Polymer electrolyte membrane fuel cells (PEMFCs) have recently acquired much attention as alternatives to combustion engines for power conversion. The primary interest in fuel cell technology is the possibility of 60% power conversion efficiency as compared to the 30% maximum theoretical efficiency limited to combustion engines and turbines. Although originally conceived to work with hydrogen as a fuel, difficulties relating to hydrogen storage have prompted much effort in using other fuels. Small organic molecules such as alcohols and formic acid have shown promise as alternatives to hydrogen in PEMFCs due to their higher stability at ambient conditions. The drawbacks for using these fuels in PEMFCs are related to their incomplete oxidation mechanisms, which lead to the production of carbon monoxide (CO). When carbon monoxide is released in fuel cells it binds strongly to the platinum anode thus limiting the adsorption and subsequent oxidation of more fuel. In order to promote the complete oxidation of fuels and limit poisoning due to CO, various metal and metal oxide catalysts have been used. Motivated by promising results seen in fuel cell catalysis, this research project is focused on the design and fabrication of novel platinum-composite catalysts for the electrooxidation of methanol, ethanol and formic acid. Various Pt-composites were fabricated including Pt-Au, PtRu, Pt-Pd and Pt-CeO2 catalysts. Electrochemical techniques were used to determine the catalytic ability of each novel composite toward the electrooxidation of methanol, ethanol and formic acid. This study indicates that the novel composites all have higher catalytic ability than bare Pt electrodes. The increase in catalytic ability is mostly attributed to the increase in CO poison tolerance and promotion of the complete oxidation mechanism of methanol, ethanol and iv formic acid. Formulations including bi- and tri-composite catalysts were fabricated and in many cases show the highest catalytic oxidation, suggesting tertiary catalytic effects. The combination of bi-metallic composites with ceria also showed highly increased catalytic oxidation ability. The following dissertation expounds on the relationship between composite material and the electrooxidation of methanol, ethanol and formic acid. The full electrochemical and material characterization of each composite electrode is provided.

Renewable energy is considered to be one of the most promising alternatives for the growing energy demand in response to depletion of fossil fuels and undesired global warming issue. With such perspective, Solar Cells and Fuel Cells are most viable, environmentally sound, and sustainable energy sources for power generation. Solar and Fuel cells have created great interests in modern applications including distributed energy generation to provide clean energy. The purpose of this thesis was to perform a detailed analysis and modeling of Solar and Fuel cells using Cadence SPICE, and to investigate dynamic interactions between the modules and power conversion circuits. Equivalent electronic static and dynamic models for Solar and Fuel Cells, their electrical characteristics, and typical power loss mechanisms associated with them are demonstrated with simulation results. Power conversion circuits for integration with the dynamic models of these renewable low voltage sources are specifically chosen to boost and regulate the input low dc voltage from the modules. The scope of this work was to analyze and model solar and fuel cells to study their terminal characteristics, power loss mechanisms, modules and their dynamics when interfaced with power converters, which would lead to better understanding of these renewable sources in power applications.

In this study, the effects of electrode microstructure and electrolyte parameters on intermediate temperature solid oxide fuel cell (ITSOFC) performance were investigated using a one-dimensional SOFC model from the Pacific Northwest National Laboratory (PNNL). After a brief review of the fundamental SOFC operating processes and a literature review incorporating more advanced SOFC topics, such as electrode microstructure modeling and mixed ionic and electronic (MIEC) composite cathodes, it was determined from the PNNL benchmark results that the dominating ITSOFC losses were caused from the activation and Ohmic overpotentials. The activation overpotential was investigated through the exchange current density term, which is dependent on the cathode activation energy, the cathode porosity, and the pore size and grain size at the cathode triple phase boundary (TPB). The cathode pore size, grain size, and porosity were not integrated in the PNNL model, therefore, an analytical solution for exchange current density from Deng and Petric (2005) was utilized to optimize their effects on performance. The Ohmic loss was determined to be entirely dependent on the electrolyte ionic conductivity, and an optimal value for this conductivity was determined. Simultaneous optimization of the above parametric evaluations led to a 388 % increase in performance from the PNNL benchmark case at 600 °C. Although this was deemed successful for this project, future research should be focused on numerically quantifying and modeling the electrode microstructure in two and·three-dimensions for more accurate results, as the electrode microstructure may be highly multi-dimensional in nature.

