Thesis (MTech (Chemical Engineering))--Cape Peninsula University of Technology, 2011 / High temperature polymer electrolyte membrane fuel cells (PEMFC) operating between 120-180 oC are currently of much research attention. The acid doped polybenzimidazole (PBI) membranes electrolyte are known for their tolerance to relatively high levels of carbon monoxide impurity in the feed. Most fuel cell modelling are theoretical in nature and are solved in commercial CFD platforms such as Fluent. The models require a lot of time to solve and are not simple enough to be used in complex systems such as CHP systems. This study therefore, focussed on developing a simple but yet accurate model of a high temperature PEMFC for a CHP system. A zero dimensional model for a single cell was developed and implemented in Engineering Equations Solver (EES) environment to express the cell voltage as a function of current density among others. Experimental results obtained from literature were used to validate and improve on the model. The validated models were employed for the simulation of the stack performance to investigate the effects of temperature, pressure, anode stoichiometry and the level of CO impurity in the synthesis gas, on the cell potential and overall performance. Good agreement was obtained from the simulation results and experimental data. The results showed that increasing temperature (up to 180oC) and acid doping level have positive effects on the cell performance. The results also show that the cell can operate with a reformate gas containing up to 2% CO without significant loss of cell voltage at elevated temperatures. The single cell model was extended to a 1 kWe high temperature PEMFC stack and micro-CHP system. The stacks model was validated with experimental data obtained from a test station. The model was used to investigate the performance of PEMFC and CHP system by using uncertainty propagation. The highest combined cogeneration system efficiency of 87.3% is obtained with the corresponding electrical and thermal efficiencies are 41.3% and 46 % respectively. The proposed fuel processing subsystem provides an adequate rate of CH4 conversion and acceptable CO-level, making it appropriate for integration with an HT PEMFC stack. In the steam methane reformer 97% of CH4 conversion is achieved and the water gas shift reactors achieve about 98% removal of CO.

>Magister Scientiae - MSc / Polymer electrolyte membrane fuel cells (PEMFCs) among other fuel cells are considered the best candidate for commercialization of portable and transportation applications because of their high energy conversion and low pollutant emission. Recently, there has been significant interest in high temperature polymer electrolyte membrane fuel cells (HT-PEMFCs), due to certain advantages such as simplified system and better tolerance to CO poisoning. Cost, durability and the reliability are delaying the commercialization of PEM fuel cell technology. Above all durability is the most critical issue and it influences the other two issues. The main objective of this work is to study the durability of membrane electrode assemblies (MEAs) for HT-PEMFC. In this study the investigation of commercial MEAs was done by evaluating their performance through polarization studies on a single cell, including using pure hydrogen and hydrogen containing various concentrations of CO as fuel, and to study the performance of the MEAs at various operating temperatures. The durability of the MEAs was evaluated by carrying out long term studies with a fixed load, temperature cycling and open circuit voltage degradation. Among the parameters studied, significant loss in the performance of the MEAs was noted during temperature cycling. The effect of temperature cycling on the performance of the cell showed that the performance decreases with increasing no. of cycles. This could be due to leaching of acid from the cell or loss of electrochemically active surface area caused by Pt particle size growth. For example at 160°C, a performance loss of 3.5% was obtained after the first cycle, but after the fourth cycle a huge loss of 80.8% was obtained. The in-house MEAs with Pt-based binary catalysts as anodes were studied for CO tolerance, performance and durability. A comparison of polarization curves between commercial and in-house MEAs illustrated that commercial MEA gave better performance, obtaining 0.52 A/cm² at 0.5V and temperature of 160°C, with in-house giving 0.39A/cm² using same parameters as commercial. The CO tolerance of both commercial and in-house MEA was found to be similar. In order to increase the CO tolerance of the in-house MEAs, Pt based binary catalysts were employed as anodesand the performance was investigated In-house MEAs with Pt/C and Pt-based binary catalysts were compared and a better performance was observed for Pt/C than Pt-alloy catalysts with Pt-Co/C showing comparable performance. At 0.5 V the performance obtained was 0.39 A/cm2 for Pt/C, and 0.34A/cm²,0.28A/cm²,0.27A/cm² and 0.16A/cm² were obtained for Pt-Co/C, Pt-Fe/C, Pt-Cu/C and Pt-Ni respectively. When the binary catalysts were tested for CO tolerance, Pt-Co showed no significant loss in performance when hydrogen containing CO was used as anode fuel. Scanning electron microscopy (SEM) revealed delamination between the electrodes and membrane of the tested and untested MEA's. Membrane thinning was noted and carbon corrosion was observed from the tested micro-porous layer between the gas diffusion layer (GDL) and catalyst layer (CL).

