Solid oxide fuel cell platforms consisting of alternating cellular layers of yttria-stabilized zirconia electrolyte and Fe-Ni metallic interconnects (Fe45Ni, Fe47.5Ni, Fe50Ni) were produced through the co-extrusion of two particulate pastes. Subsequent thermal treatment in a hydrogen atmosphere was used to reduce iron and nickel oxides and co-sinter the entire structure. Issues surrounding this process include the constrained sintering of the layers and the evolution of residual stress between the dense, fired layers. Sintering curves for individual components of the layers were measured by dilatometry to ascertain each materials impact on overall sintering mismatch. X-ray diffraction, scanning electron microscopy and weight loss were utilized to examine phase evolution within the Fe-Ni alloys during reduction. YSZ powders densified above ~1050C and shrinkage was rapid above the sintering temperature. Shrinkage of the interconnect occurred in two stages: reduction and the initial stages of sintering concluded around ~600C, plateauing shortly and continuing at ~900C as pore removal and grain growth ensued simultaneously. Constrained sintering resulted in the formation of remnant porosity within the interconnect layers. Interconnect compositions were chosen in efforts to minimize disparities in thermal expansion with the electrolyte. Residual strains on the surfaces of the layers were measured by x-ray diffraction. Corresponding stresses were calculated using the sin2y method. Grain growth within the interconnect prohibited random planes to be measured so stress measurements were confined to the ceramic layers. Various material properties such as thermal expansion were collected and employed in a modified finite element model to estimate residual stresses in the platform. A method for determining a crucial parameter, the zero stress temperature was outlined and incorporated. Modeled values were found to agree well with XRD values, providing indirect confirmation of the zero stress temperature calculations. Discrepancies were attributed to microcracks found within the layer that arose due to residual stress values surpassing the tensile strength of the zirconia.

A program of study has been established for the quantitative study of electrode reactions in solid oxide fuel cells. The initial focus of the program is the mixed conducting cathode material strontium-doped lanthanum manganate (LSM). A formalism was established treating reactions taking place at the gas-exposed surface of mixed conducting electrodes. This formalism was incorporated into a phenomenological model for oxygen reduction in LSM, which treats the phenomenon of sheet resistance. Patterned electrodes were designed that reduce the dimensionality of the appropriate model, and these electrodes were successfully fabricated using DC sputtering and photolithography. A new model for the bulk defect equilibrium in LSM was proposed and shown to be a better fit to nonstoichiometry data at low temperatures. The fitting was carried out with a particle swarm optimizer and a rigorous method for identification. It was shown that a model for the interface structure between LSM and yttria-stabilized zirconia (YSZ) that assumes free oxygen vacancies in YSZ does not accord with experimental observations. Cluster variation method (CVM) was adapted for analysis of the problem, and a new analytical method combining CVM and electrical contributions to the free energy was proposed.

Electrodes in a solid oxide fuel cell (SOFC) must possess both adequate porosity and electronic conductivity to perform their functions in the cell. They must be porous to permit rapid mass transport of reactant and product gases and sufficiently conductive to permit efficient electron transfer. However, it is nearly impossible to simultaneously control porosity and conductivity using conventional design and fabrication techniques. In this dissertation, computational design and performance optimization of microarchitectured SOFCs is first investigated in order to achieve higher power density and thus higher efficiency than currently attainable in state-of-the-art SOFCs. This involves a coupled multiphysics simulation of mass transport, electrochemical charge transfer reaction, and current balance as a function of SOFC microarchitecture. Next, the fabrication of microarchitectured SOFCs consistent with the computational designs is addressed based on anode-supported SOFC button cells using the laser ablation technique. Finally, the performance of a fabricated SOFC unit cell is characterized and compared against the performance predicted by the computational model. The results show that the performance of microarchitectured SOFCs was improved against the baseline structure and measured experimental data were well matched to simulation results.

