While there is a substantial amount of information regarding the electrochemical behavior of fuel cells and there components little to no information is available regarding the mechanical properties of fuel cell materials in stack setups. This set of experiments was set up to test mechanical properties of gas diffusion layer and bipolar plate materials in a one cell setup. Samples were clamped to specified pressures and deformation properties were observed and measured. Measurements were taken of impingements of the gas diffusion layers into the gas flow channels. A limit for compression of cell configurations was found to be approximately 300psi. Upon reaching the compression limit bipolar plates collapse and materials between plates show signs of breakage. Under compression diffusion media showed impingement into the gas flow channels as well as substantial compression of the three layer stack.

Direct hydrocarbon fuel cells are fuel cells than use hydrocarbons directly as fuel instead of the most commonly used fuel in a fuel cell, hydrogen. Studies are being done on direct hydrocarbon fuel cells because they have the potential to be energetically more efficient than hydrogen fuel cells. There are many different hydrocarbons that are available to use as a feed stock and each one reacts at different reaction rates. As the current density of a fuel cell is linked to the reaction rate, it is important to know the energetics of an oxidation reaction that is occurring. Density Functional Theory (DFT) is a technique that can be used to predict the energy states of intermediate reaction steps in a given mechanism. The focus of this study is the using DFT to explore the energetics of the oxidation of ethane to ethylene in a nickel-anode catalyst fuel cell. DFT was used in adsorption runs to optimize the geometries beginning (adsorbed ethane) and end (adsorbed ethylene) of the oxidation reaction. DFT was then used to calculate the energy of transition states by varying bond lengths. It was determined the removal of the second hydrogen from the ethyl radical is the most energy intensive step and, thus, the rate limiting step. Hydrogen, ethane, and ethylene were all explored in this study. The heats of adsorption varied from largest to smallest in the order of ethylene, hydrogen, and ethane. It was determined that the heat of adsorption of hydrogen is sufficient to meet the energy requirements for the dissociation reaction. This may help explain why hydrogen reacts so readily in fuel cells. Conversely, the heats of adsorption for the hydrocarbons did not meet the energy requirements for the dissociation reactions. This may help explain why ethane and ethylene react more slowly in a fuel cell as compared to hydrogen. Also, the oxidation of ethane to ethylene requires two large activation energies. These two additional activation energies may help explain why ethylene reacts more readily than ethane in a fuel cell.

The polymer electrolyte membrane fuel cell (PEMFC) is an electrochemical device used for the production of power, which is a key for the transition towards green and renewable power delivery devices for mobile, stationary and back-up power applications. PEMFCs consume hydrogen and oxygen to produce power, water and heat. The transient start-up from sub-zero freezing temperature conditions is a problem for the successful, undamaged and unhindered operation. The generation and presence of water in the PEMFC stack in such an environment leads to the formation of ice that hinders the flow of gases, causes morphological changes in the membrane electrode assembly (MEA) leading to reversible and irreversible degradation of stack performance. Start-up performance is highly dependent on start-up operational conditions and procedures. The previous state of the stack will influence the ability to perform upon the next start-up and operation. Water generated during normal operation is vital and improves performance when properly managed. Liquid water present at shut-down can form ice and cause unwanted start-up effects. This phase change may cause damage to the MEA and gas diffusion media due to volume expansion. Removal of high water content at shutdown decreases proton conductivity which can delay start-up times. The United States Department of Energy (DOE) has established a set of criteria that will make fuel cell technology viable when attained. As specified by DOE, an 80 kWe fuel cell will be required by 2015 to reach 50% power in 30 seconds from start-up at an ambient temperature of -20°C. This work investigates freeze start-up in a multi-kilowatt stack approaching both shut-down conditioning and start-up operations to improve performance, moderate fuel cell damage and determine the limits of current stack technology. The investigation involved a Hydrogenics Corporation 5 kW 506 series fuel cell stack. The investigation is completed through conditioning the fuel cell start-up performance at various temperatures ranging from -5°C to below -20°C. The control of system start-up temperature is achieved with an environmental chamber that maintains the desired set point during dwell time and start-up. The supply gases for the experiment are conditioned at ambient stack temperature to create a realistic environment that could be experienced in colder weather climates. Temperature controls aim to maintain steady ambient temperatures during progressive start-up in order to best simulate ambient conditions. The control and operation of the fuel cell is maintained by the use of a fuel cell automated test station (FCATS™). FCATS supplies gas feeds, coolant medium and can control temperature and reactant humidity in reactants according to a prescribed procedure for continuous operation. The iv collection of data occurs by the same system recording cell voltage, temperatures, pressures, flow rates and current densities. A procedural start-up and characterization are conducted in order improve start-of performance and examine reactant flows, coolant activation time, stack conditioning and the effects by freezing temperatures. The resulting degradation is investigated by polarization curves and various ex-situ measurements. In this work, it was found that freeze start-up of a fuel cell stack can be aided and managed by conditioning the stack at shut-down and applying a procedure to successfully start-up and mitigate the damage that freezing can cause.

