High throughput study of fuel cell proton exchange membranes: poly(vinylidene fluoride)/acrylic polyelectrolyte blends and nanocomposites with zirconium

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Zapata, Pedro José
Meredith, J. Carson
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In view of the unfavorable panorama of actual energy supply practices, alternative sustainable energy sources and conversion approaches have acquired noteworthy significance in recent years. Among these, proton exchange membrane fuel cells (PEMFCs) are being considered as a pivotal building block in the transition towards a sustainable energy economy. The proton exchange membrane (PEM) is a vital component, as well as a performance-limiting factor, of the PEMFC. Consequently, the development of high performance PEM materials is of upmost importance for the advance of the PEMFC field. In this work, alternative PEM materials based on semi-interpenetrated networks from blends of poly(vinyledene fluoride) (PVDF) and sulfonated crosslinked acrylic polyelectrolytes (PE), as well as tri-phase PVDF/PE/zirconium-based composites, are studied. To alleviate the burden resulting from the vast number of possible combinations of the different precursors utilized in the preparation of the membranes, custom high throughput screening systems have been developed for their characterization. By coupling the data spaces obtained via these systems with the appropriate statistical and data analysis tools it was found that, despite not being directly involved in the proton transport process, the inert PVDF phase plays a major role on proton conductivity. Particularly, a univocal inverse correlation between the PVDF crystalline characteristics (i.e., crystallinity and crystallite size) and melt viscosity, and membrane proton conductivity was discovered. Membranes based on highly crystalline and viscous PVDF homopolymers exhibited reduced proton conductivity due to precluded segmental motion of the PE chains during crosslinking. In addition, a maximum effective amount of PE (55-60wt%) beneficial for proton conductivity was revealed. In the case of composite membranes, despite the fact that nanoparticle dispersion was thermodynamically limited, a general improvement in proton conductivity was evidenced at low to medium nanoparticle loadings (0.5 to 1wt%) in comparison to non-hybrid PVDF/PE references. This beneficial effect was particularly noticeable in membranes based on PVDF homopolymers (7% to 14.3% increment), where the nanoparticles induced a "healing" effect by providing proton-conducting paths between non-crosslinked PE channels separated by dense PVDF areas resulting from large PVDF crystallites. In general, the results presented herein are promising for the development of new cost-effective alternative PEMs.
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