVdF based materials were in the range 1.8–2. A proton conductivity of 40 mS/cm was determined at 130 °C and 90% RH for one of the ETFE based preformed membranes. The ETFE based composite samples had slightly lower proton conductivities. Additional zirconium phosphate treatment resulted in composite ETFE samples containing up to 15 wt.% ZrP and composite PVdF samples containing up to 27 wt.%. TG analyses of the ETFE-g-PSSA and PVdF-g-PSSA composite membranes indicated no significant changes of the thermal stability in comparison to the starting materials. The presence of α-ZrP in the product membranes was indicated by 31P MAS NMR analysis, while transmission electron microscopy (TEM) and powder X-ray diffraction analyses proved the samples to be homogeneous.