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- CORROSION-RESISTANT ELECTRO-CATALYSTS AND SUPPORTS FOR ELECTROCHEMICAL ENERGY CONVERSION
- Wang, Guanxiong
- 2016, 2016-12
Polymer electrolyte fuel cells (PEFCs) convert chemical energy of fuels (eg. Hydrogen) directly to electrical energy with excellent power...
Show morePolymer electrolyte fuel cells (PEFCs) convert chemical energy of fuels (eg. Hydrogen) directly to electrical energy with excellent power density, high efficiency, and zero emissions. Several challenges have delayed the commercialization of fuel cells with one being the high cost and durability of the carbon-supported-platinum-based (Pt/C) electrocatalysts. The lifetime/durability issue is critical as insufficient durability/reliability of the catalysts affects the lifetime and economical viability of these devices. Carbon support corrosion is a major durability issue since the corrosion reaction is thermodynamically favorable but kinetically sluggish under normal operating conditions. The potential transients that occur during start and stop in automotive applications can lead to electrode potential excursions of up to 1.5 V and contribute to carbon corrosion. The best way to mitigate support corrosion in PEFCs is to replace the carbon supports with alternatives having high electronic conductivity, surface area and porosity. This dissertation investigates the following carbon alternatives: (i) tin doped indium oxide (ITO) and (ii) 1:1 mixed oxides of ruthenia and silica (RSO). Microstructure characterization and electrochemical evaluations, including accelerated stress tests (start-up/shut-down and load cycling protocols) were performed to evaluate ORR activity, fuel cell performance, and electrochemical stability under PEFC operating conditions. The ITO support and 40%Pt/ITO catalysts demonstrated exceptional electrochemical stability (and reasonable ORR activity) in rotating disk electrode (RDE) experiments under accelerated potential cycling that mimicked automotive drive cycles. However, Pt/ITO exhibited poor performance and stability during MEA evaluation in a PEFC. X-ray photoelectron spectroscopy (XPS) was employed to reveal the degradation modes of Pt/ITO during PEFC operation and it was found that the increase in the surface hydroxide concentration generates a passivating In(OH)3 layer that increases electrode resistance and undermines PEFC performance. The influence of the catalyst support on PEM degradation during PEFC operation was also studied. Rotating ring-disk electrode (RRDE) experiments were employed to estimate the fraction of H2O2 generated during the ORR on the supports (C and RSO) and catalysts (benchmark Pt/C and Pt/RSO). The percentage of H2O2 generated on C and Pt/C was 50% higher than that on RSO and Pt/RSO thus explaining the observed oxidative degradation resistance of the PEM with the latter supports/catalysts.
Ph.D. in Chemical Engineering, December 2016