<p>Solid oxide fuel cells are an efficient method of converting hydrocarbon fuels to electrical power. However, due to some problems with poisoning, these have made no headway in the energy market. The evaporation of chromium oxides from metallic current collectors causes rapid degradation of the cells on the cathode side. It has been shown that spinel coatings reduce the effects of chromium oxide evaporation. In this thesis, two spinel systems are explored for potential application. Cobalt-manganese spinel is a stable spinel which have a wide range of composition, while remaining sufficiently conductive. Copper-manganese spinel, which is much more conductive than cobalt-manganese, is slightly less stable, but nonetheless a candidate. All components of the spinels explored can be electrodeposited from aqueous solutions, at room temperature. By controlling the concentrations of metallic ions, and other additives, coatings can be deposited on interconnecting plates with reproducible results. The newly coated interconnects can be oxidized in-situ. For characterization, the samples for this thesis were oxidized at 800°C. Two substrate materials were used, ferritic stainless steel and a chromium-iron alloy. Stainless steel substrates showed good coating adhesion, but high concentrations of iron were found in the spinel structure. Chromium alloy substrates were better protected by spinel coatings. However, nitride formation at the substrate interface caused localized delamination of the coating. It was shown that plating operations can be scaled up to 10 cm by 10 cm plates, with little modification of the processes used.</p> / Master of Applied Science (MASc)

<p> The exploration of cathode materials and fabrication methods plays an important role in the development of solid oxide fuel cell (SOFC) technology. The objective of this study is first to optimize the cathode microstructure by the impregnation method, and then investigate the potential application of copper manganese spinel as a new cathode material with optimized microstructure and explore the reaction mechanism of the cathodes.</p> <p> The impregnation method was employed to fabricate a composite cathode with electrocatalyst particles dispersed in a framework of electrolyte material. The impregnation method is relatively easy to apply and yield the optimized microstructure, allowing extended three phase boundary length and absence of secondary phase formation during fabrication.</p> <p> The polarization performance of copper manganese spinel (CMO) impregnated YSZ cathodes was examined by adjusting catalyst particle size, electrode thickness and catalyst content. A critical thickness of 16.9±2.0 μm for the CMO-YSZ composite cathode was calculated from Tanner's model. Decreased catalyst particle size and a thickness close to the critical value were found to eliminate polarization loss. The composite cathode with 50 wt% CMO impregnation showed a polarization resistance as low as 0.3 Ωcm^2 at 750°C. At 800°C, an SOFC with CMO-YSZ composite cathode had a power density of 172 mW/cm^2, which was 2.5 times higher than the cell with the traditional LSM-YSZ composite cathode under the same conditions.</p> <p> The cathode reaction mechanism of CMO-YSZ and strontium doped lanthanum ferrite (LSCF) impregnated Gd doped ceria ( CGO) composite cathodes was studied, using impedance spectroscopy, cyclic voltammetry and current interruption techniques. Surface diffusion and mass transfer were determined to be the rate controlling steps for CMO-YSZ composite cathode at low and high temperatures, respectively. A low frequency process at low temperatures and at least two processes at high temperatures were identified as rate determining steps of LSCF -CGO composite cathodes. A cathodic current activation effect was observed on CMO-YSZ cathode under current passage. The catalytic activity of CMO was enhanced by the cathodic current and the effect existed in both long-term and short-term experiments.</p> <p> The results of this study suggest that copper manganese spinel has attractive properties as a new catalyst material for the cathodic reaction with the composite structure obtained by the impregnation method.</p> / Thesis / Master of Applied Science (MASc)

