The multifaceted role of boric acid in nickel electrodeposition and electroforming

This study involved an investigation of the role of boric acid in nickel electroforming from sulfamate electrolytes, especially in relation to its ability to minimise interfacial pH changes during electrodeposition. Initial speciation calculations indicated that buffering by polyborate species and nickel-borate complexes are most likely responsible for this effect. However, the concentration of nickel-borate complexes was too low even at elevated pH to be a significant electroactive species. Polarisation and electrochemical quartz crystal microbalance measurements indicated that, in the absence of boric acid, electrodeposits typically contained Ni(OH)₂, while boric acid additions resulted in pure Ni being deposited with a current efficiency approaching unity. Boric acid additions substantially modified the nickel and hydrogen partial currents, and influenced the overall current efficiency. Studies in nickel-free solutions indicated that boric acid adsorbs on the surface which explains the suppression of H₂O reduction observed in the electroforming experiments. Collectively, solution buffering due to polyborate and nickel-borate species and inhibition of H₂O reduction by adsorbed boric acid minimised interfacial pH changes and prevented the formation of nickel hydroxide.