Solid oxide fuel cells with graded electrodes consisting of multiple composite layers yield generally lower polarization resistances than single layer composite electrodes. Optimization of the performance of solid oxide fuel cells with graded electrode composition and/or microstructure requires an evaluation of both the three phase boundary length per unit volume and the effective diffusion coefficient in order to provide insight into how these properties vary over the design space. A numerical methodology for studying the three phase boundary length and effective diffusivity in composite electrode layers with controlled properties is developed. A three dimensional solid model of a sintered composite electrode is generated for which the mean particle diameter, composition, and total porosity may be specified as independent variables. The total three phase boundary length for the modeled electrode is calculated and tomographic methods are used to estimate the fraction of this length over which the electrochemical reactions can theoretically occur. Furthermore, the open porosity of the modeled electrode is identified and the effective diffusion coefficient is extracted from the solution of the concentration of the diffusing species within the open porosity. Selected example electrode models are used to illustrate the application of the methods developed, and the resulting connected three phase boundary length and diffusion coefficients are compared. A significant result is the need for thickness-specific effective diffusivity to be determined, rather than the general volume averaged property, for electrodes with porosity between the upper and lower percolation thresholds. As the demand for current increases, more of the connected three phase boundaries become active, and therefore a greater fraction of the electrode layer is utilized for a given geometry, resulting in a higher apparent effective diffusivity compared to the same electrode geometry operating at a lower current. The methods developed in this work may be used within a macroscopic electrode performance model to investigate optimal designs for solid oxide fuel cell electrodes with stepwise graded composition and/or microstructure.

A numerical model of the steady state and alternating current behaviour of a solid-oxide fuel cell is presented to explore the possibilities to diagnose and identify degradation mechanisms in a minimally invasive way using impedance spectroscopy. This is the first report of an SOFC impedance model to incorporate degradation, as well as the first one to include the ribbed interconnect geometry, using a 2-D approximation. Simulated degradation modes include: electrode/electrolyte delamination, interconnect oxidation, interconnect/electrode interface detachment, and anode sulfur poisoning. Detailed electrode-level simulation replaces the traditional equivalent circuit approach, allowing the simulation of degradation mechanisms that alter the shape of the current path. The SOFC impedance results from calculating the cell response to a small oscillatory perturbation in potential. Starting from the general equations for mass and charge transport, and assuming isothermal and isobaric conditions, the system variables are decomposed into a steady-state component and a small perturbation around the operating point. On account of the small size of the imposed perturbation, the time dependence is eliminated, and the original equations are converted to a new linear, time independent, complex-valued system, which is very convenient from a numerical viewpoint. Geometrical and physical modifications of the model simulate the aforementioned degradation modes, causing variations in the impedance. The possibility to detect unique impedance signatures is discussed, along with a study of the impact of input parameter inaccuracies and parameter interaction on the presented results. Finally, a study of pairs of concurrent degradation modes reveals the method’s strengths and limitations in terms of its diagnosis capabilities.

Humidity sensors are one of the most widely used sensors in commercial and industrial applications for environmental monitoring and controlling. Although related technology have been studied intensively, humidity sensing in harsh environments still remains a challenge. The inability of current humidity sensors to operate in high temperature environments is generally due to the degradation of the sensing films caused by high temperature, high humidity level, and/or contamination. Our goal is the design and fabrication of a humidity sensor that is capable of working under high temperatures and in a condensing environment. The targeted application of this sensor is in the polymer electrolyte membrane (PEM) fuel cell, where humidity control is crucial for performance optimization. In this work, ordered macroporous silicon is thoroughly studied as a humidity sensing layer. In addition to the advantages of traditional porous silicon for gas sensing (high resistance to high temperature and good compatibility with current IC fabrication process), the ordered macroporous silicon used in these experiment has uniform pore size, pore shape and distribution. All the vertical aligned pores can be opened to the environment at both ends, which can significantly increase the efficiency of gas diffusion and adsorption. Moreover, this special structure opens the door to uniform surface modifications for sensing enhancement. Both ordered macroporous silicon based heterostructure and self-supporting membrane are fabricated and investigated as a humidity sensor. Heterostructure sensors with different thin film surface coatings including bare Si, thermally grown SiO2, atom layer deposited ZnO, HfO2, and Ta2O5 are characterized. Post micro-fabrication is achieved on this ordered porous structure without affecting the material and its sensing properties. It has been proven that the ordered macroporous silicon with Ta2O5 surface coating shows the best sensing property due to its ultra-hydrophilic surface. The sensor shows high sensitivity, fast response times, small hysteresis, and extraordinary stability and repeatability under high temperatures and in condensing environment. It demonstrates great potential and advantages over existing commercial humidity sensors in the fuel cell application field. In addition to ordered macroporous silicon, well aligned 1D ZnO nanorods/nanowires -another widely used nanostructure in gas sensing- is also investigated as humidity sensing materials. Both vertically and laterally aligned nanorods/nanowires are fabricated and tested against humidity changes. The sensors shows increasing resistance to increasing relative humidity, which is contrary to most published works so far. Possible mechanisms have been proposed in this thesis and future work has been suggested for further study. To the best of our knowledge, this work is the first to use ordered macroporous silicon and well aligned 1D ZnO nanorods/nanowires for humidity sensing.

