An investigation was conducted to determine the feasibility of using the technique of ultrasonic nebulization of water into the anode gas stream for evaporative cooling of a Proton Exchange Membrane (PEM) fuel cell. The basic concept of this form of internal evaporative cooling of the PEM fuel cell is to introduce finely atomized liquid water into the anode gas stream, so that the finely atomized liquid water adsorbs onto the anode and then moves to the cathode via electro-osmotic drag, where this water then evaporates into the relatively dry cathode gas stream, carrying with it the waste thermal energy generated within the fuel cell. The thermal and electrical performance of a 50 cm2 PEM fuel cell utilizing this technique was compared to the performance obtained with conventional water management. Both techniques were compared over a range of humidification chamber temperatures for both the anode and cathode gas streams so as to determine the robustness of the proposed method. The proposed method produced only meager levels of evaporative cooling (at best 2 watts, for which a minimum of 30 watts was required for adequate cooling), but the average cell voltage increased considerably (as much as a 10% gain), and the technique increased the fault tolerance of the fuel cell (the Nafion™ membrane did not dry out even if cell temperature went well in excess of 70° C despite both anode and cathode humidification temperatures of 55° C). An interesting phenomena was also observed wherein the fuel cell voltage oscillated regularly with a period of tens of seconds, and that the amplitude of this oscillation corresponded inversely with the level of humidification received by the fuel cell.

Proton exchange membrane (PEM) fuel cell possesses the characteristics of microminiaturization and low temperature operation. For this reason, the proton exchange membrane fuel cell is very suitable to serve as power source of portable electronic products. In this paper, a three-dimensional numerical model to evaluate the voltage and the total current density of a PEM fuel cell stack was developed. The polarization curves of the PEM fuel cell stack under three different operating temperatures were investigated. In this study, the micro PEM fuel cell stack contains two single cells. Pure H2 gas stream was supplied as the anode inlet flow and air as the cathode inlet flow under constant pressure at 97 kPa and constant cell temperate (298K¡B308K¡B323K) conditions. Because the cell temperature may affect the chemical reaction rate on the cathode side, we discussed the influences of different temperatures on the cell performance. Solutions were compared with the experimental data. Both the value of power density and the tendency of polarization curve are in good agreement with the experimental data.

In this experiment, we are going to discuss the possibility of zero methanol crossover to the cathode target within the capacity of DMFC electrode and with proper methanol supply. After various trials, it is found that electrospray can be used to reduce fuel demand. The methanol will be consumed immediately within the electrode capacity. The methanol solution is volatile. As a result, the actual amount of electricity generated will never accord with the input. If we supply the electrode with methanol by direct contact using infusion pump, the volatility will be reduced. The total power generated then accords with the amount of methanol input. Although only low methanol concentration is supported currently, it¡¦s hoped that the crossover problem can be solved completely. In the electrode design, we try to take away the carbon cloth from the anode and leave the catalyst layer. By this way, the methanol is in touch with the catalyst. Such change is good for this experiment. In our study, following difficulties are found: (1) Methanol input (2) The impact of volatility in electrospray (3) When supplying fuels to the surface of electrode, the reaction size is too small. More attentions should be paid in the future cell design.

In this study, copper metals were used to fabricate five different flow field plates with various open ratios using MEMS technology. Five samples were prepared for experiments with rib width varying as 150, 200, 300, 450, and 600 £gm at a fixed channel width (300 £gm). The open ratio of flow field plates was varied from 60.0% to 37.9%. Experiments with different operating parameters of anode/cathode pressure drop, cell operating temperature, and gas backpressure were conducted. Furthermore, a simple lumped capacitance model was used to predict the temperature evolution of the fuel cell system. Then, the optimum flow field design and cell operating parameters were finally found. Based on the aforementioned experiments an optimal open ratio ofunity was found like 49.2%. Further, an optimal open ratio in terms of the net power gain factor (= power gain/power consumption) of 38.7% can be obtained for the cases under study. Durability and reliability for copper bipolar plate were examined for long range tests (each run with at least 5 hours duration for consecutive two months). This strongly suggests that copper sheets can be considered as one of possible candidates for flow field material.

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.

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.