Thesis (M. Tech. - (Engineering: Electrical, Department: Electronic Engineering, Faculty of Engineering and Technology))--Vaal University of Technology. / Industrial countries, such as South Africa, rely heavily on energy sources to function profitably in today’s economy. Based on the 2008 fossil fuel CO2 emissions South Africa was rated the 13th largest emitting country and also the largest emitting country on the continent of Africa, and is still increasing. It was found that fuel cells can be used to generate electricity and that hydrogen is a promising fuel source. A fuel cell is an energy generation device that uses pure hydrogen (99.999%) and oxygen as a fuel to produce electric power. A regenerative fuel cell is a fuel cell that runs in reverse mode, which consumes electricity and water to produce hydrogen. This research was aimed at designing and constructing an optimised control system to control the hydrogen pressure in a proton exchange membrane regenerative fuel cell. The hydrogen generated by the fuel cell must be stored in order to be used at a later stage to produce electricity. A control system has been designed and constructed to optimise the hydrogen pressure control in a regenerative proton exchange membrane fuel cell. An experiment that was done to optimise the hydrogen system included the effects that the cathode chamber pressure has on the production of hydrogen and the most effective method of supplying hydrogen to a storage tank. The experiment also included the effects of a hydrogen buffer tank on the output hydrogen pressure and if the system can accommodate different output pressures. It was found that the cathode chamber pressure doesn’t need to be controlled because it has no effect on the rate of hydrogen produced. The results also showed that the flow of hydrogen need not to be controlled to be stored in a hydrogen storage tank, the best method is to let the produced hydrogen flow freely into the tank. The hydrogen produced was also confirmed to be 99.999% pure. The system was also tested at different output pressures; the control system successfully regulated these different output pressures.

The work in this thesis mainly focuses on the preparation and characterization of several phosphates and solid oxide systems with the aim of developing new proton conducting materials for intermediate temperature fuel cells (ITFCs). Soft chemical methods such as sol-gel methods and conventional solid state methods were applied for the synthesis of these materials. Aluminum phosphate obtained by a solution method is single phase and belongs to one of the Al(H₂PO₄)₃ allotropies with hexagonal symmetry. The material is stable up to 200°C and decomposes into Al(PO₃)₃ at a higher temperature. The electrical conductivity of pure Al(H₂PO₄)₃ is on the order of 10⁻⁶-10⁻⁷ S/cm, very close to the value for the known proton conductors AlH₃(PO₄)₂•3H₂O and AlH₂P₃O₁₀•2H₂O. Much higher conductivity is observed for samples containing even a trace amount of excess H₃PO₄. It is likely that the conduction path gradually changes from grain interior to the surface as the acid content increases. The conductivity of Al(H₂PO₄)₃-0.5H₃PO₄ exhibited a good stability over the measured 110 hours. Although tin pyrophosphate (SnP₂O₇) has been reported to show a significantly high conductivity (~10⁻² S/cm) at 250°C in various atmospheres, we observed large discrepancies in the electrical properties of SnP₂O₇ prepared by different methods. Using an excess amount of phosphorous in the synthetic procedure generally produces SnP₂O₇ with much higher conductivity (several orders of magnitude higher) than samples with stoichiometric Sn:P ratios in their synthetic procedure. Solid state ³¹P NMR confirmed the presence of residual phosphoric acid for samples with excess starting phosphorous. Transmission Electron Microscope (TEM) confirmed an amorphous