No abstract

Water absorption, membrane swelling, and self-diffusivity of water in 1100 equivalent weight Nafion were measured as functions of temperature and water activity. Free volume per water at 80 °C, determined from water uptake and volume expansion data, decreases with water content in the membrane from 12 cm(3)/mol at λ = 0.5 H(2)O/SO(3) to 1.5 cm(3)/mol at λ = 4. The change in free volume with water content displays a transition at λ = 4. Limiting water self-diffusivity in Nafion was determined by pulsed gradient spin echo NMR at long delay times. The limiting self-diffusivity increases exponentially with water activity; the rate of increase of diffusivity with water content shows a transition at λ = 4. The tortuosity of the hydrophilic domains in Nafion decreased from 20 at low membrane water activity to 3 at λ = 4. It suggested a change in the connectivity of the hydrophilic domains absorbed water occurs at λ ∼ 4. The diffusivity results were employed to separate the contributions of diffusional and interfacial resistance for water transport across Nafion membranes, which enabled the determination of the interfacial mass transport coefficients. A diffusion model was developed which incorporated activity-dependent diffusivity, volume expansion, and the interfacial resistance, and was used to resolve the water activity profiles in the membrane.

Measurements of the mechanical and electrical properties of Nafion and Nafion/titania composite membranes in constrained environments are reported. The elastic and plastic deformation of Nafion-based materials decreases with both the temperature and water content. Nafion/titania composites have slightly higher elastic moduli. The composite membranes exhibit less strain hardening than Nafion. Composite membranes also show a reduction in the long-time creep of $40% in comparison with Nafion. Water uptake is faster in Nafion membranes recast from solution in comparison with extruded Nafion. The addition of 3-20 wt % titania particles has minimal effect on the rate of water uptake. Water sorption by Nafion membranes generates a swelling pressure of $0.55 MPa in 125-lm membranes. The resistivity of Nafion increases when the membrane is placed under a load. At 23 8C and 100% relative humidity, the resistivity of Nafion increases by $15% under an applied stress of 7.5 MPa. There is a substantial hysteresis in the membrane resistivity as a function of the applied stress depending on whether the pressure is increasing or decreasing. The results demonstrate how the dynamics of water uptake and loss from membranes are dependent on physical constraints, and these constraints can impact fuel cell performance.

Metal-oxide-recast Nafion composite membranes were studied for operation in hydrogen/oxygen protonexchange membrane fuel cells (PEMFC) from 80 to 130 °C and at relative humidities ranging from 75 to 100%. Membranes of nominal 125 µm thickness were prepared by suspending a variety of metal oxide particles (SiO 2 , TiO 2 , Al 2 O 3 , and ZrO 2 ) in solubilized Nafion. The composite membranes were characterized using electrochemical, X-ray scattering, spectroscopic, mechanical, and thermal analysis techniques. Membrane characteristics were compared to fuel cell performance. These studies indicated a specific chemical interaction between polymer sulfonate groups and the metal oxide surface for systems that provide a good elevated-temperature (i.e., fuel-cell operation above 120 °C) performance. Composite systems that incorporate either a TiO 2 or a SiO 2 phase produced superior elevated-temperature, lowhumidity behavior compared to that of a simple Nafion-based fuel cell. Improved temperature tolerance permits the introduction of at least 500 ppm CO contaminant in the H 2 fuel stream without cell failure, in contrast to standard Nafion-based cells, which fail below 50 ppm of carbon monoxide.