Structural and Electrotransport Properties of Perfluorinated Sulfocationic Membranes Modified by Silica and Zirconium Hydrophosphate

A correlation between changes in structural and electrotransport properties of membranes after modification by silica and zirconium hydrophosphate was established. The total water volume, volume fraction of the free water in the membrane and the volume fraction of the water having high binding energy were considered as structural characteristics, which were found from the curves of water distribution on the water binding energy and the effective pore radii. The conductivity, diffusion and electroosmotic permeabilities were investigated as electrotransport properties. The influence of the modifier type on the current flow paths in the membrane was analyzed within the framework of the extended three-wire model. It has been established that the treatment of membranes with alcohol before the intercalation of a modifier leads to the appearance of cavities with an effective size of more than 100 nm filled with free water with the binding energy less than 10 J/mol. It is accompanied with an increase in the diffusion permeability of hybrid membranes by approximately 3–6 times in NaCl and HCl solutions, which limits the application of such materials in proton exchange membrane fuel cells. The different conditions of modification of perfluorinated membranes with similar properties by the dopant with same type allow for the preparation of the hybrid materials for various applications such as electrodialysis concentration or electric current generation devices.