Concentrated aqueous electrolytes have received much attention in recent years due to their high ionic conductivity and electrochemical window that usually exceeds that of the water electrolysis limitation. In collaboration with Ziyue Li and Fei Wang (Fudan University) we have investigated water/polyphosphoric acid solutions ranging in concentration from 1.25 to 16.6 molar being considered for proton-based batteries. Self-diffusion coefficients measured by pulsed field gradient NMR as well as spin-lattice time relaxation measurements were determined for ³¹P and ¹H. The results shed light on the observed maximum in conductivity at the 5.9 molar concentration.

For polymer electrolyte membrane fuel cells (PEMFC), polybenzimidazole (PBI) membranes with high phosphoric acid content have been developed previously by collaborator Brian Benicewicz (University of South Carolina) using the so-called PPA process. Recently, a carefully controlled drying method has been discovered by Benicewicz and co-worker Laura Murdock in which a PBI membrane prepared by the PPA process is transformed into a dense PBI film. Though originally developed for flow battery applications, it was found that this dense film could be re-acidified to yield a mechanically robust PEM. Furthermore this method provides a synthetic route to PBI films without the use of any organic solvents. The re-doped PBI films display high ionic conductivity at elevated temperatures, similar to the starting PBI gel membranes prepared by the PPA process, while containing nearly a factor of two less acid than the latter and also exhibiting enhanced mechanical properties. NMR spectroscopy was used to characterize the structure and dynamics of the modified and the original PBI/PPA membranes. In addition to pulsed field gradient diffusion studies, we have performed solid state one-dimensional ³¹P, ¹³C and two-dimensional ³¹P{¹H} and ¹³C{¹H} HETCOR NMR measurements, which yield additional information on structural differences between the membranes and how these differences may affect transport properties.