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.

This project is aimed at developing and demonstrating highly conductive, lightweight, and low-cost thermoplastic blends to be used as flow field bipolar plates for polymer electrolyte membrane (PEM) fuel cells. <br><br> The research is focused on designing, prototyping, and testing carbon-filled thermoplastic composites with high electrical conductivity, as well as suitable mechanical and process properties. <br><br> The impact of different types of fillers on the composite blend properties was evaluated, as well as the synergetic effect of mixtures of fill types within a thermoplastic polymer matrix. A number of blends were produced by varying the filler percentages. Composites with loadings up to 65% by weight of graphite, conductive carbon black, and carbon fibers were investigated. Research results show that three-filler composites exhibit better performance than single or two-filler composites. <br><br> Injection and compression molding of the conductive carbon filled polypropylene blend was used to fabricate the bipolar plates. A Thermal Gravimetric Analysis (TGA) was used to determine the actual filler loading of composites. A Scanning Electron Microscope (SEM) technique was use as an effective way to view the microstructure of composite for properties such as edge effects, porosity, and fiber alignment. Density and mechanical properties of conductive thermoplastic composites were also investigated. During this study, it was found that 1:1:1 SG-4012/VCB/CF composites showed better performance than other blends. The highest conductivity, 1900 S/m in in-plane and 156 S/m in through plane conductivity, is obtained with the 65% composite. Mechanical properties such as tensile modulus, tensile strength, flexural modulus and flexural strength for 65% 1:1:1 SG-4012/VCB/CF composite were found to be 584. 3 MPa, 9. 50 MPa, 6. 82 GPa and 47. 7 MPa, respectively, and these mechanical properties were found to meet minimum mechanical property requirements for bipolar plates. The highest density for bipolar plate developed in this project is 1. 33 g/cm³ and is far less than that of graphite bipolar plate. <br><br> A novel technique for metal insert bipolar plate construction was also developed for this project. With a copper sheet insert, the in-plane conductivity of bipolar plate was found to be significantly improved. The performance of composite and copper sheet insert bipolar plates was investigated in a single cell fuel cell. All the composites bipolar plates showed lower performance than the graphite bipolar plate on current-voltage (I-V) polarization curve testing. Although the copper sheet insert bipolar plates were very conductive in in-plane conductivity, there was little improvement in single cell performance compared with the composite bipolar plates. <br><br> This work also investigated the factors affecting bipolar plate resistance measurement, which is important for fuel cell bipolar plate design and material selection. Bipolar plate surface area (S) and surface area over thickness (S/T) ratio was showed to have significant effects on the significance of interfacial contact resistances. At high S/T ratio, the contact resistance was found to be most significant for thermoplastic blends. Other factors such as thickness, material properties, surface geometry and clamping pressure were also found to affect the bipolar plate resistance measurements significantly.

This project is aimed at developing and demonstrating highly conductive, lightweight, and low-cost thermoplastic blends to be used as flow field bipolar plates for polymer electrolyte membrane (PEM) fuel cells. <br><br> The research is focused on designing, prototyping, and testing carbon-filled thermoplastic composites with high electrical conductivity, as well as suitable mechanical and process properties. <br><br> The impact of different types of fillers on the composite blend properties was evaluated, as well as the synergetic effect of mixtures of fill types within a thermoplastic polymer matrix. A number of blends were produced by varying the filler percentages. Composites with loadings up to 65% by weight of graphite, conductive carbon black, and carbon fibers were investigated. Research results show that three-filler composites exhibit better performance than single or two-filler composites. <br><br> Injection and compression molding of the conductive carbon filled polypropylene blend was used to fabricate the bipolar plates. A Thermal Gravimetric Analysis (TGA) was used to determine the actual filler loading of composites. A Scanning Electron Microscope (SEM) technique was use as an effective way to view the microstructure of composite for properties such as edge effects, porosity, and fiber alignment. Density and mechanical properties of conductive thermoplastic composites were also investigated. During this study, it was found that 1:1:1 SG-4012/VCB/CF composites showed better performance than other blends. The highest conductivity, 1900 S/m in in-plane and 156 S/m in through plane conductivity, is obtained with the 65% composite. Mechanical properties such as tensile modulus, tensile strength, flexural modulus and flexural strength for 65% 1:1:1 SG-4012/VCB/CF composite were found to be 584. 3 MPa, 9. 50 MPa, 6. 82 GPa and 47. 7 MPa, respectively, and these mechanical properties were found to meet minimum mechanical property requirements for bipolar plates. The highest density for bipolar plate developed in this project is 1. 33 g/cm³ and is far less than that of graphite bipolar plate. <br><br> A novel technique for metal insert bipolar plate construction was also developed for this project. With a copper sheet insert, the in-plane conductivity of bipolar plate was found to be significantly improved. The performance of composite and copper sheet insert bipolar plates was investigated in a single cell fuel cell. All the composites bipolar plates showed lower performance than the graphite bipolar plate on current-voltage (I-V) polarization curve testing. Although the copper sheet insert bipolar plates were very conductive in in-plane conductivity, there was little improvement in single cell performance compared with the composite bipolar plates. <br><br> This work also investigated the factors affecting bipolar plate resistance measurement, which is important for fuel cell bipolar plate design and material selection. Bipolar plate surface area (S) and surface area over thickness (S/T) ratio was showed to have significant effects on the significance of interfacial contact resistances. At high S/T ratio, the contact resistance was found to be most significant for thermoplastic blends. Other factors such as thickness, material properties, surface geometry and clamping pressure were also found to affect the bipolar plate resistance measurements significantly.

