PEM fuel cell catalyst degradation mechanism and mathematical modeling
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Durability of carbon-supported platinum nanoparticle is one of the limiting factors for PEM fuel cell commercial applications. In our research work, we applied both experimental and mathematical simulative tools to study the mechanisms of Pt/C catalyst degradation. An accelerated catalyst degradation protocol by cycling the cathode potential in a square-wave profile was applied to study the losses of cell performances, catalyst ORR activity, and Pt active surface areas. Post-mortem analyses of cathode Pt particle size by X-ray diffraction and platinum distributions in CCMs by SEM/EDS were also conducted. Increased cell temperature and relative humidity was found to accelerate the cathode catalyst degradation. High membrane water contents or abundant water/ionic channels within the polymer electrolyte were believed to accelerate Pt ion transport and cathode degradation. After degradation tests, significant amount of Pt loss into the membrane forming a Pt "band" was observed through cathode platinum dissolution and chemical reduction of soluble Pt ions by permeated hydrogen from the anode. Platinum deposition was confirmed at a location where the permeated hydrogen and oxygen had the complete catalytic combustion over the deposited Pt clusters/particles as the catalyst. A cathode degradation model was built including the processes of platinum oxidation, dissolution/replating, diffusion of Pt ions and Pt band formation in electrolyte. A simplified bi-modal particle size distribution was applied with equal numbers of small and large type particles uniformly distributed in the cathode initially. Processes of Pt mass exchange between two types of particles were demonstrated to cause the overall particle growth. This was due to the particle size effect that platinum dissolution from the small type particles and replating of Pt ions onto the large particles was favored. Parametric study found the increased upper cycling potential was the dominated factor to accelerate the catalyst degradation. Also high frequency of potential cycle and low surface oxide coverage accelerated the degradation rate. Pt dissolution and oxidation processes in perchloric acid were preliminary investigated, and both chemical and electrochemical processes of oxidation and dissolution were believed to be involved under closed-circuit fuel cell conditions with oxygen presence at cathode.