Solid oxide fuel cells (SOFCs) are promising devices to convert chemical energy to electrical energy due to their high efficiency, fuel flexibility, and low emissions. However, there are still some drawbacks hindering its wide application, such as high operative temperature, electrode degradation, chromium poisoning, oxidization of interconnect, and so on. Cathode plays a major role in determining the electrochemical performance of a single cell. In this dissertation, three perovskite cathode materials, La0.6Sr0.4Co0.2Fe0.8O3 (LSCF), Ba0.5Sr0.5Co0.2Fe0.8O3 (BSCF), and Sm0.5Sr0.5Co0.2Fe0.8O3 (SSCF), are comparatively studied through half-cells in the temperature range of 600-800 ºC. Sm0.2Ce0.8O1.9 (SDC) block layer on the yttria-stabilized zirconia (YSZ) electrolyte can lead to smaller polarization resistances of the three cathode materials through stopping the reaction between the cathodes and the YSZ electrolyte. SDC is also used as a catalyst to increase the oxygen reduction reaction (ORR) rate in the LSCF cathode. In addition, interconnect is protected by CoxFe1-x oxide and Co3O4/SDC/Co3O4 tri-layer coatings separately. These coatings are demonstrated to be effective in decreasing the area specific resistance (ASR) of the interconnect, inhibiting the Cr diffusion/evaporation, leading higher electrochemical performance of the SSCF-based half-cell. Only 1.54 at% of Cr is detected on the surface of the SSCF cathode with the Co0.8Fe0.2 oxide coated interconnect and no Cr is detected with the Co3O4/SDC/Co3O4 tri-layer coated interconnect. Finally, single cells with LSCF, BSCF, and SSCF as the cathodes are operated in the temperature range of 600-800 °C fueled by natural gas. BSCF has the highest power density of 39 mW cm-2 at 600 °C, 88 mW cm-2 at 650 °C, and 168 mW cm-2 at 700 °C; LSCF has the highest power density of 263 mW cm-2 at 750 °C and 456 mW cm-2 at 800 °C. Activation energies calculated from the cathode ASR are 0.44 eV, 0.38 eV, and 0.52 eV for the LSCF, BSCF, and SSCF cathodes respectively, which means the BSCF cathode is preferred. The stability test shows that the BSCF-based single cell is more stable at lower operative temperature (600 °C) while the LSCF-based single cell is more stable at higher operative temperature (800 °C). / Ph. D.

The research presented in this thesis is a collection of many different, yet connected, parts that stemmed from the development of a new alternative material intended to be utilised as anode material in solid oxide fuel cells. The main part is the research conducted in the development and characterisation of the novel A-site deficient La₀.2₂Sr₀.₇₋ₓCaₓTiO₃. Calcium introduction resulted in reducing this perovskite unit cell volume which, at the beginning, enhanced its electrical conductivity in reducing conditions. However, the ideal cubic symmetry coud not be maintained, as in the starting material LA₀.₂Sr₀.₇TiO₃, as a result of the increased A-site ionic radius mismatch and two lower symmetries were observed at room temperature. These were the tetragonal I4/mcm for 0.1 ≤ x ≤ 0.35 and orthorhombic Pbnm for 0.4 ≤ x ≤ 0.7. Higher temperature NPD data showed that the orthorhombic samples transformed into higher symmetries with Pbnm → I4/mcm → Pm3-m phase transitions. Detailed crystallographic analysis is discussed; where the different unit cells showed changes to the tilts of the BO₆ octahedra, along with distortions to these octahedra. DC conductivity measurements showed a high electrical conductivity of 27.5 S/cm for a pre-reduced composition La₀.₂Sr₀.₂₅Ca₀.₄₅TiO₃ at 900°C and pO₂ = 10⁻¹⁹ atm. This material showed very encouraging features; which makes it a very promising anode material for SOFCs. A study was also done which explores the best renewable energy options for the United Arab Emirates given its local climate and other aspects. The reliance on seawater desalination is argued to by unsustainable for different reasons. Thus, water security should be a main element in the planning process for adopting renewable energy technologies. A system that combines different technologies; with a focus on fuel cells technology; is outlined which is thought of to be a very promising basis for a broader system that will secure power and water in a very environment friendly way. Different compositions of the system La₀.₂Sr₀.₇₋ₓCaₓTiO₃ were also studied using AC impedance spectroscopy in order to establish whether or not this system can show a ferroelectric behaviour. Results showed a variation in the dielectric constant of different samples with temperature; however, no Curie point was observed. Nonetheless, the results did show that the different compositions were very homogeneous when fully oxygenated and there were some indications of possible symmetry changes at sub-ambient temperatures. The final part of this thesis outlined the work done towards the development of a new analytical instrument. An existing TGA instrument was altered in order to provide a simultaneous thermogravimetric analysis and DC conductivity measurement for solid solutions at controlled temperature and oxygen partial pressure. Results were obtained for different samples of the system La₀.₂Sr₀.₇₋ₓCaₓTiO₃ which showed a great dependence of the electrical conductivity on the oxygen stoichiometry in these oxides. Also, a direct method is possible with this instrument to estimate the oxygen chemical diffusion coefficient using the electrical conductivity relaxation method. This new setup will be very useful for different electrochemical and thermal studies which can broaden the understanding of the different mechanisms that affect the performance of different solid state materials.

