Published online by Cambridge University Press: 15 March 2011
Hybrid proton-carrier polymer composites were fabricated in an effort to develop high-performance high-temperature proton exchange membranes (PEMs) for fuel cell applications in the 100°–200°C range. The solution-cast hybrid membranes comprise a polymer host and a SiO2-based proton-carrier composite that was synthesized via sol gel approach using a functional silane and tetraethoxysilane (TEOS) in acidic conditions. The primary H+-carrying component was either a heteropoly silicotungstic acid (STA) or a sulfonic acid (SFA) that was thermooxidatively converted from a mercapto (-SH) group. The embedding level of STA on the silane-modified SiO2 sol gel composites was strongly affected by the presence and the functional group of the silane. Ion exchange capacity (IEC) of the water-washed, SiO2-based STA and SFA proton-carrier composite powders is in the range of 1.8–3.5 mmol/g, two to three times higher than that for Nafion 117 (0.9 meq/mol). A glycidylmethacrylate-type copolymer, PEMAGMA, which is stable up to ∼225°C, was able to produce mechanically robust and flexible hybrid membranes. Upon curing, the PEMAGMA composite membranes showed a ∼75% gel under the present formulation and retained the "free" STA effectively with slight loss when extracted in an 85°C water. The W12-STA-containing PEMAGMA membranes followed the weight loss trends of water from STA and the SiO2-based sol gel composite, showing a 10 wt% loss at 150°C and a 15 wt% loss at 225°C. Fuel cell performance tests of the preliminary films gave a Voc in the 0.85–0.93 V range, but a low current density of <4 mA/cm2. The resistive characteristics were attributed to inhomogeneous distribution of the sol gel nanoparticles in the PEMAGMA matrix, a result of phase separation and particulate agglomeration during film forming.