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We present a model of the cathode catalyst layer morphology before and after loading a porous catalyst support with Pt and ionomer. Support nanopores and catalyst particles within pores and on the support surface are described by size distributions, allowing for qualitative processes during the addition of a material phase to be dependent on the observed pore and particle size. A particular focus is put on the interplay of pore impregnation and blockage due to ionomer loading and the consequences for the Pt/ionomer interface, ionomer film thickness and protonic binding of particles within pores. We used the model to emulate six catalyst/support combinations from literature with different porosity, surface area and pore size distributions of the support as well as varying particle size distributions and ionomer/carbon ratios. Besides providing qualitatively and quantitatively accurate predictions, the model is able to explain why the protonically active catalyst surface area has been reported to not increase monotonically with ionomer addition for some supports, but rather decrease again when the optimum ionomer content is exceeded. The proposed model constitutes a fast translation from manufacturing parameters to catalyst layer morphology which can be incorporated into existing performance and degradation models in a straightforward way.
The effect of ionomer to carbon (I/C) weight ratio and relative humidity (RH) on cathode catalyst degradation was investigated by comprehensive in situ characterization. Membrane electrode assemblies (MEA) with I/C ratios of 0.5, 0.8 and 1.2 were subjected to an accelerated stress test performed at 40, 70 and 100% RH. The results show an increasing loss in electrochemical active surface area (ECSA) for both higher I/C ratios and RH during voltage cycling. To differentiate between ionomer and water connected ECSA, carbon monoxide stripping measurements were performed at varying RH. Before degradation, all MEAs show comparable total ECSA values, while higher I/C ratios lead to a larger fraction of ionomer connected ECSA. After degradation, ECSA measurements of the lowest I/C ratio showed a relatively higher loss of Pt in contact with ionomer than Pt in contact with water, while an opposite trend was observed for higher I/C ratios. H2 /N2 impedance measurements showed drastically increasing protonic catalyst layer resistances for decreasing RH especially at low I/C ratios, which might hinder Pt 2+ ion diffusion towards the membrane, hence decreasing the ECSA loss. Limiting current measurements show increasing molecular O 2 diffusion resistances at end of test for samples with higher I/C ratios and higher ECSA loss.
An artifact appearing during the cathodic transient of cyclic voltammograms (CVs) of low-loaded platinum on carbon (Pt/C) electrodes in proton exchange membrane fuel cells (PEMFCs) was examined. The artifact appears as an oxidation peak overlapping the reduction peak associated to the reduction of platinum oxide (PtOx). By varying the nitrogen (N2) purge in the working electrode (WE), gas pressures in working and counter electrode, upper potential limits and scan rates of the CVs, the artifact magnitude and potential window could be manipulated. From the results, the artifact is assigned to crossover hydrogen (H2X) accumulating in the WE, once the electrode is passivated towards hydrogen oxidation reaction (HOR) due to PtOx coverage. During the cathodic CV transient, PtOx is reduced and HOR spontaneously occurs with the accumulated H2X, resulting in the overlap of the PtOx reduction with the oxidation peak. This feature is expected to occur predominantly in CV analysis of low-loaded electrodes made of catalyst material, whose oxide is inactive towards HOR. Further, it is only measurable while the N2 purge of the WE is switched off during the CV measurement. For higher loaded electrodes, the artifact is not observed as the electrocatalysts are not fully inactivated towards HOR due to incomplete oxide coverage, and/or the currents associated with the oxide reduction are much larger than the spontaneous HOR of accumulated H2X. However, owing to the forecasted reduction in noble metal loadings of catalyst in PEMFCs, this artifact is expected to be observed more often in the future.