Fuel cells are electrochemical energy devices that convert the chemical energy in a fuel into electrical energy. Although they are more efficient, clean, and reliable than fossil fuel combustion systems, they have not been widely adopted because of manufacturing challenges and high production cost. The most expensive component of a fuel cell is the membrane electrode assembly (MEA), which consists of an ionomer membrane coated with catalyst material. Best performing MEAs are currently fabricated by depositing and drying liquid catalyst ink on the membrane, however, this process is limited to individual preparation by hand due to the membrane’s rapid water absorption that leads to shape deformation and coating defects. This work models the swelling and drying phenomena of the membrane and coating during manufacturing, and then applies the results to develop and control a continuous coating line for the production of defect free fuel cell MEAs. A continuous coating line can reduce the costs and time needed to fabricate the MEA, incentivizing the commercialization and widespread adoption of fuel cells. Membrane swelling is a three-dimensional, transient, coupled mass transfer, heat transfer, and solid mechanics problem. Existing models describe the membrane’s behavior in operating conditions, but none predict the behavior during manufacturing. This work develops a novel physics-based model that describes the behavior of the membrane and coating in a continuous manufacturing scenario and incorporates effects that are missing from existing models. A model that can predict wrinkles, the most commonly observed defect during manufacturing, is presented. Simulation results from the above models are used to design and develop an improved continuous MEA coating process that includes pre-swelling and two-stage drying of the coated membrane. A prototype pilot-scale coating line to implement and test the improved coating process is designed and constructed. Finally, a Linear-Quadratic-Gaussian type controller is developed using the physics-based model of the manufacturing process to optimally control the temperature and humidity of the drying zones, and its effectiveness when implemented on the coating line is discussed. / text

Proton exchange membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs) are two types of low-temperature fuel cells (LTFCs) that operate at temperatures less than 100 °C and are appealing for portable, transportation, and stationary applications. However, commercialization has been hampered by several problems such as cost, efficiency, and durability. New electrocatalysts must be developed that have higher oxygen reduction reaction (ORR) activity, lower precious metal loadings, and improved durability to become commercially viable. This dissertation investigates the development and use of new electrocatalysts for the ORR. Core-shell (shell@core) Pt@Pd[subscript x]Cu[subscript y]/C electrocatalysts, with a range of initial compositions, were synthesized to result in a Pt-rich shell atop a Pd[subscript x]C[subscript y]-rich core. The interaction between core and shell resulted in a delay in the onset of Pt-OH formation, accounting in a 3.5-fold increase in Pt-mass activity compared to Pt/C. The methanol tolerance of the core-shell Pt@PdCu₅/C was found to decrease with increasing Pt-shell coverage due to the negative potential shift in the CO oxidation peak. It was discovered that Cu leached out from the cathode has a detrimental effect on membrane-electrode assembly performance. A spray-assisted impregnation method was developed to reduce particle size and increase dispersion on the support in a consistent manner for a Pd₈₈W₁₂/C electrocatalyst. The spray-assisted method resulted in decreased particle size, improved dispersion and more uniform drying compared to a conventional method. These differences resulted in greater performance during operation of a single DMFC and PEMFC. Additionally, Pd₈₈W₁₂/C prepared by spray-assisted impregnation showed DMFC performance similar to Pt/C with similar particle size in the kinetic region while offering improved methanol tolerance. Pd₈₈W₁₂/C also showed comparable maximum power densities and activities normalized by cost in a PEMFC. Lastly, the activation of aluminum as an effective reducing agent for the wet- chemical synthesis of metallic particles by pitting corrosion was explored along with the control of particle morphology. It was found that atomic hydrogen, an intermediate, was the actual reducing agent, and a wide array of metals could be produced. The particle size and dispersion of Pd/C produced using Al was controlled using PVP and FeCl₂ as stabilizers. The intermetallic Cu₂Sb was similarly prepared with a 20 nm crystallite size for potential use in lithium-ion battery anodes. Lastly, it was found that the shape of Pd produced with Al as a reducing agent could be controlled to prepare 10 nm cubes enclosed by (100) facets with potentially high activity for the ORR. / text

