Ionic Conductivity of Bulk, Gels and Solutions of Perfluorinated Ionomer Membranes.

Perfluorinated ionomer membranes either sulfonated or carboxylated have been extensively studied in order to understand the relations between their structure and properties. In addition to their uses as separator in the Cl2/NaOH industry large potential applications exist in different fields like sensors, batteries, fuel cells, electrochromic displays, etc. Some of these applications are due to the possibility of getting solutions, gels from these materials in different solvents and of reconstructing membranes of different thicknesses. The aim of this presentation is to present conductivity measurements of solutions, gels and bulk membranes, which measurements are of primary interest for potential applications in electrochemical devices. Room temperature measurements of conductivity of solutions/gels: First of all we recall the results already published which show the high conductivity of these gels associated with a transport number t+=1 since the COO− or SO3− anions are covalently bound to the rigid perfluorinated rod like structure. Low temperature measurements: Polymers having ionic conductivity usually show drastic changes upon temperature associated to transition (Tg, Tm or sub Tg relaxations). Measurements of conductivity of NAFION® 1100 solutions in propylene carbonate or dimethoxyethane over a temperature range between +20°C and −40°C have shown only small changes mainly due to viscosity modifications of the solvent as evidenced from the calculated activation energies. Conductivity/swelling measurements: We have recently developed an experiment which permits to obtain both the conductivity and the swelling of ion exchange membranes. Equilibrium experiments with solvent mixtures permit to check the conductivity and swelling changes versus different parameters (dielectric constant of solvent, ionic radius of the counterion, etc.). Diffusion coefficients are also obtained from the time lag when immersing the membrane in the solvent.