a“Ilie Murgulescu” Institute of Physical Chemistry of Romanian Academy, Department of Chemical Thermodynamics, Splaiul Independentei 202, P.O.Box 12-194, 060021 Bucharest, Romania
bETH Zurich, Nonmetallic Inorganic Materials, Department of Materials, HCI G 533, Wolfgang-Pauli-Str. 10, CH-8093 Zurich, Switzerland
dInternational Institute for Carbon Neutral Energy Research (WPI-I2CNER), Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan
Abstract
The thermodynamic stability of the perovskite-type oxides in the BaxSr1-xCo0.8Fe0.2O3-δ (BSCF) system was investigated with varying Ba:Sr ratios (x=0.2, 0.4; 0.5, 0.6; 0.8) and correlated with the charge compensation mechanism and the change in the oxygen stoichiometry of the materials. Thermodynamic properties represented by the relative partial molar free energies, enthalpies and entropies of oxygen dissolution in the perovskite phase, as well as the equilibrium partial pressures of oxygen have been obtained in the temperature range of 823–1273 K using solid electrolyte electrochemical cells (EMF) method. The influence of the oxygen stoichiometry change on the thermodynamic properties was examined using a coulometric titration technique coupled with EMF measurements. The temperature dependence of enthalpy increment (HT-H298) in the temperature range of 700–900 K was measured by drop calorimetry. The energetic parameters allow for the correlation of the structural and electrical stability with the defect structures.
