The anisotropic mass transport issues inside a fuel cell membrane have been studied in this thesis using computer modelling. The polymer electrolyte membrane (PEM) conductivity of a PEM fuel cell (PEMFC) depends on the hydration state of the hydrophilic charged sites distributed in the pores of the membrane. Water humidification of these charged sites is crucial for sustaining the membrane conductivity and reducing concerning voltage losses of the cell. During the operation of a PEMFC, the transport of humidified inlet gases (fuel/oxidant) is influenced by external design factors such as flow field plate geometry of the gas circulating channels. As a result, there arises a distribution in the mass transport of water inside the membrane electrode assembly. A two-dimensional, cross-the-channel, fuel cell membrane layer mass transport model, developed in this work, helps the study of the impact of factors causing the distribution in the membrane ionic conductivity on ohmic losses.<p>The governing equations of the membrane mathematical model stem from the multicomponent framework of concentrated solution theory. All mass transport driving forces within the vapour and/or liquid equilibrated phases have been accounted in this research. A computational model, based on the finite control volume method, has been implemented using a line-by-line approach for solving the dependent variables of the mass transport equations in the two-dimensional membrane domain. The required boundary conditions for performing the anisotropic mass transport analysis have been obtained from a detailed agglomerate model of the cathode catalyst layer available in the literature.<p>The results obtained using boundary conditions with various flow field plate channel-land configurations revealed that the anisotropic water transport in the cathode half-cell severely affects the ohmic losses within the membrane. A partially humidified vapour equilibrated membrane simulation results show that a smaller channel-land ratio (1:1) sustains a better membrane performance compared to that with a larger one (2:1 or 4:1). Resistance calculations using the computer model revealed that ohmic losses across the membrane also depend on its physical parameters such as thickness. It was observed that the resistance offered by a thinner membrane towards vapour phase mass transport is comparatively lower than that offered by a thicker membrane. A further analysis accounting the practical aspects such as membrane swelling constraints, imposed by design limitations of a fuel cell, revealed that the membrane water content and ionic conductivity are altered with an increase in the compression constraint effects acting upon a free swelling membrane.

The effects of actively pulsing reactant flow rates into solid polymer electrolyte fuel cells were investigated in this thesis. First, work was conducted to determine the magnitude of voltage response to pulsed reactant flow on a direct hydrogen proton exchange membrane (PEM) cell. The effects of pulsed reactant flow into a direct methanol fuel cell (DMFC) were then considered. The PEM work showed substantially greater response to pulsed air flow than to pulsed fuel flow. It was found that several parameters affect the magnitude of cell response to active flow control (AFC). Increasing current load, increasing the magnitude of flow oscillation, decreasing the frequency of oscillation, and decreasing the average level of excess reactant supplied were found to maximize both the level of voltage oscillations and the decrease in cell power from steady state performance. Greater response to pulsed oxidant flow is believed to have been observed due to effects brought about by changes in membrane humidity. In contrast, pulsed fuel flow showed the greatest response in the study of DMFC technology. In this case, time averaged cell voltage was found to increase as the time averaged fuel flow rate was reduced. The increase in average cell power is the result of a reduction in methanol crossover; sustainable increases of up to 6% in power output were measured. The parameters found to effect the increase in cell power observed include the frequency of oscillation and the time-averaged NOSfuel. Pulsed air flow on the DMFC did not show any such rise in voltage, supporting the hypothesis that a reduction in methanol crossover is the phenomenon which brings about enhanced performance.

Proton exchange membrane (PEM) fuel cells, with low operating temperatures and high power density, are a reasonable candidate for use in mobile power generation. One large drawback to their use is that their fuel reformer requires not only fuel but also water, thereby requiring two separate reservoirs to be available. PEM fuel cells exhaust enough water in their oxidant stream to potentially meet the needs of the fuel reformer. If this water could be recovered and routed to the fuel reformer it would markedly increase the portability of PEM fuel cells. The goal of this research was to test a previously designed axial flow moisture separator. The separator was employed in a test bed which utilized compressed, heated air mixed with steam to simulate the oxidant exhaust conditions of a 25 kW PEM fuel cell. The simulated exhaust was saturated with water. The mixture was expanded through the turbine side of an automotive turbocharger, which dropped the temperature and pressure of the mixture, causing water to condense, making it available for separation. The humid air mixture was passed over an axial flow centrifugal separator and water was removed from the flow. The separator was tested in a variety of conditions with and without passing chilled water through the separator. The axial separator was tested independently, with a flow straightener preceding it, and with a commercially available centrifugal moisture separator in series following it. It was shown that cooling makes a significant impact on the separation rate while adding a flow straightener does not. Separation efficiencies of 19% on average were experienced without cooling, while efficiencies of 50% were experienced with 3.1 kW of cooling. The separation efficiency of the two moisture separators combined was found to be 31.7% which is 165% that of the axial separator alone under uncooled conditions.

