PhD, University of Cincinnati, 2014, Engineering and Applied Science: Materials Science

One of the major obstacles encountered when using solid oxide fuel cells with hydrocarbon fuels is sulfur poisoning. The current anode material used is Ni/YSZ and Ni is not sulfur tolerant; therefore, the performance of the cell will degrade over time due to the formation of NiS. Perovskites have demonstrated superior sulfur tolerance but lack the high conductivity and catalytic activity of Ni/YSZ cermets. One of the objectives of this effort is to explore the substitution of the A-site in an A2MgMoO6 perovskite with Sr and Ba, to create Sr2MgMoO6 (SMMO) and Ba2MgMoO6 (BMMO), respectively, to improve the sulfur tolerance of solid oxide fuel cells (SOFCs). Sr2MgMoO6, a double perovskite, has been previously studied and is suggested as a material of interest because of its relatively high conductivity and catalytic potential. Barium has not been previously studied and was selected as the dopant because the ionic radii (1.61 A) resulted in a calculated tolerance factor of 1.036 for BMMO when compared to SMMO, which has an ionic radii of 1.44 A and a calculated tolerance factor of 0.978. The tolerance factor for BaSrMgMoO6, a bi-substituted material synthesized for comparison as an intermediate formulation, was calculated to be 1.00. Another objective is to synthesize and characterize a series of lanthanum (La) doped Sr2MgMoO6 (SMMO) or La doped Sr2MgNbO6 (SMNO) anode materials, which can be used in combination with electrolytes containing lanthanum to mitigate the effects of lanthanum poisoning in SOFCs. Currently, a La0.4Ce0.6O1.8 (LDC) transition layer is used with many perovskite-based anode materials to prevent La diffusion into the anode from the La0.8Sr0.2Ga0.8Mg0.2O2.8 (LSGM) electrolyte, which can create a resistive La species that impedes electrochemical performance. To accomplish this, a new class of anode materials was synthesized with the goal of balancing La chemical potential between these neighboring materials. It was hypothesized that by incorpo (open full item for complete abstract)

Committee: Raj Singh Sc.D. (Committee Chair); Relva Buchanan Sc.D. (Committee Member); Rodney Roseman Ph.D. (Committee Member); Vesselin Shanov Ph.D. (Committee Member) Subjects: Materials Science

Doctor of Philosophy, The Ohio State University, 2004, Materials Science and Engineering

An electrochemical CO2 gas sensor with lithium ion conductor was developed and characterized in order to examine the potential for real-life applications and understand its sensing mechanism. Li2CO3 and Li2TiO3+TiO2 mixture were used as a sensing and a reference auxiliary phase, respectively. This electrochemical cell with a solid state Li3PO4 electrolyte has shown good selectivity, sensitivity and linear response in laboratory and automobile exhaust tests. However, the sensor response to CO2 gas showed a systematic deviation from the Nernst equation. Measured EMF did not agree with that calculated from the Nernst equation, even though it followed logarithmic behavior. Moreover, high sensitivity was observed for high CO2 concentrations (5~50%), compared to that for concentrations (500~5000 ppm). Two possible reasons for this deviation are: (1) reversibility of electrode reaction and (2) mixed ionic and electronic conduction of the electrolyte. Unless electrode reaction is fast enough, electrode polarization can easily induce overpotential. Pure ionic conduction of electrolyte is also necessary to avoid EMF loss during open circuit potential measurement. EIS (Electrochemical Impedance Spectroscopy) was used to study electrode kinetics. We found that Li2TiO3+TiO2 mixture reference electrode reaction is sluggish showing large electrode impedance. This impedance, however, was not affected by gas concentration change. On the other hand, that at the Li2CO3 sensing electrode is relatively small and it increased with decreased CO2 and O2 concentration. It was also observed that these electrode impedances induced the overpotential when the current flowed through the sensor. This electrode overpotential problem was minimized by mixing gold powder or porous sputtered gold electrode increasing effective reaction sites of the electrode. New electrode design improved the sensor EMF closer to the Nernstian values, however, the discrepancy still remained. Moreover, at higher sensor (open full item for complete abstract)

Committee: Sheikh Akbar (Advisor) Subjects: Engineering, Materials Science