Papers by Author: Andréy V. Kovalevsky

Abstract: Due to relatively high oxygen permeability, lanthanum-strontium ferrite phases are of interest as ceramic membrane materials for the partial oxidation of natural gas. This work was focused on the study of perovskite-type ferrites co-doped with Sr2+ and Ce4+ or Nb5+, with particular emphasis on the ionic transport and thermodynamic stability limits at low oxygen chemical potentials. Dense membranes of La0.5-2xCexSr0.5+xFeO3-δ (x = 0 - 0.2) and La0.5-2ySr0.5+2yFe1-yNbyO3-δ (y = 0 - 0.1) were characterized employing X-ray diffraction (XRD), scanning electron microscopy (SEM), dilatometry, oxygen permeation and faradaic efficiency studies, and the measurements of total conductivity and Seebeck coefficient in the oxygen partial pressure range from 10-20 to 0.5 atm. The incorporation of Ce4+ or Nb5+ was found to decrease thermal expansion and electronic transport parameters, whereas the ionic conductivity behavior is complex, indicating the relevance of redox interactions of the variable-valence cations and the concentration of mobile oxygen vacancies.

Abstract: Ceramic anodes, made of perovskite-type rare-earth and strontium cobaltites substituted in both sublattices, exhibit a high electrocatalytic activity towards oxygen evolution in alkaline media. This work analyzes the relationships between cation composition, defect structure, electronic conductivity and electrochemical performance for a wide group of perovskite-like cobaltites, including Ln1-yAyCoO3-δ (Ln= Pr, Nd, Sm; A= Sr, Ca; y= 0-0.4), La1-x-ySrxBiyCoO3-δ (x= 0-0.6, y= 0-0.1), La0.7-xSr0.3CoO3-δ (x= 0-0.10), Sr1-xBaxCoO3-δ (x= 0.1-0.2) and SrCo1-yMyO3-δ (M=Fe, Ni, Ti, Cu; y= 0.1-0.6). The materials were prepared by the standard ceramic technique and characterized employing XRD, TGA, iodometric titration, and total conductivity measurements. A relatively high electrochemical performance in alkaline solutions was observed for (La,Sr)CoO3-based compositions with a moderate A-site deficiency. For SrCoO3-based materials, an increase in the oxygen evolution rate was found when co-substituting cobalt with several transition metal cations, such as Fe3+/4+ and Cu2+/3+. The results show that, in general, the key composition-related factors influencing electrochemical activity in alkaline media include the oxygen vacancy concentration, the average positive charge density in the crystal lattice, and possible blocking of active sites on the electrode surface.