Solid oxide fuel cells (SOFCs) are electrochemical devices based on solid oxide electrolytes that convert chemical energy in fuels directly into electricity via electrode reactions. SOFCs have the advantages of high energy efficiency and low emissions and hold the potential to be the power of the future, especially for small power generation systems (1-10 kW). Another unique advantage of SOFCs is the potential to directly utilize hydrocarbon fuels such as natural gas through internal reforming. However, all hydrocarbon fuels contain some sulfur compounds, which transform to hydrogen sulfide (H2S) in the reforming process and dramatically degrade the performance of the existing SOFCs. In this study, the interactions between sulfur contaminant (in the form of H2S) and the anodes for SOFCs were systematically investigated in order to gain a fundamental understanding of the mechanism of sulfur poisoning and ultimately to achieve rational design of sulfur-tolerant anodes. The sulfur poisoning behavior of the state-of-the-art Ni-YSZ cermet anodes was characterized using electrochemical measurements performed on button cells (of different structures) under various operating conditions, including H2S concentration, temperature, cell current density/terminal voltage, and cell structure. Also, the mechanisms of interactions between sulfur and the Ni-YSZ cermet anode were investigated using both ex situ and in situ characterization techniques such as Raman spectroscopy. Results suggest that the sulfur poisoning of Ni-YSZ cermet anodes at high temperatures in fuels with ppm-level H2S is due not to the formation of multi-layer conventional nickel sulfides but to the adsorption of sulfur on the nickel surface. In addition, new sulfur-tolerant anode materials were explored in this study. Thermodynamic principles were applied to predict the stability of candidate sulfur-tolerant anode materials and explain complex phenomena concerning the reactivity of candidate materials with hydrogen sulfide. The enhanced sulfur tolerance for some candidate anode materials such as (Gd2Ti1.4Mo0.6O7) is attributed to the transition of the surface from metal oxides to sulfides (i.e., MoS2), which enhances the catalytic activity and increases the number of reaction sites.

Thesis (Ph.D.) - University of St Andrews, March 2010.

This study has focused on the implementation of a stack system for a novel design of solid oxide fuel cell (SOFCRoll). The issues affecting the commercialization of SOFCs are mainly based on durability and cost. The new design offers a number of advantages over the existing designs; it seeks to retain the specific advantages of both the tubular (high unit strength, no sealing problems) and planar arrangements (high power density). This design also aims to achieve low manufacturing cost by utilizing a cheap, easily scalable production technique: tape casting, together with co-firing all components, in one single step. In this study aspects of the design and operation of SOFCRoll stacks were studied particularly those affecting the single cell test reproducibility such as pre test quality control and scale up issues such as bundle and stack gas distribution. Initially the performance of single cells was characterized and the variation of their power output with temperature was observed. The maximum power, 0.7W at 800°C was achieved with a high silver content. The OCV and total resistance of this cell were 0.93V, 0.30Ω respectively. A standard pre-test quality control and current collection technique was introduced. At 800°C reproducible performance of 0.5W power obtained, average OCV was 0.935V and average series and polarization resistances of 0.18Ω and 0.19Ω was achieved respectively. Once single cell reproducibility was achieved, the design and operation of a 5 cell SOFCRoll bundle was investigated. A FLUENT CFD model was used to optimize the gas distribution in the five cell manifold design. The value of the model as a design tool was demonstrated by the comparison of 3 different gas manifold designs. The final manifold design M3 achieved 2.5W which is consistent with the 0.5W per a cell target. This manifold was then used as the basis for the development of a 25 cell stack which was built and tested. The 25 cell stack testing results were down to 0.35W per a cell. The performance drop highlighted the problem of fuel cell manufacturing reproducibility and also the importance of introducing reproducible manufacturing tequniques. That been the case for single cell manufacturing reproducibility issue, the fundamental concern for performance drop remains a design issue. To optimize the SOFCRoll design and to assist with the development program a single-cell CFD model was developed using FLUENT. The model was validated by comparison with data from experimental measurements for the single cell. The model work was used to predict the geometrical effect of the SOFCRoll tubular and the spiral gas channel configuration and current collector configuration. Results indicate the outlet gas flow velocity is higher around the spiral, near the gas inlet (the gas interring the cell preferentially flows around the spiral) therefore, velocity decrease as the gas moves along the cell. The lowest outlet velocity is registered opposite to the gas inlet, thus creating non-uniform gas distribution. The current density distribution is not uniform and is affected primarily by reactant flow distributions along the cell and possible current collection issues particularly around the spiral part of the cell.

