Many modeling studies have been carried out to simulate the current distribution across the channel and shoulder direction in a proton exchange membrane (PEM) fuel cell. However the modeling results do not show agreement on the current density distribution. At the same time, no experimental measurement result of current density distribution across the channel and the shoulder direction is available to testify the modeling studies. Hence in this work, an experiment was conducted to separately measure the current densities under the channel and the shoulder in a PEM fuel cell by using the specially designed membrane electrode assemblies. The experimental results show that the current density under the channel is lower than that under the shoulder except when the fuel cell load is high. Afterwards two more experiments were carried out to find out the reason causing the higher current density under the shoulder. The effects of the electric resistance of gas diffusion layer (GDL) in the lateral and through-plane directions on the current density distribution were studied respectively. The experimental results show that it is the through-plane electric resistance that leads to the higher current density under the shoulder. Moreover, a three-dimensional fuel cell model is developed using FORTRAN. A new method of combining the thin-film model and homogeneous model is utilized to model the catalyst layer. The model is validated by the experimental data. The distribution of current density, oxygen concentration, membrane phase potential, solid phase potential and overpotential in a PEM fuel cell have been studied by the model. The modeling results show that the new modeling method provides better simulations to the actual transport processes and chemical reaction in the catalyst layer of a PEM fuel cell.

In this dissertation, new high frequency link power conversion systems for the fuel cell power conditioning are proposed to improve the performance and optimize the cost, size, and weight of the power conversion systems. The first study proposes a new soft switching technique for the phase-shift controlled bi-directional dc-dc converter. The described dc-dc converter employs a low profile high frequency transformer and two active full-bridge converters for bidirectional power flow capability. The proposed new soft switching technique guarantees soft switching over wide range from no load to full load without any additional circuit components. The load range for proposed soft switching technique is analyzed by mathematical approach with equivalent circuits and verified by experiments. The second study describes a boost converter cascaded high frequency link direct dc-ac converter suitable for fuel cell power sources. A new multi-loop control for a boost converter to reduce the low frequency input current harmonics drawn from the fuel cell is proposed, and a new PWM technique for the cycloconverter at the secondary to reject the low order harmonics in the output voltages is presented. The performance of the proposed scheme is verified by the various simulations and experiments, and their trade-offs are described in detail using mathematical evaluation approach. The third study proposes a current-fed high frequency link direct dc-ac converter suitable for residential fuel cell power systems. The high frequency full-bridge inverter at the primary generates sinusoidally PWM modulated current pulses with zero current switching (ZCS), and the cycloconverter at the secondary which consists of only two bidirectional switches and output filter capacitors produces sinusoidally modulated 60Hz split single phase output voltage waveforms with near zero current switching. The active harmonic filter connected to the input terminal compensates the low order input current harmonics drawn from the fuel cell without long-term energy storage devices such as batteries and super capacitors.

This thesis deals with modeling of two types of fuel cells:the polymer electrolyte fuel cell (PEFC) and the directmethanol fuel cell (DMFC), for which we address four majorissues: a) mass transport limitations; b) water management(PEFC); c) gas management (DMFC); d) thermal management. Four models have been derived and studied for the PEFC,focusing on the cathode. The first exploits the slenderness ofthe cathode for a two-dimensional geometry, leading to areduced model, where several nondimensional parameters capturethe behavior of the cathode. The model was extended to threedimensions, where four di.erent flow distributors were studiedfor the cathode. A quantitative comparison shows that theinterdigitated channels can sustain the highest currentdensities. These two models, comprising isothermal gasphaseflow, limit the studies to (a). Returning to a two-dimensionalgeometry of the PEFC, the liquid phase was introduced via aseparate flow model approach for the cathode. In addition toconservation of mass, momentum and species, the model wasextended to consider simultaneous charge and heat transfer forthe whole cell. Di.erent thermal, flow fields, and hydrodynamicconditions were studied, addressing (a), (b) and (d). A scaleanalysis allowed for predictions of the cell performance priorto any computations. Good agreement between experiments with asegmented cell and the model was obtained. A liquid-phase model, comprising conservation of mass,momentum and species, was derived and analyzed for the anode ofthe DMFC. The impact of hydrodynamic, electrochemical andgeometrical features on the fuel cell performance were studied,mainly focusing on (a). The slenderness of the anode allows theuse of a narrow-gap approximation, leading to a reduced model,with benefits such as reduced computational cost andunderstanding of the physical trends prior to any numericalcomputations. Adding the gas-phase via a multiphase mixtureapproach, the gas management (c) could also be studied.Experiments with a cell, equipped with a transparent end plate,allowed for visualization of the flow in the anode, as well asvalidation of the two-phase model. Good agreement betweenexperiments and the model was achieved. Keywords:Fuel cell; DMFC; PEFC; one-phase; two-phase;model; visual cell; segmented cell; scale analysis; asymptoticanalysis.