The durability and performance of commercially available polymer electrolyte membrane fuel cell (PEMFC) technology depends heavily on adequate humidification of the membrane electrode assembly (MEA). Early generation automotive fuel cell stacks will likely rely on an external humidification process based on gas-to-gas membrane planar humidifiers to humidify the inlet cathode stream. The membrane-based humidifier systems allow the reactants to receive recycled heat and moisture from the cathode outlet stream. The objective of this thesis is to develop a flexible, computer-based simulation tool that can be used to aid in the design of these planar humidifier systems. The simulation is based on fundamental mass transfer concepts and experimental membrane behaviour based on literature results. It was determined that the mass transfer resistance through the membrane is several orders of magnitude higher than the resistance contributed by the gas diffusion media (GDM) and thus the mass transfer resistance through the GDM are not considered. An important point to note is that the Schroeder’s Paradox observed in perfluorosulfonic acid (PFSA) membranes implies that membranes in contact with liquid water will exhibit higher mass transfer than membranes in contact with saturated water vapour despite the fact that the water activity in both situations are unity. Initial simulations for which no liquid water was present resulted in a humidifier water transfer rate less than half the rate observed experimentally. Thus it was hypothesized that condensed liquid water was present on the wet-side of the humidifier membrane and as such this work assumes a fraction of the membrane surface is covered by liquid water while the rest of the membrane is exposed to gaseous water concentrations comparable to the bulk channel stream above the GDM. For typical operating conditions the outlet wet-side stream retains 92% of the inlet water content and as such it was hypothesized that constant fractional liquid water coverage across the membrane could be assumed. Later simulations confirmed the validity of this hypothesis. Six models of water coverage estimation were derived using least squares and factorial design methods. The models were compared however no single method was determined to be superior for all situations as the methods exhibit similar sums of squared error.

Research was performed on the development of relationships between the microstructure of nickel and yttria-stabilized zirconia (YSZ) coatings and the processing parameters used for their deposition by atmospheric plasma spraying (APS). Research was also performed on the development of relationships between the microstructure of plasma sprayed Ni-YSZ coatings and the electrochemical performance of metal-supported solid oxide fuel cells (SOFCs) incorporating these coatings as anodes. Three APS processes were used to deposit Ni-YSZ coatings: dry-powder plasma spraying (DPPS), suspension plasma spraying (SPS), and solution precursor plasma spraying (SPPS). These processes differ in the form of the feedstock injected into the plasma. The composition of the Ni-YSZ coatings deposited with each spray process could be controlled through adjustment of the plasma gas composition and stand-off distance, as well as adjustment of feedstock properties including agglomerate size fraction for DPPS, NiO particle size and suspension feed rate in SPS, and the enthalpy of decomposition of the precursors used in SPPS. The porosity of the Ni-YSZ coatings could be controlled through the addition of a sacrificial pore forming material to each feedstock, with coating porosities up to approximately 35% being achieved for each coating type. Metal-supported SOFCs were fabricated to each have anodes deposited with a different plasma spray process, where all anodes had nominally identical composition. The microstructures obtained for each anode type were distinctly different. SPPS led to the most uniform mixing of the smallest Ni and YSZ particles. These anodes most resembled typical structures from anodes fabricated using conventional methods. It was found that the polarization resistance, Rp, associated with the high frequency (> 1 kHz) range of the impedance spectrum correlated to the three phase boundary length (TPBL) density of each anode, with lower Rp values corresponding to higher TPBL densities. It was also found that the Knudsen diffusion coefficient and effective ordinary diffusion coefficient of the porous anodes correlated with the Rp associated with the low frequency (< 1 kHz) range of the impedance spectrum. Therefore, the impedance spectrum can be used to compare microstructural differences among plasma sprayed Ni-YSZ anodes.

