Ion and water transport characteristics of Nafion ionomer membranes were investigated systematically in the mixed cation form of H+ and various kinds of alkali metal cation systems, which were prepared by equilibrating the membranes in the mixtures of HCl and alkali chloride in aqueous solutions of various mixing ratios. The membrane cationic composition showed that cations of larger atomic number had a higher affinity to sulfonic acid groups but less water content in the membrane than those of smaller atomic numbers. The net ionic conductivity was decreased, in any case, by the presence of alkali metal cations in the membrane. Different kinds of the interaction mode among cations were observed between H/Li or H/Na systems and H/K, H/Rb, or H/Cs systems. The interaction between alkali metal cations appeared to increase as the atomic number of the alkali metal cation increased. The water transference coefficient (electro-osmosis drag coefficient) increased from 2.5 to more than 10 by the presence of alkali metal cations. In the mixed systems, these cations were found to cause less water molecule drag than in the case of individual ions, in the presence of H+ ion. Overall, the transport characteristics of H+ and alkali metal cations influenced each other by way of the water molecules when they coexist in the membrane.

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Ion and water transport characteristics of perfluorosulfonated ionomer membranes are investigated in the mixed cation form of H/Fe, H/Ni, and H/Cu systems. Nafion membranes, which were equilibrated with HCl/FeCl3, HCl/NiCl2, or HCl/CuCl2 mixed aqueous solutions of various mixing ratios, were prepared as test samples, and equilibrium and transport properties were measured systematically. Membrane cationic composition showed that trivalent cations had more affinity than divalent cations. Also larger valence cations caused less water content in the membrane. The membrane ionic conductivity was markedly influenced by counterions, and H+ mobility u H + was altered according to the nature of coexisting cations. In the presence of Cu2+, u H + increased from its inherent value, while in the presence of Fe3+, u H + decreased to a large extent, Ni2+ bringing about nearly no change in u H + . The ionic transference number of H+ was also influenced by coexisting cations in several ways. Despite the unique influence of impurity cations on the mobility of H+, the mobility of impurity cations was not affected by the presence of H+. The interaction between adjacent cationic species in the membrane ion exchange sites, although plausible in general for multivalence cations, appeared to be not specific due probably to the shielding of the cationic charge by water molecules or by sulfonic acid groups. The water transference coefficient t H 2 O as measured by streaming potential measurements showed unique changes with membrane ionic composition, and t H 2 O increased from 2.5 to over 13 by the presence of impurity ions. These impurity ions were found to result in more water molecules dragged than in the case of individual ions, when coexisting with the H+ ion. Overall, it was noted that the water molecules within the influence of impurity cations appeared to play a large role in the H+ movement in the membrane.

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The effect of contamination by Ca2 ions in proton conductive membranes f or polymer electrolyte fuel cells was investigated systematically. Ion and water transport characteristics of Nafion membranes, which were equilibrated with 0.02 to 0.03 kmol m3 of HC1/CaCl2 mixed solutions of various mixing ratios, were studied by electromotive force analysis. Membrane composition analysis, showed that Ca2 has much higher affinity than H to the ion exchange sites in Naf ion membranes. The water content in the membrane, as expressed by the amount of water per cationic site }120/SO;, decreased about 19% from 21 for H-form membrane to 17 for Ca-form membrane. The water transference coefficient was obtained from streaming potential measurements of Nafion 115 membranes of various H/Ca2 cationic compositions. The water transference coefficient increased from 2.5 toward 11 as the Ca2 content in the membrane increased, especially when the equivalent fraction of H in the cationic exchange sites x became less than 0.5. Ionic transference numbers for H in the membrane, determined by a new electromotive force method, showed rapid decrease when the cationic site occupancy by H became less than 0.5. Membrane conductivity changed linearly with H composition in the membrane. In strong contrast to the interaction mode between H and Ca cations during ionic conduction, which appeared almost independent, a certain extent of interference was observed among water molecules as they were carried along by cations in the membrane. It was predicted that if Ca2 ions enter the fuel-cell membrane, they cause serious effects to membrane drying and result in deterioration of fuel-cell performance. The advantage of this methodology in the study of transport characteristics of fuel-cell membranes is stressed due to ease and accuracy of measurements.) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 169.230.243.252 Downloaded on 2015-02-07 to IP