layer covered the SnP₂O₇ granules which was probably phosphoric acid or condensed phases. Thereby, it is quite likely that the high conductivity of SnP₂O₇ results mainly from the contribution of the residual acid. The conductivity of these samples exhibited a good stability over the measured 80 hours. Based on the observations for SnP₂O₇, we developed a nano core-shell structure based on BPO₄ and P₂O₅ synthesised by solid state methods. The particle size of BPO₄ using this method varied between 10-20 nm depending on the content of P₂O₅. TEM confirmed the existence of an amorphous layer that is homogeneously distributed. The composite exhibits the highest conductivity of 8.8×10⁻² S/cm at 300°C in air for 20% extra P₂O₅ and demonstrates a good stability during the whole measured 110 hours. Polytetrafluoroethylene (PTFE) was introduced into the composites in order to increase malleability for fabrication. The conductivity and mechanical strength were optimized by adjusting the PTFE and P₂O₅ content. These organic-inorganic composites demonstrate much better stability at elevated temperature (250°C) over conventional SiC-H₃PO₄-PTFE composites which are common electrolytes for phosphoric acid fuel cells (PAFCs). Fuel cells based on BPO₄-H₃PO₄-PTFE composite as the electrolyte were investigated using pure H₂ and methanol as fuels. A maximum power density of 320 mW/cm² at a voltage of 0.31 V and a maximum current density of 1.9 A/cm² at 200°C were observed for H₂/O₂ fuel cells. A maximum power density of 40 mW/cm² and maximum current of 300 mA/cm² 275°C were observed when 3M methanol was used in the cell. Phosphoric acid was also introduced into materials with internal open structures such as phosphotungstic acid (H₃PW₁₂O₄₀) and heteropolyacid salt ((NH₄)₃PW₁₂O₄₀), for the purpose of acquiring additional connections. The hybrids obtained have a cubic symmetry with enlarged unit cell volume, probably due to the incorporation of phosphoric acid into the internal structures. Solid state ³¹P NMR performed on H₃PW₁₂O₄₀-xH₃PO₄ (x = 0-3) showed additional peaks at high acid content which could not assigned to phosphorus from the starting materials, suggesting a strong interaction between H₃PW₁₂O₄₀ and H₃PO₄. The conductivity of hybrids was improved significantly compared with samples without phosphoric acid. Fourier transform infrared spectra (FT-IR) suggest the existence of large amount of hydrogen bonds (OH••••O) that may responsible for the high conductivity. A H₂/O₂ fuel cell based on H₃PW₁₂O₄₀-H₃PO₄-PTFE exhibited a peak power density of 2.7 mW/cm² at 0.3 V in ambient temperature. Solid oxide proton conductors based on yttrium doped BaZrO₃ were investigated by introducing potassium or lanthanum at the A-sites. The materials were prepared by different methods and were obtained as a single phase with space group Pm-3m (221). The unit cell of these samples is slightly smaller than the undoped one. The upper limit of solid solution formation on the A-sites for potassium is between 5 ~ 10% as introducing more K results in the occurrence of a second phase or impurities such as YSZ (yttrium stabilized zirconium). K doped Barium zirconates showed an improved water uptake capability even with 5% K doping, whereas for La doped ones, water uptake is strongly dependent on particle size and synthetic history. The conductivity of K doped BaZrO₃ was improved by a factor of two (2×10⁻³ S/cm) at 600°C compared with undoped material. Fuel cells based on Pt/Ba₀₋₉₅K₀₋₀₅Zr₀₋₈₅Y₀₋₁₁Zn₀₋₀₄O[subscript(3-δ)]/Pt under humidified 5% H₂/air conditions gave a maximum power density 7.7 mWcm⁻² at 718°C and an interfacial resistance 4 Ωcm⁻². While for La doped samples, the conductivity was comparable with undoped ones; the benefits of introducing lanthanum at A-sites may not be so obvious as deficiency of barium is one factor that leads to the diminishing conductivity.