Polymer electrolyte membrane fuel cells (PEMFCs) have recently acquired much attention as alternatives to combustion engines for power conversion. The primary interest in fuel cell technology is the possibility of 60% power conversion efficiency as compared to the 30% maximum theoretical efficiency limited to combustion engines and turbines. Although originally conceived to work with hydrogen as a fuel, difficulties relating to hydrogen storage have prompted much effort in using other fuels. Small organic molecules such as alcohols and formic acid have shown promise as alternatives to hydrogen in PEMFCs due to their higher stability at ambient conditions. The drawbacks for using these fuels in PEMFCs are related to their incomplete oxidation mechanisms, which lead to the production of carbon monoxide (CO). When carbon monoxide is released in fuel cells it binds strongly to the platinum anode thus limiting the adsorption and subsequent oxidation of more fuel. In order to promote the complete oxidation of fuels and limit poisoning due to CO, various metal and metal oxide catalysts have been used. Motivated by promising results seen in fuel cell catalysis, this research project is focused on the design and fabrication of novel platinum-composite catalysts for the electrooxidation of methanol, ethanol and formic acid. Various Pt-composites were fabricated including Pt-Au, PtRu, Pt-Pd and Pt-CeO2 catalysts. Electrochemical techniques were used to determine the catalytic ability of each novel composite toward the electrooxidation of methanol, ethanol and formic acid. This study indicates that the novel composites all have higher catalytic ability than bare Pt electrodes. The increase in catalytic ability is mostly attributed to the increase in CO poison tolerance and promotion of the complete oxidation mechanism of methanol, ethanol and iv formic acid. Formulations including bi- and tri-composite catalysts were fabricated and in many cases show the highest catalytic oxidation, suggesting tertiary catalytic effects. The combination of bi-metallic composites with ceria also showed highly increased catalytic oxidation ability. The following dissertation expounds on the relationship between composite material and the electrooxidation of methanol, ethanol and formic acid. The full electrochemical and material characterization of each composite electrode is provided.

The majority of this dissertation focuses on proton conducting materials that could be used at high operating temperatures. Higher operating temperatures are desirable as they will increase fuel cell efficiency, reduce cost, and simplify the heat management system. The factors governing proton conduction including segmental mobility, protogenic group identity, and charge carrier density were investigated on a variety of polymers containing 1H-1,2,3-triazole moieties. Proton conductivity measurements were made using AC impedance spectroscopy. Random copolymers and terpolymers of triazole-containing acrylates and poly(ethylene glycol)methyl ether acrylate (PEGMEA) have been synthesized. Conductivity increased with increasing degree of PEG incorporation until reaching a maximum at 30% mole PEGMEA. In comparison to benzimidazole-functionalized polyacrylate with 35% mole PEGMEA, the triazole analog showed a higher proton conductivity, and a less pronounced conductivity temperature dependence. Further increases in conductivity was achieved through the addition of trifluoroacetic acid. To study the effect of charge carrier density on proton conduction, polyacrylates containing a different number of triazole groups per repeat unit were synthesized. The result showed that introduction of more than one triazole per repeat unit did not result in an increase in conductivity as there was an accompanying increase in Tg. To improve the thermal and mechanical properties, triazole groups were tethered to a higher Tg backbone polymer, polynorbornene. Introduction of polyhedral oligomeric silsesquioxane (POSS) into triazole-functionalized polynorbornene was also investigated. In a parallel set of investigations, poly(2-(dimethylamino)ethyl methacrylate), PDMAEMA, and copolymers of DMAEMA and methyl methacrylate (PDMAEMA-co-PMMA) were synthesized via atom transfer radical polymerization (ATRP). Fluorescently-labeled PDMAEMAs were synthesized using fluorescent ATRP initiators to ensure the presence of one dye molecule on every polymer chain. PDMAEMAs and PDMAEMA-co-PMMA with different molecular weights have been deposited onto a negatively-charged silica surface via controlled flow deposition. The results show that the polymer deposition rate depends on molecular weight, and is inversely proportional to molecular weight. A preliminary adhesion study of 1-μm negatively charged silica spheres onto these functionalized surfaces indicates that by varying the molecular weight, the adhesion threshold can be changed. System modeling is being conducted to support experimental observations.

