Stabilised zirconias have a remarkable variety of technological and commercial applications, e.g., thermal barrier coatings, gas sensors, solid oxide fuel cells, ceramic knives and even fashion jewelry. This amazing versatility seems to originate from the creation of atomic defects (oxide ion vacancies) in the zirconia crystal. Indeed, these vacancies, and their interactions with other vacancies or cations, dramatically affect the structural, thermal, mechanical and electrical properties of zirconia. This thesis is concerned with the study of the role of the vacancy interactions on the conducting properties of these materials. This study was performed by using realistic, first-principles based molecular dynamics simulations. The first system studied in this thesis is Zr0:5 0:5xY0:5+0:25xNb0:25xO7. This has a fixed number of vacancies across the series but its conductivity changes by almost two orders of magnitude as a function of x. For this reason, Zr0:5 0:5xY0:5+0:25xNb0:25xO7 represents an ideal test-bed for the role of the cation species on the defect interactions and therefore on the ionic conductivity of these materials. Realistic inter-atomic potentials for Zr0:5 0:5xY0:5+0:25xNb0:25xO7 were developed on a purely first-principles basis. The observed trends of decreasing conductivity and increasing disorder with increasing Nb5+ content were successfully reproduced. These trends were traced to the influences of the cation charges and relative sizes and their effect on vacancy ordering by carrying out additional calculations in which, for instance, the charges of the cations were equalised. The effects of cation ordering were considered as well and their influence on the conductivity understood. The second part of this thesis deals with Sc2O3–doped (ScSZ) and Y2O3–doped (YSZ) zirconias. These systems are of great academic and technological interest as they find use in solid oxide fuel cells. Inter-atomic potentials were parametrised and used to predict the structural and conducting properties of these materials, which were found to agree very well with the experimental evidence. The simulations were then used to study the role of the vacancy interactions on the conducting properties of these materials. Two factors were found to influence the ionic conductivity in these materials: cation-vacancy and vacancy-vacancy interactions. The former is responsible for the difference in conductivity observed between YSZ and ScSZ. Vacancies, in fact, prefer to bind to the smaller Zr4+ ions in YSZ whereas there is not a strong preference in the case of ScSZ, since the cations have similar sizes in this case. This effect is observed at temperatures as high as T = 1500 K. Finally, it was found that vacancies tend to order so that they can minimise their mutual interaction and that this ordering tendency is what ultimately is responsible for the observed anomalous decrease of the ionic conductivity with increasing dopant concentration. The consequences of such a behaviour are discussed.

The first part of the research is motivated to provide citations deeper to the literature of optimal control principles that could be linked to the system optimization problem, discuss these principles and various ways to apply them. Then we describe one fuel cell, accumulator and photovoltaic standalone system along with the most used equations from the literature. Next, we formulate the problem of optimal control for this system to optimize the system financial cost in the best case and we process to describe and discuss the numerical optimal control algorithm - multiple shooting - that will be used to solve the problem, that was not used in literature so far in conjunction with the problem. The codes and numerical simulations are also provided. Powered by TCPDF (www.tcpdf.org)

M. Tech. (Electrical, Applied Electronics and Electronic Communication, Faculty of Engineering and Technology) Vaal University of Technology| / The demand for efficient and environmentally friendly power sources has become a major topic around the world. This research explores the capability of the zinc-air fuel cell to replace conventional power sources for various applications, more specifically telecommunication systems. The research consisted of a theoretical study of the zinc-air fuel cell and its components, as well as their performance characteristics. A zinc-air fuel ce.ll and test rig were built, and the system was tested under various conditions. It was found that the zinc-air fuel cell has an advantage over other fuel cells in that it does not require any expensive materials or noble metals, reducing the overall cost of such a system. The fuel cell showed the potential to power various applications, but problems persisted in the fueling process as well as constant leaking of the aqueous electrolyte.

