Accounting for the Dynamic Oxidative Behavior of Nickel Anodes.

The dynamic behavior of the anodic peak for amorphous nickel oxy/hydroxide (a-NiOx) films in basic media was investigated. Chronocoulometry of films with known nickel concentrations reveals that a total of four electrons per nickel site comprise the signature anodic peak at 1.32 V during the first oxidative scan, and two electrons are passed through the associated cathodic peak on the reverse scan. The anodic and cathodic signals each contain two electrons on the successive scans. Catalytic oxygen evolution reaction (OER) was detected within the anodic peak, which is at a lower potential than is widely assumed. In order to rationalize these experimental results, we propose that the four-electron oxidation event is the conversion of the film from nickel(II) hydroxide ([Ni(II)-OH](-)) to a higher valent nickel peroxide species (e.g., Ni(IV)-OO or Ni(III)-OO·). The subsequent reduction of the nickel peroxide species is confined by a chemical step resulting in the accumulation of [Ni(II)-OOH](-), which is then oxidized by two electrons to form Ni(IV)-OO during the subsequent oxidative scan on the time scale of a cyclic voltammetric experiment. Our proposed mechanism and the experimental determination that each nickel site is oxidized by four electrons helps link the myriad of seemingly disparate literature data related to OER catalysis by nickel electrodes. The faster catalysis that occurs at higher oxidative potentials is derived from a minority species and is not elaborated here.