Thesis (M. Tech. - (Engineering: Electrical, Department: Electronic Engineering, Faculty of Engineering and Technology)) -- Vaal University of Technology, 2011. / “Never before in peacetime have we faced such serious and widespread shortage of energy” according to John Emerson, an economist and power expert for Chase Manhattan Bank. Many analysts believe that the problem will be temporary, but others believe the energy gap will limit economic growth for years to come. A possible solution to this problem can be fuel cell technology. Fuel cells (FCs) are energy conversion devices that generate electricity from a fuel like hydrogen. The FC however, could also be used in the reverse or regenerative mode to produce hydrogen. The reversible fuel cell (RFC) can produce hydrogen and oxygen by introducing water to the anode electrode chamber, and applying a potential across the anode and cathode. This will cause the decomposition of the water to produce oxygen at the anode side and hydrogen at the cathode side. In order to make this process as efficient as possible several aspects need to be optimised, for example, the operation temperature of the RFC, water management inside the RFC and supply voltage to the RFC. A three cell RFC and its components were constructed. The three cell RFC was chosen owing to technical reasons. The design factors that were taken into consideration were the different types of membranes, electrocatalysts, bipolar plates and flow topologies. A water trap was also designed and constructed to eliminate the water from the hydrogen water mixture due to water crossover within the MEA. In order to optimise the operation of the RFC a number of experiments were done on the RFC. These experiments included the optimal operating voltage, the effect that the temperature has on the production rate of hydrogen, and the effect that the water flow through the RFC has on the production rate of hydrogen. It was found that there is no need to control the water flow through the RFC because it had no effect on the production rate of hydrogen. The results also showed that if the operating temperature of the RFC were increased, the energy it consumes to warm the RFC significantly decreases the efficiency of the whole system. Thus the RFC need not be heated because it consumes significantly more energy to heat the RFC compared to the energy available from the hydrogen produced for later use. The optimised operating voltage for the three cell RFC was found to be 5.05 V. If the voltage were to be increased or decreased the RFC efficiency would decrease.

This thesis presents a novel hybrid biological solid-state system which makes use of biological components in an in-vitro environment to produce functionality incapable by CMOS circuits alone. A "biocell" comprised of lipids and ion pumps is mated to a CMOS IC in a compact configuration and the IC is powered solely from adenosine triphosphate (ATP), often referred to as the 'life energy currency.' The biocell is a fuel cell that produces a membrane potential in the presence of ATP which is used by the IC as an electrical power supply. The design represents the first of a new class of devices combining both biological and solid-state components, which exploit the unique properties of transmembrane proteins in engineered solid-state systems. This work also suggests that the richness of function of biological ion channels and pumps, functionality that is impossible to achieve in CMOS alone, may be exploited in systems that combine engineered transmembrane proteins as biological components integrated with solid-state devices.

The high temperature oxidation of ferritic stainless steel interconnects results in chromium poisoning of the solid oxide fuel cell (SOFC) electrodes, which is a limiting factor for their utilisation as SOFC interconnects. Chromium-rich spinel materials were studied as electrode supports that would be situated at the interface between interconnect and electrode, in order to reduce the effect of chromium poisoning of the electrodes. The main goal of this thesis was to find chromium-rich spinel materials with good electrical conductivity (σ ≥ 0.1 S∙cm⁻¹) in air and reducing atmosphere, chemically and mechanically stable in SOFC testing conditions. The structure and properties of newly formulated chromium-rich spinels, such as Mn₁₊ₓCr₂₋ₓO₄ (x = 0, 0.5), MnFeₓCr₂₋ₓO₄ (x = 0.1, 1), MgMnCrO₄, MnLiₓCr₂₋ₓO₄ (x = 0.1) and MgMₓCr₂₋ₓO₄, (M = Li, Mg, Ti, Fe, Cu, Ga) were studied aiming at their application as electrode support material for solid oxide fuel cells. Cation distributions were determined by Rietveld refinement from X-ray diffraction (XRD), within the limits of XRD precision and correlated with electrical properties determined experimentally. The chemical stability in reducing conditions was studied and the reduction effects upon materials were evaluated by XRD phase analysis and microstructure analysis. It was found that MnMₓCr₂₋ₓO₄ materials have a limited stability to reduction, only MnCr₂O₄ proved to have good stability when reduced, with negative influence