In this thesis, direct hydrogen Proton Exchange Membrane (PEM) fuel cell systems in vehicles are investigated through modelling, field tests and public acceptance surveys. A computer model of a 50 kW PEM fuel cell system was developed. The fuel cell system efficiency is approximately 50% between 10 and 45% of the rated power. The fuel cell auxiliary system, e.g. compressor and pumps, was shown to clearly affect the overall fuel cell system electrical efficiency. Two hydrogen on-board storage options, compressed and cryogenic hydrogen, were modelled for the above-mentioned system. Results show that the release of compressed gaseous hydrogen needs approximately 1 kW of heat, which can be managed internally with heat from the fuel cell stack. In the case of cryogenic hydrogen, the estimated heat demand of 13 kW requires an extra heat source. A phase change based (PCM) thermal management solution to keep a 50 kW PEM fuel cell stack warm during dormancy in a cold climate (-20 °C) was investigated through simulation and experiments. It was shown that a combination of PCM (salt hydrate or paraffin wax) and vacuum insulation materials was able to keep a fuel cell stack from freezing for about three days. This is a simple and potentially inexpensive solution, although development on issues such as weight, volume and encapsulation materials is needed Two different vehicle platforms, fuel cell vehicles and fuel cell hybrid vehicles, were used to study the fuel consumption and the air, water and heat management of the fuel cell system under varying operating conditions, e.g. duty cycles and ambient conditions. For a compact vehicle, with a 50 kW fuel cell system, the fuel consumption was significantly reduced, ~ 50 %, compared to a gasoline-fuelled vehicle of similar size. A bus with 200 kW fuel cell system was studied and compared to a diesel bus of comparable size. The fuel consumption of the fuel cell bus displayed a reduction of 33-37 %. The performance of a fuel cell hybrid vehicle, i.e. a 50 kW fuel cell system and a 12 Ah power-assist battery pack in series configuration, was studied. The simulation results show that the vehicle fuel consumption increases with 10-19 % when the altitude increases from 0 to 3000 m. As expected, the air compressor with its load-following strategy was found to be the main parasitic power (~ 40 % of the fuel cell system net power output at the altitude of 3000 m). Ambient air temperature and relative humidity affect mostly the fuel cell system heat management but also its water balance. In designing the system, factors such as control strategy, duty cycles and ambient conditions need to taken into account. An evaluation of the performance and maintenance of three fuel cell buses in operation in Stockholm in the demonstration project Clean Urban Transport for Europe (CUTE) was performed. The availability of the buses was high, over 85 % during the summer months and even higher availability during the fall of 2004. Cold climate-caused failures, totalling 9 % of all fuel cell propulsion system failures, did not involve the fuel cell stacks but the auxiliary system. The fuel consumption was however rather high at 7.5 L diesel equivalents/10km (per July 2004). This is thought to be, to some extent, due to the robust but not energy-optimized powertrain of the buses. Hybridization in future design may have beneficial effects on the fuel consumption. Surveys towards hydrogen and fuel cell technology of more than 500 fuel cell bus passengers on route 66 and 23 fuel cell bus drivers in Stockholm were performed. The passengers were in general positive towards fuel cell buses and felt safe with the technology. Newspapers and bus stops were the main sources of information on the fuel cell bus project, but more information was wanted. Safety, punctuality and frequency were rated as the most important factors in the choice of public transportation means. The environment was also rated as an important factor. More than half of the bus passengers were nevertheless unwilling to pay a higher fee for introducing more fuel cell buses in Stockholm’s public transportation. The drivers were positive to the fuel cell bus project, stating that the fuel cell buses were better than diesel buses with respect to pollutant emissions from the exhausts, smell and general passenger comfort. Also, driving experience, acceleration and general comfort for the driver were reported to be better than or similar to those of a conventional bus. / QC 20101020