The corrosion of current collector materials in MoltenCarbonate Fuel Cells (MCFC) is investigated. The essential aimsof this investigation were to study the corrosion behaviour ofdifferent materials, in varying cathode and anode MCFCenvironments, and to study the contact corrosion resistancesbetween the MCFC current collector and electrodes. For thesepurposes, pure iron, iron-chromium binary alloys and severalcommercial steels were investigated in molten carbonate meltswithin the pot-cell laboratory set-up. In addition, the contactcorrosion resistances, between an AISI 310 current collectorand two cathodes (NiO and LiCoO2), were studied in a laboratory fuel cell.Post-tests were done to study the corrosion products formed atthe surfaces. In cathode environments, corrosion potential increased overtime as a protective corrosion layer slowly formed. Eventually,the potential reached a stable value close to the cathodeoperating potential. The main cathode reaction, as corrosionpotential increased, changed from water reduction to oxygenreduction. Corrosion rate under the operating cathode conditiondepended on the chromium content; the higher the concentrationof chromium, the lower the corrosion rate. The corrosion ratesof ferritic steels, with high chromium content, and AISI 310were higher at the so-called outlet operating condition incomparison to the standard and so-called inlet conditions. Thecorrosion rate was higher at the beginning of the exposure,which resulted in a relatively fast corrosion layer growth thatslowed as the protective layer was formed. It was shown thatthe corrosion layers, formed on iron-chromium alloys, AISI 310and ferritic high chromium-containing steels, consisted of twolayers. The outer layer was porous and iron rich, while theinner layer was quite compact and rich in chromium and/oraluminiumTherefore, the corrosion behaviour was dependent onthe corrosion layer structure at the metal surface. In anode environments, the beneficial behaviour of aluminiumin ferritic alloys, with high aluminium contents, was due tothe formation of aluminium oxide and/or lithium aluminium oxideat the surface. The corrosion rates at the standard and outletconditions were of the same order of magnitude, while thecorrosion rates at the inlet conditions were considerablyhigher. The lower temperatures and higher carbon dioxideconcentrations in the inlet conditions appeared to result in asurface layer deficient in aluminium. A modified theoreticalmodel was developed to evaluate the corrosion current densitiesfrom experimental polarisation curves or linear polarisationresistance measurements in anode environments. The fittingswere found to be very good. An experimental method was developed forin-situmeasurements of the contributions to the totalohmic losses at the cathode in a laboratory scale MCFC. Thecontact resistance between the cathode and current collectorcontributed quite a large value to the total cathodepolarization. The corrosion layer, formed between the LiCoO2cathode and AISI 310 current collector, wasiron-rich and more porous, and contained a small amount ofcobalt. This was deemed to consist of a two-phase oxide, whichresulted in a lower conductivity. The corrosion layer, formedbetween the NiO cathode and AISI 310 current collector, wasrich in nickel. The corrosion layers on the AISI 310, incontact with the cathode, had a different composition comparedto samples immersed in carbonate melts. <b>Key words</b>: molten carbonate fuel cell (MCFC), corrosion,current collector, contact corrosion resistance.

Vehicles powered by fuel cells are from an environmentalaspect superior to the traditional automobile using internalcombustion of gasoline. Power systems which are based upon fuelcell technology require hydrogen for operation. The ideal fuelcell vehicle would operate on pure hydrogen stored on-board.However, storing hydrogen on-board the vehicle is currently notfeasible for technical reasons. The hydrogen can be generatedon-board using a liquid hydrogen carrier such as methanol andgasoline. The objective of the work presented in this thesiswas to develop a catalytic hydrogen generator for automotiveapplications using methanol as the hydrogen carrier. The first part of this work gives an introduction to thefield of methanol reforming and the properties of a fuel cellbased power system. Paper I reviews the catalytic materials andprocesses available for producing hydrogen from methanol. The second part of this thesis consists of an experimentalinvestigation of the influence of the catalyst composition,materials and process parameters on the activity andselectivity for the production of hydrogen from methanol. InPapers II-IV the influence of the support, carrier andoperational parameters is studied. In Paper V an investigationof the catalytic properties is performed in an attempt tocorrelate material properties with performance of differentcatalysts. In the third part of the thesis an investigation isperformed to elucidate whether it is possible to utilizeoxidation of liquid methanol as a heat source for an automotivereformer. In the study which is presented in Paper VI a largeseries of catalytic materials are tested and we were able tominimize the noble metal content making the system more costefficient. In the final part of this thesis the reformer prototypedeveloped in the project is evaluated. The reformer which wasconstructed for serving a 5 kWe fuel cell had a highperformance with near 100 % methanol conversion and COconcentrations below 1 vol% in the product stream. The resultsof this part are presented in Paper VII. <b>Keywords:</b>methanol, fuel cell, vehicle, catalyst,copper, hydrogen, on-board, steam reforming, partial oxidation,combined reforming, oxidative steam reforming, auto-thermalreforming, zinc, zirconium, chromium, aluminium oxide,manganese, characterization, temperature programmed reduction,X-ray diffraction, chemisorption, carbon monoxide, poisoning,reformer.

