Papers by Author: E.N. Naumovich

Abstract: The p(O2)-T- diagrams of La2Ni1-xMxO4+ (M=Co and Cu, x= 0-0.20), determined by the coulometric titration technique at 923-1223 K in the oxygen partial pressure range 10-4 to 0.6 atm, can be adequately described by equilibrium processes of oxygen intercalation into the rock-salt type layers and hole localization on B-site cations forming 3+ oxidation states. For the hole activity, a non-ideal solution model taking into account the repulsion of p-type electronic charge carriers can be used. The electrostatic repulsion excludes occupation of nearest neighboring sites and leads to splitting of the energy levels for more distant sites. The affinity of Ni and Cu cations with respect to the hole localization is similar and cannot be statistically separated analyzing the oxygen nonstoichiometry data only. On the contrary, cobalt cations tend to remain in the trivalent state and Co3+ should be treated as a separate type of charged point defect. Oxygen vacancies formed in the perovskite-like layers due to intrinsic Frenkel disorder have no essential effect on the oxygen thermodynamics. As expected, the thermodynamic functions governing the intercalation-related processes are independent of defect concentrations.

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.