As the world sets its sight into the future, energy remains a great challenge. Proton exchange membrane (PEM) fuel cell is part of the solution to the energy challenge because of its high efficiency and diverse application. The purpose of the PEM is to provide a path for proton transport and to prevent direct mixing of hydrogen and oxygen at the anode and the cathode, respectively. Hence, PEMs must have good proton conductivity, excellent chemical stability, and mechanical durability. The current state-of-the-art PEM is a perfluorosulfonate ionomer, Nafion. Although Nafion has many desirable properties, it has high methanol crossover and it is expensive.
The objective of this research was to develop a cost effective two-phase, composite PEM wherein a dispersed conductive organic phase preferentially aligned in the transport direction controls proton transport, and a continuous hydrophobic phase provides mechanical durability to the PEM. The hypothesis that was driving this research was that one might expect better dispersion, higher surface to volume ratio and improved proton conductivity of a composite membrane if the dispersed particles were nanometer in size and had high ion exchange capacity (IEC, = [mmol sulfonic acid]/gram of polymer). In view of this, considerable efforts were employed in the synthesis of high IEC organic nanoparticles and fabrication of a composite membrane with controlled microstructure.
High IEC, ~ 4.5 meq/g (in acid form, theoretical limit is 5.4 meq/g) nanoparticles were achieved by emulsion copolymerization of a quaternary alkyl ammonium (QAA) neutralized-sulfonated styrene (QAA-SS), styrene, and divinylbenzene (DVB). The effects of varying the counterion of the sulfonated styrene (SS) monomer (alkali metal and QAA cations), SS concentration, and the addition of a crosslinking agent (DVB) on the ability to stabilize the nanoparticles to higher IECs were assessed. The nanoparticles were ion exchanged to acid form. The extent of ion exchange was characterized with solid state 13C NMR spectroscopy, FTIR spectroscopy, TGA, elemental analysis, and titration. The results indicate the extent of ion exchange was ~ 70-80%. Due to the mass of QAA, the remaining QAA reduced the IEC of the nanoparticles to < 2.2 meq/g.
In fabricating the composite membranes, the nanoparticles and polystyrene were solution cast in a continuous process with and without electric field. The electric field had no effect on the water uptake. Based on the morphology and the proton conductivity, it appears orientation of the nanoparticles did not occur. We hypothesize the lack of orientation was caused by swelling of the particles with the solvent. The solvent inside the particle minimized polarizability, and thus prevented orientation. The composite membranes were limited to low proton conductivity of ~ 10-5 S/cm due to low IEC of the nanoparticles, but good dispersion of the nanoparticles was achieved. Future work should look into eliminating the QAA during synthesis and developing a rigid core for the nanoparticles.