In general, a PEMFC was assembled by using a number of locked bolts. But this assembly will cause concentrated loads existed on the upper and lower portions of the end plates, so that the pressure distributed non-uniformly at the internal structures in the PEMFC and thus causing uneven distributed deformations of flow-channel plates. This phenomenon may lead to the leak of reaction gas, and causing not only the decrease of the efficiency of PEMFC, but also the increase of the dangerous. If the fuel cell size getting smaller, the influence may be more severely. The main aim of this study is to simulate the response of a micro-PEMFC numerically by utilizing a 3-D FEM model while the micro-PEMFC was assembled by three pairs of bolts along the upper and lower portions, respectively, of the end plates. The effects of different bolts locking sequences on the deformation and pressure distributions at flow-channel plates and on the porosity of gas diffusion layers in the micro-PEMFC were investigated. The simulated results showed that if one locked the middle bolt either on the upper or lower portion first, then the obtained uniformities of warpage, deformation, von Mises stress and porosity were superior than the corresponding obtained results if one locked either one of the four corner bolts first. Also, among the three pairs of bolts used for assembling the cell, the first locking bolt of the first pair of locking bolts and the first locking bolt of the rest of two pairs of locking bolts were suggested on the reverse portions of the end plates.

¡@¡@In this thesis, we develop a self-humidifying PEMFC. The humidifying effects on the stability and impedance of the fuel cell are studied. A portable and passive PEMFC stack usually exposes in the ambient no matter that it works or not. However, the ambient is far from saturated. The water within MEA will diffuse to the membrane¡¦s surface and evaporate continuously. The membrane will be short in water without water supplying. Because the conductivity of H+ of the membrane is highly dependent on water content, the dehydration of the membrane will reduce the interconnected passageway of H+ and affect the performance of fuel cell directly. And because of the different expansion rate the electrode of MEA is also possible to separate from its membrane when it operates repeatedly. This separation will make the performance of fuel cell an unrecovered decay. ¡@¡@At first, the hydration status of the dry membrane is observed. We measure the addition weight of water into membrane by using cotton thread humidifying, and estimate the water permeation distances. The maximum water supply rate of cotton thread is 4.26mg/min, and the permeation rate of water through membrane where is 2.5cm from water surface is 0.15mg/cm¡Dmin. Then we design the self-humidifying devices of PEMFC stack. The humidifying effects on performance and stability of the fuel cell are studied. ¡@¡@When the active area is 0.7¡Ñ4.5cm2 and the cotton thread is 5mm from the center of electrode the supplying water can arrive at the reaction area under the electrode through the membrane in one minute. The difference of the supplying water between the bottom and top is 7% by using 6cm cotton thread. Therefore water can hydrate the membrane and the difference of the supplying water between bottom and top is not oversize. The higher current load, the voltage efficiency is lower. The increasing heat generation rate results in the water evaporation rate would be greater than the water generation rate. So the drop of voltage under higher current is greater than lower current. By comparing with the difference of high frequency impedance the change of humidifying is smaller between 1hr operating. It indicates that humidifying by cotton thread keeps the membrane hydration.

