This work is focused on a state-of-the-art tubular micro-solid oxide fuel cell (TSOFC), ~3 millimeters in diameter and ~300 microns thick, with Ni/YSZ and LSM/YSZ composite electrodes and a YSZ electrolyte. A 2D axi-symmetric, multi-scale CFD model is developed which includes the fluid flow, mass transfer, and heat transfer within the gas channels and the porous electrodes. The electrochemical reactions are modeled within the volume of the electrodes, enabling the model to account for the extent of the reaction zone. Thermodynamic expressions are developed to estimate the single-electrode reversible heat generation and the single-electrode electromotive force of a non-isothermal electrochemical cell. The isothermal, non-isothermal, and transient models are each validated against the experimental results, and consistent with the physical reality of the TSOFC. A novel approach is used to estimate the kinetic parameters, enabling the simulations to be used as a diagnostic tool. The model is used to gain a thorough insight about the TSOFC. The cathode electrochemical activity and the anode support ohmic loss are identified as the two major performance bottlenecks for this cell. Including radiation is found to be essential for a physically meaningful heat transfer model. The thermoelectric effects on the cell overall electromotive force is found to be negligible. It is found that the anode reaction is always endothermic, while the cathode reaction is always exothermic, and that the temperature gradients across the cell layers are less than 0.05C The cell transient response is found to be fast, and dominated by the thermal transients. Several physical properties used in the model are measured experimentally, indicating that that the correlations used in the literature are not always suitable, especially when new fabrication techniques are used. The conductivity of the anode support was measured to be several orders of magnitude lower than expected and very sensitive to temperature, which explains the lower than expected and occasionally degrading cell performance. A hypothesis is proposed to explain this phenomenon based on the thermal expansion effects which result in the formation and disruption of particle to particle contacts within the composite electrode. / Chemical Engineering

As the demand for green energy and fuel cells grows, more attention is drawn towards Solid Oxide Fuel Cells (SOFCs). Random and complex structure of composite electrodes and underlying electrochemical process has not been completely unveiled yet and further study is required to acquire more understanding. Modeling in this regard plays an important role as it pinpoints key parameters in optimum design of the cell without resorting to costly and uncertain experiments which might even lead to misinterpretations due to random nature of experimental data. The aim of this work is to develop a new rigorous model to study the structure performance relationship of (SOFC) composite electrodes. The work has been conducted in two phases, a two-dimensional continuous approach and three-dimensional discrete model. A new two-dimensional, geometrical model which captures the inhomogeneous nature of the location of electrochemical reactions based on random packing of electronic and ionic conducting particles has been developed. The results show that the concentration of oxygen inside the cathode in the two-dimensional model is not only a function of the electrode depth but also changes along the width of the electrode. Furthermore the effect of composition of the electrode on the length of three phase boundary (TPB) and total polarization resistance has been demonstrated. A parametric study of the effect of the conductivity of ionic conductor and diffusion coefficient on the performance of the electrode has been given. To make a more realistic analysis, a three-dimensional reconstruction of (SOFC) composite electrodes was developed to evaluate the performance and further investigate the effect of microstructure on the performance of electrodes. To enhance connectivity between particles and increase the length of TPB, sintering process is mimicked by enlarging particles to certain degree. Geometrical characteristics such as length of TBP and active contact area as well as porosity can easily be calculated using the current model. Electrochemical process is simulated using resistor-network model and complete Butler-Volmer equation is used to deal with charge-transfer process on TBP. The model shows that TPBs are not uniformly distributed across the electrode and location of TPBs as well as amount of electrochemical reaction is not homogeneous. Effects of particle size, electrode thickness, particle size ratio, electron and ion conductor conductivities and rate of electrochemical reaction on overall electrochemical performance of electrode are investigated. / Chemical Engineering