Fuel cells are electricity generators which convert chemical energy of hydrogen directly to electricity by means of electrochemical oxidation and reduction reactions. A single proton exchange membrane (PEM) fuel cell can only generate electricity with a potential between 0.5V and 1V. The useful potential can be achieved by stacking cells in series to form a PEM fuel cell stack. There is a potential to utilize 100W class fuel cells. Fuelling is the major problem of the portable fuel cells. The aim of this thesis is to design and manufacture a PEM fuel cell stack which can be used for portable applications. The PEM fuel cell stack is planned to be incorporated to a NaBH4 hydrolysis reactor for H2 supply. Within the scope of this thesis a new coating technique called &ldquo / ultrasonic spray coating technique&rdquo / is developed for membrane electrode assembly (MEA) manufacturing. New metal and graphite bipolar plates are designed and manufactured by CNC technique. A fuel cell controller hardware is developed for fuel supply and system control. The power densities reached with the new method are 0.53, 0.74, 0.77, and 0.88 W/cm2 for 20%, 40%, 50%, 70% Pt/C catalyst by keeping 0.4mg Pt/cm2 platinum loading constant, respectively. The power density increase is 267% compared to &ldquo / spraying of catalyst ink with air pressure atomizing spray gun&rdquo / . All parts of the PEM fuel cell stack designed were produced, assembled, and tested. The current density reached is 12.9A at 12 V stack potential and the corresponding electrical power of the stack is 155W.

Current environmental and energy sustainability trends have instigated considerable interest in alternative energy technologies that exhibit reduced dependence on fossil fuels. The advantages of such a direction are two-fold: reduced greenhouse gas emissions (notably CO2) and improved energy sustainability. Fuel cells are recognized as a potential technology that achieves both of these goals. However, improvements to fuel cell power density and stability must be realized to make them economically competitive with traditional, fossil-based technologies. The work in this dissertation is largely focused on the use of analytical tools for the study of transport processes in three fuel cell systems toward improvement of fuel cell performance. Polymer electrolyte membrane fuel cells (PEMFCs) are fueled by hydrogen and oxygen to generate electrical current. Microbial fuel cells (MFCs) use bacteria to degrade carbon compounds, such as those found in wastewaters, and simultaneously generate an electric current. Enzyme fuel cells (EFCs) operate similarly to PEMFCs but replace precious metal catalysts, such as platinum, with biologically-derived enzymes. The use of enzymes also allows EFCs to utilize simple carbon compounds as fuel. The operation of all three fuel cell systems involves different modes of ion and electron transport and can be affected negatively by transport limitations. Electrochemical impedance spectroscopy (EIS) was used in this work to study the distribution of transport resistances in all three fuel cell systems. The results of EIS were used to better understand the transport resistances that limited fuel cell power output. By using this technique, experimental conditions (including operating conditions, construction, and materials) were identified to develop fuel cells with greater power output and longevity. In addition to EIS, neutron imaging was employed to quantify the distribution of water in PEMFCs and EFCs. Water content is an integral aspect of providing optimal power output from both fuel cell systems. Neutron imaging contributed to developing an explanation for the loss of water observed in an operating EFC despite conditions designed to mitigate water loss. The findings of this dissertation contribute to the improvement of fuel cell technology in an effort to make these energy devices more economically viable.