for its p-type semiconductor conductivity. Even though MnFeCrO₄ had limited stability to reduction, in reducing conditions the conductivity changed from p-type to n-type semiconductor. A similar behaviour to reduction was observed for MgFeCrO₄. Also the mechanical and chemical compatibility of some spinels with YSZ was studied in terms of thermal expansion coefficient (TEC/K⁻¹), sintering step and possible chemical reactions. Lithium titanate spinels, starting with LiCrTiO₄, were investigated in terms of structure, properties and spinel - ramsdellite phase transition temperature also with the purpose of new material development. For these materials positive results were obtained in conductivity and chemical stability in reducing conditions. The performance of MnFeCrO₄ and MgFeCrO₄ as electrode support materials was investigated when used alone or impregnated with (La₀.₇₅Sr₀.₂₅)₀.₉₇Cr₀.₅Mn₀.₅O₃, La₀.₈Sr₀.₂FeO₃, Ce₀.₉Gd₀.₁O₂, CeO₂ or Pd. Composite anodes for SOFC were prepared by aqueous infiltration of nitrate salts into porous MnFeCrO₄ and MgFeCrO₄ scaffolds and studied by electrochemical impedance spectroscopy (EIS) in symmetrical cell configuration. The performance of the composite anodes was evaluated in humidified 5%H₂/Ar in order to understand their stability and performance at 850 °C or lower temperature with respect to the porous substrates. It was found that all the impregnated phases adhere very well to the spinel and considerably enhance performance and stability to a level required for SOFC applications. An interesting next step in this work would be to apply such spinel materials on steel interconnects, integrate them into testing SOFC devices and evaluate their effect upon chromium poisoning of the electrodes.

The decarbonization of the energy system is one of the most complex and consequential challenges of the 21st century. Meeting this challenge will require the deployment of existing low carbon technologies at unprecedented scales and rates and will necessitate the development of new technologies that have the ability to transform variable renewable energy into high energy density products. Reversible Solid Oxide Cells (RSOCs) are electrochemical devices that can function both as fuel cells or electrolyzers: in fuel cell mode, RSOCs consume a chemical fuel (H₂, CO, CH₄, etc.) to produce electrical power, while in electrolysis mode they consume electric power and chemical inputs (H₂O, CO₂) to produce a chemical fuel (H₂, CO, CH₄, etc.). As such, RSOC systems can be thought of as flexible “energy hubs” that have unique potential to bridge the low power density renewable infrastructure with that of high energy density fuels in an efficient, dynamic, and bidirectional fashion. This dissertation explores the different operational sensitivities and design trade-offs of a methane based RSOC system, investigates the optimum operating strategies for a system that adapts to variations in the hourly spot electricity and fuel prices in Western Denmark, and provides an economic analysis of the system under a wide variety of design assumptions, operational strategies, and fuel and electricity market structures. In order to perform such comprehensive analyses, a 0-D computational model of a methane based RSOC system was developed in Python. In fuel cell mode, the system generates power by consuming natural gas, while in electrolysis mode the system generates synthetic natural gas (SNG) by electrolyzing steam and catalytically hydrogenating recycled CO₂ into CH₄ downstream of the RSOC. The model's flexibility enables the simulation of “part-load” operation, allowing the user to assess the changes in output, efficiency, and operating cost as the system is operated across multiple points. The model has the ability to evaluate the impact that changes in design choices and operating parameters (Area Specific Resistance, temperatures, current density, etc.) have on the system as it interfaces with time varying exogenous factors such as fuel and electricity prices. As such, one of the main contributions of this model is the ability to run simulations in which the operating strategy of the RSOC system responds and adapts to varying market signals. The computational model is used to develop a series of hourly optimizations for finding the optimal operating strategy for an RSOC system that can buy or sell electricity and gas in the spot electricity and natural gas markets in Western Denmark. After receiving an electricity and gas price signal, the optimization determines the operating mode (fuel cell, electrolysis or idle) and operating point (e.g., current density) that maximize the operating profits every hour for the given electricity and gas price pair. In order to avoid the speculation associated with traditional energy storage simulations, the system is “opened” at both ends, allowing it to instantaneously buy and sell any electricity or gas that is generated. Thus, the system never stores any of the products and it buys and sells them at the instantaneously available market price. By assuming that market prices