Anhydrous proton conducting polymers are highly sought after for applications in high temperature polymer electrolyte membrane fuel cells (PEMFCs). N-heterocycles (eg. imidazole, triazole, and benzimidazole), owing to their amphoteric nature, have been widely studied to develop efficient anhydrous proton transporting polymers. The proton conductivity of N-heterocyclic polymers is influenced by several factors and the design and development of polymers with a delicate balance among various synergistic and competing factors to provide appreciable proton conductivities has been a challenging task. In this thesis, the proton transport (PT) characteristics of polymers functionalized with two diverse classes of functional groups - N-heterocycles and phenols have been investigated and efforts have been made to develop the molecular design criteria for the design and development of efficient proton transporting functional groups and polymers. The proton conduction pathway in 1H-1,2,3-triazole polymers is probed by employing structurally analogous N-heterocyclic (triazole, imidazole, and pyrazole) and benz-N-heterocyclic (benzotriazole, benzimidazole, and benzopyrazole) polymers. Imidazole-like pathway was found to dominate the proton conductivity of triazole and pyrazole-like pathway makes only a negligible contribution, if any. Polymers containing benz-N-heterocycles exhibited higher proton conductivity than those with the corresponding N-heterocycles. Pyrazole-like functional groups, i.e. the molecules with two nitrogen atoms adjacent to each other, were found not to be good candidates for PT applications. A new class of proton transporting functional groups, phenols, has been introduced for anhydrous PT. One of the highlighting features of phenols over N-heterocycles is that the hydrogen bond donor/acceptor reorientation can happen on a single -OH site, allowing for facile reorientational dynamics in Grotthuss PT and enhanced proton conductivities in phenolic polymers. Unlike the case of N-heterocycles, comparable conductivities were achieved between poly (3,4,5-trihydroxy) styrene and the corresponding small molecule, pyrogallol. This observation suggests that reorientation should be considered as a crucial design parameter for PT functional groups. The PT characteristics of phenol-based biaryl polymers are studied and compared with the analogous phenol-based linear styrenic polymers. The two-dimensional disposition of -OH moieties in biaryl polymers, although resulted in lower apparent activation energies (Ea), did not improve the net proton conductivity due to the accompanying increase in glass transition temperature (Tg). Thus, the ease of synthesis and lower Tg values of phenol-based styrene polymers make the styrenic polymer architecture preferable over the biaryl architecture. Finally, the synthesis of a series of poly(3,4-dihydroxy styrene)-b-polystyrene block copolymers has been demonstrated via anionic polymerization. These block copolymers will provide an opportunity to systematically investigate the effect of nanoscale morphology on proton transport.

No description available.

No description available.

