To clarify the mechanisms of transport of ions and water molecules in perfluorosulfonated ionomer membranes for fuel cells, the temperature dependence of their transport behaviors was investigated in detail. Two types of Flemion membranes having different equivalent weight values (EW) were utilized along with Nafion 117 as the perfluorinated ionomer membranes, and H-, Li-, and Na-form samples were prepared for each membrane by immersion in 0.03 M HCl, LiCl, and NaCl aqueous solutions, respectively. The ionic conductivity, water self-diffusion coefficient (D_H₂_O), and DSC were measured in the fully hydrated state as a function of temperature. The ionic conductivity of the membranes was reflected by the cation transport through the intermediary of water. Clearly, H⁺ transports by the Grotthuss (hopping) mechanism, and Li⁺ and Na⁺ transport by the vehicle mechanism. The differences of the ion transport mechanisms were observed in the activation energies through the Arrhenius plots. The D_H₂_O in the membranes exhibited a tendency similar to the ionic conductivity for the cation species and the EW value. However, no remarkable difference of D_H₂_O between H- and the other cation-form membranes was observed as compared with the ionic conductivity. It indicates that water in each membrane diffuses almost in a similar way; however, H⁺ transports by the Grotthuss mechanism so that conductivity of H⁺ is much higher than that of the other cations. Moreover, the D_H₂_O and DSC curves showed that a part of water in the membranes freezes around −20 °C, but the nonfreezing water remains and diffuses below that temperature. This fact suggests that completely free water (bulk water) does not exist in the membranes, and water weakly interacting with the cation species and the sulfonic acid groups in secondary and higher hydration shells freezes around −20 °C, while strongly binding water in primary hydration shells does not freeze. The ratio of freezing and nonfreezing water was estimated from the DSC curves. The D_H₂_O in the membranes was found to be influenced by the ratio of freezing and nonfreezing water. DFT calculation of the interaction (solvation) energy between the cation species and water molecules suggested that the water content and the ratio of freezing and nonfreezing water depend strongly on the cation species penetrated into the membrane.

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