Journal of the Electrochemical Society, Vol.141, No.11, 3040-3049, 1994
Corrosion of Nickel in Molten-Carbonate
Cyclic voltammetry and polarization measurements on nickel under reducing gas atmospheres were performed to investigate the corrosion behavior of nickel as a base metal for molten carbonate fuel-cell separator plate alloys. The anodic reactions observed and oxidation of hydrogen, oxidation of nickel to nickel oxide and to dissolved nickel ions, and oxidation of bivalent nickel to trivalent nickel incorporated in the oxide scale. The cathodic reactions are reduction of trivalent to bivalent nickel in the scale and reduction of bivalent nickel to metallic nickel. During the cathodic scan of the cyclic voltammogram a change in the morphology of the oxide takes place. This is probably due to recrystallization of the oxide. During the cathodic reduction of NiO the scale loses contact from the metal at approximately - 1200 mV; a small crevice is formed between the metal and the scale. The stresses in the loose scale cause cracking. Consequently, the crevice is filled with carbonate. Then nickel oxide dissolves, forming complexes of nickel and carbonate ions. These complexes are reduced to nickel (and carbonate ions) in the crevice. Due to the basic nature of the melt in the crevice, the nickel is oxidized in the following anodic scan, at lower potential (approximately - 1200 mV) than observed for an oxide-free surface (approximately - 700 mV).