Dynamics of the hydrogen and phosphate ions in proton conducting gel/D3PO4 electrolytes:: A 2H and 31P nuclear magnetic resonance study

The synthesis and characterization of protonic conducting polymeric gels is motivated by their possible application in various electrochemical devices. Nonaqueous proton-conducting gel electrolytes are being developed for use in various sensors and electrochromic devices operating at ambient temperatures. The electrolyte must have a relatively high conductivity and chemical and physical stability. One method of producing nonaqueous conducting polymeric gel electrolytes is to entrap organic solutions of a strong acid such as H3PO4 in a polymer matrix. Results are reported on the system consisting of phosphoric acid dissolved in N,N-dimethyl formamide (DMF) within a gel network formed with poly(glycidyl methacrylate) (PGMA). Using selective deuteration, the diffusion coefficients for both the deuteron and phosphorus from the phosphoric acid and the DMF are measured by field gradient nuclear magnetic resonance (NMR) techniques. Combining the diffusion with conductivity measurements in the Nernst-Einstein equation leads to a better understanding of the number of charge carriers in the mixture and the temperature dependence of this number. Nuclear spin-lattice relaxation is used as a tool to probe the ion dynamics in these materials. In addition to NMR measurements, the samples have been characterized by electrical conductivity, differential scanning calorimetry, and viscosity measurements. The results show that the Grotthus mechanism involving the hopping of the proton from one molecular site to another, as well as the vehicular mechanism due to the motion of the D2PO4- and D4PO4+ ions are most responsible for the motion of the proton in these electrolytes. The variety of protonation sites in the PGMA/DMF/H3PO4 system is much more diverse that in the previously studied PMMA/PC/D3PO4 system. In the PGMA/DMF/H3PO4 system there are sites on the polymer, DMF and H3PO4. (C) 2003 American Institute of Physics.