In this work characterisation methods and fuel cell hardwarewere developed for studying the components of the polymerelectrolyte fuel cell (PEFC). Humidifiers and other componentswere tested in order to develop reproducible and reliableexperimental techniques. A set-up for testing larger cells andstacks was developed. A new type of polymer electrolyte membrane fuel cell wasdeveloped for laboratory investigations. Current collectormaterial and gas flow channels can easily be modified in thisconstruction. The electrode potentials can be measured at thegas backing layers, thereby allowing measurement of contactresistances. The use of a reference electrode is alsopossible. Contact resistances were studied in situ as a function oftime, clamping pressure, gas pressure and current density.Ex-situ measurements were used to validate the in-situ contactresistance measurements. The validity and error sources of theapplied in-situ measurement methods with reference electrodesand potential probes were studied using both computersimulations and experiments. An in-house membrane electrode assembly (MEA) productionline was developed. In-house produced MEAs were utilised inboth membrane degradation and mass transport studies. The durability testing of PVDF based membranes membranes wasstudied both by fuel cell experiments and ex-situ testing.Raman spectra were measured for used membranes. A current distribution measurement method was developed. Theeffect of inlet humidification and gas composition at thecathode side was studied. In addition, two different flow fieldgeometries were studied. The results of current distributionmeasurements were used to validate a PEFC model. Methods for characterising gas diffusion layer (GDL)performance by fuel cell testing and ex-situ measurements weredeveloped. The performance of GDL materials was tested withvarying cell compression and cathode humidity. Porosity, poresize distribution and contact angle were determined. Electricalcontact resistance, thermal impedance and gas permeabilitieswere measured at different compression levels. Development work on a stack with stainless steel net wascarried out as well as characterisation studies of differentstack components. Thermal impedances and flow fieldpermeability were measured. Mass transport limitations in the cathodes were studied byvarying the electrode thickness, partial pressure and humidityof oxygen. <b>Keywords:</b>polymer electrolyte membrane fuel cell (PEFC),contact resistance, clamping pressure, stainless steel,membrane degradation, current distribution, gas diffusionlayer, stack, thermal impedance, permeability.

Computational methods are combined with synchrotron-based techniques to analyze the structure and bonding of water and water plus hydroxyl at metal surfaces under UHV and at near-ambient conditions. Water-metal interaction plays a crucial role in a multitude of cosmic, atmospheric and biological phenomena as well as heterogeneous catalysis, electrochemistry and corrosion. A spotlight of renewed interest has recently been cast on water-metal systems due to their relevance for surface chemical reactions related to the production and utilization of hydrogen as a clean energy carrier. In particular, H2O and OH are essential reaction intermediates in the renewable production of hydrogen from sunlight and water and in fuel cell electrocatalysis. Fuel cells are considered one of the most promising power generation technologies for a sustainable energy future. A mechanistic understanding of the oxygen reduction reaction (ORR) pathway, including the role of electronic and geometric structure of the catalyst, is essential to the design of more efficient fuel cell catalysts. This is intimately connected to fundamental factors that affect the ability to form water-metal bonds as well as the site occupation and orientation of the adsorbed H2O and OH at active metal surfaces. Key relationships related to critical issues in the fuel cell reaction are illuminated by the synergy of theory and experiment in this thesis. We emerge with a detailed understanding of the structure of the water-metal interface and the factors that rule the wettability of a metal surface, including geometric and electronic structure effects and the influence of coadsorbed species. We show that the preferred microscopic orientation of the water monolayer has consequences for macroscopic properties, and reveal the origin of the hydrophobic water layer. Finally, we identify a cooperativity effect that drives the stability of the mixed water/hydroxyl layer at metal surfaces, an important ORR intermediate.