Philosophiae Doctor - PhD / Proton exchange membrane fuel cells (PEMFC) converts chemical energy from the electrochemical reaction of oxygen and hydrogen into electrical while emitting heat, oxygen depleted air (ODA) and water as by-products. The by-products have useful functions in aircrafts, such as heat that can be used for ice prevention, deoxygenated air for fire retardation and drinkable water for use on board. Consequently, the PEMFC is also studied to optimize recovery of the useful products. Despite the progress made, durability and reliability remain key challenges to the fuel cell technology. One of the reasons for this is the limited understanding of PEMFC behaviour in the aeronautic environment. The aim of this thesis was to define a comprehensive non-intrusive diagnostic technique that provides real time diagnostics on the PEMFC State of Health (SoH). The framework of the study involved determining factors that have direct influence on fuel cell life in aeronautic environment through a literature survey, examining the effects of the factors by subjecting the PEMFC to simulated conditions, establishing measurable parameters reflective of the factors and defining the diagnostic tool based on literature review and this thesis finding.

Células a combustível de óxido sólido (SOFC) produzem energia elétrica em elevadas temperaturas e, devido a isto, não necessitam da utilização de metais nobres para a promoção das reações eletródica em seus eletrodos. Entretanto, independentemente deste fato, quando biocombustíveis são utilizados diretamente há a formação de carbono nos eletrodos, o que promove a rápida degradação do dispositivo. Neste trabalho são preparados e estudados catalisadores anódicos baseados em níquel e num segundo metal para utilização como pré-camada anódica em células a combustível SOFC operando a 800 °C visando-se mitigar os efeitos da formação de carbono, aumentar o desempenho e prolongar a vida útil do dispositivo em operação com biocombustíveis, especialmente o etanol. Foram estudados os metais Co, Cu, Ru, Pd, Rh, e Ba. Os materiais foram caracterizados fisicamente para se estabelecer as suas estruturas cristalográficas bem como composição e morfologia. Estudou-se também o desempenho eletroquímico através do levantamento de curvas de polarização em estado estacionário, espectroscopia de impedância eletroquímica e cronoamperometria. Por fim, utilizou-se a técnica de espectrometria de massas para identificação de produtos reacionais. Da maneira como utilizadas, as camadas préanódicas atuaram como um filtro catalítico, promovendo reações de reforma e entregando ao ânodo um combustível com menor teor carbonáceo. Desta maneira todos os materiais mostraram-se em certa extensão capazes de promover a operação de células SOFC com etanol. Observou-se também atividade catalítica para outros combustíveis, sendo possível até mesmo a operação com metano e propano. Para fins deste estudo, o material que demonstrou melhor comportamento ante a operação com etanol tratou-se do NiRu, sendo alcançadas densidades de potência próximas a 0,9 W cm-2 a 500 mV. Em teste de durabilidade observou-se que a célula contendo este material operou por 150 h ininterruptas, ante 15 minutos possíveis para a célula sem proteção. / Solid Oxide Fuel Cells produce electrical energy at high temperatures without the need of noble metals. However, when a biofuel is directly used, carbon formation takes place, also known as \"coking\", which promotes rapid system degradation. In this work, bimetallic nickel based anodic catalysts are prepared and studied as anode prelayers for SOFC working at 800 °C fed with ethanol. The aims are to mitigate the effects of coking, improve the cell performance and extend the life usage of these devices when operating with biofuels, specially ethanol. As second metals Co, Cu, Ru, Pd, Rh and Ba were studied. The catalysts were physically characterized to establish their crystal structures as well as their chemical composition, and morphology. Electrochemical performance was studied using steady state olarization curves, electrochemical impedance spectroscopy and chronoamperometry for lifetime tests. Mass spectrometry was used in order to identify reactional products. In the way they were conceived and used, the anodic pre-layers worked as catalytic filters, promoting reforming reactions, delivering to anode surface a fuel with lower carbon content. All the studied materials showed in some extent activity for SOFC operating with biofuels, even making possible the operations with methane and propane. In the studies, NiRu material showed the best performance when operating with ethanol, reaching power densities as high as 0,9 W cm-2 at 500 mV. Endurance test made with this material showed that by using the NiRu based anode pre-layer fed with ethanol, under different load conditions, it is possible to operate the SOFC for about 150 h without interruption, versus 15 minutes for the uncovered anode.