Ammonia has emerged as an attractive potential hydrogen carrier due to its extremely high energy density (hydrogen density), ease of storage and transportation as a liquid, and carbon-free nature. Direct utilization of ammonia in high-temperature solid oxide fuel cells (SOFCs) has been demonstrated over the past decade. Concurrence of in situ endothermic ammonia decomposition and exothermic electrochemical hydrogen oxidation permit efficient heat integration. In this study, the experimental analyses of axial temperature and concentration profiles along the tubular SOFC (t-SOFC) fed directly with ammonia are performed to investigate the coupled ammonia decomposition and hydrogen oxidation reactions as well as the effect of polarization. Fast ammonia decomposition over the Ni catalyst is evident at the inlet of t-SOFC and complete ammonia conversion is confirmed above 600ºC. It is found that direct ammonia-fueled t-SOFC and an equivalent hydrogen-nitrogen fueled t-SOFC provide identical performances. With 100 SCCM of ammonia fuel feed, a maximum power of 12.2 W and fuel utilization of 81% are obtained at 800ºC in a t-SOFC with active area of 32 cm2. The temperature and concentration profiles validate that the efficient heat integration inside ammonia-fueled t-SOFC is feasible if t-SOFC is operated at the temperature of 700ºC and below. The 23-hour performance test and SEM-EDS images of the fresh and used Ni-YSZ cermet surfaces confirm uniform performance and good durability of ammonia t-SOFC.

The aim of this dissertation is to appraise and critically reflect on the physical pertinence of governing equations and closure relations often used for the modeling of gas-phase transport phenomena in high-temperature solid-oxide fuel cells (SOFCs). More precisely, this work conducts a critical literature review on the concentration-induced voltage losses (i.e., concentration polarization) resulting from mass transfer limitations. Thus, the overall object of this work was to stress awareness of the limits of mathematical models studied and developed in the SOFC literature to date, and which are specifically related to concentration polarization processes. To a great extent, the design of SOFC porous layers is likened to that of optimizing the transport of multicomponent gas mixtures in structured porous catalysts, for which diffusional and flow limitations are of cardinal importance. In both cases, severe inconsistencies in mass transport models cannot be simply ignored and the main uncertainties in utilizing such models should be clarified. It is hoped that the information herein will serve usefully to support future developments of more consistent theoretical frameworks, thereby improving the confidence on the results of numerical simulations. The critical literature review has been carried out so to identify a number of physical inconsistences, ill-defined approximations, and misleading mathematical derivations. Along the review, it is argued that the choice (or, more properly, the lack of conceptual refinement) of a particular mathematical model can significantly impair the \"prediction\" of transport processes relevant to concentration-induced power losses in SOFCs. One of the keystones of this work was therefore to re-interpret and thus to reassess the frequently contradictory literature related to certain classes of gas-phase transport models pertinent to the evaluation of concentration polarization. With this revisionary approach, it is expected that one could reduce confusion, clear up apparent contradictions, and improve the possibility of gaining new insights. / Esta dissertação tem o objetivo de avaliar e refletir criticamente sobre a pertinência física de equações de conservação e de relações de fechamento, frequentemente utilizadas na modelagem multiescala de fenômenos de transporte em células a combustível de óxido-sólido (SOFC). Dêu-se atenção especial ao escoamento em \"microescala\" de misturas gasosas multicomponentes, dentro de meios porosos quimicamente reativos. Em outras palavras, esta monografia busca ressaltar quais os limites para aplicação de certas classes de modelos matemáticos, os quais têm sido desenvolvidos e utilizados na literatura de SOFCs até o presente momento. O projeto de camadas porosas de SOFCs assemelha-se à tarefa de otimizar processos de transporte em catalisadores estruturados, para os quais a existência de limitações de transporte por difusão e por escoamento tem importância primordial. Por esta razão, inconsistências originadas em modelos de fenômenos de transporte não podem ser, simplesmente, negligenciadas e, portanto, as principais incertezas ao se utilizar tais modelos devem ser devidamente esclarecidas. Espera-se, com efeito, que as informações contidas neste trabalho sejam úteis para futuros desenvolvimentos teóricos mais consistentes, de forma a aumentar a confiabilidade no uso de resultados obtidos por simulações numéricas.