The thesis is focussed on the performance of the fuel cell and the design of the cell for operation with natural gas and renewable fuels, e.g. biogas or gasified biomass. The performance is one of the important issues for the development and commercialisation of fuel cell stacks. In order to operate fuel cell on renewable fuels, without preceding reforming of the fuel, a high temperature fuel cell is needed, i.e. a solid oxide fuel cell (SOFC) or a molten carbonate fuel cell (MCFC). At present, the latter fuel cell type is much more mature when regarding the technical aspects than is the solid oxide fuel cell. The German company MTU has up to date installed about thirty MCFC plants, mainly in Europe and the USA but also in Japan. Moreover the European Commission has decided that the use of renewable fuels must increase at the expense of fossil fuels. This decision is one step towards a smaller dependence on fossil energy sources and limited emissions of greenhouse gases. The objective of this work is to better understand the factors that influence the cell performance: to determine the kinetic parameters of the hydrogen oxidation and the carbon monoxide oxidation and to get more information about the reaction mechanism, even when dealing with gases of low hydrogen content. The latter is of special importance when operating the cells on biogas or gasified biomass. These fuels also contain higher concentrations of carbon monoxide and carbon dioxide. It was found that the hydrogen mechanism proposed by Jewulski and Suski describes the anode performance even at lower concentrations of hydrogen, i.e. gases corresponding to gasified biomass. Furthermore, the carbon monoxide reaction will only slightly influence the anode performance but if the rate of the shift reaction is small the influence of direct oxidation of carbon monoxide will increase. Experimental investigations have shown that mass transfer limitations in the gas phase exist. By mathematical modelling it was found that the current collector has a larger affect on the concentration gradients than the porous electrode. The concentrations gradients in the current collector are caused by the shift reaction that mainly takes place at the electrode. However, if the gas corresponds to equilibrium at the current collector the profiles will become almost uniform. Furthermore the influence of wetting properties, the pore structure and pore size distribution have also been investigated in this thesis. The outcome of this thesis may be used for electrode development and design, as well as for input to reliable cell and stack models for system simulations. / QC 20101008

Excessive water formation inside the polymer electrolyte membrane (PEM) fuel cell’s structures leads to the flooding of the cathode gas diffusion layer (GDL) and cathode gas flow channels. This results in a negative impact on water management and the overall cell performance. Liquid water generated in the cathode catalyst layer and the water moved from anode to cathode side due to electro-osmotic drag transport through the GDL to reach the gas flow field channels, where it is removed by air cathode gas stream. Due to high and uniform capillary force distribution effect of the pores through the GDL plane and surface tension between the water droplets and gas flow field channels surfaces, liquid water tends to block/fill the pores of the GDL and stick to the surface of the GDL and gas flow channels. Therefore, it is difficult to remove the trapped water in GDL structure which can lead to flood of the PEM fuel cell. The GDL surfaces are commonly treated uniformly with a hydrophobic material in order to overcome the flooding phenomena inside PEM fuel cell. Despite the importance impact of the surface wettability of both channel and GDL surface characteristics especially for the cathode side on the water management, few experimental studies have been conducted to investigate the effect of the two-phase flow in cathode gas flow channel and their crucial role. The work presented in this thesis covers contributions that provide insight, not only into the investigation of the effects of hydrophobic cathode GDL and cathode gas flow channels, on water removal, two phase flow inside the channel, and on PEM fuel cell performance, but also the superhydrophobic and superhydrophilic GDLs and gas flow channels effects. Further, the effects of a novel GDL designs with sandwich and gradient wettability with driving capillary force through GDL plane have been investigated. Two-phase flow especially in the cathode gas flow field channels of PEM fuel cell has a crucial role on water removal. Hence, in this research, ex-situ investigations of the effects of channels with different surface wettability; superhydrophobic, hydrophobic, slightly hydrophobic, and superhydrophilic on the two-phase flow characteristics have been tested and visualized at room temperature. Pressure drop measurements and two-phase flow visualization have been carried out using high speed camera. The effect of the various coating materials on graphite and GDL surface morphology, roughness, static contact angle (θ), and sliding contact angle (α) have been investigated using scanning electron microscopy (SEM), Profilometry, and sessile drop technique, respectively. It has been observed that the two-phase flow resistance is considerably affected by surface wettability of the channels. Further, the overall cell performance can be improved by superhydrophobic gas flow channels mainly at high current density over slightly hydrophobic and superhydrophilic cases tested. In addition, sandwich wettability GDL has been coated with a silica particle/ Polydimethylsiloxane (PDMS) composite. The porometric characteristics have been studied using, method of standard porosimetry (MSP). It has been found that sandwich wettability GDL has superhydrophobic surfaces with (θ = 162±2°), (α = 5±1°), and the internal pores are hydrophilic, while the mean pore radius is 7.1μm. This shows a low resistance to gas transport. On the other hand, performance testing indicates that (PEM) fuel cell equipped with sandwich wettability GDL results in the best performance compared to those with raw (non-coated) (slightly hydrophobic), PTFE coated (commercial with micro-porous layer (MPL)) (superhydrophobic), and silica coated (superhydrophilic) GDL. The wettability gradient has been introduced through plane of the one side hydrophobic GDL by coating one side of non-coated GDL with 15 wt. % of PTFE solution; however, the other side remains uncoated. The effects of wettability gradient on the water removal rate, droplet dynamics, and PEM fuel cell performance have been covered in this thesis. Water removal rate is determined using a 20 ml syringe barrel, wherein a 13 mm diameter GDL token is fixed on the barrel opening. The droplets penetrating through the GDL are visualized via a high speed camera to study the droplets’ dynamic characteristics. The GDL wettability gradient has a significant impact on water removal rate, droplets’ dynamic characteristics, and consequently enhances the overall PEM fuel cell performance.