A new type of heterogeneous carbon fiber bunch bipolar plate developed in our lab is applied to portable pure hydrogen proton exchange membrane fuel cell stacks. Several different types of bipolar plate structures have been designed, and the voltages and currents of these fuel cell stacks are measured to compare their performance. The new type of heterogeneous carbon fiber bunch bipolar plate is well in low contact resistance, weight low, small volume and the flexible geometry shape. Due to its flexible structure of carbon fiber bunch, the compressing pressure is small while assembling stack so that the electrode can not be over compressed and out of shape. Therefore the high porosity of diffusion layer can be keep and reaction gas can enter and distribute to all reaction areas easily. For using to portable equipments, a small 6-cell flat type of fuel cell stack are developed firstly. The total weight is about 75g and the total volume is about 68cm . The second stack is cylinder-type(I) fuel cell stack. The total weight is about 60g and the total volume is about 71cm . The third stack is cylinder-type (II). The total weight has been reduced to about 20g and the total volume has been reduced to about 30cm . Above three kinds of the 6-cell stacks the total electrode area is 13.5cm . Using Nafion, the catalyst content anode Pt 0.4mg/cm , cathode Pt 1.0mg/cm , On room temperature and inlet hydrogen gauge pressure 0.15atm air-breathing, total output power of the cylinder (II) can reach 1.85W, and the power density of unit area can reach about 137mW/cm^2.

Proton exchange membrane fuel cells are one of the most promising hydrogen energy conversion devices for portable, mobile and stationary applications. For wide spread usage to produce electricity platinum loading has to be decreased by using highly active electrocatalysts. Even 10 ppm carbon monoxide or higher than 30% carbon dioxide cause performance losses via deactivation which can be diminished by using binary catalysts. The aim of this thesis is to develop new platinum based electrocatalysts with high catalytic activity and to overcome the problems due to the deactivation. platinum and platinum-ruthenium based catalysts on different carbon supports have been prepared by supercritical carbon dioxide deposition and microwave irradiation methods. By using supercritical carbon dioxide deposition platinum on Vulcan XC72R (VXR), multi wall carbon nanotube (MWCNT) and Black Pearl 2000 (BP2000) catalysts were prepared and characterized by XRD, TEM and cyclic voltammetry (CV). XRD results showed that in catalysts prepared by using supercritical carbon dioxide deposition method, the particle sizes as low as 1-2 nm can be obtained. From the CV results the electrochemical surface areas obtained were Platinum/VXR&gt / Platinum/MWCNT&gt / PlatinumBP2000. By means of the oxygen reduction reaction (ORR), the number of electrons transferred per oxygen molecule was calculated as 3.5, 3.6 and 3.7 for Platinum/BP2000, Platinum/VXR and Platinum/MWCNT, respectively. The microwave irradiation was used to prepare platinum on VX, Regal and BP2000 and platinum-ruthenium on VX. The effects of microwave duration, base concentration, carbon support used and surfactant/precursor ratios were investigated. The particle sizes of the catalysts were ranging between 2-6 nm. The prepared catalysts were characterized by XRD, XPS, and then PEMFC tests were performed. The performance was ordered as Platinum/VX&gt / Platinum/Regal&gt / Platinum/BP2000. The power losses arising from carbon dioxide in hydrogen feed were decreased by using prepared platinum-ruthenium based catalysts.

A mathematical model for a proton exchange membrane fuel cell is the focus of this thesis. Modeling and simulations are carried out with an aim to understand the influence of operational and geometrical parameters on the inner reaction and performance of a proton exchange membrane fuel cell, and discuss the distributions of physical phenomena in membrane and catalyst layer. Than, the results of modeling are compared and analyzed with the experiments, and discuss the reasons of influences of the performance of PEMFC. The results show that activation overpotential is the major reason of influence of the performance at low current density (less than ), and diffusion and ohmic overpotential are substantially increased at high current density (great than ). The membrane of higher membrane conductivity and more thin, increasing pressure of cathode gas and use oxygen can enhance the performance of a PEMFC. The performance almost no influence for the catalyst layer over 0.3£gm. The catalyst layer thin and uniform can decrease coating of this layer. The results of modeling and experiments show that experiments have contact resistance between materials, and the performance slightly lower than performance of modeling, and the differences that at high current density great than low current density.

