In this study, Lithium iron oxide (LiFeO₂ – LFO) was investigated as a new anode material for the high temperature SOFCs. From the DC conductivity measurement in argon containing 5% H₂, LFO exhibits good electronic conductivity of 5.08 Scm⁻¹ at 650 °C. LFO poses a high TEC value of 19.5 x 10⁻⁶ K⁻¹ in air. However, the TEC values of the commonly used 8YSZ and CGO electrolytes are much lower, 10.5 x 10⁻⁶ K⁻¹ and 12.5 x 10⁻⁶ K⁻¹ respectively. In order to resolve the mismatch in the TEC values between the electrode and the electrolyte, button fuel cells were fabricated via tape casting. LFO was infiltrated onto the porous and stable scaffold. Presently, the predominant electrolyte material used for the high temperature SOFC is 8YSZ. Due to this reason, the initial performance of LFO as an anode material was tested on tape-cast 8YSZ electrolyte-supported cell. The 8YSZ electrolyte-supported infiltrated with 30 wt% LFO for the anode and 40 wt% LSF for the cathode achieved a maximum power density of 50 mWcm⁻² at 700 °C in humidified H₂. Increasing the weight loading of LFO to 40 wt% worsen the performance. XRD pattern of the sintered powder containing 50 wt% LFO and 50 wt% 8YSZ confirmed that LFO and 8YSZ react with each other. CGO was considered as an alternative electrolyte material to 8YSZ. XRD pattern of the sintered powder containing 50 wt% LFO and 50 wt% CGO confirmed that they are compatible with each other. The CGO electrolyte supported cell infiltrated with 40 wt% LFO for the anode and 40 wt% LSC for the cathode achieved a maximum power density of 180 mWcm⁻² at 650 °C in humidified H₂. The addition of 10 wt% ceria to the LFO anode enhances the electrochemical activities of the cell. However, the overall performance of the cell decreased due to a larger increase in the series resistance. Since CGO electrolyte is easily reduced when testing at temperature higher than 550 °C, LSGM was used to increase the testing temperature. The 245 µm thick LSGM electrolyte-supported cell infiltrated with 40 wt% LSC and 30 wt% LFO obtained a maximum power density of 227 mWcm⁻² at 700 °C in humidified H₂. Decreasing the electrolyte thickness from 245 µm to 130 µm increased the performance of the cell. The 130 µm LSGM electrolyte-supported cell infiltrated with 40 wt% LSC and 30 wt% LFO was tested with the carbon/carbonate fuel as a HDCFC. Performance measurements of the cell was conducted at 650 °C and 700 °C with N₂ flowing at 20 ml/min. The cell performed better when testing at higher temperature. Recently, there has been great interest in developing a SOFC system for the cogeneration of electricity and valuable C₂ chemicals. The catalytic testing for oxidative methane coupling of methane revealed a high C₂ selectivity for the LFO powder. Cell testing of a sample infiltrated with 40 wt% LSC and 30 wt% LFO also achieved a methane conversion of ~3% and a C₂ selectivity of ~80% in methane at 700 °C.

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A novel concept has been developed for the direct carbon fuel cell (DCFC) based on molten carbonate recirculating electrolyte. In the cathode, co-current flow of electrolyte with entrained gases carbon dioxide and oxygen is sent in the upward direction through a porous bed grid. In the anode, co-current flow of a slurry of electrolyte entrained with carbon particles is sent in the downward direction through a porous bed grid. The gases carbon dioxide and oxygen in the cathode react on the grid surface to form carbonate ions. The carbonate ions are then transported via conduction to the anode for reaction with carbon to produce carbon dioxide for temperatures under 750 deg C. A mathematical model based on this novel DCFC concept has been developed. The model includes governing equations that describe the transport and electrochemical processes taking place in both the anode and cathode and a methodology for solving these equations. Literature correlations from multi-phase packed-bed chemical reactors were used to estimate phase hold-up and mass transfer coefficients. CO production and axial diffusion were neglected. The results demonstrated that activation and ohmic polarization were important to the cell output. The impact of concentration polarization to the cell output was comparatively small. The bed depths realized were of the order of 10cm which is not large enough to accommodate the economies of scale for a large scale plant, however thousands of smaller cells (10 m^2 area) in series could be built to scale up to a 10 MW industrial plant. Limiting current densities of the order of 1000-1500 A/m^2 were achieved for various operating conditions. Maximum power densities of 200-350 W/m^2 with current densities of 500-750 A/m^2, and cell voltages of 0.4-0.5 V have been achieved at a temperature of 700 deg C. Over temperatures ranging from 700 to 800 deg C, results from the modeled cell are comparable with results seen in the literature for direct carbon fuel cells that are similar in design and construction. / Ph. D.

Direct carbon fuel cell (DCFC) is a high temperature fuel cell (around 700 "C) that produces electrical energy from the direct conversion of the chemical energy of carbon. DCFC has a higher achievable efficiency of 80% compared to other fuel cells and the corresponding CO2 emission is very low compared to conventional coal-burning power plants. Moreover, a DCFC can use diversified fuel resources even waste material, which is advantageous compared to other types of fuel cells which are limited to specific fuels. DCFCs are still under development due to a number of fundamental and technological challenges such as the efficiency of carbon fuels and the effect of impurities on the performance and lifetime of the DCFC. These are key factors for the development and commercialization of these devices. In this study, three biochars obtained from the pyrolysis of poultry litters (PL) collected from Tunisian and US farmers, were characterized to see whether they can be potential anode fuels for DCFC or not. PL biochars have low fixed carbon contents (19-35 wt%) and high ash contents (32.5-63 wt%). These ashes contain around 40 wt% catalytic oxides for carbon oxidation reaction, however, these oxides have very low electrical conductivities, which resulted in the very low (negligible) electrical conductivity of the PL biochars (7.7x10-9-70.56x10-9 S/cm) at room temperature. Moreover, the high ash contents resulted in low surface areas (3.34-4.2 m"/g). These findings disqualified PL biochar from being a potential anode fuel for DCFCs. Chemical demineralization in the sequence HF/HCl followed by carbonization at 950" C of the PL biochars will result in higher fixed carbon content, higher surface area, and higher electrical conductivities. Moreover, the treated PL biochars would contain a potential catalyst (Calcium in the form of CaF2) for carbon oxidation. All these criteria would qualify the treated PL biochars to be potential fuels for DCFC. / Master of Science