<p>This thesis concerns system studies of power plants wheredifferent types of fuel cells accomplish most of the energyconversion.</p><p>Ever since William Grove observed the fuel cell effect inthe late 1830s fuel cells have been the subject or more or lessintense research and development. Especially in the USA theseactivities intensified during the second part of the 1950s,resulting in the development of the fuel cells used in theApollo-program. Swedish fuel cell activities started in themid-1960s, when ASEA (now ABB) ran a fuel cell projectdeveloping fuel cells to power submarines.</p><p>When the then project manager, Olle Lindström, wasappointed professor of Chemical Technology at KTH, the fuelcell activities at KTH were initiated, these activities havesince then been pursued at varying levels of intensity.</p><p>The fuel cell development experienced a recession during thelatter part of the 1970s and early 1980s, only to bere-vitalised during the 1990s as the full potential of theadvantages of environmental benefits and efficiency wereidentified.</p><p>System studies and process simulation utilising differentcomputer software programs may be used to study the behaviourand characteristics of fuel cells and their supportsystems.</p><p>Paper I describes the characteristics of a naturalgas-fuelled fuel cell power plant using alkaline fuel cells,both regarding efficiency and economics.</p><p>In paper II, a benchmark study of three different types ofsimulation software is presented. Theintention was to clarifyhow the selection of software might influence the resultsobtained, and some of the associated possible pitfalls.</p><p>Paper III presents a study of a fuel cell power plant wherethe primary source of energy is biomass (wood chips), which viahigh-pressure gasification and subsequent gas cleaning is madeavailable for conversion into electricity and heat by moltencarbonate fuel cells.</p><p>The last paper, paper IV, presents a s system study of ahigh-temperature fuel cell system, where the primary fuel iscoal, which through gasification is converted into a gaseousform. This study was a vital part of an EU-project studying thetechnical and economical feasibility of such systems.</p><p><b>Keywords</b>: fuel cells, fuel cell systems, system studies,process simulation, system analysis, alkaline fuel cells,high-temperature fuel cells.</p>

When designing a direct methanol fuel cell and evaluating the appropriateness of new materials, it is helpful to consider the impact of material properties on the performance of a complete system. To some degree, poor fuel utilization and performance losses from methanol crossover and low reactant concentrations can be mitigated by proper system design. In order to facilitate system design, an analytical model is developed to evaluate the methanol and oxygen concentration profiles across the membrane electrode assembly of the direct methanol fuel cell. In the first part of this work, the model is used to determine fuel utilization as a function of the feed concentration, backing layer properties, and membrane properties. A minimum stoichiometric ratio is determined based on maintaining zero-order methanol kinetics, which allows the fuel efficiency to be optimized by controlling these physical properties. The size of system components such as the methanol storage tank and the fuel pump can be estimated based on the minimum methanol flow rate that those components must produce to deliver a specified current; in this way, the system-level benefits of reduced membrane crossover can be evaluated. In the second section, the model is extended by using the Bulter-Volmer equation to describe the anodic and cathodic overpotentials along a single cross-section of the fuel cell. An iterative technique is then used to determine the methanol and oxygen concentration profiles in the flow channels. The model is applied to examine the benefits of new low-crossover membranes and to suggest new design parameters for those membranes. Also, the tradeoff between the power output of the fuel cell stack and the size of system components is examined across a range of methanol and oxygen flow rates. / text

The driving force behind research in alternative clean and renewable energy has been the desire to reduce emissions and dependence on fossil fuels. In the United States, ground vehicles account for 30% of total carbon emission, and significantly contribute to other harmful emissions. This issue causes environmental concerns and threat to human health. On the other hand, the demand on fossil fuel grows with the increasing energy consumption worldwide. Particularly in the United States of America, transportation absorbs 75% of this energy source. There is an urgent need to reduce the transportation dependence on fossil fuel for the purpose of national security. Polymer electrolyte membrane (PEM) fuel cells are strong potential candidates to replace the traditional combustion engines. Even