reflect all existing information, this design choice removes the necessity of having to speculate about the future in order to determine the optimum operating strategy. This approach is one of the innovations presented in this work. The optimizations aim at maximizing the operating profits at each hour of the year, and decisions of operating mode and point are based on marginal operating costs for each electricity and natural gas price pair. The full economic analysis, however, requires the understanding of how design choices (e.g. operating limits, heat management, gas recycling systems, etc.) affect the investment costs, and therefore a Total Plant Cost (TPC) model is developed. For each design choice, the TPC model is used to compute a cost of the system per m² of active electrode area or kW of output. This value, assumed to be a sunk cost that does not affect the operating decision, together with the operating profits resulting from the optimization is used to assess the overall profitability of the system. For a system with 100m² of active electrode area, conventional costing metrics suggest that the balance of plant (BoP) components for managing the system's heat (Heat exchangers, evaporators, condensers) are the main cost drivers and represent roughly 50% of the TPC. The cost of the electrochemical RSOC stack, assembly, power inverter and piping represent 35% of the cost, with the other 15% coming from pumps, compressors and the methanation system. Twenty different optimization scenarios are developed in order to quantify the effect that system design choices, operating limits, and market prices have on the operating profile and on the overall economics of the system. The first 12 case studies are based on real hourly spot electricity and natural gas prices for the years 2009-2014 in Western Denmark. For the last 8 scenarios, a forecasted hourly time-series for electricity in the Danish grid for the year 2050 and two fixed SNG prices (high and a low) are used. The 2050 prices, which assume a fossil fuel free system, are used to understand the role and value that RSOC systems can offer in deeply decarbonized energy systems. For each optimization, different parameters such as the initial ASR and the operating limits (maximum current densities for each mode of operation) are varied in order to find the impact that these changes have on the system's design (balance of plant components), hourly operating mode, investment costs, hourly operating profits, and overall plant profits. For the 2009-2014 optimizations, it is found that the sale of electricity (fuel cell mode) and fuel (electrolysis mode) is not large enough to cover the fixed costs associated with the plant. Fuel cell mode dominates the operation (61% of the time) with electrolysis representing only ~ 4% of the operating hours. ASR is found to have an important impact on the system's economics, due to the fact that a lowering of the ASR leads to a reduction in the size of the heat management system, which in turn reduces the Total Plant Cost. For the 2050 dataset, it is found that under the high gas price scenario electrolysis mode dominates (50% of the time), and fuel cell operation represents 15% of the hours in the year. For the low SNG price, electrolysis still dominates (48% of the time), and fuel cell operation increases to 30% of the operating hours. Furthermore, for the high SNG scenario, the sale of fuel and electricity are large enough to cover the system's fixed cost, making the system attractive from an investment perspective. For the low SNG price, the system also becomes profitable when using ASR values of 0.4 ASR or below.

Solid oxide fuel cells (SOFCs) are high temperature (600C-1000C) composite metallic/ceramic-cermet electrochemical devices. There is a need to effectively manage the heat transfer through the cell to mitigate material failure induced by thermal stresses while yet preserving performance. The present dissertation offers a novel thermodynamic optimization approach that utilizes dimensionless geometric parameters to design a SOFC. Through entropy generation minimization, the architecture of a planar SOFC has been redesigned to optimally balance thermal gradients and cell performance. Cell performance has been defined using the 2nd law metric of exergetic efficiency. One constrained optimization problem was solved. The optimization sought to maximize exergetic efficiency through minimizing total entropy production while constraining thermal gradients. Optimal designs were produced that had exergetic efficiency exceeding 92% while maximum thermal gradients were between 219 C/m and 1249 C/m. As the architecture was modified, the magnitude of sources of entropy generation changed. Ultimately, it was shown that the architecture of a SOFC can be modified through thermodynamic optimization to maximize performance while limiting thermal gradients. The present dissertation highlights a new design methodology and provides insights on the connection between thermal gradients, performance, sources of entropy generation, and cell architecture.