A numerical model of the steady state and alternating current behaviour of a solid-oxide fuel cell is presented to explore the possibilities to diagnose and identify degradation mechanisms in a minimally invasive way using impedance spectroscopy. This is the first report of an SOFC impedance model to incorporate degradation, as well as the first one to include the ribbed interconnect geometry, using a 2-D approximation. Simulated degradation modes include: electrode/electrolyte delamination, interconnect oxidation, interconnect/electrode interface detachment, and anode sulfur poisoning. Detailed electrode-level simulation replaces the traditional equivalent circuit approach, allowing the simulation of degradation mechanisms that alter the shape of the current path. The SOFC impedance results from calculating the cell response to a small oscillatory perturbation in potential. Starting from the general equations for mass and charge transport, and assuming isothermal and isobaric conditions, the system variables are decomposed into a steady-state component and a small perturbation around the operating point. On account of the small size of the imposed perturbation, the time dependence is eliminated, and the original equations are converted to a new linear, time independent, complex-valued system, which is very convenient from a numerical viewpoint. Geometrical and physical modifications of the model simulate the aforementioned degradation modes, causing variations in the impedance. The possibility to detect unique impedance signatures is discussed, along with a study of the impact of input parameter inaccuracies and parameter interaction on the presented results. Finally, a study of pairs of concurrent degradation modes reveals the method’s strengths and limitations in terms of its diagnosis capabilities.

Solid oxide fuel cells with graded electrodes consisting of multiple composite layers yield generally lower polarization resistances than single layer composite electrodes. Optimization of the performance of solid oxide fuel cells with graded electrode composition and/or microstructure requires an evaluation of both the three phase boundary length per unit volume and the effective diffusion coefficient in order to provide insight into how these properties vary over the design space. A numerical methodology for studying the three phase boundary length and effective diffusivity in composite electrode layers with controlled properties is developed. A three dimensional solid model of a sintered composite electrode is generated for which the mean particle diameter, composition, and total porosity may be specified as independent variables. The total three phase boundary length for the modeled electrode is calculated and tomographic methods are used to estimate the fraction of this length over which the electrochemical reactions can theoretically occur. Furthermore, the open porosity of the modeled electrode is identified and the effective diffusion coefficient is extracted from the solution of the concentration of the diffusing species within the open porosity. Selected example electrode models are used to illustrate the application of the methods developed, and the resulting connected three phase boundary length and diffusion coefficients are compared. A significant result is the need for thickness-specific effective diffusivity to be determined, rather than the general volume averaged property, for electrodes with porosity between the upper and lower percolation thresholds. As the demand for current increases, more of the connected three phase boundaries become active, and therefore a greater fraction of the electrode layer is utilized for a given geometry, resulting in a higher apparent effective diffusivity compared to the same electrode geometry operating at a lower current. The methods developed in this work may be used within a macroscopic electrode performance model to investigate optimal designs for solid oxide fuel cell electrodes with stepwise graded composition and/or microstructure.

Reducing fabrication and operation costs while maintaining high performance is a major consideration for the design of a new generation of solid-state ionic devices such as fuel cells, batteries, and sensors. The objective of this research is to fabricate nanostructured materials for energy storage and conversion, particularly porous electrodes with nanostructured features for solid oxide fuel cells (SOFCs) and high surface area films for gas sensing using a combustion CVD process. This research started with the evaluation of the most important deposition parameters: deposition temperature, deposition time, precursor concentration, and substrate. With the optimum deposition parameters, highly porous and nanostructured electrodes for low-temperature SOFCs have been then fabricated. Further, nanostructured and functionally graded La0.8Sr0.2MnO2-La0.8SrCoO3-Gd0.1Ce0.9O2 composite cathodes were fabricated on YSZ electrolyte supports. Extremely low interfacial polarization resistances (i.e. 0.43 Wcm2 at 700¡ãC) and high power densities (i.e. 481 mW/cm2 at 800¡ãC) were generated at operating temperature range of 600¡ãC-850¡ãC. The original combustion CVD process is modified to directly employ solid ceramic powder instead of clear solution for fabrication of porous electrodes for solid oxide fuel cells. Solid particles of SOFC electrode materials suspended in an organic solvent were burned in a combustion flame, depositing a porous cathode on an anode supported electrolyte. Combustion CVD was also employed to fabricate highly porous and nanostructured SnO2 thin film gas sensors with Pt interdigitated electrodes. The as-prepared SnO2 gas sensors were tested for ethanol vapor sensing behavior in the temperature range of 200-500¡ãC and showed excellent sensitivity, selectivity, and speed of response. Moreover, several novel nanostructures were synthesized using a combustion CVD process, including SnO2 nanotubes with square-shaped or rectangular cross sections, well-aligned ZnO nanorods, and two-dimensional ZnO flakes. Solid-state gas sensors based on single piece of these nanostructures demonstrated superior gas sensing performances. These size-tunable nanostructures could be the building blocks of or a template for fabrication of functional devices. In summary, this research has developed new ways for fabrication of high-performance solid-state ionic devices and has helped generating fundamental understanding of the correlation between processing conditions, microstructure, and properties of the synthesized structures.

