PFSA Membrane Thickness Impact on Chemical Degradation Rates

Abstract

As the large-scale commercialization of proton exchange membrane fuel cells (PEMFC) for numerous applications, including heavy-duty trucks draws nearer, there is increasing interest in optimizing fuel cell membranes for both improved efficiency and durability. One of the major membrane attributes being considered for optimization is thickness. The current range of (perfluorosulfonic acid) PFSA membrane thicknesses employed for commercial applications range from 8 -25 µm. As with most adjustable materials parameters, there are a host of properties (cost, gas permeability, proton conductivity, etc.) that require co-optimization to provide the overall preferred position. For example, thin membranes will minimize proton resistance, facilitating high power densities, but will simultaneously allow increased gas crossover fluxes that can contribute to both reduced fuel efficiency and increased oxidative stress. On the other end of the spectrum, thick membranes will decrease gas crossover fluxes, offering improved fuel efficiency while simultaneously decreasing power density. A major question surrounding the tradeoffs of membrane thickness involves the chemical durability impact. Here, we report our investigations of PFSA membrane chemical durability as a function of thickness. For the studies reported here, a thickness series (8, 12 and 20 µm) of ePTFE reinforced Nafion®-like PFSA standalone membranes (SAMs) were prepared.A two-pronged approach was taken for this study. The first involves investigation of intrinsic chemical stability of the ionomer as a function of membrane thickness using an ex-situ H2O2 vapor test. The second investigative mode, which targets the oxidative stress generated by crossover gas flux, employs OCV durability tests of full MEAs. In addition to membrane thickness, gas crossover rates are known to be functions of membrane hydration and gas pressures.1,2 Accordingly, a 3(4-1) fractional factorial experimental design was executed to probe the role of membrane thickness as well as the other factors known to affect gas crossover. The fractional factorial design allows all main effects to be determined and further allows estimation of two factor interactions, if present.References T. Sakai, H. Tanenaka, E, Torikai, “Gas Diffusion in Dried and Hydrated Nations” J. Electrochem. Soc., 1986, 133, 88-92R. Jiang, T. Fuller, S. Brawn, C. Gittleman, “Perfluorocyclobutane and poly(vinylidene fluoride) blend membranes for fuel cells” Electrochimica, Acta, 2013, 110, 306-315