Addition of Cobalt to Lead Anodes Used for Oxygen Evolution—A Literature Review

A review of the literature dealing with the effect of cobalt on lead-based anodes for oxygen evolution during electrolysis of sulfuric acid solutions verifies that the presence of cobalt at the anode–electrolyte interface, either as constituent of the anode material or as ions in the electrolyte, catalyzes the evolution of oxygen and reduces the corrosion of the anodes and the contamination by lead of metal cathodes produced during electrowinning. However, due to harmful effects of cobalt ions on the cathodic reaction in some processes, these benefits are limited to the electrowinning of copper. Efforts to develop a way of introducing cobalt at the anode–electrolyte interface without interfering with the cathodic reactions are reviewed in this paper. The use of lead–cobalt alloy anodes has had limited success due to issues arising from the low solubility of cobalt in lead, segregation during casting of the alloys, and nonuniform distribution of cobalt which affects the integrity of the anodes. This has been overcome in part lately by inclusion of cobalt into only the surface layer of a lead or lead alloy substrate, by thermal treatment of a cobalt salt to form a catalytic cobalt oxide surface species, or by electrodeposition of composite lead–cobalt oxide anodes. The last approach in particular has been actively investigated by several groups, but to our knowledge it is yet to find application in the industry. The review also critically examines the likely reaction mechanisms involved.