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The effect of ionomer distribution on the oxygen mass transport resistance, the proton resistivity of the cathode catalyst layer, and the H 2 /air fuel cell performance was investigated for catalysts with surface modified carbon supports. By introducing nitrogen containing surface groups, it was shown that the ionomer distribution in the cathodic electrode can be optimized to decrease mass transport related voltage losses at high current density. The in house prepared catalysts were fully characterized by TEM, TGA, elemental analysis, and XPS. Thin-film rotating disk electrode measurements showed that the carbon support modification did not affect the oxygen reduction activity of the catalysts, but exclusively affects the ionomer distribution in the electrode during electrode preparation. Limiting current measurements were used to determine the pressure independent oxygen transport resistance -primarily attributed to oxygen transport in the ionomer film -which decreases for catalysts with surface modified carbon support. Systematically lowering the ionomer to carbon ratio (I/C) from 0.65 to 0.25 revealed a maximum performance at I/C = 0.4, where an optimum between ionomer thickness and proton conductivity within the catalyst layer is obtained. From this work, it can be concluded that not only ionomer film thickness, but more importantly ionomer distribution is the key to high performance low Pt loaded electrodes.

The effect of the catalyst synthesis method on the location of platinum nanoparticles on a high surface area Ketjenblack is investigated with respect to the high current density performance in low loaded proton exchange membrane fuel cells (PEMFC). Catalysts were prepared using various synthetic methods to deposit platinum nanoparticles at different locations on the carbon surface, e.g. inside or outside the pores of the primary particle. Transmission electron microscopy (TEM) suggested, that the Pt-particle deposition can be controlled to be preferentially on the outer carbon surface or within the pores. Electrochemical characterization was performed in thin-film rotating disk electrode (RDE) setup as well as in 5 cm 2 single cell MEA tests. Although the carbon support was identical for all catalysts, the one with more Pt particles deposited on the outer carbon surface performed superior at high current which was attributed to a lower oxygen mass transport resistance. From the presented data, it can be concluded that not only the type or the surface area of the carbon black support affects the fuel cell performance, but that the synthesis approach is an additional parameter to tune the fuel cell performance at high current density.

This study examines the effect of ink composition on the ionomer distribution in the catalyst layer of membrane electrode assemblies (MEA) prepared by decal transfer. We combine both structural and electrochemical characterization techniques to investigate the influence of the ionomer distribution on MEA performance determined by 50 cm 2 active area single-cell proton exchange membrane (PEM) fuel cell measurements. Cathodic catalyst layers were prepared from inks with different alcohols (1-propanol or 2-propanol) and varying water content (16-65 wt% H 2 O). The H 2 /air performance of cathode catalyst layers prepared from the different inks with 700 EW ionomer differed drastically, particularly under wet operating conditions, whereby the best performance was obtained for an ink based on 16 wt% H 2 O in 1-propanol. This was successfully correlated with the observation of ionomer patches at the cathode electrode surface (i.e., the surface facing the diffusion medium) determined by scanning electron microscopy (SEM), with N 2 adsorption analysis of the electrodes using a QSDFT model, and with dynamic light scattering data of ionomer/solvent mixtures. No correlation could be obtained between H 2 /air performance and the proton conductivity of the cathodes obtained by electrochemical impedance spectroscopy, and a model to rationalize this behavior will be proposed.

Using near ambient pressure X-ray photoelectron spectroscopy we probe in situ the double layer at the Pt/liquid electrolyte interface.

Over its lifetime in a fuel cell electric vehicle, a polymer electrolyte membrane fuel cell inevitably suffers from certain duration of dry operational conditions, where significant performance losses of the fuel cell take place. In this study, we investigate the activity changes of the fuel cell after a prolonged degradation protocol under dry operational condition, followed by various recovery procedures under wet conditions. The utilization of diluted air on the cathode side is found to be advantageous for the recovery due to the superior heat and water management. This more efficient recovery protocol allows the deconvolution of reversible and irreversible voltages losses after dry operations. A subsequent mechanistic study reveals an irreversible decrease of the effective ionomer coverage on the catalyst particles, while the proton conductivity of the catalyst layer drops. These observations point towards ionomer structural changes caused by the dry conditions. This is confirmed by post-mortem analysis via scanning electron microscope, showing clearly that ionomer redistributes and migrates, an additional mechanism which leads to the performance losses. Overall, the degradation mechanisms seem to be mitigated by higher ionomer content in the catalyst layer, while the investigated surface modification of carbon support shows minor sensitivities.

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