Fully hydrocarbon ionomer catalyst layers in proton- and anion-exchange membrane fuel cells

The structure and morphology of fuel cell catalyst layers and concomitant system properties, particularly mass transport, were investigated through electrochemical and physical characterization techniques. Catalyst layers designed for proton-exchange membrane fuel cells (PEMFCs) incorporated a hydrocarbon ionomer (sP4c) soluble in low-boiling solvents. These were used to probe the property alterations effected by increasing ionomer coverage within the catalyst layer, and also to measure the impact an extremely small quantities (0.38 wt%) of a commonly employed high-boiling solvent, DMF, in the catalyst ink. High-boiling solvents are difficult to eliminate during electrode formation, and resultant solvent-annealed catalyst layers lost electrocatalytic surface area, resulting in markedly greater kinetic losses compared to catalyst layers formed without high-boiling solvents. Catalyst layers designed for anion-exchange membrane fuel cells (AEMFCs) incorporating hydrocarbon ionomer in the catalyst layer (FAA-3) requiring high-boiling solvent (NMP, 2.3 wt% of total solvent) were formed over a broad array of conditions. Catalyst layers formed slowly at high temperatures to drive off high-boiling solvent displayed significantly enhanced mesoporosity, relating to enhanced transport characteristics, over solvent-annealed analogues with low mesoporosity, despite comparable total volumes. The impacts of solvent annealing on AEMFC electrode properties and resultant achievable power density and degradation were disproportionate compared to the similar PEMFC study. A new methodology for fuel cell membrane-electrode assembly construction, direct membrane deposition (DMD), enables lower interfacial resistances and enhanced water transport for a given thickness of membrane. These are desired properties for both PEMFCs and AEMFCs. Initially developed with inkjet printers designed for single-cell biological printing applications, this method was adapted to spray-coating systems in order to address issues with fuel and electrical crossover, suitability for hydrocarbon ionomers, and scalability / large-scale reproducibility. A perfluorinated sulfonic acid ionomer reference material (Nafion D520) was employed for direct comparison to initial methods. Highly reproducible DMDs with low fuel and electrical crossover resulted