though research effort has transferred the fuel cell technology into real‒world vehicle applications, there are still several challenges hindering the fuel cell technology commercialization, such as hydrogen supply infrastructure, cost of the fuel cell vehicles, on‒board hydrogen storage, public acceptance, and more importantly the performance, durability, and reliability of the PEM fuel cell vehicles themselves. One of the key factors that affect the fuel cell performance and life is the run‒time thermal and water management. The temperature directly affects the humidification of the fuel cell stack and plays a critical role in avoiding liquid water flooding as well as membrane dehydration which affect the performance and long term reliability. There are many models exists in the literature. However, there are still lacks of control‒oriented modeling techniques that describe the coupled heat and mass transfer dynamics, and experimental validation is rarely performed for these models. In order to establish an in‒depth understanding and enable control design to achieve optimal performance in real‒time, this research has explored modeling techniques to describe the coupled heat and mass transfer dynamics inside a PEM fuel cell. This dissertation is to report our findings on modeling the temperature dynamics of the gas and liquid flow in the porous media for the purpose of control development. The developed thermal model captures the temperature dynamics without using much computation power commonly found in CFD models. The model results agree very well with the experimental validation of a 1.5 kW fuel cell stack after calibrations. Relative gain array (RGA) was performed to investigate the coupling between inputs and outputs and to explore the possibility of using a single‒input single‒output (SISO) control scheme for this multi‒input multi‒output (MIMO) system. The RGA analyses showed that SISO control design would be effective for controlling the fuel cell stack alone. Adding auxiliary components to the fuel cell stack, such as compressor to supply the pressurized air, requires a MIMO control framework. The developed model of describing water transport in porous media improves the modeling accuracy by adding catalyst layers and utilizing an empirically derived capillary pressure model. Comparing with other control‒oriented models in the literature, the developed model improves accuracy and provides more insights of the liquid water transport during transient response. / text

Microbial fuel cells (MFCs) are emerging energy production technology which converts the chemical energy stored in biologically degradable compounds to electricity at high efficiencies. Microbial fuel cells have some advantages such as use of an inexpensive catalyst, operate under mild reaction conditions (i.e. ambient temperature, normal pressure and neutral pH), and generate power from a wide range and cheap raw materials. These make microbial fuel cell as an attractive alternative over other electricity generating devices. However, so far the major problem posses by this technology is the low power outputs of the microbial fuel cells that hinder its commercialization. Restriction in the electron transfer from bacteria to the anode electrode of a MFC is thought to be one cause for the low power output. Most recent MFC research is focused on using contaminants present in industrial, agricultural, and municipal wastewater as the energy source, with very few studies utilising gaseous substrates. Mediators can be added to MFCs to enhance the electron transfer from the microbe to the anode, but have limited practical applicability in wastewater applications because of the difficulty in recovering the expensive and potentially toxic compound. This thesis describes an investigation of electricity generation in a microbial fuel cell by combining a gaseous substrate with a mediator in the anode compartment. The emphasis being placed on the selection of a mediator to improve the electron transfer process for electricity production in an MFC. Subsequently, methods to improve the performance of a mediator MFC in respect of power and current density were discussed. This type of MFC is purposely aimed to be applied for treating gaseous contaminants in an anaerobic biofilter while simultaneously produce electricity. In this study, ethanol was the first gaseous substrate tested for the possibility to generate electricity in the MFC. Various mediators were previously compared in their reversibility of redox reactions and in the current production, and three best mediators were then selected for the power production. The highest electrical current production i.e. 12 μA/cm2 was obtained and sustained for 24 hrs with N,N,N',N'-tetramethyl-1,4- phenylendiamine TMPD (N-TMPD) as the mediator using glassy carbon (GC) electrode. The maximum power density reached 0.16 mW/cm2 by using carbon cloth (CC) anode. The absorption of these mediators by the