Stability of the Ternary Phases in the La-Co-O System and the Nonstoichiometry of Lanthanum Cobaltate

摘要

The crystal structure of La sub 4 Co sub 3 O sub 10 , which is a new ternary phase identified in the present study, was determined by means of X-ray diffraction. It has an orthorhombic symmetry and its space group is most likely Fsub(mmm) (face-centered). On the basis of the thermodynamical studies of the La-Co-O system, the stable ternary phases are LaCoO sub 3 , La sub 4 Co sub 3 O sub 10 and La sub 2 CoO sub 4 . The stability limits of these phases were determined as a function of oxygen activity and temperature, and their molar Gibbs standard formation functions were calculated. Electrons, e', and electron holes, hsup(.), are majority defects in lanthanum cobaltate and their concentrations are exceptionally high and nearly constant in the temperature range 1178 - 1295 K. Under thermodynamically well defined conditions the nonstoichiometry of lanthanum cobaltate was determined as a function of oxygen activity and temperature by coulometric titration. In the oxygen partial pressure and temperature range of the present study the oxygen vacancies were ionic minority defects dependent on the activity of oxygen. Due to the high concentration of electronic defects the oxygen vancancy concentration increases high at low oxygen pressures. Oxygen vacancies behave ideally in lanthanum cobaltate i.e. obey Henry's law when their concentrations are <=0.01. (Atomindex citation 11:554655)