Solid oxide fuel cells (SOFCs) are the most efficient electrochemical devices to directly convert stored chemical energy to usable electrical energy. The infiltration of ceramic conductors and catalytic metals (e.g. Ni, Pt and Pd) into porous scaffolds that had been pre-sintered onto the electrolyte is regarded as an effective way of promoting the electrode performance via producing nano-scale particles by in-situ sintering at relatively low temperatures. Large-scale fuel cells (5 cm x 5 cm) are prepared with this method and tested to demonstrate its scalability so as to achieve industrial applications. Four configurations are examined in respect of variation in the thickness of cathode, anode and electrolyte to investigate their effect on the infiltration process and electrochemical losses. To further improve infiltration as a method of fabricating high-performance electrodes, much effort is also devoted to optimising and understanding the microstructure of pre-sintered scaffold and its effect on infiltration using image analysis and electrochemical impedance. First, we have prepared the nano-structured electrodes on the 200-μm thick electrolyte-supported planar fuel cell with a 5 x 5 cm dimension. The 8YSZ scaffold is impregnated with La₀.₈Sr₀.₂Cr₀.₅Mn₀.₅O₃ (LSCM) for the anode and La₀.₈Sr₀.₂FeO₃ (LSF) for the cathode. The large planar cell achieved a maximum power density of 116 mWcm⁻² at 700°C and 223 mWcm⁻² at 800°C in humidified hydrogen. Moreover, with the addition of catalyst of 10 wt.% CeO₂ and 1 wt.% Pd, the cell performance reached 209 mWcm⁻² at 700°C and 406 mWcm⁻² at 800°C. Compared to the cell without catalysts, ceria and Pd are efficient in decreasing the electrochemical reaction resistance but making the diffusion resistance more obvious. Second, supported thin electrolytes are prepared by scalable tape casting to reduce the ohmic losses as that in electrolyte-supported cell. The cell with thick LSF-infiltrated support is very efficient in decreasing the ohmic loss thanks to the high solubility of its nitrate precursors in water and fairly high electric conductivity, but the thick cathode causes higher diffusional losses, especially at 800°C. Even though with thinner electrolyte, the ohmic loss from the cell with thick infiltrated anode is comparable to that of 200-μm electrolyte supported cell. The extra ohmic loss can be attributed to the compositional segregation of La₀.₇Sr₀.₃VO₃ (LSV) in the infiltration process in the anode, and lower loading, ca. 25 wt %. A trade-off between the diffusional loss from the cathode and the extra ohmic loss from the thick anode can be achieved by sandwiching the electrolyte between electrodes with identical thickness. A flat large area cell prepared with this method can achieve a high performance of 300 mW cm⁻² and 489 mW cm⁻² at 700°C and 800°C, respectively, if Pd-ceria is added to the anode LSV as catalyst. Third, image analyses and modelling are performed on the constrained sintering of porous thin film on a rigid substrate to study the evolution of pores at different stages. Result shows that both the anisotropy of the pore former/pores in the green body and transport of materials during the sintering process have effect on the orientation of the final microstructure. Specifically, the in-plane orientation of large-scale pores will be intensified during the constrained sintering process, while those small pores whose shape are subjected to materials transport during sintering tend to erect during the constrained sintering process at 1300°C. Fourth, image analyses and semi-quantification are used to predict the correlation between the microstructure and performance of the LSF-infiltrated electrode. Two types of YSZ powders, Unitec 1-μm powder with a broad particle-size distribution having two maxima at ~ 0.1 μm and 0.8 μm, and Unitec 2-μm powder with only one at ~1 μm are selected to fabricate the porous scaffold for infiltration. The porous structure using Unitec 2-μm powder shows finer YSZ grains and a higher boundary length than the 2-μm powder. Ac impedance on symmetrical cells was used to evaluate the performance of the electrode impregnated with 35-wt.% La₀.₈Sr₀.₂FeO₃. At 700°C, the electrode from Unitec 2-μm powder shows a polarization resistance (Rp) of 0.21 Ω cm², and series resistance (Rs) of 8.5 Ω cm², lower than the electrode from Unitec 1-μm powder does. The quantitative study on image indicates that Unitec 2-μm powder is better in producing architecture of high porosity or long triple phase boundary (TPB), which is attributed as the reason for the higher performance of the LSF-impregnated electrode. Finally, oxides of transition metals are doped into the YSZ-infiltrated LSF electrode and the impedances of symmetrical cells are tested to evaluate their effect on the ohmic and polarization resistance. Cobalt oxides are able to reduce the ohmic resistance and polarization resistance only when it is calcined at 700°C, but nickel oxide can reduce both the ohmic and polarization resistance if it is well-mixed and fully reacted with the previously infiltrated LSF. Doping of manganese oxide into LSF-YSZ electrode slightly changes the ohmic resistance but significantly increases the polarization resistance. Detailed analyses of the impact of infiltration process on the impedance data and oxygen reduction process are also presented.