bacterial cells was shown to correlate with the obtained energy production, with no N-TMPD was absorbed by the bacterial cells. The 24 hr current production was shown to be accompanied by the decrease in the ethanol concentration (i.e. 1.82 g/L), however ethanol crossover through the proton exchange membrane and ethanol evaporation around the electrodes were most likely to be the major cause of the decrease in the ethanol concentration. A theoretical coulombic efficiency of 0.005% was calculated for this system. The electrokinetics of microbial reduced mediator in the ethanol-mediator MFCs was also examined. Two methods i.e. linear sweep voltammetry (LSV) and cyclic voltammetry (CV) were used to obtained the kinetic parameters. CV method gave a better estimation of the kinetic parameters than LSV method due to the low concentration of the mediators used, affecting the Tafel behaviors. All CVs showed quasi-reversible behaviors compared to the CVs in the absence of the bacteria, which is thought due to the bacteria decreased the amount of the reduced and the oxidised mediator available at the surface of GC electrode. The highest exchange current density (i o ) was obtained by using N-TMPD as the mediator with the same concentration of the mediator used i.e. 0.13±0.01 mA/cm 2. The power output achieved also the highest (0.008 mW/cm 2) with N-TMPD as the mediator. The power density was improved to 0.03 mW/cm2 by using CC electrode. Another main objective of this thesis is to prove anoxic methane oxidation which was believed to occur only in marine sediments, and applies this for power generation in microbial fuel cells. Ferricyanide looked promising when it was used as the electron acceptor (thus as the mediator for the MFC). It was shown that ferricyanide was fully reduced by methanotrophs bacteria with methane as the substrate (versus abiotic and nitrogen control). The highest reduction rate achieved was 3 x10-3 mM/min.g. This finding was supported by ferricyanide peak heights disappearance (spectrophotometry at 420 nm), CO 2 production (sensor readings), ferrocyanide formation (cyclic voltammetry), and no other alternate electron acceptor was present. The total CO 2 produced was equal to 0.015 mmoles of CO 2 from starting concentration ferricyanide of 0.2 mmoles (after substraction with an offset value). CV results show 2.4 mM of ferrocyanide was produced after a total addition of 3 mM ferricyanide into the anoxic methanotrophic suspension. The current and voltage generation in microbial fuel cell reactor from the reduced ferricyanide confirmed that ferricyanide received electrons from the bacterial metabolism. The maximum power density of 0.02 mW/cm2 and OCV of 0.6 V were obtained with 3 mM ferricyanide using LSV method.

Research was performed on the development of metal-supported solid oxide fuel cell (SOFC) electrolytes by suspension and solution precursor plasma spraying (SPS and SPPS). Experiments were conducted to understand the effects of many plasma-, feedstock-, and substrate-related process parameters on the microstructure, permeability, and conductivity of the resulting coatings. Most work was performed with yttria-stabilized zirconia (YSZ), but samaria-doped ceria (SDC) was also considered. The plasma-to-substrate heat flux behaviour of the process is particularly relevant for producing dense electrolytes with low segmentation cracking. Heat flux profiles for various processing conditions were experimentally determined and then used to model temperature distributions in the electrolyte and substrate during deposition. The results showed a strong correlation between segmentation crack severity and the peak temperature difference between the electrolyte surface and the metal support during deposition. Building on these findings, two strategies were developed for improving electrolyte performance. The first strategy is to use a bi-layer electrolyte structure, in which one layer is dense but has segmentation cracks and the other layer is more porous but contains relatively few segmentation cracks. A cell with a bi-layer electrolyte achieved a peak power density of 0.718 W cm-2 at 750 °C using hydrogen as fuel. The second strategy involves reducing the thickness and roughness of the electrode on which the electrolyte is deposited, which first required the development of improved metal supports. A thinner electrode reduces the thermal stresses that drive segmentation cracking and a smoother surface minimizes the formation of concentrated porosity. A cell with a 16 μm thick anode and a 21 μm thick electrolyte achieved an open circuit voltage (OCV) of 1.053 V, a series resistance of 0.284 Ω cm2, and a peak power density of 0.548 W cm-2 at 750 °C using hydrogen as fuel. A separate cell with a 28 μm thick electrolyte achieved an OCV of 1.068 V. At the end of the thesis, cell performance is compared to that of state-of-the-art cells produced in other facilities and using other production methods.