With increasing interest in energy storage and conversion devices for automobile applications, the necessity to understand and predict life behavior of rechargeable batteries, PEM fuel cells and super capacitors is paramount. These electrochemical devices are most beneficial when used in hybrid configurations rather than as individual components because no single device can meet both range and power requirements to effectively replace internal combustion engines for automobile applications. A system model helps us to understand the interactions between components and enables us to determine the response of the system as a whole. However, system models that are available predict just the performance and neglect degradation. In the first part of the thesis, a framework is provided to account for the durability phenomena that are prevalent in fuel cells and batteries in a hybrid system. Toward this end, the methodology for development of surrogate models is provided, and Pt catalyst dissolution in PEMFCs is used as an example to demonstrate the approach. Surrogate models are more easily integrated into higher level system models than the detailed physics-based models. As an illustration, the effects of changes in control strategies and power management approaches in mitigating platinum instability in fuel cells are reported. A system model that includes a fuel cell stack, a storage battery, power-sharing algorithm, and dc/dc converter has been developed; and preliminary results have been presented. These results show that platinum stability can be improved with only a small impact on system efficiency. Thus, this research will elucidate the importance of degradation issues in system design and optimization as opposed to just initial performance metrics. In the second part of the thesis, modeling of silicon negative electrodes for lithium ion batteries is done at both particle level and cell level. The dependence of the open-circuit potential curve on the state of charge in lithium insertion electrodes is usually measured at equilibrium conditions. Firstly, for modeling of lithium-silicon electrodes at room temperature, the use of a pseudo-thermodynamic potential vs. composition curve based on metastable amorphous phase transitions with path dependence is proposed. Volume changes during lithium insertion/de-insertion in single silicon electrode particle under potentiodynamic control are modeled and compared with experimental data to provide justification for the same. This work stresses the need for experiments for accurate determination of transfer coefficients and the exchange current density before reasoning kinetic hysteresis for the potential gap in Li-Si system. The silicon electrode particle model enables one to analyze the influence of diffusion in the solid phase, particle size, and kinetic parameters without interference from other components in a practical porous electrode. Concentration profiles within the silicon electrode particle under galvanostatic control are investigated. Sluggish kinetics is established from cyclic voltammograms at different scan rates. Need for accurate determination of exchange current density for lithium insertion in silicon nanoparticles is discussed. This model and knowledge thereof can be used in cell-sandwich model for the design of practical lithium ion cells with composite silicon negative electrodes. Secondly, galvanostatic charge and discharge of a silicon composite electrode/separator/ lithium foil is modeled using porous electrode theory and concentrated solution theory. Porosity changes arising due to large volume changes in the silicon electrode with lithium insertion and de-insertion are included and analyzed. The concept of reservoir is introduced for lithium ion cells to accommodate the displaced electrolyte. Influence of initial porosity and thickness of the electrode on utilization at different rates is quantitatively discussed. Knowledge from these studies will guide design of better silicon negative electrodes to be used in dual lithium insertion cells for practical applications.

Interessante Optionen in der dezentralen Energieversorgung ergeben sich mit dem Einsatz von erdgasbetriebenen Gas-Otto-Motor-, Mikrogasturbinen-, Stirlingmotor- und PEMFC-Modulen. In dem Zusammenhang ist zu beachten, dass die Nutzungsmöglichkeiten dieser KWK-Systeme auch durch die elektrischen und thermischen Bedarfswerte und -strukturen der zu versorgenden Objekte bestimmt werden. Der Schwerpunkt dieser Arbeit ist, neben einer experimentellen und theoretischen Untersuchung ausgewählter KWK-Module, die vergleichende Bewertung von KWK-Anwendungen in der Hausenergieversorgung. Am Beispiel der Energieversorgung von Modell-Siedlungen nach VDI 2067-7 wird der stationäre Betrieb der untersuchten KWK-Module im bi- und polyvalenten Einsatz nachgebildet und bilanziert. Zur Bewertung der KWK-Konzepte erfolgt ein Vergleich zu einer konventionellen Energieversorgungsstrategie mit getrennter Bereitstellung elektrischer und thermischer Energie. Als Indikatoren zur Beurteilung der dezentralen Energieversorgungsvarianten dienen definierte energetische, ökologische und ökonomische Faktoren. Im Rahmen von Simulationsanalysen wird die Bedeutung der Integrations- und Einsatzweise der KWK-Module untersucht. Ein Variantenvergleich der Energieversorgungsstrategien verdeutlicht, welche Einsatzmöglichkeiten der KWK-Module für die untersuchte Struktur der Hausenergieversorgung beim gegenwärtigen Stand der Technik zweckmäßig sind.