A series of cermet powders of composition NixCo(1-x)O-YSZ were synthesized for testing as cermet anode materials for SOFCs. The Co is found by powder XRD to become incorporated into the crystal lattice of the NiO, thus forming a true alloyed material. SEM and EDS results show two types of particles upon sintering to 1380oC: small, amorphous particles of YSZ and large, crystalline particles of nickel. The electrochemical oxidation of hydrogen on a cermet anode composed of Ni0.7Co0.3O-YSZ was investigated using a series of many button cells. Through EIS data, cyclic voltammetry data, the exchange current densities for these button cells were determined. Although a relatively large variation was found (expected to be due to microstructural variation) the average values for both methods of measurement is in good agreement in hydrogen. Following reduction in pure hydrogen, the fuel was changed to a mixture with high concentration of H2S. It was found that a concentration of 10 % H2S/H2 produced a sudden change in anode microstructure and resulted in loss of exchange current density. Lowering the amount of H2S in the initial fuel feed, which allowed for a more gradual microstructural change, allowed the cell to eventually function at concentrations in excess of 10 % H2S/H2. It was determined by OCV values in various concentrations of H2S/H2 that hydrogen is the predominant fuel of choice, even if H2S is available. Following electrochemical testing, slow cooling in a 10 % H2S/H2 mixture following produced metal sulfide spheres, as determined by SEM and EDS. Investigation in hydrocarbon, alcohol and biodiesel fuels was then undertaken to test the fuel variability of the given cermet anode material. Methane containing 10 % H2S was found to have increased exchange current density relative to poisoned hydrogen. Ethane and biodiesel experienced no increase in exchange current density, but a lengthening of the functional lifetime of the cell was observed, indicating reduced carbon poisoning. Methanol is a promising oxygen-containing SOFC fuel since it produced exchange current density values larger than hydrogen, and showed no evidence of coke formation by post-mortem SEM. Since oxygen-containing fuels are known to decompose in the gas phase at typical SOFC operating temperatures, the performance in a mixture of various CO/H2 fuels was then investigated. The Ni0.7Co0.3O-YSZ cermet anode gave higher exchange current density values for low ratio of CO/H2 fuels in the range 20/80 and 30/70 compared to pure H2. This is the first example of a Ni-based anode providing higher performance with a CO/H2 mixed fuel than for a pure H2 fuel. Finally, continuous running of a cell with fuel ratio 25/75 CO/H2 for 7 days produced exchange current density values, which were observed to increase significantly above the values for pure H2 during days 1-4 followed by deterioration below the value for hydrogen on subsequent days.

This thesis is concerned with the thermodynamic analyses of ion and proton-conducting solid oxide fuel cells (SOFC) fed with ammonia and urea as fuels. A multi-level approach was used to determine the feasibility and the performance of the fuel cells. First, the cell-level thermodynamics were examined to capture the effect of various operating parameters on the cell voltage under open-circuit conditions. Second, electrochemical studies were conducted to characterize the cell-level performance under closed-circuit conditions. Third, the fuel cells were individually integrated in a combined-cycle power generation system and parametric studies were performed to assess the overall performance as well as the thermal and exergy efficiencies. The findings of this study showed that the overall performance and efficiency of the ammonia fed SOFC is superior in comparison to that of the urea fed counterpart. In particular, the ammonia fed system combined with proton-conducting SOFC achieved a thermal efficiency as high as 85% and exergy efficiency as high as 75%. The respective efficiencies of the ammonia fed system combined with ion-conducting SOFC were lower by 5-10%. However, the urea fed system combined with ion or proton-conducting SOFC demonstrated much lower performance and efficiencies due to higher thermodynamic irreversibilities. / UOIT

The reduction of manufacturing costs and the facilitation of direct-oxidation of hydrocarbon fuels have been identified as means of promoting the commercialization of the solid oxide fuel cell, a technology that offers both environmental and fuel conservation benefits compared to conventional energy conversion technologies. This research was conducted with the aim of realizing the production of direct-oxidation anodes using atmospheric plasma spraying, which has been identified as a fabrication technique that has the potential to reduce the manufacturing costs of solid oxide fuel cells. This thesis details the rationale behind the selection of the anode compositions (BaO-Ni-YSZ, CeO2-Ni-YSZ, and Sn-Ni-YSZ) and the specifics of the specialized fabrication strategy (SPS-SPPS) that was devised with the aim of realizing microstructures similar to those where the secondary phases (BaO, CeO2, and Sn) coat the surfaces of the primary Ni and YSZ phases. Results of XRD, SEM and EDS analyses are presented.

With increasing attention paid to metal-supported SOFCs recently, metal supports have become important factors in the performance of the cells. The formation of surface oxides and the poisoning of Cr from Cr2O3-forming metal supports often result in the degradation of the cells. However, few studies have focused on developing oxidation resistance and decreasing Cr migration from porous alloys in intermediate temperature metal-supported SOFCs. In this work, Y2O3 and CeO2 coatings were applied to porous AISI 430 stainless steels by sol-gel dip coating. Phases and microstructures of the coatings on the porous metal supports were characterized by XRD and SEM with EDS, respectively. The effects of the coatings on oxidation resistance of the supports were evaluated by cyclic oxidation testing. Electrical and electrochemical properties of LSCF-SDC cathodes and symmetrical cells deposited on the Y2O3-protected metal supports were also investigated. The issue of Cr depletion of the supports was also discussed.

