Study of NiO cathode modified by rare earth oxide additive for MCFC by electrochemical impedance spectroscopy

Abstract

The preparation and subsequent oxidation of nickel cathodes modified by impregnation with rare earth oxide were evaluated by surface and bulk analysis. The electrochemical behaviors of rare earth oxide impregnated nickel oxide cathodes were also evaluated in a molten 62 mol% Li 2CO 3+38 mol% K 2CO 3 eutectic at 650 °C by electrochemical impedance spectroscopy (EIS) as a function of rare earth oxide content and immersion time. The rare earth oxide-impregnated nickel cathodes show almost the similar porosity, pore size, and morphology to the reference nickel cathode. The stability tests of rare earth oxide-impregnated nickel oxide cathodes show that the rare earth oxide additive can dramatically reduce the solubility of nickel oxide in a eutectic carbonate mixture under the standard cathode gas condition. The impedance response of all cathode materials at different immersion time is characterized by the presence of depressed semicircles in the high frequency range changing over into the lines with the angles of which observed with the real axis differing 45° or 90° in the low frequency range. The experimental Nyquist plots can be well analyzed theoretically with a modified model based on the well-known Randles–Ershler equivalent circuit model. In the new model, the double layer capacity ( C d) is replaced by the parallel combination of C d and b/ ω; therefore, this circuit is modified to be the parallel combination of ( C d), b/ ω, and the charge transfer resistance ( R ct) based on the Randles–Ershler equivalent circuit, to take into consideration both the non-uniformity of electric field at the electrode/electrolyte interface owing to the roughness of electrode surface, and the variety of relaxation times with adsorbed species on the electrode surface. The impedance spectra for all cathode materials show important variations during the 200 h of immersion. The incorporation of lithium in its structure and the low dissolution of nickel oxide and rare earth oxide are responsible for these changes. After that, the structure reaches a stable state. The rare earth oxide-impregnated nickel oxide cathodes show higher catalytic activity for oxygen reduction and lower dissolution of nickel oxide than the pure nickel oxide cathode. The cathode material having 1.0 wt.% of rare earth oxide shows the optimum behavior.