Hydration, self-diffusion and ionic conductivity of Li+, Na+ and Cs+ cations in Nafion membrane studied by NMR

Hydration of Nafion 117 perfluorinated sulfonic cation-exchange membrane in alkaline ion forms was investigated by high resolution 1H NMR. Hydration numbers of Li+, Na+ and Cs+ cations were 5 ± 1, 6 ± 1 and 1 ± 0.2, correspondingly for membrane equilibrated with water vapor at 98% RH. As opposed to Li+ and Na+, which form separate ion pair, Cs+ cation directly contacts with membrane sulfonate group. Cation self-diffusion coefficients were measured by pulsed field gradient NMR technique on 7Li, 23Na and 133Cs nuclei for the first time. Self-diffusion coefficients are changed in the next rows Li+ ≤ Na+ > Cs+. Self-diffusion activation energies of Li+ and Na+ cations are about 20 kJ/mol which is close to water self-diffusion activation energy in these membranes, but Cs+ self-diffusion activation energy is distinctly more (25 kJ/mol). Ionic conductivities calculated on the basis of Nernst–Einstein equation from cation self-diffusion coefficients 1.6∙10−2, 2∙10−2, 6∙10−3 S/cm for Li+, Na+, Cs+ cations, correspondingly, are closely approximating to conductivities measured by impedance spectroscopy: 1.3∙10−2, 1.1∙10−2, 2.3∙10−3 S/cm for Li+, Na+, Cs+ cations, correspondingly, but calculated values are appreciably more compared with experimental meanings. •Membrane humidity determines an interaction between counter ion and membrane SO3-group.•The hydration peculiarities control the cation translational mobilities by-turn.•Cs + translational mobility is essentially low compare with Li + and Na+.•In solutions and high water content membranes Li, Na and Cs cations and anions form ion pairs.•There is an opportunity to control ionic mobility by membrane humidity variation.