O dióxido de cério (CeO2), pode apresentar condutividade iônica e eletrônica (condutor misto) em temperaturas relativamente baixas (considerando a faixa de trabalho 1000°C de uma SOFC). Esta característica torna este material promissor para uso em células a combustível de óxido sólido (SOFC ou CCOS) assim como em catalisadores. Vale destacar que em altas temperaturas o dióxido de cério puro é um mau condutor iônico, contudo pode-se obter um aumento significativo com a substituição estrutural do íon cério (Ce+4) por outro íon metálico de menor valência (La+3 e Ca+2). O estudo proposto consiste em sintetizar óxido de cério dopado com lantânio e cálcio com características microestruturais e elétricas adequadas para uso em uma CCOS. Utilizando o método de síntese de combustão foi estudado a influência que o excesso de combustível (sacarose) pode proporcionar nas características finais dos pós cerâmicos. A caracterização dos pós foi realizada pelas técnicas de raios-X (DRX), área superficial especifica (BET), análise termogravimétrica (TGA), Microscopia Eletrônica de: Varredura (MEV) e Transmissão (MET), Microscopia de Calefação (MC) e por fim a análise elétrica por meio da Espectroscopia de Impedância Eletroquímica (EIE). Os principais resultados mostraram que a técnica de síntese por combustão é um método eficiente para obtenção de pós nanoparticulados, bem dispersos e com elevada homogeneidade. Observou-se ainda que a troca do tipo de dopante assim como o teor de combustível utilizado na síntese interfere diretamente nas propriedades microestruturais, físicas e elétricas dos compostos finais a base de céria dopada. As amostras apresentaram comportamento condutor em baixas temperaturas (500°C) o que viabiliza sua utilização como catalizadores e também em CCOS após tratamentos térmicos em atmosferas adequadas para aplicação como eletrodos ou eletrólitos. Os resultados também demonstram que a céria dopada com cálcio tem características que se torna viável a substituição do lantânio para uso em uma CCOS. / The cerium dioxide (CeO2) has ionic and electronic conductivity (mixed conductor) properties at relatively low temperatures (considering a working range of 1000°C for a SOFC). These characteristics make this material appropriate for use as anode in solid oxide fuel cells (SOFC or CCOS). It should be mentioned that pure cerium dioxide is a bad ionic conductor in high temperatures, but we have a significant increase with the structural substitution of the cerium ion (Ce+4) by another metal ion of lower valence (in its crystalline lattice). The proposed study consisted in the synthesis of ceria oxide with lanthanum and/ or calcium with microstructural and electrical characteristics, suitable for use in a CCOS. Using the combustion synthesis, the influence of excess of fuel (sucrose) on the final characteristics of the ceramic powder has been analyzed. The characterization of the powders was realized using X-ray (XRD), specific surface area (BET), Thermogravimetric Analysis (TGA), Scanning Electron Microscopy (SEM), Electron Microscope Transmission (TEM), Microscope Heating (HSM) and Electrochemical Impedance Spectroscopy (EIS). The main results showed that the combustion synthesis technique is an efficient method to obtain nanoparticulate and well dispersed powders with high homogeneity. It was observed that the exchange of the dopant type as well as the fuel content used in the synthesis interferes directly in the microstructural, physical and electrical properties of the final compounds of ceria doped. Therefore, the calcium doped ceria has interesting characteristics for use in a CCOS.

