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<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)

The interactions between different components of solid oxide cells (SOCs) are critical issues for achieving the tens of thousands of hour's goal for long-term performance stability and lifetime. The interactions between the ceramic electrolyte, porous ceramic air electrode, and metallic interconnect materials — including solid state interfacial reactions and vaporization/deposition of some volatile elements — have been investigated in the simulated SOC operating environment. The interactions demonstrate the material degradation mechanisms of the cell components and the effects of different factors such as chemical composition and microstructure of the materials, as well as atmosphere and current load on the air electrode side. In the aspect of materials, this work contributes to the degradation mechanism on the air electrode side and provides practical material design criteria for long-term SOC operation. In this research, an yttria-stabilized zirconia electrolyte (YSZ)/strontium-doped lanthanum manganite electrode (LSM)/AISI 441 stainless steel interconnect tri-layer structure has been fabricated in order to simulate the air electrode working environment of a real cell. The tri-layer samples have been treated in dry/moist air atmospheres at 800°C for up to 500 h. The LSM air electrode shows slight grain growth, but the growth is less in moist atmospheres. The amount of Cr deposition on the LSM surface is slightly more for the samples thermally treated in the moist atmospheres. At the YSZ/LSM interface, La enrichment is significant while Mn depletion occurs. The Cr deposition at the YSZ/LSM interface is observed. The stoichiometry of the air electrode is an important factor for the interactions. The air electrode composition has been varied by changing the x value in (La0.8Sr0.2)xMnO₃ from 0.95 to 1.05 (LSM95, LSM100, and LSM105). The enrichment of La at the YSZ/LSM interface inhibits the Cr deposition. The mechanisms of Cr poisoning and LSM elemental surface segregation are discussed. A 200 mA·cm-2 current load have been applied on the simulated cells. Mn is a key element for Cr deposition under polarization. Excessive Mn in the LSM lessens the formation of La-containing phases at the YSZ/LSM interface and accelerates Cr deposition. Deficient Mn in LSM leads to extensive interfacial reaction with YSZ forming more La-containing phase and inhibiting Cr deposition. / Ph. D.

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.

Seal glass is essential and plays a crucial role in solid oxide fuel/electrolyzer cell performance and durability. A seal glass should have a combination of thermal, chemical, mechanical, and electrical properties in order to seal different cell components and stacks and prevent gas leakage. All the desired properties can simultaneously be obtained in a seal glass by suitable compositional design. In this dissertation, SrO-La₂O₃-A₂O₃-B₂O₃3-SiO₂ based seal glasses have been developed and composition-structure-property relationships have been investigated. B₂O₃ free SrO-La₂O₃-Al₂O₃-SiO₂ based seal glass is the most suitable and its compatibility with the metallic interconnects and sealing performances have been evaluated. A seal glass should be stable for 5,000-40,000 hrs in the oxidizing and reducing atmospheres at 600-900°C but both the thermal and chemical stability is a persistent problem. The effect of Al₂O₃ on a SrO-La₂O₃-Al₂O₃-B₂O₃-SiO₂ based seal glass has been studied to improve the thermal properties, such as glass transition temperature, softening temperature and thermal expansion coefficient, and the thermal stability. Al₂O₃ improves the thermal stability but does not significantly affect the thermal properties of the seal glass. Comprehensive understanding of composition-structure-property relationships is needed to design a suitable seal glass. The thermal properties and stability of a borosilicate seal glass depend on the B2O3:SiO2 ratio in the composition. The role of B₂O₃:SiO₂ ratio on the glass network structure of the SrO-La₂O₃-Al₂O₃-B₂O₃-SiO₂ based seal glasses has been studied using Raman spectroscopy and nuclear magneto resonance spectroscopy. The thermal properties and thermal stability were correlated with the glass network structure and the calculated network connectivity. This study shows that the thermal properties degrade with increasing B₂O₃:SiO₂ ratio due to increase in the non-bridging oxygen and decrease in the network connectivity. High B₂O₃:SiO₂ ratio induces BO4 and SiO4 structural unit ordering, increases micro-heterogeneity, and subsequently degrades thermal stability. B₂O₃ free SrO-La₂O₃-Al₂O₃-SiO₂ seal glass shows the best combination of the thermal properties and thermal stability among the studied glasses. Nickel or nickel oxide is added into a seal glass to modify the thermal properties depending on the specific composition. The role of nickel as a network former or modifier and its effect on the thermal properties and thermal stability of the SrO-La₂O₃-Al₂O₃-SiO₂ based seal glasses have been investigated. Nickel is a modifier in this glass system and does not improve the thermal properties but degrades thermal stability by decreasing network connectivity and inducing micro-heterogeneity. The interconnect-seal glass interface stability is the most crucial for solid oxide fuel/electrolyzer cell. Crofer 22 APU and AISI 441 alloys are the preferred interconnects. The interfacial stability of the SrO-La₂O₃-Al₂O₃-SiO₂ based seal glass with these alloys have been studied as a function of time (0-1000 hrs), temperature (700-850°C), atmospheres (air, argon, and H₂O/H₂) using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction analysis (XRD). Complementary analytical techniques such as wave length dispersive spectroscopy (WDS) and SEM of thin samples were also carried out for selected samples. This study shows good interfacial stability of the SrO-La₂O₃-Al₂O₃-SiO₂ based seal glass with these alloys for the studied conditions. A suitable seal glass should be hermetic and withstand 100-1000 thermal cycles for practical application. Sealing performances of the SrO-La2O3-Al2O3-SiO2 based seal glass have been evaluated by pressure-leakage method. The seal glass is hermetic for at least 2000 hrs and withstands 100 thermal cycles. Overall, present work shows that the SrO-La₂O₃-Al₂O₃-SiO₂ based glass has all the desired properties and suitable for solid oxide fuel/electrolyzer cell seal. / Ph. D.