A dissertation submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfillment of the requirements for the degree of Master of Science. April, 2015 / Microbial fuel cell (MFC) technology presents great potential for use as a dual system for industrial waste water remediation and electricity generation. The hurdle in up-scaling this technology has been identified as MFC-bioreactor architecture, both with regards to bioremediation and carbon source to electricity conversion rates. In addition to the latter’s limitations, the use of expensive mediators and membrane to enhance MFC performance renders the technology uneconomic to employ industrially. A 60mm high double chamber membrane and mediator-less MFC-bioreactor was designed, and constructed. The novel MFC-bioreactor made of transparent polyacrylic plastic had a total working volume of 8 litres with the anode chamber situated at the bottom and the cathode chamber at the top separated by a 10cm deep artificial membrane made up of glass wool, glass beads and marble balls. The MFC was operated under various operating parameters including; feeding modes (batch and continuous), with different substrate concentration at a range of external resistance (100-9000Ω) .The voltage produced during MFC operation was monitored and used to estimate the power density output of the MFC. The pseudo membrane was able to sufficiently separate the anode and cathode chambers allowing the development of potential difference and hence generation of current. The MFC demonstrated the potential for sustainable operation by producing and maintaining a stable power density of 2000mW/m2 when operated with an external resistance of 1000Ω. This power density was accompanied by a 73% remediation efficiency of the synthetic wastewater. It was concluded that the results of this research show proof of concept for a membrane-less MFC that can produce electrical energy in the absence of an electron shuffling mediator.

MSc, Faculty of Science, University of the Witwatersrand, 2011 / A growing interest is on the biological remediation of pollutants with the added benefit of generating electricity in microbial fuel cells (MFCs). Therefore, the analyses of suitability and potential of full-strength paper mill effluent and cheese whey were separately investigated in such devices. The most promising effluent was selected for biofilm optimization studies. In the biofilm buildup studies, anodes were enriched with microorganisms inherent to whey for a period between one and three months before their application in reactors. Independently, pre-incubated electrodes which were two-month-old were used serially in four MFCs of seven days each. In the preliminary study, the maximum power densities were 24 ± 3 mW/m2 (0.02 % coulombic efficiency − εcb) and 16.7 ± 1.8 W/m2 (εcb = 3.7 %) in paper mill effluent and whey, respectively. Following a three-month acclimation of whey anodophilic microbes, the power increased to 1 800 W/m2 (εcb = 80.9 %) and 92.8 % total chemical oxygen demand (tCOD) removal after a single batch cycle in MFCs. In anode recycling experiments, the operation was characterised by power of 390 ± 21 W/m2 (εcb = 0.25 %) in the third anode reuse; whilst the second reactor cycle had the highest tCOD removal (44.6 %). The anodophilic microbial species identified in cheese whey were from the Lactobacillus genus. This study concluded that wastes can supply fuel for power generation with simultaneous remediation; whey had greater potential than paper mill effluent; and both continual acclimation of inherent waste microbes and anode recycling improved the performance of MFCs.

The technical and scientific challenges to provide reliable sources energy for US and global economy are enormous tasks, and especially so when combined with strategic and recent economic concerns of the last five years. It is clear that as part of the mix of energy sources necessary to deal with these challenges, fuel cells technology will play critical or even a central role. The US Department of Energy, as well as a number of the national laboratories and academic institutions have been aware of the importance such technology for some time. Recently, car manufacturers, transportation experts, and even utilities are paying attention to this vital source of energy for the future. In this thesis, a review of the main fuel cell technologies is presented with the focus on the modeling, and control of one particular and promising fuel cell technology, aluminum air fuel cells. The basic principles of this fuel cell technology are presented. A major part of the study consists of a description of the electrochemistry of the process, modeling, and simulations of aluminum air FC using Matlab Simulink™. The controller design of the proposed model is also presented. In sequel, a power management unit is designed and analyzed as an alternative source of power. Thus, the system commutes between the fuel cell output and the alternative power source in order to fulfill a changing power load demand. Finally, a cost analysis and assessment of this technology for portable devices, conclusions and future recommendations are presented. / Includes bibliography. / Thesis (M.S.)--Florida Atlantic University, 2013.