Proton exchange membrane fuel cell (PEMFC) is a potential alternative energy conversion device for stationary and automotive applications. Wide commercialization of PEMFC depends on progress that can be achieved to enhance its reliability and durability along with cost reduction. It is desirable to operate the PEMFC at uniform local current density and temperature distributions over the surface of the membrane electrode assembly (MEA). Non-uniform distributions of both current and temperature over the MEA could result in poor reactant and catalyst utilization as well as overall cell performance degradation. Local current distribution in the PEMFC electrodes are closely related to operating conditions, but it is also affected by the organization of the reactant flow arrangements in PEMFCs. Reactant depletion and water formation along the flow channel leads to current variation from the channel inlet to the exit, which leads to non-uniformity of local electrochemical reaction activity, and degradation of the cell performance. Flow arrangements between the anode and cathode streams, such as co-, counter- and cross- flow can exacerbate the effect of the non-uniformity considerably, producing complex current distribution patterns over the electrode surfaces. Thus, understanding of the local current density and its spatial characteristics, as well as the temperature distributions under different physical and operating conditions, is crucially important in order to develop optimum design and operational strategies. Despite the importance of the influence of the flow arrangement on the local current and temperature distributions under various operating conditions, few systematic studies have been conducted experimentally to investigate this effect. In this research, an experimental setup with special PEMFC test cells are designed and fabricated in-house, in order to conduct in-situ mapping of the local current and temperature distributions over the electrode surfaces. A segmented flow field plate and the printed circuit board (PCB) technique is used to measure the current distribution in a single PEMFC. In situ, nondestructive temperature measurements are conducted using thermocouples to determine the actual temperature distribution. Experimental studies have been conducted to investigate the effect of different flow arrangements between the anode and cathode (co-, counter-, and cross- flow) on the local current density distribution over the MEA surface. Furthermore, local current distribution has been characterized for PEMFCs under various operating conditions such as reactant stoichiometry ratios, reactant backpressure, cell temperature, cell potentials, and relative humidity for each one of the reactant flow arrangements. The dynamic characteristics of the local current in PEMFC under different operating conditions also have been studied. Temperature distributions along the parallel and serpentine flow channels in PEMFs under various operating conditions are also investigated. All independent tests are conducted to identify and optimize the key design and operational parameters for both local current and temperature distributions. It has been found that the local current density distribution is strongly affected by the flow arrangement between the anode and cathode streams and the key operating conditions. It has also been observed that the counter-flow arrangement generates the most uniform distribution for the current density, whereas the co-flow arrangement results in a considerable variation in the current density from the reactant gas stream inlet to the exit. Low stoichiometry ratio of hydrogen at the anode side has a predominant effect on the current distribution and cell performance. Further, it has been found that the dynamic characteristics and the degree of fluctuation of local current density inside PEMFC are strongly influenced by the crucial operating conditions. In-situ, nondestructive temperature measurements indicate that the temperature distribution inside the PEMFC is strongly sensitive to the cell’s current density. The temperature distribution inside the PEMFC seems to be virtually uniform at low current density, while the temperature variation increases up to 2 oC at the high current density. Finally, the present work contribution related to the local current and temperature distributions is required to understand the effect of each individual or even several operating parameters combined together on the local current and temperature distributions. This will help to develop an optimum design, which leads to enhancing the reliability and durability in operational PEMFCs.