Structures and Properties of Sulfonated Ionomers Probed by Transport and Mechanical Measurements: The Role of Solute Activity

Abstract

This work is focused on advancing the understanding of the structures and properties of sulfonated ionomer membranes in the context of Polymer Electrolyte Membrane Fuel Cell applications by transport and mechanical measurements. Transport and mechanical properties are two critical elements of ionomer membranes that govern the performance and longevity of fuel cells. Additionally, transport and mechanical property measurements can also provide valuable information about the structure of the ionomer membranes. It is essential to develop a comprehensive understanding of them under well controlled environmental conditions.

The mechanism of water transport through Nafion membranes was found to be governed by water diffusivity, swelling of the hydrophilic phase and the interfacial transport across membrane/vapor interface. A transport model incorporating these parameters was developed and successfully employed to resolve water activity profiles in the membrane and make quantitative predictions under steady state and dynamic conditions. Experimental results of diffusivity, volume of mixing and tortuosity also provided hints about the hydration shell structure around in the hydrophilic domains of Nafion. The alcohol sorption and transport was found to be qualitatively similar to the behavior of water and the quantitative differences were attributed to the difference in molecular size. The transport of alcohol water mixtures through Nafion displayed significant non-ideality which was connected to the abnormal swelling and incomplete mixing within the hydrophilic domains.

The mechanical properties of several perfluoro-sulfonated ionomer (PFSI) membranes were studied as functions of temperature and solute activity. The thermal transition found between 60-100oC was described as an order-disorder transition of the ionic clusters. Water and other polar solutes were found to plasticize PFSI below the transition but stiffen PFSI above the transition. The stiffening effect was attributed to polar solute induced re-clustering of the ionic domains.

Two hydrocarbon model ionomer SPS and SPEEK were studied to further understand the structural-property relationships of ionomers. Water sorption and proton conductivity were enhanced with increasing ion content but water content was independent of ion content and proton conductivity scaled with hydrophilic volume fraction. Water transport was dependent on diffusion and interfacial transport, both of which were affected by the size and shape of the hydrophilic domains.