The solid oxide fuel cell (SOFC) is a potential high efficient electrochemical device for vehicles, auxiliary power units and large-scale stationary power plants combined heat and power application. The main challenges of this technology for market acceptance are associated with cost and lifetime due to the high temperature (700-1000 oC) operation and complex cell structure, i.e. the conventional membrane electrode assemblies. Therefore, it has become a top R&amp;D goal to develop SOFCs for lower temperatures, preferably below 600 oC. To address those above problems, within the framework of this thesis, two kinds of innovative approaches are adopted. One is developing functional composite materials with desirable electrical properties at the reduced temperature, which results of the research on ceria-based composite based low temperature ceramic fuel cell (LTCFC). The other one is discovering novel energy conversion technology - Single-component/ electrolyte-free fuel cell (EFFC), in which the electrolyte layer of conventional SOFC is physically removed while this device still exhibits the fuel cell function. Thus, the focus of this thesis is then put on the characterization of materials physical and electrochemical properties for those advanced energy conversion applications. The major scientific content and contribution to this challenging field are divided into four aspects except the Introduction, Experiments and Conclusions parts. They are: Continuous developments and optimizations of advanced electrolyte materials, ceria-carbonate composite, for LTCFC. An electrolysis study has been carried out on ceria-carbonate composite based LTCFC with cheap Ni-based electrodes. Both oxygen ion and proton conductance in electrolysis mode are observed. High current outputs have been achieved at the given electrolysis voltage below 600 oC. This study also provides alternative manner for high efficient hydrogen production.  Compatible and high active electrode development for ceria-carbonate composite electrolyte based LTCFC. A symmetrical fuel cell configuration is intentionally employed. The electro-catalytic activities of novel symmetrical transition metal oxide composite electrode toward hydrogen oxidation reaction and oxygen reduction reaction have been experimentally investigated. In addition, the origin of high activity of transition metal oxide composite electrode is studied, which is believed to relate to the hydration effect of the composite oxide. A novel all-nanocomposite fuel cell (ANFC) concept proposal and feasibility demonstration. The ANFC is successfully constructed by Ni/Fe-SDC anode, SDC-carbonate electrolyte and lithiated NiO/ZnO cathode at an extremely low in-situ sintering temperature, 600 oC. The ANFC manifests excellent fuel cell performance (over 550 mWcm-2 at 600 oC) and a good short-term operation as well as thermo-cycling stability. All results demonstrated its feasibility and potential for energy conversion. Fundamental study results on breakthrough research Single-Component/Electrolyte-Free Fuel Cell (EFFC) based on above nanocomposite materials (ion and semi-conductive composite) research activities. This is also the key innovation point of this thesis. Compared with classic three-layer fuel cells, EFFC with an electrolyte layer shows a much simpler but more efficient way for energy conversion. The physical-electrical properties of composite, the effects of cell configuration and parameters on cell performance, materials composition and cell fabrication process optimization, micro electrochemical reaction process and possible working principle were systematically investigated and discussed. Besides, the EFFC, joining solar cell and fuel cell working principle, is suggested to provide a research platform for integrating multi-energy-related device and technology application, such as fuel cell, electrolysis, solar cell and micro-reactor etc. This thesis provides a new methodology for materials and system innovation for the fuel cell community, which is expected to accelerate the wide implementation of this high efficient and green fuel cell technology and open new horizons for other related research fields. / <p>QC 20131122</p>

A CO2 emission analysis and system investigation of a direct fuel cell waste energy recovery and power generation system (DFC-ERG) for pressure letdown stations was undertaken. The hybrid system developed by FuelCell Energy Inc. is an integrated turboexpander and a direct internal reforming molten carbonate fuel cell system in a combined circle. At pressure letdown stations, popularly called city gates, the pressure of natural gas transported on long pipelines is reduced by traditional pressure regulating systems. Energy is lost as a result of pressure reduction. Pressure reduction also results in severe cooling of the gas due to the Joule Thompson effect, thus, requiring preheating of the natural gas using traditional gas fired-burners. The thermal energy generated results in the emission of green house gases. The DFC-ERG system is a novel waste energy recovery and green house gas mitigation system that can replace traditional pressure regulating systems on city gates. A DFC-ERG system has been simulated using UniSim Design process simulation software. A case study using data from Utilities Kingston’s city gate at Glenburnie was analysed. The waste energy recovery system was modelled using the design specifications of the FuelCell Energy Inc’s DFC 300 system and turboexpander design characteristics of Cryostar TG120. The Fuel Cell system sizing was based on the required thermal output, electrical power output, available configuration and cost. The predicted performance of the fuel cell system was simulated at a current density of 140mA/cm2, steam to carbon ratio of 3, fuel utilization of 75% and oxygen utilization of 30%. The power output of the turboexpander was found to strongly depend on the high pressure natural gas flowrate, temperature and pressure. The simulated DFC-ERG system was found to reduce CO2 emissions when the electrical power generated by the DFC-ERG system replaced electrical power generated by a coal fired plant. / Thesis (Master, Chemical Engineering) -- Queen's University, 2010-08-31 02:02:11.392