The direct methanol fuel cell (DMFC) is considered to be a promising power source for portable electronic applications and transportation. At present there are several challenges that need to be addressed before the widespread commercialization of the DMFC technology can be implemented. The methanol electro oxidation reaction is sluggish, mainly due to the strong adsorption of the reaction intermediate carbon monoxide on platinum. Further, methanol crosses over to the cathode, which decreases the fuel utilization and causes cathode catalyst poisoning. Another issue is the accumulation of the reaction product CO₂ (g) in the anode, which increases the Ohmic resistance and blocks reactant mass transfer pathways. A novel anode configuration is proposed to address the aforementioned challenges. An extended reaction zone (thickness = ∼100-300 µm) is designed to facilitate the oxidation of methanol on sites that are not close to the membrane-electrode interface. Thus, the fuel concentration near the membrane may decrease significantly, which may mitigate adverse effects caused by methanol cross-over. The structure of the fibrous electrode, with its high void space, is believed to aid the disengagement of CO₂ gas. In this thesis the first objective was to deposit dispersed nanoparticle PtRu(Mo) catalysts onto graphite felt substrates by surfactant mediated electrodeposition. Experiments, in which the surfactant concentration, current density, time and temperature were varied, were conducted with the objective of increasing the active surface area and thus improving the reactivity of the electrodes with respect to methanol electro-oxidation. The three-dimensional electrodes were characterized with respect to their deposit morphology, surface area, composition and catalytic activity. The second objective of this work was to utilize the catalyzed electrodes as anodes for direct methanol fuel cell operation. The fuel cell performance was studied as a function of methanol concentration, flow rate and temperature by using a single cell with a geometric area of 5 cm². Increased power densities were obtained with an in-house prepared 3D PtRu anode compared to a conventional PtRu catalyst coated membrane. Coating graphite felt substrates with catalytically active nanoparticles and the utilization of these materials, is a new approach to improve the performance of direct fuel cells.

Polymer electrolyte membrane fuel cells (PEFCs) have long been thought of as a promising clean alternative energy electrochemical device. They are lightweight, highly efficient, modular and scalable devices. A fuel such as H2 or methanol that can be readily produced from a variety of sources can be utilized in PEFCs to generate electricity with low or no emissions. Despite these advantages, fuel cell technologies have failed to reach mass commercialization mainly due to short operational lifetimes and the high cost of materials. In particular, the polymer membrane and the catalyst layer have been problematic in reducing the material cost. Currently, platinum is the dominant material used to catalyze fuel cell reactions. However platinum is very expensive and scarce. In order to pursue the mass commercialization of fuel cells, two methods have been proposed: 1) increasing the utilization of platinum to lower the loading required, and 2) replacing platinum completely with a non-precious material. The latter has been suggested to be the long term solution due to the increasing cost of platinum. This thesis explores the elimination of platinum through the use of nanostructured non-precious metal catalysts for polymer electrolyte fuel cells. Several catalysts have been synthesized without the use of platinum that are active for the oxygen reduction reaction (ORR) which occurs at the cathode. Three different synthetic techniques were utilized using different nitrogen precursors. Aside from the different nitrogen precursors, each set of experiments utilize a different approach to optimize the oxygen reduction performance. Different characterization techniques are used to learn more about the ORR on non-precious metal fuel cells. The first experiment utilizes ethylenediamine, a well-known nitrogen precursor for non-precious metal fuel cell catalysts. Ethylenediamine is deposited onto two different porous carbon black substrates to determine the effectiveness of different porosities in creating active sites for the ORR. Of the two carbon black species, Ketjenblack EC-600JD and Ketjenblack ED-300J, the former was found to be more porous and effective. This result was mainly attributed to the increased surface area of the carbon black which allowed for better dispersion and a greater active site density. In this experiment, the coating of ethylenediamine on carbon black was also refluxed for 3 hours prior to the pyrolysis. It was found that refluxed catalyst samples showed much improved performance than catalyst samples without this procedural modification. The next experiment utilized cyanamide as a nitrogen precursor. Cyanamide was chosen due to its ability to form larger amounts of pyridinic nitrogen on the surface of the catalyst after a high temperature pyrolysis stage. The catalysts were heat-treated at 1000oC and the performance was measured. NH3 was introduced during the pyrolysis, which could remove