Microscopic Analysis of PEMFC Catalyst Layers

Abstract Proton exchange membrane fuel cell (PEMFC) electrodes have a complex structure of carbon supported platinum (Pt) nanoparticles intermixed with proton conducting ionomer. This structures creates a porous network facilitating transport of electrons, protons, and reactants. These catalyst layers have been shown to exist with a non-homogenous distribution of ionomer, with aggregates and agglomerates of carbon and ionomer. To better understand the catalyst layer structure, we have applied atomic force microscopy (AFM) to investigate fuel cell catalyst layer properties at high resolution. Various ionomer-carbon (I/C) ratios were analyzed in order to identify correlations between carbon agglomerate size, pore distribution, and structure. Surface and cross-sectional images of topography, adhesion, and roughness were collected. Scanning electron microscopy (SEM) was performed to allow for additional depictions of the samples. Several other techniques are planned to further explore structures. Electrochemical capabilities of the AFM will be utilized to inspect the effects of current on the aforementioned properties and provide better control in measurements. Additionally, samples will be placed in a water-filled holder to study effects of swelling through in situ AFM. Transmission electron microscopy (TEM) will also be performed to complement these measurements. A Bruker AFM was used in PeakForce tapping mode with a ScanAsyst Air tip to obtain the images in Figure 1. Figure 1a shows the height map of a sample with an I/C ratio of 1. Figure 1b is the adhesion map of the same sample, showing clear spatial adhesion contrast. In this map, lighter colors correspond to the more adhesive ionomer. Darker areas signify hard materials like carbon. Figure 1c depicts the adhesion map overlaid on the height map, indicating how the adhesion and topography relate. The arrows in Figure 1c illustrate where the ionomer thickness can be measured between carbon aggregates. Figure 2a summarizes the average ionomer thickness calculated for a range of I/C ratios from 0.25 to 1.25. There is a positive correlation between I/C ratio and average ionomer thickness, suggesting that increased availability of ionomer leads to thicker surface coatings and more separation between the carbon aggregates. Figure 2b shows the relationship between I/C ratio and aggregate diameter. These values were measured by processing the images in ImageJ and reducing aggregates to approximated spheres. Although no clear relationship is apparent now, further investigation with differing I/C ratios may reveal a trend. Acknowledgements : This research is supported by the U.S. Department of Energy Fuel Cell Technologies Office, through the Fuel Cell Performance and Durability (FC-PAD) Consortium (Technical Development Manager: Greg Kleen and Fuel Cells Program Manager: Dimitrios Papageoropoulos). This work was also performed, in part, at the Center for Integrated Nanotechnologies, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science. Figure 1