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CORROSION-RESISTANT ELECTRO-CATALYSTS AND SUPPORTS FOR ELECTROCHEMICAL ENERGY CONVERSION
Title
CORROSION-RESISTANT ELECTRO-CATALYSTS AND SUPPORTS FOR ELECTROCHEMICAL ENERGY CONVERSION
Creator
Wang, Guanxiong
Date
2016, 2016-12
Description
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
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INVESTIGATION OF PERFORMANCE AND DURABILITY OF POLYMER ELECTROLYTES FOR ELECTROCHEMICAL ENERGY STORAGE AND CONVERSION TECHNOLOGIES
Title
INVESTIGATION OF PERFORMANCE AND DURABILITY OF POLYMER ELECTROLYTES FOR ELECTROCHEMICAL ENERGY STORAGE AND CONVERSION TECHNOLOGIES
Creator
Jung, Min-suk
Date
2016, 2016-07
Description
Polymeric ion exchange membranes are integral components of electrochemical conversion/storage devices such as fuel cells, water electrolyzers...
Show morePolymeric ion exchange membranes are integral components of electrochemical conversion/storage devices such as fuel cells, water electrolyzers, and redox flow batteries. There has been dramatic progress in the research and development of cation exchange membranes (CEM). Nafion® (perfluorosulfonic acid membranes) is one example of a state-of-the-art CEM and has been successfully demonstrated in various electrochemical energy devices. Unlike CEMs, anion exchange membranes (AEMs) have been of limited utility to date due to their drawbacks, including poor chemical/mechanical stability and low ionic conductivity. However, alkaline environments result in better activity for electrochemical reactions and afford the possibility of using non-platinum group metal (PGM) electrocatalysts. AEMs, therefore, are still being studied in order to resolve existing challenges in terms of conductivity and stability in alkaline media and in strongly oxidizing solutions. In this work, AEMs derived from different types of polymer backbones were prepared, and their chemical stability and electrochemical property were investigated. Polysulfone (PSF) AEMs were prepared by first chloromethylating polysulfone, then by functionalizing chloromethylated polysulfone (CMPSF) with different base reagents. PSF-trimethylamine (TMA) AEMs showed a 40-fold reduction in vanadium (IV) ion (VO2+) permeability when compared to a Nafion® membrane and exceptional oxidative stability after exposure to a 1.5 M vanadium (V) ion (VO2 +) solution for 90 days. PSF-TMA AEMs were successfully demonstrated in the all-vanadium redox flow battery. Excellent energy efficiencies (>75 %) were attained and sustained over 75 chargedischarge cycles for a vanadium redox flow battery prepared using the PSF-TMA separator. Crosslinking of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) AEMs using diamine was tried with intentions to improve the mechanical stability and electrochemical property of PPO AEM. Crosslinked PPO AEMs (30 ± 4 % at 25 oC) showed less liquid water uptake than non-crosslinked PPO AEMs (46 ± 5% at 25 oC) while maintaining comparable ionic conductivities (hydroxide ion conductivity of 45 mS/cm at 60 oC). Crosslinked PPO AEMs maintained mechanical integrity and still showed some mechanical stability (ultimate tensile strength of 3~4 MPa and elongation at break of 13~17 %) after exposure to 1 M KOH at 60 oC for 14 days, while noncrosslinked PPO AEMs completely lost their mechanical durability. Finally, this dissertation presents research related to perfluorinated AEMs prepared using a Grignard reagent. These membranes exhibited 0.7 mmol/g of Cl- ion exchange capacity (IEC), 20 mS/cm of hydroxide ion conductivity at 20 oC, and 10 % of water uptake at room temperature. The membranes also maintained 90 % of their initial conductivity after an exposure to 1.5 M VO2+ in 3 M H2SO4 solution for seven days.
Ph.D. in Chemical Engineering, July 2016
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