Neste trabalho foi estudado o efeito dos parâmetros de síntese na resposta de polarização de híbridos Nafion-SiO2 como eletrólitos em células a combustível poliméricas (PEMFC) em elevadas temperaturas (até 130 °C). A fase inorgânica foi adicionada à matriz polimérica com o objetivo de aumentar a retenção de água na membrana em elevadas temperaturas (acima de 100 °C); melhorar as propriedades mecânicas do Nafion e favorecer cineticamente as reações eletródicas. As membranas foram preparadas a partir da incorporação in-situ de sílica em membranas comerciais de Nafion por rota sol-gel acompanhada de catálise ácida. Os parâmetros de síntese, tais como: concentração do catalisador ácido, natureza do solvente, temperatura e tempo de reação e concentração do precursor de silício (Tetraetil-Ortosilicato TEOS) foram avaliados em função do grau de incorporação e resposta de polarização. Os híbridos Nafion-SiO2 foram física e quimicamente caracterizados por gravimetria, termogravimetria (TG), microscopia eletrônica de varredura e espectroscopia de energia dispersiva de raios X (MEV-EDX), espectroscopia de impedância eletroquímica (EIS) e espalhamento de raios X em baixos ângulos (SAXS). Por fim, os híbridos sintetizados foram avaliados diretamente como eletrólitos em células PEM unitárias alimentadas com hidrogênio (H2) e oxigênio (O2) no intervalo de temperatura de 80 ºC a 130 ºC e a 130 ºC em condições de umidade relativa reduzida (75 e 50%). Resumidamente, o desempenho dos híbridos se mostrou fortemente dependente dos parâmetros de síntese, principalmente, o tipo de álcool utilizado e concentração inicial de TEOS. / In this work, the effect of sol-gel synthesis parameters on the preparation and polarization response of Nafion-SiO2 hybrids as electrolytes for proton exchange membrane fuel cells (PEMFC) operating at high temperatures (130 oC) was evaluated. The inorganic phase was incorporated in a Nafion matrix with the following purposes: to improve the Nafion water uptake at high temperatures (> 100 oC); to increase the mechanical strength of Nafion and; to accelerate the electrode reactions. The hybrids were prepared by an in-situ incorporation of silica into commercial Nafion membranes using an acid-catalyzed sol-gel route. The effects of synthesis parameters, such as catalyst concentration, sol-gel solvent, temperature and time of both hydrolysis and condensation reactions, and silicon precursor concentration (Tetraethylorthosilicate TEOS), were evaluated as a function on the incorporation degree and polarization response. Nafion-SiO2 hybrids were characterized by gravimetry, thermogravimetric analysis (TGA), scanning electron microscopy and X-ray dispersive energy (SEM-EDS), electrochemical impedance spectroscopy (EIS), and X-ray small angle scattering (SAXS). The hybrids were tested as electrolyte in single H2/O2 fuel cells in the temperature range of 80 130 oC and at 130 oC and reduced relative humidity (75% and 50%). Summarily, the hybrid performance showed to be strongly dependent on the synthesis parameters, mainly, the type of alcohol and the TEOS concentration.

Thesis advisor: Chia-kuang Frank Tsung / Pt-based alloy and core-shell nanoparticles have been intensively studied to regulate its size and shape. It has known that these nanoparticles show enhanced catalytic activity in various important fields such as heterogeneous catalysis, and electrochemical energy storage including fuel cells and metal-air batteries. Here, we report a facile hydrothermal synthesis of sub-10 nm PdPt alloy and sub-20 nm Au@PdPt core-shell structures. By using a mild reducing agent in aqueous solution, metal precursors are co-reduced. Specific gases are introduced during the synthesis to optimize the reaction conditions. The PdPt alloy and Au@PdPt core-shell nanostructures were characterized and confirmed by TEM, HRTEM, EDS, ICP-OES and XRD. The resulting PdPt and Au@PdPt particles are monodispersed single crystalline and octahedral shape enclosed by (111) facets. The electrocatalytic activity for the oxidation of formic acid was tested. It was found that the catalytic activity toward the formic acid oxidation of Au@PdPt core-shell particles were much higher than those of PdPt alloy particles. In addition, Pt-rich compositions were the most active in both PdPt alloy and Au@PdPt core-shell nanoparticles. Further studies on thinner alloy-shell core-shell nanoparticles reveal that there is a volcano-curve relationship between the lattice strain strength related to alloy-shell thickness and the catalytic performance. It is proposed that there are three key parameters that can determine the catalytic activity: the alloy composition, the presence of the gold core, and the thickness of alloy-shell. / Thesis (MS) — Boston College, 2012. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.