Les travaux précédents trouvés dans la littérature ont mis l'importance sur la pile à combustible PEM ou électrolyseur PEM. Certains articles ont étudié également la pile à combustible réversible et le système d'alimentation en hydrogène par énergie solaire en intégrant à la fois la pile à combustible et électrolyseur. Contrairement à un « Unitised regenerative fuel cell (URFC)», notre conception a un compartiment individuel pour chaque système de PEM-Fuel Cell et d'electrolyseur-PEM et nommé Quasi - URFC. Grâce à ce nouveau concept, l'objectif principal est de réduire le coût de la pile à combustible régénératrice (RFC) en minimisant le rapport de surface superficielle géométrique du catalyseur de l'assemblage membrane électrodes (AME) des deux modes dans la cellule. D'ailleurs, nous visons également à construire un RFC plus compact, léger et portable par rapport à une pile à combustible ou l'électrolyseur classique. Ce travail de recherche est divisé en trois parties : la modélisation et simulation numérique, l'assemblage du prototype et le travail d'expérimentation. Quant à la partie de modélisation, un modèle physique multi-2D a été développé dans le but d'analyser les performances d'une pile à combustible à régénérée à trois-compartiments, qui se compose d'une piles à combustible et d'électrolyseur. Ce modèle numérique est basée sur la résolution des équations de conservation de masse, du momentum, des espèces et du courant électrique en utilisant une approche par éléments finis sur des grilles 2D . Les simulations permettent le calcul de la vitesse, de la concentration de gaz, la densité de courant et les distributions de potentiels en mode pile à combustible et en mode d'électrolyse, ainsi nous aider à prédire le comportement de quasi - RFC. En outre, l'assemblage du premier prototype du nouveau concept de pile à combustible à combustible régénérée a été achevée et testée au cours des trois années d'études dans le cadre d'une thèse. Les résultats expérimentaux de la 3 Compartiments R-PEMFC ont été prometteurs dans les deux modes, soit en mode piles à combustible et soit en mode d'électrolyseur. Ces résultats valideront ensuite les résultats de la simulation, obtenus auparavant par la modélisation. / The past works found in the literature have focused on either PEM fuel cell or electrolyzer-PEM. Some of the papers even studied the unitised reversible regenerative fuel cell (URFC) and the solar power hydrogen system by integrating both fuel cell and electrolyzer. Unlike the URFC, our design has an individual compartment for each PEMFC and E-PEM systems and named Quasi-URFC. With this new concept, the main objective is to reduce the cost of regenerative fuel cell (RFC) by minimizing the ratio of the catalyst’s geometric surface area of the membrane electrode assembly (MEA) of both cell modes. Apart from that, we also aim to build a compact, light and portable RFC.This research work is divided into three parts: the modeling, assembly of the prototype and the experimentation work. As for the modeling part, a 2D multi-physics model has been developed in order to analyze the performance of a three chamber-regenerative fuel cell, which consists of both fuel cell and electrolyzer systems. This numerical model is based on solving conservation equations of mass, momentum, species and electric current by using a finite-element approach on 2D grids. Simulations allow the calculation of velocity, gas concentration, current density and potential's distributions in fuel cell mode and electrolysis mode, thus help us to predict the behavior of Quasi-RFC. Besides that, the assembly of the first prototype of the new concept of regenerative fuel cell has been completed and tested during the three years of PhD studies. The experimental results of the Three-Chamber RFC are promising in both fuel cell and electrolyzer modes and validate the simulation results that previously obtained by modeling.

Nowadays, PEM fuel cell systems for passenger cars are always realized as hybrid systems. If the architecture of a hybrid system is given, then the dimensioning of the fuel cell and battery subsystems is crucial in terms of costs, dynamics, and driving behavior in general. In order to analyze these dependencies correctly, the ZBT fuel cell model was integrated into a fuel cell system and a full vehicle simulation. The subject of the investigation is the interaction of different drive cycles, which in part are very different, with differently dimensioned sub models for the fuel cell system and the battery. The ZBT fuel cell model is integrated into the simulation environment AVL CRUISE™ M for the fuel cell system and the vehicle. An analysis is presented that compares the different drive cycles and system dimensions and provides specific recommendations for different use cases.

This paper presents analytical and experimental studies on optimization of the gas delivery and current collection system in a proton exchange membrane (PEM) fuel cell for the objective of reducing ohmic loss, thereby achieving higher power density. Specifically, the dimensions of current collection ribs as well as the rib distribution were optimized to get a maximized power density in a fuel cell. In the modeling process, the power output from a fixed area of membrane is calculated through analysis of an electrical circuit simulating the current from electrochemical reaction flowing to the current collectors. Current collectors of two-dimensional ribs and three-dimensional pillars were considered. Analyses found that three-dimensional pillars allow higher power density in a PEM fuel cell. Considering the mass transfer enhancement effect, three-dimensional pillars as current collectors in gas flow field may be a good choice if the fuel cell operates at low current density and there is no liquid water blocking the flow channels. The analyses did not consider the existence of liquid water, meaning the current density is not very high. The study concluded that decreasing the size of both the current collector and its control area yields a significant benefit to a higher power density. A preliminary experimental test in a PEM fuel cell has verified the conclusion of the analytical work.

