Electrochemical and Spectroscopic Evidence on the Participation of Quadrivalent Nickel in the Nickel Hydroxide Redox Reaction

Electrochemical and iodometric measurements on anodically charged thin film nickel hydroxide electrodes indicated an average nickel valence of . In situ visible spectroscopy of nickel hydroxide deposited on optically transparent electrodes featured one strong and broad absorption band with an intensity proportional to the state of charge. The results are not consistent with the presence of separate trivalent and quadrivalent phases or the participation of peroxide radicals in the nickel hydroxide redox reaction, but are best explained by the formation of a single mixed valence phase such as which has a 3.67 average nickel valence. Full utilization of the proposed oxidized phase could increase the discharge capacity of nickel battery electrodes by 67% beyond the previously assumed one‐electron theoretical capacity. That the discharge is generally incomplete may be due to electronic isolation of portions of the oxidized material by a high resistivity layer of divalent nickel hydroxide produced at the surface during discharge.