Transport Mechanism in Nafion Revealed by Detailed Comparison of 1H and 17O Nuclear Magnetic Resonance Diffusion Coefficients.

We use 1H and 17O NMR static field gradient diffusometry to measure self-diffusion coefficients of protons (DH) and oxygens (DO) in Nafion 212 with various hydration levels (λ = 4-18). For all samples and both nuclei, we obtain activation energies (Ea) of ≈0.19 eV. Analyzing the hydration-level dependence of DH and DO, we find DO/DH ≈ 1 at λ ≈ 18, resembling the situation in bulk water, while oxygen diffusion becomes faster than proton diffusion when the water content is decreased, leading to DO/DH ≈ 1.2 at λ ≈ 4. A comparison with literature data for acidic bulk solutions implies that faster oxygen than proton diffusion results from the existence of the polymer framework. To rationalize the observed ratios DO/DH ≥ 1, we consider a bimodal dynamical model in which the interactions of H+(H2O)m ions with neighboring SO3- groups lead to slower water dynamics in the vicinity of the polymer framework than in the center of the water nanochannels.

Development of High-Performance Hydrogen-Air Fuel Cell with Flourine-Free Sulfonated Co-Polynaphthoyleneimide Membrane.

This paper presents research on the technological development of hydrogen-air fuel cells with high output power characteristics using fluorine-free co-polynaphtoyleneimide (co-PNIS) membranes. It is found that the optimal operating temperature of a fuel cell based on a co-PNIS membrane with the hydrophilic/hydrophobic blocks = 70/30 composition is in the range of 60-65 °C. The maximum output power of a membrane-electrode assembly (MEA), created according to the developed technology, is 535 mW/cm2, and the working power (at the cell voltage of 0.6 V) is 415 mW/cm2. A comparison with similar characteristics of MEAs based on a commercial Nafion 212 membrane shows that the values of operating performance are almost the same, and the maximum MEA output power of a fluorine-free membrane is only ~20% lower. It was concluded that the developed technology allows one to create competitive fuel cells based on a fluorine-free, cost-effective co-polynaphthoyleneimide membrane.

Self-diffusion micromechanism in Nafion studied by 2H NMR relaxation dispersion.

Field Cycling (FC) 2H nuclear magnetic resonance (NMR) relaxometry was applied to study dynamics in Nafion NR 212 in the temperature range from 300 K to 190 K and water content of λ = 8.2. The sensitive time window of FC was extended up to eight decades using the temperature-frequency superposition principle and master curve. The rotational correlation times obtained from 2H FC NMR coincide with translational correlation times gained from static field 2H NMR diffusometry in the temperature range applied. This fact means that a long-range mass transport in Nafion is coupled to molecular rotations. It is assumed that confined water in Nafion has more ordered oxygen sublattices as compared with bulk water, on a short range is similar to ice. We discuss the possible role of D and L defects, typical for the ordered ice structure and using this concept to describe the processes of self-diffusion of confined water in Nafion, as well as the similarity of temperature and humidity dependence of self-diffusion and proton conductivity.

Preparation and Study of Sulfonated Co-Polynaphthoyleneimide Proton-Exchange Membrane for a H2/Air Fuel Cell.

The sulfonated polynaphthoyleneimide polymer (co-PNIS70/30) was prepared by copolymerization of 4,4'-diaminodiphenyl ether-2,2'-disulfonic acid (ODAS) and 4,4'-methylenebisanthranilic acid (MDAC) with ODAS/MDAC molar ratio 0.7/0.3. High molecular weight co-PNIS70/30 polymers were synthesized either in phenol or in DMSO by catalytic polyheterocyclization in the presence of benzoic acid and triethylamine. The titration reveals the ion-exchange capacity of the polymer equal to 2.13 meq/g. The membrane films were prepared by casting polymer solution. Conductivities of the polymer films were determined using both in- and through-plane geometries and reached ~96 and ~60 mS/cm, respectively. The anisotropy of the conductivity is ascribed to high hydration of the surface layer compared to the bulk. SFG NMR diffusometry shows that, in the temperature range from 213 to 353 K, the 1H self-diffusion coefficient of the co-PNIS70/30 membrane is about one third of the diffusion coefficient of Nafion® at the same humidity. However, temperature dependences of proton conductivities of Nafion® and of co-PNIS70/30 membranes are nearly identical. Membrane-electrode assemblies (MEAs) based on co-PNIS70/30 were fabricated by different procedures. The optimal MEAs with co-PNIS70/30 membranes are characterized by maximum output power of ~370 mW/cm2 at 80 °C. It allows considering sulfonated co-PNIS70/30 polynaphthoyleneimides membrane attractive for practical applications.