Anhydrous Proton-Conducting Polymeric Electrolytes for Fuel Cells

The need to design proton-conducting electrolytes for fuel cells operating at temperatures of 120 °C and above has prompted the investigation of various “water-free” polymeric materials. The present study investigates the properties of “water-free” proton-conducting membranes prepared from high-molecular-weight polymeric organic amine salts. Specifically, the properties of bisulfates and dihydrogenphosphates of poly-2-vinylpyridine (P2VP), poly-4-vinylpyridine (P4VP), and polyvinylimidazoline (PVI) have been investigated over the temperature range of 25−180 °C. Nanocomposites of these polymeric organic amine salts and hydroxylated silica have also been investigated in this study. These polymers are found to be stable and proton-conducting at temperatures up to 200 °C. In all the polymer examples studied herein, the phosphates are more conducting than the bisulfates. The activation energy for ionic conduction was found to decrease with increasing temperature, and this is associated with the increased polymer mobility and ionization of the proton. This is confirmed by the high degree of motional narrowing that is observed in proton NMR experiments. The measured values of conductivity and the differences in pK a values of the polymeric organic amine and the mineral acid are clearly correlated. This observation provides the basis for the design of other water-free acid−base polymer systems with enhanced proton conductivity. The results presented here suggest that anhydrous polymer systems based on acid−base polymer salts could be combined with short-range proton conductors such as nanoparticulate silica to achieve acceptable conductivity over the entire temperature range.