the excess coating from the carbon surface, and increase the surface area of the catalyst by unblocking the carbon pores. A third modification to the procedure was carried out, where the heat-treated sample was ball-milled, re-coated, and heat-treated again in ammonia conditions to increase the nitrogen functionalities and increase the active site density. The performance was slightly increased from the original heat-treated sample. However due to the decreased surface area, the limiting current density also decreased. It was believed that ball-milling the sample crushed the pores within the catalyst sample, thereby lowering the active surface area and thus the current density. Therefore, the last sample was prepared similarly to the procedure for the third sample, but without ball-milling. This sample had restored surface area and improved ORR performance over all the synthesized catalyst samples – these experiments allowed for important realizations regarding the nature of the Fe-cyanamide-KJ600 catalysts and allowed for a drastic improvement in onset and half-wave potentials from the first catalyst. The final experiment discussed in this thesis describes the work done with 1,2,4,5-tetracyanobenzene and tetracyanoethylene as phthalcyanine precursors for non-precious metal catalysts (NPMCs). Iron(II) acetate was mixed with these phthalocyanine precursors to form polymer sheets of iron phthalocyanine or its monomeric units. By the creation of these polymer sheets of iron phthalocyanine, it allowed for a uniform distribution of iron centres on the surface of the carbon after a heat-treatment step. This allowed for high active site density through the design of these sheet polymers and prevented agglomeration or blockage of active sites which is thought to be a common problem in the synthesis of many NPMCs. Both tetracyanobenzene and tetracyanoethylene as precursors were tested. The tetracyanobenzene catalyst was heat-treated at different temperature ranging from 700-1100oC and characterized through electrochemical tests for the ORR. As an overall conclusion to this work, several catalyst samples were made and different approaches were successfully employed to improve the ORR performance. Of the synthesis treatments utilized to improve performance, each specific catalyst had different parameters to tweak in order to improve ORR performance. With X-ray photoelectron spectroscopy (XPS) analysis, conclusions were also specific to the catalysts structure and synthesis procedure, however quaternary and pyrrolic nitrogen groups seemed to play an influential role to the ORR final performance. Although relative amount of pyridinic nitrogen was not seen to increase with increasing catalyst performance during the studies; it may still play an essential role in the reduction of oxygen on the catalyst surface. The author of this work has not ruled out that possibility. Several recommendations for future work were suggested to broaden the knowledge and understanding of nanostructure non-precious metal catalysts to design a high performing, durable, and low-cost alternative to platinum based catalysts.

Research was performed on the development of metal-supported solid oxide fuel cell (SOFC) electrolytes by suspension and solution precursor plasma spraying (SPS and SPPS). Experiments were conducted to understand the effects of many plasma-, feedstock-, and substrate-related process parameters on the microstructure, permeability, and conductivity of the resulting coatings. Most work was performed with yttria-stabilized zirconia (YSZ), but samaria-doped ceria (SDC) was also considered. The plasma-to-substrate heat flux behaviour of the process is particularly relevant for producing dense electrolytes with low segmentation cracking. Heat flux profiles for various processing conditions were experimentally determined and then used to model temperature distributions in the electrolyte and substrate during deposition. The results showed a strong correlation between segmentation crack severity and the peak temperature difference between the electrolyte surface and the metal support during deposition. Building on these findings, two strategies were developed for improving electrolyte performance. The first strategy is to use a bi-layer electrolyte structure, in which one layer is dense but has segmentation cracks and the other layer is more porous but contains relatively few segmentation cracks. A cell with a bi-layer electrolyte achieved a peak power density of 0.718 W cm-2 at 750 °C using hydrogen as fuel. The second strategy involves reducing the thickness and roughness of the electrode on which the electrolyte is deposited, which first required the development of improved metal supports. A thinner electrode reduces the thermal stresses that drive segmentation cracking and a smoother surface minimizes the formation of concentrated porosity. A cell with a 16 μm thick anode and a 21 μm thick electrolyte achieved an open circuit voltage (OCV) of 1.053 V, a series resistance of 0.284 Ω cm2, and a peak power density of 0.548 W cm-2 at 750 °C using hydrogen as fuel. A separate cell with a 28 μm thick electrolyte achieved an OCV of 1.068 V. At the end of the thesis, cell performance is compared to that of state-of-the-art cells produced in other facilities and using other production methods.