O envelhecimento dos eletrocatalisadores utilizados em cátodos de células a combustível de eletrólito polimérico (PEMFCs) é um dos principais fatores que restringem sua aplicação como conversores de energia em larga escala. Esse trabalho visa contribuir para o aprimoramento da estabilidade de nanopartículas de platina (NPs de Pt) por meio da modificação do suporte catalítico aos quais encontram-se impregnadas. Desse modo, foram realizadas sínteses de suportes catalíticos baseados em óxidos de molibdênio (MoO3 e MoO2) ancorados em carbono Vulcan® XC72-R, sendo os materiais produzidos caracterizados física, estrutural e eletroquimicamente antes e após a impregnação de NPs de Pt. Para investigar a estabilidade dos eletrocatalisadores, foi realizado um teste de degradação eletroquímico acelerado, o qual consistiu em aplicar os ciclos de potenciais entre 0,6 e 1,0 V vs. ERH por curto período de tempo. Os resultados mostraram que os métodos de síntese utilizados foram satisfatórios, levando a formação dos catalisadores com as proporções bem próximas das requeridas. O catalisador Pt/MoO3-C apresentou a maior atividade específica frente a reação de redução de oxigênio (RRO), atribuída a efeitos sinérgicos metal/suporte. Quando investigada a estabilidade dos materiais frente ao teste de degradação eletroquímico acelerado, observou-se que, a princípio, nenhum dos óxidos de molibdênio diminui a extensão da degradação da platina. Analisando-se as atividades específicas frente à RRO para cada catalisador antes e após o envelhecimento eletroquímico, foi observado que Pt/MoO2-C apresentou-se como o material mais estável dentre os demais. / The aging of Pt based electrocatalysts used in the polymer electrolyte fuel cell (PEMFC) cathodes is one of the main issues that restrict its wide application as energy converters. This work aims to contribute to the improvement of the stability of platinum nanoparticles (Pt NPs) by modification of the catalyst support at which they are impregnated. Thus, syntheses of catalyst supports based on molybdenum oxide (MoO3 and MoO2) anchored on Vulcan® XC72-R carbon were carried out and the produced materials were characterized physically, structurally and electrochemically prior and after impregnation of the Pt NPs. To investigate their stability, an electrochemical accelerated degradation test was performed, which consisted of applying a large number of short duration potential cycling steps between 0.6 and 1.0 V vs. RHE. The results showed that the synthetic methods used here were satisfactory, leading to the formation of catalysts with compositions near to those expected. The Pt/MoO3-C catalyst showed the highest specific activity toward the oxygen reduction reaction (ORR), and this was attributed to metal/support synergistic effects. When the stability against electrochemical accelerated degradation test of the materials was investigated, it was observed that, in principle, none of the molybdenum oxides really decreases the extent of platinum degradation. However, comparing the specific activities towards the ORR for each catalyst, before and after electrochemical aging, it is concluded that Pt/MoO2-C is the most stable material among all others.

A procedure is presented to analyze select geometric and effective properties of the porous transport layer (PTL) of the polymer electrolyte membrane fuel cell (PEMFC) in com- pressed and uncompressed states using micro-computed X-ray tomography (Micro CT). A method of compression using a novel device design was employed to mimic the non-homogeneous compression conditions found in functioning fuel cells. The process also features open source image processing and CFD analysis through the use of software packages Fiji and OpenFOAM (proprietary software is also used such as Matlab). Tomographic images of a PTL sample in different compressive states are first analyzed by measuring local porosity values in the through-plane and both in- plane directions. The objective of this study was to develop a method for imaging the PTL structure to show directionality within its properties using relatively inexpensive and non-destructional means. Three different PTL types were tested, one without any additives, one with Polytetrafluoroethylene (PTFE) and one with PTFE and a microporous layer (MPL). Non-homogeneous porosity was shown to exist with the highest and least variable porosity values obtained from the in-plane direction that was in-line with the direction of fibres. Porosity values compared well with values obtained from the literature. The profile of the PTL with MPL added was unattainable using this procedure as the resolution of the Micro CT was too low to resolve its pore space. The next stage involved the effective properties analysis which included effective electronic conductivity and effective diffusivity. It was found that the through-plane values for the effective electronic conductivity study were higher than expected. The ratio between through-plane and in-plane was found to be much higher than expected from literature. Lack of sufficient resolution of fibre contacts has been shown to play a role in this discrepancy. These contact problems were shown not too affect measurements of diffusivity in the pore phase. The in-plane direction parallel to the direction of fibres was found to have the highest values of effective transport properties. Effective diffusivity ratios of between 0.1 and 0.37 were found to be reasonable with the limited experimental evidence found in literature. The it was found that the Bruggeman relation for calculating diffusivity and percolation theory by Tomadakis and Sotirchos over predicted the values for diffusion within the PTL and it is suggested that these theories are not suitable for predicting diffusivity for this material. / Thesis (Master, Mechanical and Materials Engineering) -- Queen's University, 2012-02-02 15:46:29.395