This thesis is an investigation of the anode of a direct methanol fuel cell (DMFC) through numerical modeling and simulation. This model attempts to help better understand the two phase flow phenomena in the anode as well as to explain some of the many problems on the anode side of a DMFC and show how changing some of the anode side properties could alleviate these problems. This type of modeling is important for designing and optimizing the DMFC for specific applications like portable electronics. Understanding the losses within the DMFC like removable of carbon dioxide, conversion losses, and methanol crossover from the anode to the cathode will help the DMFC become more commercially viable. The model is based on two phase flow in porous media combined with equilibrium between phases in a porous media with contributions from a capillary pressure difference. The effect of the physical parameters of the fuel cell like the thickness, permeability, and contact angle as well as the operating conditions like the temperature and methanol feed concentration, have on the performance of the DMFC during operation will be investigated. This will show how to remove the gas phase from the anode while enabling methanol to reach the catalyst layer and minimizing methanol crossover. / text

Bakalauro darbą „Metanolio kuro elemento statinių charakteristikų tyrimas“ sudaro įvadas, keturi skyriai, išvados bei rekomendacijos. Darbo apimtis 33 lapai. Likusioji dalis pateikiami priedai (eksperimento rezultatai). Darbe išanalizuotos metanolio kuro elemento voltamperinės bei galių charakteristikos, esant skirtingoms metanolio koncentracijos tirpalams. Įvadinėje dalyje iškeliamas darbo tikslas, uždaviniai, problematika bei tematikos aktualumas. Pirmame skyriuje aptariami kuro elementai, jų veikimo principai, panaudojimas. Antrame skyriuje aptariamas tiesioginio veikimo metanolio kuro elementas. Sekantis skyrius skirtas eksperimento matavimo metodikai, o ketvirtame skyriuje pateikiami eksperimento metu gauti rezultatai naudojant metanolio kuro elementą, esat skirtingoms metanolio koncentracijos tirpalams. / The bachelor’s thesis “Methanol fuel cell static characteristic and power characteristic research” consists of the introduction, 3 sections, conclusions and recommendations. The thesis comprises 33 pages. The rest of the accessories (experimental results). At the thesis is presented analysis methanol fuel cell power characteristic and performance at different methanol concentration solutions. The introduction sets the problem, the aims, the goals of the study and relevance of the topic. The first chapter is devoted to fuel cells, their operating principles to use. The second section deals with the direct methanol fuel cell operation. Next chapter for the experimental measurement methods, and the fourth section presents the experimental results obtained using methanol fuel cell, you are a different concentration of methanol solutions.

In this work, a microfluidics approach is applied to two fuel cell related projects; the study of deformation and contact angle hysteresis on water invasion in porous media and the introduction of bubble fuel cells. This work was carried out as collaboration between the microfluidics and CFCE groups in the Department of Mechanical Engineering at the University of Victoria. Understanding water transport in the porous media of Polymer Electrolyte Membrane fuel cells is crucial to improve performance. One popular technique for both numeric simulations and experimental micromodels is pore network modeling, which predicts flow behavior as a function of capillary number and relative viscosity. An open question is the validity of pore network modeling for the small highly non-wetting pores in fuel cell porous media. In particular, current pore network models do not account for deformable media or contact angle hysteresis. We developed and tested a deformable microfluidic network with an average hydraulic diameter of 5 μm, the smallest sizes to date. At a capillary number and relative viscosity for which conventional theory would predict strong capillary fingering behavior, we report almost complete saturation. This work represents the first experimental pore network model to demonstrate the combined effects of material deformation and contact angle hysteresis. Microfluidic fuel cells are small scale energy conversion devices that take advantage of microscale transport phenomena to reduce size, complexity and cost. They are particularly attractive for portable electronic devices, due to their potentially high energy density. The current state of the art microfluidic fuel cell uses the laminar flow of liquid fuel and oxidant as a membrane. Their performance is plagued by a number of factors including mixing, concentration polarization, ohmic polarization and low fuel utilization. In this work, a new type of microfluidic fuel cell is conceptualized and developed that uses bubbles to transport fuel and oxidant within an electrolyte. Bubbles offer a phase boundary to prevent mixing, higher rates of diffusion, and independent electrolyte selection. One particular bubble fuel cell design produces alternating current. This work presents, to our knowledge, the first microfluidic chip to produce bubbles of alternating composition in a single channel, class of fuel cells that use bubbles to transport fuel and oxidant and fuel cell capable of generating alternating current. / Graduate

