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

As the demand for clean and renewable energy sources continues to grow, much attention has been given to solid oxide fuel cells (SOFCs) due to their efficiency and low operating temperature. However, the components of SOFCs must still be improved before commercialization can be reached. Of particular interest is the solid electrolyte, which conducts oxygen ions from the cathode to the anode. Samarium-doped ceria (SDC) is the electrolyte of choice in most SOFCs today, due mostly to its high ionic conductivity at low temperatures. However, the underlying principles that contribute to high ionic conductivity in doped ceria remain unknown, and so it is difficult to improve upon the design of SOFCs. This thesis focuses on identifying the atomistic interactions in SDC which contribute to its favourable performance in the fuel cell. Unfortunately, information as basic as the structure of SDC has not yet been found due to the difficulty in experimentally characterizing and computationally modelling the system. For instance, to evaluate 10.3% SDC, which is close to the 11.1% concentration used in fuel cells, one must investigate 194 trillion configurations, due to the numerous ways of arranging the Sm ions and oxygen vacancies in the simulation cell. As an exhaustive search method is clearly unfeasible, we develop a genetic algorithm (GA) to search the vast potential energy surface for the low-energy configurations, which will be most prevalent in the real material. With the GA, we investigate the structure of SDC for the first time at the DFT+U level of theory. Importantly, we find key differences in our results from prior calculations of this system which used less accurate methods, which demonstrate the importance of accurately modelling the system. Overall, our simulation results of the structure of SDCagree with experimental measurements. We identify the structural significance of defects in the doped ceria lattice which contribute to oxygen ion conductivity. Thus, the structure of SDC found in this work provides a basis for developing better solid electrolytes, which is of significant scientific and technological interest. Following the structure search, we perform an investigation of the electronic properties of SDC, to understand more about the material. Notably, we compare our calculated density of states plot to XPS measurements of pure and reduced SDC. This allows us to parameterize the Hubbard (U) term for Sm, which had not yet been done. Importantly, the DFT+U treatment of the Sm ions also allowed us to observe in our simulations the magnetization of SDC, which was found by experiment. Finally, we also study the SDC surface, with an emphasis on its structural similarities to the bulk. Knowledge of the surface structure is important to be able to understand how fuel oxidation occurs in the fuel cell, as many reaction mechanisms occur on the surface of this porous material. The groundwork for such mechanistic studies is provided in this thesis.

As the demand for clean and renewable energy sources continues to grow, much attention has been given to solid oxide fuel cells (SOFCs) due to their efficiency and low operating temperature. However, the components of SOFCs must still be improved before commercialization can be reached. Of particular interest is the solid electrolyte, which conducts oxygen ions from the cathode to the anode. Samarium-doped ceria (SDC) is the electrolyte of choice in most SOFCs today, due mostly to its high ionic conductivity at low temperatures. However, the underlying principles that contribute to high ionic conductivity in doped ceria remain unknown, and so it is difficult to improve upon the design of SOFCs. This thesis focuses on identifying the atomistic interactions in SDC which contribute to its favourable performance in the fuel cell. Unfortunately, information as basic as the structure of SDC has not yet been found due to the difficulty in experimentally characterizing and computationally modelling the system. For instance, to evaluate 10.3% SDC, which is close to the 11.1% concentration used in fuel cells, one must investigate 194 trillion configurations, due to the numerous ways of arranging the Sm ions and oxygen vacancies in the simulation cell. As an exhaustive search method is clearly unfeasible, we develop a genetic algorithm (GA) to search the vast potential energy surface for the low-energy configurations, which will be most prevalent in the real material. With the GA, we investigate the structure of SDC for the first time at the DFT+U level of theory. Importantly, we find key differences in our results from prior calculations of this system which used less accurate methods, which demonstrate the importance of accurately modelling the system. Overall, our simulation results of the structure of SDCagree with experimental measurements. We identify the structural significance of defects in the doped ceria lattice which contribute to oxygen ion conductivity. Thus, the structure of SDC found in this work provides a basis for developing better solid electrolytes, which is of significant scientific and technological interest. Following the structure search, we perform an investigation of the electronic properties of SDC, to understand more about the material. Notably, we compare our calculated density of states plot to XPS measurements of pure and reduced SDC. This allows us to parameterize the Hubbard (U) term for Sm, which had not yet been done. Importantly, the DFT+U treatment of the Sm ions also allowed us to observe in our simulations the magnetization of SDC, which was found by experiment. Finally, we also study the SDC surface, with an emphasis on its structural similarities to the bulk. Knowledge of the surface structure is important to be able to understand how fuel oxidation occurs in the fuel cell, as many reaction mechanisms occur on the surface of this porous material. The groundwork for such mechanistic studies is provided in this thesis.

No description available.