Lowering the operating temperature of the high-temperature, solid oxide fuel cell (SOFC) improves both the thermodynamic efficiency and the lifetime of this energy efficient technology. Unfortunately the rate of oxygen-ion transport through the solid electrolyte is temperature dependent, and materials previously employed as electrolytes in the high-temperature SOFC perform poorly at intermediate temperatures. Therefore new oxygen-ion conductors with enhanced ionic conductivity at intermediate temperatures are required. The bulk of the existing literature on high-temperature SOFCs has focussed on zirconia-based binary systems as electrolytes, due to their high ionic conductivity and negligible electronic conductivity. Only select compositions within the zirconia-scandia system have demonstrated acceptable ionic conductivity levels at intermediate temperatures; however unstable phase assemblage and the high economic cost of scandia are clear disadvantages. Ceria-based binary systems have demonstrated improved oxygen-ion conductivity at intermediate temperature compared to many zirconia systems, however significant levels of n-type electronic conductivity are observed at low oxygen partial pressures. Consequently it was thought unlikely that significant increases in ionic conductivity would be found in existing zirconia- and ceria-based binary systems, therefore another approach was required in an attempt to improve the performance of these established fluorite systems. The fluorite systems Zr0.75Ce0.08M0.17O1.92 (M = Nd, Sm, Gd, Dy, Ho, Y, Er, Yb, Sc) were prepared and investigated as possible, intermediate-temperature SOFC electrolytes in an attempt to combine the higher conductivity found in the ceria systems with the low electronic conductivity observed in the zirconia systems. Also it was anticipated that systems containing dopants not previously observed to confer high ionic conductivity in either zirconia- and ceria-based binary systems, might exhibit enhanced ionic conductivity with expansion of the zirconia lattice resulting from the addition of ceria. All the as-fired Zr0.75Ce0.08M0.17O1.92 compositions possessed the face-centred cubic structure and lattice parameter measurements revealed the anticipated unit cell enlargement as the size of the dopant cation increased. No unusual microstructural parameters were identified that could be expected to interfere with the ionic transport properties in the as-fired compositions. The electrical conductivity was found to be influenced by the dopant-ion radius, the presence of ceria, low oxygen partial pressures and, in some compositions, the formation of poorly conducting, ordered-pyrochlore microdomains dispersed amongst the cubic defect-fluorite matrix. In a second approach to the formulation of new oxygen-ion conductors suitable for the intermediate-temperature SOFC, compounds possessing structures other than the fluorite structure were considered. An examination of the literature for oxides having the pyrochlore, scheelite and perovskite structures showed that the Sr+2- and Mg+2-doped LaGaO3 perovskites (LSGM) possessed ionic conductivity equal to the highest conducting, zirconia and ceria binary compounds. Therefore the perovskite systems La0.9Sr0.1Ga(0.8-x)InxMg0.2O2.85 (X = 0, 0.05, 0.1, 0.2, 0.4, 0.6, 0.8) (I-LSGM) were prepared and examined, the objective being to favourably influence structural parameters believed responsible for optimal ionic conductivity, namely the unit cell symmetry and volume. It was found that In+3 systematically substituted for Ga+3 on to the B-site of LSGM at least up to the X = 0.4 composition. While In+3 was found to replace the Ga+3 as expected, Mg+2, which occupies the same crystallographic site, was also replaced by In+3. Up to the X = 0.2 composition, at least two trace level secondary phases were observed to form along with the bulk I-LSGM phase. For I-LSGM compositions with X > 0.2, significantly larger concentrations of the secondary phases were identified. Evidence of a strontium-rich, high-temperature liquid phase was observed also near the grain boundaries on as-sintered and thermally etched surfaces in LSGM and I-LSGM compositions. It is believed that the observed, high sintered density in the complex, doped-LaGaO3 systems is due to the formation of this high-temperature liquid phase. Increasing levels of diffuse scatter and superstructure formation were observed in electron diffraction patterns in the I-LSGM bulk phase (up to X = 0.2), indicating a possible decrease in vacancy concentration and reduced, localised unit cell symmetry. The electrical conductivity in the I-LSGM compositions was believed to be influenced by the distortion of the oxygen-ion conduction path, a reduction in vacancy concentration, formation of stronger dopant-vacancy associates at low temperature and the presence of ordered structures. In addition, phase instability, in the form of subtle ordering in specific crystalline planes, was observed to influence the electrical conductivity as a function of time at intermediate temperatures.