Atmospheric plasma spraying is attractive for manufacturing solid oxide fuel cells (SOFCs) because it allows functional layers to be built rapidly with controlled microstructures. The technique allows SOFCs that operate at low temperatures (600 to 750°C) to be fabricated by spraying directly onto robust and inexpensive metallic supports. Processes were developed to manufacture metal-supported SOFC cathodes by axial-injection plasma spraying. Cathodes consisted of LSCF (La0.6Sr0.4Co0.2Fe0.8O3-δ) or SSC (Sm0.5Sr0.5CoO3) as the primary material. Initially, the plasma spray process parameters were varied, and x-ray diffraction analyses were performed on the cathode coatings to detect material decomposition and the formation of undesired phases. These results determined the envelope of plasma spray parameters in which coatings of LSCF and SSC can be manufactured, and the range of conditions in which composite cathode coatings could potentially be manufactured. Subsequently, composite cathodes were fabricated by mixing up to 40 wt. % of the ionic conducting SDC (Ce0.8Sm0.2O1.9) material into the feedstock. The deposition efficiencies of these cathodes were calculated based on the mass of the sprayed cathode. Particle surface temperatures were measured in-flight to enhance understanding of the relationship between spray parameters, microstructure, and deposition efficiency. Electrochemical impedance spectroscopy was performed in symmetrical cells: at 750°C, LSCF-SDC cathodes had polarization resistances as low as 0.101 Ωcm², and SSC cathodes had polarization resistances as low as 0.0056 Ωcm². Finer mixing of the ceramic phases was achieved by using a nano-structured feedstock that contained both LSCF and SDC phases agglomerated together in larger particles. Fuel cells containing a yttria-stabilized zirconia (YSZ) electrolyte and a nickel-YSZ anode were fabricated, and the effect of the cathode microstructure on cell impedance was studied using the analysis of differential impedance spectra. The degradation of composite LSCF-SDC cathodes on porous 430 stainless steel supports was also investigated. To reduce degradation, La2O3 and Y2O3 reactive element oxide coatings were deposited on the internal pore surfaces of the metal supports. As a result, polarization resistance degradation rates as low as 0.00256 Ω·cm2 /1000 h were observed over 100 hours on coated substrates, compared to 0.1 Ω·cm2 /1000 h on uncoated substrates.

Atmospheric plasma spraying is attractive for manufacturing solid oxide fuel cells (SOFCs) because it allows functional layers to be built rapidly with controlled microstructures. The technique allows SOFCs that operate at low temperatures (600 to 750°C) to be fabricated by spraying directly onto robust and inexpensive metallic supports. Processes were developed to manufacture metal-supported SOFC cathodes by axial-injection plasma spraying. Cathodes consisted of LSCF (La0.6Sr0.4Co0.2Fe0.8O3-δ) or SSC (Sm0.5Sr0.5CoO3) as the primary material. Initially, the plasma spray process parameters were varied, and x-ray diffraction analyses were performed on the cathode coatings to detect material decomposition and the formation of undesired phases. These results determined the envelope of plasma spray parameters in which coatings of LSCF and SSC can be manufactured, and the range of conditions in which composite cathode coatings could potentially be manufactured. Subsequently, composite cathodes were fabricated by mixing up to 40 wt. % of the ionic conducting SDC (Ce0.8Sm0.2O1.9) material into the feedstock. The deposition efficiencies of these cathodes were calculated based on the mass of the sprayed cathode. Particle surface temperatures were measured in-flight to enhance understanding of the relationship between spray parameters, microstructure, and deposition efficiency. Electrochemical impedance spectroscopy was performed in symmetrical cells: at 750°C, LSCF-SDC cathodes had polarization resistances as low as 0.101 Ωcm², and SSC cathodes had polarization resistances as low as 0.0056 Ωcm². Finer mixing of the ceramic phases was achieved by using a nano-structured feedstock that contained both LSCF and SDC phases agglomerated together in larger particles. Fuel cells containing a yttria-stabilized zirconia (YSZ) electrolyte and a nickel-YSZ anode were fabricated, and the effect of the cathode microstructure on cell impedance was studied using the analysis of differential impedance spectra. The degradation of composite LSCF-SDC cathodes on porous 430 stainless steel supports was also investigated. To reduce degradation, La2O3 and Y2O3 reactive element oxide coatings were deposited on the internal pore surfaces of the metal supports. As a result, polarization resistance degradation rates as low as 0.00256 Ω·cm2 /1000 h were observed over 100 hours on coated substrates, compared to 0.1 Ω·cm2 /1000 h on uncoated substrates.