Thermo-mechanical failure of components in planar-type solid oxide fuel cells (SOFCs) is a major obstacle on the path to bringing this technology to commercial viability. The probability of material degradation and failure in SOFCs depends strongly on the local temperature gradients at the interfaces of different materials. Therefore, it is of paramount importance to accurately predict and manage the temperature fields within the stack, especially near the interfaces. In this work we consider three effects in detail. First, we analyze radiative heat transfer effects within the semi-transparent solid electrolyte and compared them to thermal conduction. We also, present the modeling approach for calculation of surface-to-surface exchange within the flow channels and from the stack to the environment. The simplifying assumptions are identified and their carefully justified range of applicability to the problem at hand is established. This allows thermal radiation effects to be properly included in overall thermal modeling efforts with the minimum computational expense requirement. Second, we developed a series of reduced-order models for the transient heating and cooling of a cell, leading to a framework for optimization of these processes. The optimal design is one that minimizes heating time while maintaining thermal gradients below an allowable threshold. To this end, we formulated reduced order models (validated by rigorous CFD simulations) that yield simple algebraic design rules for predicting maximum thermal gradients and heating time requirements. Several governing dimensionless parameters and time scales were identified that shed light on the essential physics of the process. Finally, an analysis was performed to assess the degree of local thermal non-equilibrium (LTNE) within porous SOFC electrodes, and through a simple scaling analysis we discovered the parameter that gives an estimate of the magnitude of LTNE effects. We conclude that because of efficient heat transfer between the solid and gas in the microscale pores of the electrodes, the temperature difference between gas and solid is often negligible. However, if local variations in current density are significant, the LTNE effects may become significant and should be considered.

Solid oxide cells are best known in the energy sector as novel power generation devices through solid oxide fuel cells (SOFCs), which enable the direct conversion of chemical energy to electrical energy and result in high efficiency power generation. However, solid oxide electrolysis cells (SOECs) are receiving increased attention as a hydrogen production technology through high temperature electrolysis applications. The development of higher fidelity methods for modeling transport phenomena within solid oxide cells is necessary for the advancement of these key technologies. The proposed thesis analyzes the increased transport path lengths caused by constriction resistance effects in prevalent solid oxide cell designs. Such effects are so named because they arise from reductions in active transport area. Constriction resistance effects of SOFC geometry on continuum level mass and electronic transport through SOFC anodes are simulated. These effects are explored via analytic solutions of the Laplace equation with model verification achieved by computational methods such as finite element analysis (FEA). Parametric studies of cell geometry and fuel stream composition are performed based upon the models developed. These studies reveal a competition of losses present between mass and electronic transport losses and demonstrate the benefits of smaller SOFC unit cell geometry. Furthermore, the models developed for SOFC transport phenomena are applied toward the analysis of SOECs. The resulting parametric studies demonstrate that geometric configurations that demonstrate enhanced performance within SOFC operation also demonstrate enhanced performance within SOEC operation. Secondarily, the electrochemical degradation of SOFCs is explored with respect to delamination cracking phenomena about and within the critical electrolyte-anode interface. For thin electrolytes, constriction resistance effects may lead to the loss of electro-active area at both anode-electrolyte and cathode-electrolyte interfaces. This effect (referred to as masking) results in regions of unutilized electrolyte cross-sectional area, which can be a critical performance hindrance. Again analytic and computational means are employed in analyzing such degradation issues.

In this study, we have developed a dense La0.85Sr0.15MnO3-δ (LSM) Ce0.9Gd0.1O1.95 (GDC) composite electrode system for studying the surface modification of cathodes. The LSM and GDC grains in the composite were well defined and distinguished using energy dispersive x-ray (EDX) analysis. The specific three-phase boundary (TPB) length per unit electrode surface area was systematically controlled by adjusting the LSM to GDC volume ratio of the composite from 40% up to 70%. The TPB length for each tested sample was determined through stereological techniques and used to correlate the cell performance and degradation with the specific TPB length per unit surface area. An overlapping spheres percolation model was developed to estimate the activity of the TPB lines on the surface of the dense composite electrodes developed. The model suggested that the majority of the TPB lines would be active and the length of those lines maximized if the volume percent of the electrolyte material was kept in the range of 47 57%. Additionally, other insights into the processing conditions to maximize the amount of active TPB length were garnered from both the stereology calculations and the percolation simulations. Steady-state current voltage measurements as well as electrochemical impedance measurements on numerous samples under various environmental conditions were completed. The apparent activation energy for the reduction reaction was found to lie somewhere between 31 kJ/mol and 41 kJ/mol depending upon the experimental conditions. The exchange current density was found to vary with the partial pressure of oxygen differently over two separate regions. At relatively low partial pressures, i0 had an approximately dependence and at relatively high partial pressures, i0 had an approximately dependence. This led to the conclusion that a change in the rate limiting step occurs over this range. A method for deriving the electrochemical properties from proposed reaction mechanisms was also presented. State-space modeling was used as it is a robust approach to addressing these particular types of problems due to its relative ease of implementation and ability to efficiently handle large systems of differential algebraic equations. This method combined theoretical development with experimental results obtained previously to predict the electrochemical performance data. The simulations agreed well the experimental data and allowed for testing of operating conditions not easily reproducible in the lab (e.g. precise control and differentiation of low oxygen partial pressures).

Fuel cells represent a promising energy alternative to the traditional combustion of fossil fuels. In particular, solid oxide fuel cells (SOFCs) have been of interest due to their high energy densities and potential for stationary power applications. One of the key obstacles precluding the maturation and commercialization of planar SOFCs has been the absence of a robust sealant. A leakage computational model has been developed and refined in conjunction with leakage experiments and material characterization tests at Oak Ridge National Laboratory to predict leakage in a single interface metal-metal compressive seal assembly as well as multi-interface mica compressive seal assemblies. The composite model is applied as a predictive tool for assessing how certain parameters (i.e., temperature, applied compressive stress, surface finish, and elastic thermo physical properties) affect seal leakage rates.

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.