<!--[if !mso]> <object classid="clsid:38481807-CA0E-42D2-BF39-B33AF135CC4D" id=ieooui></object><mce:style><! st1\:*{behavior:url(#ieooui) } --> The present work was initiated to study the synthesis and properties of lanthanum gallate based oxides as intermediate temperature electrolyte for solid oxide fuel cells. The wet chemical method, polymer complexing route, was used to prepare the precursor powders. To further investigate the polymer complexing method, it was also applied to the preparation of lanthanum aluminate based oxides.   Single perovskite phase La0.8Sr0.2Ga0.83Mg0.17O2.815 can be prepared by the polymer complexing method using PVA as complexing agent. The thermal decomposition of the precursor powder undergoes three stages. While complete decomposition of the precursor is obtained at 1000°C. Further investigation of LaGaO3 doped with various amounts Sr or/and Mg was conducted. Three secondary phases were identified by X-ray diffraction, e.g. LaSrGaO4, LaSrGa3O7 and La4Ga2O9. The relative amount of these secondary phases depends on the doping compositions. Sr doping produced more Sr rich secondary phases with increasing content, while enhanced solid solubility was observed with Mg addition. Sintered samples showed dense microstructures with well-developed equiaxed grains, and the secondary phases were mainly in the grain boundaries. The oxygen ionic conductivity was enhanced by doping with Sr and Mg. Mg doping showed the increased activation energy of conductivity.   Preliminary study showed that the lanthanum gallate and ceria composite electrolyte is mainly fluorite CeO2 phase after sintering. The minority secondary phase, Sm3Ga5O12, was also detected by XRD. The composite electrolyte showed superior electrical performance. It exhibited the highest conductivity in the temperature range of 250–600°C, compared with lanthanum gallate and ceria specimens.   The phase pure perovskite La0.9Sr0.1Al0.85Mg0.1Co0.05O2.875 powders can easily be obtained by the polymer method using PVA as complexing agent. No secondary phase was detected after calcination at various temperatures (500–1100°C). The fully crystallized LaAlO3 phase was prepared after calcination at 900°C. Meanwhile the secondary phases were difficult to eliminate in the Sr- and Mg- doped LaGaO3 powder prepared by the same polymer method. It is thus concluded that the polymer, PVA in this work, provides more homogeneous mixing for cations of lanthanum aluminate based oxides, compared with the one for doped lanthanum gallate.   The influence of different complexing agents, e.g. PVA and PEG, was investigated in the synthesis of lanthanum aluminate powders. Minority impurity La2O3 existed in the PEG powder, but it could be eliminated after sintering at high temperatures. Although the pure phase LaAlO3 can be easily obtained in PVA powders calcined at 950°C, more seriously aggregated particles existed. PEG showed advantages over PVA in terms of better densification and microstructure control in the sintered products. To select proper polymers in complex oxide synthesis, the agglomeration and morphology of the powder are the most important factors to be considered. / QC 20100727

Ba(Zr0.1Ce0.7Y0.2)O3-£_ (BZCY) shows high proton conductivity as well as high chemical stability over a wide range of solid oxide fuel cell (SOFC) operating conditions. Sm0.5Sr0.5CoO3-£_ (SSC) cathode deposited by electrostatic spray deposition (ESD) on SOFC half cell obtained via tape-casting shows porous and reticular microstructure, and the SOFC single cell consists of substrate/ BZCY+NiO/ BZCY/ SSC. The electrolyte thickness decrease from 22 £gm, 20 £gm, 17.6 £gm to 15.1 £gm after sintering as the content of carbon pore former in the corresponding anode functional layer increased from 0.0 wt.%, 5.0 wt.%, 10.0 wt.% to 15.0 wt.%, and the maximum power density of corresponding cells at 700¢J varies from 476.89 mW/cm2, 713.34 mW/cm2, 862.50 mW/cm2 to 706.89 mW/cm2, respectively.

Diffusive mass transport within porous SOFC components is explored using two modeling approaches that can better inform the SOFC electrode design process. These approaches include performance metrics for electrode cross-sectional design and a fractal approach for modeling mass transport within the pore structure of the electrode reaction zone. The performance metrics presented are based on existing analytical models for transport within SOFC electrodes. These metrics include a correction factor for button-cell partial pressure predictions and two forms of dimensionless reactant depletion current density. The performance impacts of multi-dimensional transport phenomena are addressed through the development of design maps that capture the trade-offs inherent in the reduction of mass transport losses within SOFC electrode cross-sections. As a complement to these bulk electrode models, a fractal model is presented for modeling diffusion within the electrochemically active region of an SOFC electrode. The porous electrode is separated into bulk and reaction zone regions, with the bulk electrode modeled in one-dimension based on the dusty-gas formalism. The reaction zone is modeled in detail with a two-dimensional finite element model using a regular Koch pore cross-section as a fractal template for the pore structure. Drawing on concepts from the analysis of porous catalysts, this model leads to a straightforward means of assessing the performance impacts of reaction zone microstructure. Together, the modeling approaches presented provide key insights into the impacts of bulk and microstructural geometry on the performance of porous SOFC components.