Electrocatalytic Properties of Nanocrystalline Calcium-Doped Lanthanum Cobalt Oxide for Bifunctional Oxygen Electrodes.

Calcium-doped lanthanum cobalt oxide is a promising electrocatalyst for oxygen evolution and oxygen reduction in rechargeable metal-air batteries and water electrolyzers operating with alkaline electrolyte. Nanocrystalline perovskite of composition La0.6Ca0.4CoO3 with a unique cellular internal structure was prepared at 350 °C and then annealed in air at progressively higher temperatures in the range of 600-750 °C. The samples were characterized by electrochemical techniques and X-ray photoelectron spectroscopy. The area-specific electrocatalytic activity for oxygen evolution/oxygen reduction, the oxidation state of cobalt, and the crystallite size increased with annealing temperature, while the Tafel slope remained constant. These trends provide new insights into the role of the cobalt center in oxygen evolution and oxygen reduction, and how preparation conditions can be altered to tune the activity of the cobalt center for electrocatalysis. We expect these findings to guide the design of electrocatalysts for bifunctional oxygen electrodes, in general.