An Experimental and Modelling Study of Oxygen Reduction in Porous LSM/YSZ Solid Oxide Fuel Cell Cathodes
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Solid oxide fuel cells (SOFCs) are electrochemical devices that can convert a variety of fuels directly into electricity. Their commercialization requires efficient operation of its components. The sluggish kinetics for the oxygen reduction reaction (ORR) at the SOFC cathode contributes to the loss in the fuel cell efficiency. In this work, the ORR was investigated for the strontium-doped lanthanum manganite cathode (LSM) and yttria-stabilized zirconia electrolyte (YSZ) system. A combined mathematical modelling and experimental framework was developed to estimate, for the first time, the kinetics of the elementary processes of the ORR for porous LSM cathodes. The kinetics of each process was then analyzed to identify the contribution to the cathode resistance. The steady state and impedance response for polarized and unpolarized LSM cathodes was collected over a temperature range between 750C and 850C and two different oxygen partial pressure (pO2) ranges: (i) between 0.0001atm and 0.001atm, where LSM is considered to be stoichiometric with respect to oxygen and (ii) between 0.01atm and 0.21atm, where LSM is considered to be superstoichiometric with respect to oxygen. A mathematical model was developed to analyze both the steady state and impedance data. Two pathways for the ORR were considered: one where oxygen is transported in the gas phase and one where oxygen is transported along the surface of the LSM cathode. Rate constants, transport coefficients and their respective activation energies were obtained for the adsorption/desorption, surface diffusion and charge transfer processes. The experimental results indicated different polarization behavior between low and high pO2. It is hypothesized that the concentration of cation vacancies on the LSM surface changes with both pO2 and extent of polarization and that cation vacancies on the LSM surface can promote the ORR. Modelling results at low pO2 suggested that the adsorption reaction was slow and that thermodynamic limitations resulting in low equilibrium oxygen surface coverage can play an important role at both low and high polarizations. Modelling in high pO2 was complicated by the nature of the LSM surface in these conditions and suggests an electrochemical reaction at the gas/LSM interface and the transport of charged adsorbed oxygen atoms.