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Alternative Materials and Manufacturing Technologies for Fabrication
of Proton Exchange Membranes
Alternative Materials and Manufacturing Technologies for Fabrication of
Proton Exchange Membranes
A. Mokrini, M.F. Champagne, L. Robitaille
Industrial Materials Institute – National Research Council of Canada. 75 de Mortagne, Boucherville (QC) Canada
asmae.mokrini@cnrc-nrc.gc.ca
Ion exchange membranes are extensively used as electrolytes in electrochemical devices such as fuel cells, batteries and electrolyzers, as well as barriers in separation processes such as filtration, gas separation, dialysis etc. This contribution reports on alternative routes to prepare functional proton exchange membranes (PEM) for fuel cell applications. PEM are typically phase-segregated materials where a percolated network of a hydrophilic domain conducts protons while the hydrophobic phase confers mechanical strength as well as dimensional and hydrolytic stability during fuel cell operation. The major challenges in the development of new polymer materials suitable as electrolytes for fuel cell applications are to design materials that combine high ionic conductivity and durability, good mechanical strength, reduced fuel permeability, and low cost for high-volume production.
Melt-processing technologies, such as twin-screw extrusion and melt-blowing, were used to prepare advanced reinforced polymer membranes based on fluoropolymers and hydrocarbon elastomers. In this study, blends of polyvinylidene fluoride (PVDF) as a reinforcing polymer and poly(styrene-ethylene-butylene) block copolymer (SEBS) were examined. The aryl groups of SEBS were sulfonated following membrane melt-processing to confer ionic conductivity to the hydrophilic domain. The properties of these polymer membranes are to a large level determined by the phase morphology and the interfacial properties, both directly related to the processing history. The materials developed in this work exhibit a valuable combination of mechanical, chemical and electrochemical properties while being melt-processable. The use of melt-processable ionomers is also expected to provide a significant cost reduction compared to conventional PEM fabrication technologies and will ease the scale-up toward mass production. Aspects related to interface modification to obtain optimized semi-fluorinated composite membranes were previously addressed [1-2]. Two pilot scale processes were used for membranes prototyping: melt-casting and melt-blowing (Figure 1).
A large range of compositions, processing parameters, thicknesses and functionalization times have been screened, allowing to tailor membrane properties. Results show that the two processing technologies used generate different morphologies (Figure 2), which translate in different properties of the final membranes.
Figure 2. AFM phase micrographs using tapping mode in the machine direction (MD) and transverse direction (TD) of reinforced membranes obtained by melt-blowing (top) and melt-casting (bottom)
Optimized membranes show room temperature conductivity of 8.10-2 S/cm when fully humidified, with a fuel cell performance similar to or higher than Nafion ® benchmark membrane. The mechanical resistance was up to 20 MPa for an elongation at break of 200%. The membranes maintained their mechanical strength after an outstanding 6000 hydration/dehydration cycles.
[1] A.Mokrini, M. A. Huneault. Proton Exchange Membranes Based on PVDF/SEBS Blends. Journal of Power Sources 154 (2006) 51
[2] A. Mokrini, M. A. Huneault, P. Gerard. Partially Fluorinated Proton Exchange Membranes Based on PVDF–SEBS blends Compatibilized with Methyl Methacrylate based Block Copolymers. Journal of Membrane Science. 283 (2006) 74
MD TD
