OPTIMIZATION OF THE CATHODE LONG-TERM STABILITY IN MOLTEN CARBONATE FUEL CELLS: EXPERIMENTAL STUDY AND MATHEMATICAL MODELING

Abstract

The dissolution of NiO cathodes during cell operation is a limiting factor to the successful commercialization of molten carbonate fuel cells (MCFCs). Lithium cobalt oxide coating onto the porous nickel electrode has been adopted to modify the conventional MCFC cathode which is believed to increase the stability of the cathodes in the carbonate melt. The material used for surface modification should possess thermodynamic stability in the molten carbonate and also should be electro catalytically active for MCFC reactions. Lithium Cobalt oxide was coated on Ni cathode by a sol-gel coating. The morphology and the LiCoO{sub 2} formation of LiCoO{sub 2} coated NiO was studied using scanning electron microscopy and X-Ray diffraction studies respectively. The electrochemical performance lithium cobalt oxide coated NiO cathodes were investigated with open circuit potential measurement and current-potential polarization studies. These results were compared to that of bare NiO. Dissolution of nickel into the molten carbonate melt was less in case of lithium cobalt oxide coated nickel cathodes. LiCoO{sub 2} coated on the surface prevents the dissolution of Ni in the melt and thereby stabilizes the cathode. Finally, lithium cobalt oxide coated nickel shows similar polarization characteristics as nickel oxide. Conventional theoretical models for the molten carbonate fuel cell cathode are based on the thin film agglomerate model. The principal deficiency of the agglomerate model, apart from the simplified pore structure assumed, is the lack of measured values for film thickness and agglomerate radius. Both these parameters cannot be estimated appropriately. Attempts to estimate the thickness of the film vary by two orders of magnitude. To avoid these problems a new three phase homogeneous model has been developed using the volume averaging technique. The model considers the potential and current variation in both liquid and solid phases. Using this approach, volume averaged concentrations of both gaseous and liquid phase reactants are obtained separately. The polarization characteristics of the electrode have been studied for different electrode parameters. The effect of different design parameters on the electrode performance has also been analyzed. Finally, the model has been used to analyze the impedance response of the MCFC cathode.