This study investigated the overpotential performance enhancement of cathodes in low temperature solid oxide fuel cells (LT-SOFCs) due to the addition of carbonates to traditional Ce0.9Gd0.1O2 solid oxide fuel cell (SOFC) electrolytes. It was postulated in this study that this enhancement was due to the protonic conductivity of the carbonates. This provided an electrolyte with a dual conduction mechanism which improves the catalytic performance of the cathode. The cathode systems investigated were characterised for overpotential loss, conductivity and thermal expansion matching with the electrolyte. This produced results which predicted power outputs for a standard SOFC configuration as high as 970, 524 and 357 mW/cm2 at operational temperatures of 650oC, 600oC and 550oC. The benefits of these high power outputs and their potential to further reduce SOFC operational temperature was discussed. This study developed a cost-effective, reliable and commercially scalable manufacturing process for carbonate/Ce0.9Gd0.1O2 electrolytes. This pressureless sintering method is the first reported in literature, and is a promising replacement for the current hot-pressing technique currently used for these electrolytes. The electrolyte composition examined was 70 wt% Ce0.9Gd0.1O2 with 30 wt% carbonates (67 mol% Li2CO3 / 33 mol% Na2CO3). The cathode examined in this study was a composite cathode consisting of 50-90 wt% functional cathode material (Gd1-xSrxCoO3 with 10 to 30 mol% Sr doping on the Gd site) with a balance of electrolyte. It was determined that the composite cathode system with 10 wt% electrolyte and 20-30 mol% Sr doping was the optimal composition when operating at 600oC and above, with predicted power densities of 524 and 510 mW/cm2 at 600oC. At operational temperatures between 550oC and 600oC (and potentially lower), it was determined that a composite cathode system with 30 wt% electrolyte and 10-30 mol% Sr doping was the optimal composition. It was found that the presence of carbonates in the electrolyte decreased the overpotential losses of the cathode by 50-70% at 600oC for system studied; indicating that an improvement in cathodic performance coupled with the high conductivities of the electrolyte is most likely responsible for the high power outputs seen in literature. / Thesis (Ph.D, Mechanical and Materials Engineering) -- Queen's University, 2009-04-25 15:53:37.928

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Alkaline fuel cells (AFC's) using renewable fuels are a developing technology capable of meeting market niches in standby, standalone and distributed power generation. AFC's generate electricity, heat and water using hydrogen and oxygen as fuels. While AFC's have been known and the principles demonstrated for over sixty years, their use has been restricted primarily to space applications. Recent technological developments have seen the cost of AFC stacks fall considerably; this together with several other advantages over competing fuel cell technology, has rekindled interest in commercial systems. The main deterrent to wide spread commercialisation of AFC systems is susceptibility to carbon dioxide (CO2) in atmospheric air used as the oxygen supply. AFC's require a low cost, low energy, continuous scrubbing device to reduce CO2 in air from approximately 380 parts per million (ppm) atmospheric concentration to below 50 ppm. Current technology to overcome this problem, a solid expendable absorbent called soda lime, is not viable for commercial systems. The project scope included concept generation of a device to remove CO2 from air, the development of a CO2 measurement technique, investigation of chemistry and flow phenomena to determine design relations, and product design and embodiment. The scrubber system conceived specifically for AFC systems uses the temperature swing chemistry of a liquid chemical absorbent, monoethanolamine, and a packed bubble column apparatus to provide intimate gas-liquid interaction. Prototype development proved the Carbon Dioxide Continuous Scrubber (CDOCS) concept and a Patent Cooperation Treaty (PCT) patent was granted, followed by a full American patent. A gas chromatographic measurement technique was developed to measure low ppm concentration CO2 in air, enabling regular monitoring of scrubbed gas. Carbon dioxide was separated from a small sample of scrubbed air by chromatographic columns, and the gases analysed with a thermal conductivity detector. The GC system was capable of measuring to 10 ppm with good resolution and accuracy. Experimental studies were carried out to characterise the flow dynamics and absorption phenomena in the packed bubble column absorber. The relationship between absorption performance and gas-liquid contact time, an important operating parameter for use with AFC's, was theoretically determined and later confirmed by experiment. The regeneration process was studied and the optimal regenerator design determined to be second, smaller packed bubble column. Experiments were conducted to establish design relations for regeneration temperature, flush gas flow rate and the effect of multiple regeneration cycles. A prototype CDOCS system was built to enable experimental characterisation of scrubbing performance as a function of primary design and operating parameters including liquid depth, regenerator operating temperature and solution composition. This resulted in a good understanding of the system, and an optimised experimental run was performed for cost and performance comparison to existing scrubbing technology. The CDOCS was capable of reducing CO2 in air from 380 to 80 ppm for thirty days, providing low cost, low maintenance scrubbing compared to soda lime. The capital cost of the CDOCS is considerably more than for soda lime scrubbers, and the penalty for extended operation is parasitic power consumption by the CDOCS system totalling less than 7% of fuel cell output. It is suggested that a combination of the two technologies be used initially to provide effective, low cost scrubbing for AFC and CDOCS co-development. Future work on the CDOCS project should include reduction of chemical vapour carry over to the fuel cell, followed by integration with an AFC system. This would allow further development, refinement and design for production to reduce capital cost.