O envelhecimento dos eletrocatalisadores utilizados em cátodos de células a combustível de eletrólito polimérico (PEMFCs) é um dos principais fatores que restringem sua aplicação como conversores de energia em larga escala. Esse trabalho visa contribuir para o aprimoramento da estabilidade de nanopartículas de platina (NPs de Pt) por meio da modificação do suporte catalítico aos quais encontram-se impregnadas. Desse modo, foram realizadas sínteses de suportes catalíticos baseados em óxidos de molibdênio (MoO3 e MoO2) ancorados em carbono Vulcan® XC72-R, sendo os materiais produzidos caracterizados física, estrutural e eletroquimicamente antes e após a impregnação de NPs de Pt. Para investigar a estabilidade dos eletrocatalisadores, foi realizado um teste de degradação eletroquímico acelerado, o qual consistiu em aplicar os ciclos de potenciais entre 0,6 e 1,0 V vs. ERH por curto período de tempo. Os resultados mostraram que os métodos de síntese utilizados foram satisfatórios, levando a formação dos catalisadores com as proporções bem próximas das requeridas. O catalisador Pt/MoO3-C apresentou a maior atividade específica frente a reação de redução de oxigênio (RRO), atribuída a efeitos sinérgicos metal/suporte. Quando investigada a estabilidade dos materiais frente ao teste de degradação eletroquímico acelerado, observou-se que, a princípio, nenhum dos óxidos de molibdênio diminui a extensão da degradação da platina. Analisando-se as atividades específicas frente à RRO para cada catalisador antes e após o envelhecimento eletroquímico, foi observado que Pt/MoO2-C apresentou-se como o material mais estável dentre os demais. / The aging of Pt based electrocatalysts used in the polymer electrolyte fuel cell (PEMFC) cathodes is one of the main issues that restrict its wide application as energy converters. This work aims to contribute to the improvement of the stability of platinum nanoparticles (Pt NPs) by modification of the catalyst support at which they are impregnated. Thus, syntheses of catalyst supports based on molybdenum oxide (MoO3 and MoO2) anchored on Vulcan® XC72-R carbon were carried out and the produced materials were characterized physically, structurally and electrochemically prior and after impregnation of the Pt NPs. To investigate their stability, an electrochemical accelerated degradation test was performed, which consisted of applying a large number of short duration potential cycling steps between 0.6 and 1.0 V vs. RHE. The results showed that the synthetic methods used here were satisfactory, leading to the formation of catalysts with compositions near to those expected. The Pt/MoO3-C catalyst showed the highest specific activity toward the oxygen reduction reaction (ORR), and this was attributed to metal/support synergistic effects. When the stability against electrochemical accelerated degradation test of the materials was investigated, it was observed that, in principle, none of the molybdenum oxides really decreases the extent of platinum degradation. However, comparing the specific activities towards the ORR for each catalyst, before and after electrochemical aging, it is concluded that Pt/MoO2-C is the most stable material among all others.