Planar solid oxide fuel cells (SOFCs) were designed, fabricated and characterized in order to develop a (1) cost-effective method for fabrication of thin electrolyte layers, (2) hermetic sealing and (3) stable interconnects. Electrophoretic deposition (EPD) was discovered to be an excellent method for fabricating dense electrolyte layers of about 5m thick on porous non-conducting substrates. The EPD process was thoroughly studied from proof-of-concept to statistical reproducibility, deposition mechanism, modeling and process optimization. Deposition on non-conducting substrates was found to follow many of the same fundamental trends as that on conductive substrates except for the voltage efficiency and detailed charge transfer mechanism. Eventually, the process was optimized such that an SOFC was fabricated that achieved 1.1W/cm2 at 850C. Further, a novel sealless planar SOFC was designed that incorporates a hermetic interface between the electrolyte and interconnect similar to tubular and honeycomb designs. The hermetic interface successfully acted as a blocking electrode under DC polarization, indicating its potential to act as a sealant. Leakage rates across the interface were 0.027sccm at 750c, similar to polycrystalline mica seals. Through a process of tape casting and lamination, a two-cell stack without sealant was fabricated and achieved a power density of 75mW/cm2 at 750C. Finally, the degradation rate of silver and silver-based interconnects was studied under static and dual-atmosphere conditions. Corrosion of silver grain boundaries along with sublimation losses results in the formation of large pores, resulting in up to 30 of anode oxidation after 8hrs testing at 750c. Further stability studies indicated that silver-based interconnects would be better suited for applications at operating temperatures less than 650C.

According to the previous experimental fact that an interdigitated single PEMFC has a better performance than other flow type single PEMFC, therefore this research is aimed to predict a two-cell stack interdigitated PEMFC via a numerical simulation. Investigation the effects of the cell temperature, the cell operating pressure, the fuel flow rate and the air flow rate are performed. This research can provide design reference for application of interdigitated PEMFC stack.

PEM (Proton Exchange Membrane) fuel cell is one of the most important green energy, because it has high energy density, lifetime, small and light.etc advantages. Nafion , the major material for PEM now, However, has some disadvantages such as high cost ($600¡V1000/m2) and limited choices for operation temperature about 25¢J~80¢J. Consequently, there is an increasing interest in the development of alternative ionomer membranes with lower cost, and higher proton conductivity, and that are more easily processed. Here we present polymeric membranes made of sulfonic Poly(arylene ether)s (PAEs) which is achieved by nucleophilic displacement reactions of dihalo or dinitro compounds with alkali metal bisphenolates and direct polymer sulfonation was carried out in heterogeneous media using chlorosulfonic acid as both solvent and sulfonating agent. In our PAEs which has high Tg values about 225¡ã250¢XC depends on the barriers to rotation along the main polymer chain. And weight losses above 500 ¢XC by thermogravimetric (TGA) analysis, indicative of their high thermal stability. After FTIR analysis we preparation sulfonated polymer successfully by using chlorosulfonic acid as sulfonating agent. Thermogravimetric analysis (TGA) studies were carried out to investigate the thermal stability of sulfonated PAEs (Td≈ 500¢XC). The proton conductivity of polymer s(DFB+M3) sulfonated with chlorosulfonic acid about 10-6¡ã10-7S cm-1 .Compared with Nafion membrane measured in the same condition, the conductivity of our membrane is smaller than 3~4 order. In the future, it is possible to improve the conductivity of our membrane with optimization.

With the escalating number of vehicles on the road, great concerns are drawn to the large amount of fossil fuels they use and the detrimental environmental impacts from their emissions. A lot of research and development have been conducted to explore the alternative energy sources. The fuel cell has been widely considered as one of the most promising solutions in automobile applications due to its high energy density, zero emissions and sustainable fuels it employs. However, the cost and low power density of the fuel cell are the major obstacles for its commercialization. This thesis designs a novel converter topology and proposes the control method applied in the Fuel Cell Hybrid Vehicles (FCHVs) to minimize the fuel cell's cost and optimize the system's efficiency. Unlike the previous work, the converters presented in the thesis greatly reduce the costs of hardware and energy losses during switching. They need only three Metal-Oxide-Semiconductor Field-Effect Transistors (MOSFETs) to smoothly accomplish the energy management in the cold start, acceleration, steady state and braking modes. In the converter design, a boost converter connects the fuel cell to the DC bus because the fuel cell's voltage is usually lower than the rating voltage of the motor. In this way, the fuel cell's size can be reduced. So is the cost. With the same reason, the bidirectional converter connected to the ultracapacitor works at the buck pattern when the power is delivered from the DC bus to the ultracapacitor, and the boost converter is selected when the ultracapacitor provides the peaking power to the load. Therefore, the two switches of the bi-directional converter don't work complementarily but in different modes according to the power flow's direction. Due to the converters' simple structure, the switches' duty cycles are mathematically analyzed and the forward control method is described. The fuel cell is designed to work in its most efficient range producing the average power, while the ultracapacitor provides the peaking power and recaptures the braking power. The simulation results are presented to verify the feasibility of the converter design and control algorithm.