Detailed thermodynamic, kinetic, geometric, and cost models are developed, implemented, and validated for the synthesis/design and operational analysis of hybrid solid oxide fuel cell (SOFC) – gas turbine (GT) – steam turbine (ST) systems ranging in size from 1.5 MWe to 10 MWe. The fuel cell model used in this thesis is based on a tubular Siemens-Westinghouse-type SOFC, which is integrated with a gas turbine and a heat recovery steam generator (HRSG) integrated in turn with a steam turbine cycle. The SOFC/GT subsystem is based on previous work done by Francesco Calise during his doctoral research (Calise, 2005). In that work, a HRSG is not used. Instead, the gas turbine exhaust is used by a number of heat exchangers to preheat the air and fuel entering the fuel cell and to provide energy for district heating. The current work considers instead the possible benefits of using the exhaust gases in an HRSG in order to produce steam which drives a steam turbine for additional power output. Four different steam turbine cycles are considered in this M.S. thesis work: a single-pressure, a dual-pressure, a triple-pressure, and a triple-pressure with reheat. The models have been developed to function both at design (full load) and off-design (partial load) conditions. In addition, different solid oxide fuel cell sizes are examined to assure a proper selection of SOFC size based on efficiency or cost. The thermoeconomic analysis includes cost functions developed specifically for the different system and component sizes (capacities) analyzed. A parametric study is used to determine the most viable system/component syntheses/designs based on maximizing total system efficiency or minimizing total system life cycle cost. / Master of Science

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.

Functional materials, particularly metal oxides, have been the focus of much attention in solid state chemistry for many years and impact every aspect of modern life. The approach adopted in this thesis to access desirable functionality for enhanced fundamental understanding is via modifying existing materials by deploying reducing synthetic procedures. This work spans several groups of inorganic crystalline materials, but is unified by the development of new properties within host compounds of particular relevance to solid oxide fuel cell technology, which allow interstitial oxide ion conduction at elevated temperatures. The Ca₁₂Al₁₄O₃₂e₂ electride was successfully synthesized by replacing the mobile extra-framework oxygen ions with electrons acting as anions. The high concentration of electrons in the C12A7 electride gives rise to an exceptionally high electronic conductivity of up to 245 S cm⁻¹ at room temperature. Making use of the high density of electrons in Ca₁₂Al₁₄O₃₂e₂ electride, the strong N-N bonds in N₂ was found to be broken when heating Ca₁₂Al₁₄O₃₂e₂ in a N₂ atmosphere. A reaction between silicate apatites and the titanium metal yielded another completely new electride material La₉.₀Sr₁.₀(SiO₄)₆O₂.₄e₀.₂ which was found to be a semiconductor. To fully understand the role of oxygen interstitials in silicate apatites, high-resolution transmission electron microscopy (HRTEM) was employed as the main technique in probing how the oxygen nonstoichiometry is accommodated at the atomic level. Atomic-resolution imaging of interstitial oxygen in La₉.₀Sr₁.₀(SiO₄)₆O₂.₅ proved to be a success in this thesis. Substitution of oxygen in 2a and interstitial sites with fluoride ions in La[subscript(8+y)]Sr[subscript(2- z)](SiO₄)₆O[subscript(2+(3y-2z)/2)] (0<y<2, 0<z<2) could be an approach to enriching the functionalities in the apatite structure. A wide range of fluoride substitution levels was tolerated in La[subscript(10-x)]Sr[subscript(x)](SiO₄)₆O[subscript(3-1.5x)]F[subscript(2x)] (x= 0.67, 1, 1.5, 2) and AC impedance measurements were found in support of a tentative conclusion that fluoride ions could be mobile in fluorinated apatites. The last part of this thesis was focused on a new class of fast oxide ion conductors based on Ge₅P₆O₂₅ whose performance was superior to both La₉.₀Sr₁.₀(SiO₄)₆O₂.₅ and Ca₁₂Al₁₄O₃₃ in the low temperature range.