Planar solid oxide fuel cells (SOFCs) were designed, fabricated and characterized in order to develop a (1) cost-effective method for fabrication of thin electrolyte layers, (2) hermetic sealing and (3) stable interconnects. Electrophoretic deposition (EPD) was discovered to be an excellent method for fabricating dense electrolyte layers of about 5m thick on porous non-conducting substrates. The EPD process was thoroughly studied from proof-of-concept to statistical reproducibility, deposition mechanism, modeling and process optimization. Deposition on non-conducting substrates was found to follow many of the same fundamental trends as that on conductive substrates except for the voltage efficiency and detailed charge transfer mechanism. Eventually, the process was optimized such that an SOFC was fabricated that achieved 1.1W/cm2 at 850C. Further, a novel sealless planar SOFC was designed that incorporates a hermetic interface between the electrolyte and interconnect similar to tubular and honeycomb designs. The hermetic interface successfully acted as a blocking electrode under DC polarization, indicating its potential to act as a sealant. Leakage rates across the interface were 0.027sccm at 750c, similar to polycrystalline mica seals. Through a process of tape casting and lamination, a two-cell stack without sealant was fabricated and achieved a power density of 75mW/cm2 at 750C. Finally, the degradation rate of silver and silver-based interconnects was studied under static and dual-atmosphere conditions. Corrosion of silver grain boundaries along with sublimation losses results in the formation of large pores, resulting in up to 30 of anode oxidation after 8hrs testing at 750c. Further stability studies indicated that silver-based interconnects would be better suited for applications at operating temperatures less than 650C.

In this study, deposition of La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) oxide films on Gd-doped ceria (CGO) substrates by an electrostatic assisted ultrasonic spray pyrolysis (EAUSP) method was demonstrated for the first time. The electrostatic field employed for directing the aerosol stream towards the substrate was shown to be indispensable for film deposition. The XRD result indicates that a single phase of cubic perovskite was obtained in the calcined films. SEM examination reveals that the electric field strength had a profound effect on film porosity with weaker field resulting in higher porosity. The results of impedance measurement on LSCF//CGO//LSCF cells indicate that the area specific resistance (ASR) values of current LSCF films and their activation energies are comparable to that obtained by conventional sample preparation routes. In view of the simplicity, efficiency and economy of film deposition and the sound electrochemical characteristics of the obtained films manifested in current work, it is concluded that EAUSP method is a promising method for preparation of SOFC electrode films. Besides the EAUSP method, electrostatic spray deposition (ESD) method was also employed to deposit LSCF films. The growth mechanism of LSCF films deposited on silicon wafer was studied by examining a series of films obtained with increasing deposition durations. The results show that the film formation mechanism in the initial stage depends on the deposition temperature, and films with a unique porous structure were obtained when a deposition temperature lower than the boiling point of the precursor solution was used. Deposition parameters were also varied systematically to deposit LSCF cathode films on CGO substrates to obtain symmetrical cells. The microstructure and morphology of obtained films were investigated by X-ray diffraction and SEM, and the area specific resistances of the symmetrical cells measured by electrochemical impedance spectroscopy (EIS). The minimum interfacial ASR value associated with the LSCF cathodes was 0.25 ohm¡Ecm2 at700 ¢XC. NiO-SDC (Sm0.2Ce0.8O1.9)/SDC/LSCF (La0.6Sr0.4Co0.2Fe0.8O3-£_) cells with either single layer or double layer cathode were also fabricated and tested. The single layer LSCF cathode was made by stencil printing while the double layer one was prepared by depositing a thin porous layer on the SDC electrolyte by ESD before stencil printing LSCF. The maximum power density increased from 1.04 to 1.18 Wcm-2 at 700¢XC when the LSCF inter-layer was introduced. The results showed that the ASRs of the cells reduced to half with the addition of the LSCF inter-layer.

Thesis (M.S.)--Engineering, Georgia Institute of Technology, 2004. / McDowell, David, Committee Chair; Neu, Richard, Committee Member; Lee, Jim, Committee Member; Cochran, Joe, Committee Member. Includes bibliographical references (leaves 159-162).

Thesis (M.S.)--West Virginia University, 2003. / Title from document title page. Document formatted into pages; contains xii, 100 p. : ill. (some col.). Vita. Includes abstract. Includes bibliographical references (p. 85-90).

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Research was performed on the development of relationships between the microstructure of nickel and yttria-stabilized zirconia (YSZ) coatings and the processing parameters used for their deposition by atmospheric plasma spraying (APS). Research was also performed on the development of relationships between the microstructure of plasma sprayed Ni-YSZ coatings and the electrochemical performance of metal-supported solid oxide fuel cells (SOFCs) incorporating these coatings as anodes. Three APS processes were used to deposit Ni-YSZ coatings: dry-powder plasma spraying (DPPS), suspension plasma spraying (SPS), and solution precursor plasma spraying (SPPS). These processes differ in the form of the feedstock injected into the plasma. The composition of the Ni-YSZ coatings deposited with each spray process could be controlled through adjustment of the plasma gas composition and stand-off distance, as well as adjustment of feedstock properties including agglomerate size fraction for DPPS, NiO particle size and suspension feed rate in SPS, and the enthalpy of decomposition of the precursors used in SPPS. The porosity of the Ni-YSZ coatings could be controlled through the addition of a sacrificial pore forming material to each feedstock, with coating porosities up to approximately 35% being achieved for each coating type. Metal-supported SOFCs were fabricated to each have anodes deposited with a different plasma spray process, where all anodes had nominally identical composition. The microstructures obtained for each anode type were distinctly different. SPPS led to the most uniform mixing of the smallest Ni and YSZ particles. These anodes most resembled typical structures from anodes fabricated using conventional methods. It was found that the polarization resistance, Rp, associated with the high frequency (> 1 kHz) range of the impedance spectrum correlated to the three phase boundary length (TPBL) density of each anode, with lower Rp values corresponding to higher TPBL densities. It was also found that the Knudsen diffusion coefficient and effective ordinary diffusion coefficient of the porous anodes correlated with the Rp associated with the low frequency (< 1 kHz) range of the impedance spectrum. Therefore, the impedance spectrum can be used to compare microstructural differences among plasma sprayed Ni-YSZ anodes.