No abstract

The results of NMR, and especially pulsed field gradient NMR (PFG NMR) investigations, are summarized. Pulsed field gradient NMR technique makes it possible to investigate directly the partial self-diffusion processes in spatial scales from tenth micron to millimeters. Modern NMR spectrometer diffusive units enable to measure self-diffusion coefficients from 10−13 m2/sec to 10−8 m2/sec in different materials on 1 H, 2 H, 7 Li, 13 C, 19 F, 23 Na, 31 P, 133 Cs nuclei. PFG NMR became the method of choice for reveals of transport mechanism in polymeric electrolytes for lithium batteries and fuel cells. Second wide field of application this technique is the exchange processes and lateral diffusion in biological cells as well as molecular association of proteins. In this case a permeability, cell size, and associate lifetime could be estimated. The authors have presented the review of their research carried out in Karpov Institute of Physical Chemistry, Moscow, Russia; Institute of Problems of Chemical Physics RAS, Chernogolovka, Russia; Kazan Federal University, Kazan, Russia; Korea University, Seoul, South Korea; Yokohama National University, Yokohama, Japan. The results of water molecule and Li+, Na+, Cs+ cation self-diffusion in Nafion membranes and membranes based on sulfonated polystyrene, water (and water soluble) fullerene derivative permeability in RBC, casein molecule association have being discussed.

No abstract

NMR is the method of choice for molecular and ionic structures and dynamics investigations. The present review is devoted to solvation and mobilities in solid electrolytes, such as ion-exchange membranes and composite materials, based on cesium acid sulfates and phosphates. The applications of high-resolution NMR, solid-state NMR, NMR relaxation, and pulsed field gradient 1H, 7Li, 13C, 19F, 23Na, 31P, and 133Cs NMR techniques are discussed. The main attention is paid to the transport channel morphology, ionic hydration, charge group and mobile ion interaction, and translation ions and solvent mobilities in different spatial scales. Self-diffusion coefficients of protons and Li+, Na+, and Cs+ cations are compared with the ionic conductivity data. The microscopic ionic transfer mechanism is discussed.

The interconnection of ionogenic channel structure, cation hydration, water and ionic translational mobility was revealed in Nafion and MSC membranes based on polyethylene and grafted sulfonated polystyrene. A local mobility of Li+, Na+ and Cs+ cations and water molecules was estimated via the 1H, 7Li, 23Na and 133Cs spin relaxation technique. The calculated cation and water molecule self-diffusion coefficients were compared with experimental values measured using pulsed field gradient NMR. It was shown that macroscopic mass transfer is controlled by molecule and ion motion near sulfonate groups. Lithium and sodium cations whose hydrated energy is higher than water hydrogen bond energy move together with water molecules. Cesium cations in possession of low hydrated energy are directly jumping between neighboring sulfonate groups. Cation Li+, Na+ and Cs+ hydration numbers (h) in membranes were calculated from 1H chemical shift water molecule temperature dependences. The values calculated from the Nernst–Einstein equation and the experimental conductivity values were close to each other in Nafion membranes. In MSC membranes, calculated conductivities were one order of magnitude more compared to the experimental ones, which is explained by the heterogeneity of the membrane pore and channel system.