The reduction of manufacturing costs and the facilitation of direct-oxidation of hydrocarbon fuels have been identified as means of promoting the commercialization of the solid oxide fuel cell, a technology that offers both environmental and fuel conservation benefits compared to conventional energy conversion technologies. This research was conducted with the aim of realizing the production of direct-oxidation anodes using atmospheric plasma spraying, which has been identified as a fabrication technique that has the potential to reduce the manufacturing costs of solid oxide fuel cells. This thesis details the rationale behind the selection of the anode compositions (BaO-Ni-YSZ, CeO2-Ni-YSZ, and Sn-Ni-YSZ) and the specifics of the specialized fabrication strategy (SPS-SPPS) that was devised with the aim of realizing microstructures similar to those where the secondary phases (BaO, CeO2, and Sn) coat the surfaces of the primary Ni and YSZ phases. Results of XRD, SEM and EDS analyses are presented.

With increasing attention paid to metal-supported SOFCs recently, metal supports have become important factors in the performance of the cells. The formation of surface oxides and the poisoning of Cr from Cr2O3-forming metal supports often result in the degradation of the cells. However, few studies have focused on developing oxidation resistance and decreasing Cr migration from porous alloys in intermediate temperature metal-supported SOFCs. In this work, Y2O3 and CeO2 coatings were applied to porous AISI 430 stainless steels by sol-gel dip coating. Phases and microstructures of the coatings on the porous metal supports were characterized by XRD and SEM with EDS, respectively. The effects of the coatings on oxidation resistance of the supports were evaluated by cyclic oxidation testing. Electrical and electrochemical properties of LSCF-SDC cathodes and symmetrical cells deposited on the Y2O3-protected metal supports were also investigated. The issue of Cr depletion of the supports was also discussed.

A series of cermet powders of composition NixCo(1-x)O-YSZ were synthesized for testing as cermet anode materials for SOFCs. The Co is found by powder XRD to become incorporated into the crystal lattice of the NiO, thus forming a true alloyed material. SEM and EDS results show two types of particles upon sintering to 1380oC: small, amorphous particles of YSZ and large, crystalline particles of nickel. The electrochemical oxidation of hydrogen on a cermet anode composed of Ni0.7Co0.3O-YSZ was investigated using a series of many button cells. Through EIS data, cyclic voltammetry data, the exchange current densities for these button cells were determined. Although a relatively large variation was found (expected to be due to microstructural variation) the average values for both methods of measurement is in good agreement in hydrogen. Following reduction in pure hydrogen, the fuel was changed to a mixture with high concentration of H2S. It was found that a concentration of 10 % H2S/H2 produced a sudden change in anode microstructure and resulted in loss of exchange current density. Lowering the amount of H2S in the initial fuel feed, which allowed for a more gradual microstructural change, allowed the cell to eventually function at concentrations in excess of 10 % H2S/H2. It was determined by OCV values in various concentrations of H2S/H2 that hydrogen is the predominant fuel of choice, even if H2S is available. Following electrochemical testing, slow cooling in a 10 % H2S/H2 mixture following produced metal sulfide spheres, as determined by SEM and EDS. Investigation in hydrocarbon, alcohol and biodiesel fuels was then undertaken to test the fuel variability of the given cermet anode material. Methane containing 10 % H2S was found to have increased exchange current density relative to poisoned hydrogen. Ethane and biodiesel experienced no increase in exchange current density, but a lengthening of the functional lifetime of the cell was observed, indicating reduced carbon poisoning. Methanol is a promising oxygen-containing SOFC fuel since it produced exchange current density values larger than hydrogen, and showed no evidence of coke formation by post-mortem SEM. Since oxygen-containing fuels are known to decompose in the gas phase at typical SOFC operating temperatures, the performance in a mixture of various CO/H2 fuels was then investigated. The Ni0.7Co0.3O-YSZ cermet anode gave higher exchange current density values for low ratio of CO/H2 fuels in the range 20/80 and 30/70 compared to pure H2. This is the first example of a Ni-based anode providing higher performance with a CO/H2 mixed fuel than for a pure H2 fuel. Finally, continuous running of a cell with fuel ratio 25/75 CO/H2 for 7 days produced exchange current density values, which were observed to increase significantly above the values for pure H2 during days 1-4 followed by deterioration below the value for hydrogen on subsequent days.

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