Proton NMR relaxometry study of Nafion membranes modified with ionic liquid cations.

Proton nuclear magnetic resonance (NMR) relaxometry was used to study the ionic mobility and levels of confinement within Nafion membranes modified by incorporation of selected ionic liquid (IL) cations. These studies were performed aiming at understanding the effect of using different types of ionic liquid cations, and their degree of incorporation, in the values of the spin-lattice relaxation times (T(1)) obtained at different values of frequency and thus detect the influence of confinement level on the ions mobility. The frequency dependence of the proton spin-lattice relaxation rate, R(1) = 1/T(1), for the modified Nafion/IL cation membranes was compared with that obtained for an unmodified Nafion membrane, allowing for distinguishing different contributions of the motions of the molecules depending on the frequency tested. The experimental R(1) results were analyzed in terms of models that consider the sum of the most effective relaxation contributions, to estimate the translational self-diffusion coefficient of the moving molecular species in the modified membranes. The stability of these membranes with temperature in terms of the spin-lattice relaxation was compared with results obtained by thermogravimetric analysis.