Thesis (M.S.)--University of Missouri--Rolla, 2007. / Vita. The entire thesis text is included in file. Title from title screen of thesis/dissertation PDF file (viewed April 17, 2007) Includes bibliographical references (p. 77-80).

The mathematical analysis has been developed by using finite volume method, experimental data from literatures, and solving numerically to predict solid oxide fuel cell performances with different operating conditions and different material properties. The in-house program presents flow fields, temperature distributions, and performance predictions of typical solid oxide fuel cells operating at different temperatures, 1000 C, 800 C, 600 C, and 500 C, and different electrolyte materials, Yttria-Stabilized zirconia (YSZ) and Gadolinia-doped ceria (CGO). From performance predictions show that the performance of an anode-supported planar SOFC is better than that of an electrolyte-supported planar SOFC for the same material used, same electrode electrochemical considerations, and same operating conditions. The anode-supported solid oxide fuel cells can be used to give the high power density in the higher current density range than the electrolyte-supported solid oxide fuel cells. Even though the electrolyte-supported solid oxide fuel cells give the lower power density and can operate in the lower current density range but they can be used as a small power generator which is portable and provide low power. Furthermore, it is shown that the effect of the electrolyte materials plays important roles to the performance predictions. This should be noted that performance comparisons are obtained by using the same electrode materials. The YSZ-electrolyte solid oxide fuel cells in this work show higher performance than the CGO-electrolyte solid oxide fuel cells when SOFCs operate above 756 C. On the other hand, when CGO based SOFCs operate under 756 C, they shows higher performance than YSZ based SOFCs because the conductivity values of CGO are higher than that of YSZ temperatures lower than 756 C. Since the CGO conductivity in this work is high and the effects of different electrode materials, they can be implied that conductivity values of electrolyte and electrode materials have to be improved.