Fundamental studies of heterogeneous catalysis were performed and presented in this dissertation to gain a better understanding of heterogeneous catalytic reactions at a molecular level. Surface science techniques were employed in achieving the goal. Low energy ion scattering spectroscopy (LEISS) is the main surface science technique which will be used in all the studies discussed throughout this dissertation. The main objectives of LEISS measurements are to: 1) obtain the information of surface composition of heterogeneous catalysts from the topmost layer; 2) observe the effects of reaction conditions on the surface composition of heterogeneous catalysts. The surface composition and morphology of Au-Pd clusters bimetallic model catalysts supported on SiO2 were characterized using LEISS, infrared reflection absorption spectroscopy (IRAS), and temperature programmed desorption (TPD). It is observed that relative to the bulk, the surface of the clusters is enriched in Au. Ethylene adsorption and dehydrogenation show a clear structure-reactivity correlation with respect to the structure/composition of these Au-Pd model catalysts. Fundamental studies of heterogeneous catalysis were performed and presented in this dissertation to gain a better understanding of heterogeneous catalytic reactions at a molecular level. Surface science techniques were employed in achieving the goal. Low energy ion scattering spectroscopy (LEISS) is the main surface science technique which will be used in all the studies discussed throughout this dissertation. The main objectives of LEISS measurements are to: 1) obtain the information of surface composition of heterogeneous catalysts from the topmost layer; 2) observe the effects of reaction conditions on the surface composition of heterogeneous catalysts. The surface composition and morphology of Au-Pd clusters bimetallic model catalysts supported on SiO2 were characterized using LEISS, infrared reflection absorption spectroscopy (IRAS), and temperature programmed desorption (TPD). It is observed that relative to the bulk, the surface of the clusters is enriched in Au. Ethylene adsorption and dehydrogenation show a clear structure-reactivity correlation with respect to the structure/composition of these Au-Pd model catalysts.

Abstract Traditional unipolar/bipolar plates, such as the metal and the graphite unipolar/bipolar plates, are expensive, weight heavy and volume large, so that it is hard to be used in the portable application. A high efficiency, low cost and lightweight portable proton exchange membrane fuel cell (called PEMFC or called HFC when using pure hydrogen fuel), which is made with a new heterogeneous composite carbon fiber bipolar plate and a MEA, is developed in our lab. There are many advantages of the new carbon fiber unipolar/bipolar plates, such as low contact resistance, low cost, lightweight and small volume. We hope that the new unipolar/bipolar plate will be able to replace the conventional metal and graphite unipolar/bipolar plates in the future. The characteristics of a portable PEMFC in different operational conditions are studied in this research. From our experimental result, we find that the factors which affect the HFC performance include the gas temperature, humidity ratio, inlet gas pressure in anode, the geometry of inlet ports, the flow channels within cell, and the oxidant flow rate etc. In addition, the contact resistances between different materials within each cell all strongly influence HFC performance. The ribs of the carbon fiber unipolar/bipolar plates is pored structure, and the gas diffusion layer is no deformation because of only slight compression in stack assembly; therefore, the reactive gas can easily flow into the most of active area. In addition, the contact resistance between the carbon fiber unipolar plate and the gas diffusion layer is lower than that between the traditional unipolar plate and the gas diffusion layer, so that the electrons in active layer is easily to exit or enter this region. The experimental result at 1.15 atm and 40 oC displays that the current density with the new unipolar plate is about twice higher than that with the graphite unipolar plate at overpotential 0.6 V. With air as an oxidizer, we find that increasing the fan rotation speed can avoid output-voltage decay in high current density, but the design with fan is unfavorable for portable application. So a front open unipolar plate and air-breathing design is adopted on the cathode. The power density of this design is slightly lower than that with fan, but it still can reach a value 160 mW/cm2 without any heating and humidification in the anode. Because this design needs little supplement device, the application in portable fuel cells of the new design will be wider than that of a traditional design.

The experimental test and analysis of the direct methanol fuel cell (DMFC), which is made with a newly developed heterogeneous composite carbon fiber unipolar/bipolar plate, is performed in our lab. The work from the making of carbon fiber unipolar plate to the design of single-cell DMFC is also included in this study. The experimental work of various control parameters, such as methanol concentration, operating temperature, and the air flow rate, is also conducted in this thesis. The formation of carbon dioxide in anode is inspected during experiment. From a series of experimental test, we have understood the characteristics of DMFC better. The experimental result and experience can also provide the references of the application and development of DMFC in the future. According to our experiment, we find that the assembling of the new-type unipolar/bipolar plate doesn¡¦t need to use the large compressing force to reduce the contact resistance like those of the traditional unipolar/bipolar plates. The structure of the DMFC stack made with the new carbon fiber unipolar/bipolar plate is simple and weight light. However, the experimental results still show that the factors that affect the performance of the DMFC fuel cell are similar to those with the conventional unipolar/bipolar plates. For example, increasing the reactive temperature of fuel, proper methanol concentration, and proper content of catalyst all can effectively improve the power density of a DMFC. The structure of the methanol mixture directly stored in the flow channel of the anode is simple. However, the design exists the problems of the crossover of methanol, the stripping of the anode electrode, and the removal of the carbon dioxide. Special attention is needed to overcome and improve those problems in making DMFC stacks. Or the performance of the cell will decline after long period operation.