Chemistry / The efforts described in this thesis were bifurcated along two distinct projects, but generally were directed toward the development of new materials to solve outstanding issues in contemporary electrochemical applications. The first project involved the synthesis and application of redox-switchable olefin metathesis catalysts. N-heterocyclic carbenes (NHCs) bearing ferrocene and other redox-active groups were designed, synthesized, and incorporated into model iridium complexes to evaluate their intrinsic electrochemical and steric parameters. Using these complexes, the ability to switch the electron donating ability of the ligands via redox processes was quantified using a variety of electrochemical and spectroscopic techniques. The donicity was either enhanced or attenutated upon reduction or oxidation of the redox-active group, respectively. The magnitude of the change in donicity upon reduction or oxidation did not vary significantly as a function of the proximity of the redox-active group from the metal center. Thus, other factors, including synthetic considerations, sterics, and redox potential requirements, were determined to guide ligand design. Regardless, redox-active NHCs were adapted into ruthenium-based olefin metathesis catalysts and used to gain control control over various ring-opening metathesis polymerizations and ring-closing metathesis reactions. The second project was focused on the development of new basic polymers for acid/base crosslinked proton exchange membranes intended for applications in direct methanol fuel cells. Polymers containing pendant pyridinyl and pyrimidinyl groups were obtained via the post polymerization functionalization of UDEL® poly(sulfone) and then blended with sulfonated poly(ether ether ketone) (SPEEK). Fuel cells containing these blends were found to exhibit reduced methanol crossover, higher open circuit voltages, and higher maximum power densities compared to plain SPEEK. The differences in fuel cell performance were attributed to the basicity and sterics of the pendant N-heterocycles. / text

Glycerol is a very promising alternative fuel to hydrogen in fuel cells. However, the utilisation of glycerol as a fuel requires a good catalyst, due to the slow kinetics of glycerol electrooxidation. Gold has been identified as a promising catalyst due to its high activity and stability for glycerol electrooxidation – although the overpotentials are higher than on platinum and palladium. Modification of a nano-Au/C catalyst by the addition of MnO2, in an attempt to further improve the activity and lower the overpotential for glycerol oxidation, was therefore first explored. This was followed by investigations into the effects of gold particle size and loading. Finally, the effect of gold particle size on oxidation of gold-catalysed glycerol oxidation intermediates was also briefly explored. Studies into MnO2 addition showed that the pre-deposition of MnO2 yielded catalysts with smaller, more uniform gold particles, and catalysts with MnO2 contents of 5 and 9 wt % had higher mass activities and lower onset- and peak- potentials than Au/C. All the Au/xMnO2/C catalysts were more active than the palladium- and platinum-based catalysts reported in literature, which effectively demonstrated the advantage of using a gold-based catalyst for glycerol oxidation – especially when supported by MnO2 which lowered the overpotential for glycerol oxidation over gold. For the study into gold particle size, small gold particles of average diameter ≤ 4.7 nm had higher gold mass-based activities than medium-sized (14.7 nm) particles and were at least twice as active as catalysts containing large (≥ 43 nm) gold particles. The small gold particles also gave lower glycerol oxidation onset potentials, which was attributed to the predominance of Au(110) planes on those particles. Glycerol oxidation also appeared to proceed further along the oxidation pathway over small gold particles, which was confirmed in preliminary studies into the oxidation of glycerol oxidation intermediates. However, specific activity increased with increasing gold particle size, due mainly to the higher intrinsic activity of the Au(111) plane, which increased relative to Au(110) with increasing gold particle size. The important requirements for fuel cell applications are factors such as high mass activity, low overpotentials and high stability – all of which were met by the catalysts containing small gold particles defined by predominantly Au(110) facets. Investigations into the gold loading effect showed similar mass- and specific- activities for catalysts with 5-20 % gold loading. However, only the catalysts with higher gold loadings (15-20 %) did not deactivate early during CV, indicating that a larger gold surface area is necessary to resist poisoning at high potentials. On the basis of low onset potentials, high mass activity, and stability at low overpotentials, a minimum gold loading of 12.5 % appears to be necessary for a supported gold catalyst with small gold nanoparticles; although even higher loadings may be preferable for a higher power output in a fuel cell. Importantly, the insights gleaned from this study on the fundamental properties required for early activation, activity and stability of the gold catalysts could lead to a more intelligent design of gold-based catalysts in future.