Infrared spectroscopic and conductivity studies of ureasil-based proton conducting membranes for medium temperature fuel cell applications.

Proton conducting membranes for fuel cells were prepared by the sol-gel process from two different ureasil organic-inorganic hybrid precursors: bis[(N-(3-triethoxysilylpropyl)ureido]-terminated poly(propylene glycol) 4000 (PPGU) and bis[3-(N-(3-triethoxysilylpropyl)ureido)propyl]-terminated poly(dimethylsiloxane) 1000 (PDMSU). Heteropoly silicotungstic acid was added to actuate the reactions of hydrolysis and condensation and to introduce proton conductivity. XRD measurements of membranes revealed the presence of a diffraction peak at 6.3°, which could be ascribed to gradual formation of R-(SiO3/2) silsesquioxane clusters, i.e. arrangement of the Si-O-Si skeleton on the nano-scale. TG and DSC measurements showed thermal stability of the membranes above 120 °C. Proton conductivities at room temperature were of the order of 10-4 to 10-3 S/cm, classifying the membranes in the group of super ionic conductors. At elevated temperatures up to 160 °C and at conditions of autogenous pressure, conductivities increased up to values acceptable for fuel cells of 10-1 S/cm, which could be the result of the presence of H3O+ ions. The protonation of the urea groups and the formation of amidonium ions [C(OH)=NH+] were followed using IR ATR spectroscopy.