A numerical model of a solid oxide fuel cell electrode is presented. Using an already established algorithm for dropping spheres as a base, alterations are made to the algorithm to increase the realism of the model. Two changes are analyzed in detail: the ability to drop pore former particles, and the use of pre-agglomerated solid particles. These changes are characterized by their impact on mean pore size, tortuosity, and effective diffusivity. As pore former volume fraction is increased, so too are mean pore size and tortuosity. A higher mean pore size has a beneficial effect on effective diffusivity due to Knudsen effects, while a higher tortuosity has a detrimental effect on effective diffusivity. The impact of mean pore size and tortuosity on diffusivity generally balances and if the impact of porosity is ignored, pore former volume fraction does not greatly affect effective diffusivity. As pore former particle size is increased, mean pore size and tortuosity also increase. Similarly to before, the effects of mean pore size and tortuosity balance. However, effective diffusivity is shown to decrease slightly with an increasing pore former particle size, suggesting a change in tortuosity has greater impact on diffusivity than a change in mean pore size. For a domain constructed with pre-agglomerated particles, the tortuosity and mean pore size were both noticeably larger than when no pre-agglomerated particles are used. Effective diffusivity was only slightly higher for a domain constructed with pre-agglomerated particles than with no pre-agglomerated particles. It is also shown that the relationship of effective diffusivity with porosity for a domain constructed with pre-agglomerated particles does not fit the correlation proposed by Berson et al. [1] for low porosity structures. A secondary goal of this work is to examine pore size measurement techniques, and present a novel technique that allows the determination of a local pore size, and therefore, a local Knudsen number. Results from the local pore size technique do not match those of the random walk method and so although the novel technique may prove to be a good starting point, it is deemed not yet suitable for use. / Thesis (Master, Mechanical and Materials Engineering) -- Queen's University, 2011-06-13 15:30:00.25

With continually increasing concern over anthropogenic carbon dioxide emissions and their effect on global climate, the search for alternative fuels, especially for mobile applications such as in vehicles, is of immediate concern. Herein, research towards hydrogen as an alternative energy carrier is discussed; first, with the investigation of “hybrid” hydrogen storage systems that are meant to provide hydrogen for a fully fuel cell powered vehicle via a chemical reaction; and second, that of a thermally regenerative fuel cell system (TRFC) to partially supplant the energy needs of transport trucks by harnessing engine waste heat. Hybrid storage systems are comprised of a heterocyclic carrier that undergoes endothermic hydrogen release (indoline) and an organic hydride that undergoes exothermic release (amine boranes). Different embodiments are considered, varying in the mechanism of exothermic release (thermolysis vs. hydrolysis) and the mode of combination (physical vs. chemical). A thorough investigation into the effect of catalyst, sterics and temperature on the heterogeneously catalyzed dehydrogenation rate of N-heterocycles was executed. A number of trends with respect to the catalyst identity and the level of steric protection around the nitrogen atom were observed. The study towards a TRFC involved an investigation of the heterogeneous hydrogenation of benzylic ketones. Screening of a myriad of different catalysts was performed, including those with various supports, metals and modifications, and the examination of how both the sterics and electronics of the ketone affect the hydrogenation rate. A rapid hydrogenation at relatively low metal loadings and hydrogen pressures with extreme selectivity (>99.9%) is required. To date, however, such a combination has been elusive. The best selectivity was obtained with commercial Pd/SiO2 (99.99%), yet at a low conversion of 6%, after 1 h under 1 atm of H2 at 100 ˚C. In addition to the poor conversion, SiO2 is not electronically conductive and is therefore not fit for this application. The best viable catalyst, then, was a Pd/Vulcan XC-72 (carbon) catalyst made by the author with an observed 14% conversion and 98% selectivity under the same conditions. However, trends in activity and selectivity with respect to the catalyst and ketone have been characterized herein. / Thesis (Ph.D, Chemistry) -- Queen's University, 2012-05-23 13:37:53.172