Ion Conduction and Its Activation in Hydrated Solid Polyelectrolyte Complexes.

For the first time, temperature-dependent conductivities at constant water content for a series of solid polyelectrolyte complexes with varying mixing ratios of anionic poly(sodium 4-styrene sulfonate) and poly(diallyldimethylammonium chloride) are presented. For water absorption, the samples are first equilibrated at an ambient temperature and at fixed relative humidity (RH). During the conductivity measurements, the so achieved water content of the samples is kept constant. At all of the hydration levels, the dc conductivities of the hydrated polyelectrolyte complexes (PEC) display Arrhenius behavior with activation enthalpies that are significantly lower than those of dry complexes. The activation enthalpy decreases linearly with water content. The lower activation enthalpies in case of hydrated as compared to dried complexes are attributed to a lowering of the energy barriers for ion motion. Finally, it is shown that the temperature-dependent conductivity spectra at constant water content obey the time-temperature superposition principle. Additionally, temperature-dependent conductivities at constant water content are compared to data sets determined in a separate study with constant RH at all of the temperatures. For the latter case, the influence of the type of alkali ion is also considered. Using the broad variety of data sets, the influences of water content and temperature on the conductivity mechanism can be separated from each other.