Oxygen evolution reaction nickel oxide

Ponce et al. (2001) studied the oxygen reduction reaction and the oxygen evolution reaction on mixed oxides NqAl] Mn02 (0 < x < 1). The substitution of Al by Ni increases the catalytic activity, the maximum being exhibited by NiMn204. Nickel hydrous oxide and mixed Co and Ni oxides as electrocatalysts were found active towards oxygen reduction and evolution reaction (Rashkova et al. 2002). 

In normal battery operation several electrochemical reactions occur on the nickel hydroxide electrode. These are the redox reactions of the active material, oxygen evolution, and in the case of nickel-hydrogen and nickel-metal hydride batteries, hydrogen oxidation. In addition there are parasitic reactions such as the corrosion of nickel current collector materials and the oxidation of organic materials from separators. The initial reaction in the corrosion process is the conversion of Ni to Ni(OH)2. 

Oxygen evolution occurs on nickel oxide electrodes throughout charge, on overcharge, and on standby. It is the anodic process in the self-discharge reaction of the positive electrode in nickel-cadmium cells. Early work in the field has been reviewed [9], No significant new work has been reported in recent years. 

Electrochemically generated nickei(lll) oxide, deposited onto a nickel plate, is generally useful for the oxidation of alcohols in aqueous alkali [49]. The immersion of nickel in aqueous alkali results in the formation of a surface layer of nickel(ll) oxide which undergoes reversible electrochemical oxidation to form nickel(lll) oxide with a current maximum in cyclic voltammetry at 1.13 V vj. see, observed before the evolution of oxygen occurs [50]. This electrochemical step is fast and oxidation at a prepared oxide film, of an alcohol in solution, is governed by the rate of the chemical reaction between nickel oxide and the substrate [51]. When the film thickness is increased to about 0.1 pm, the oxidation rate of organic species increases to a rate that is fairly indifferent to further increases in the film thickness. This is probably due to an initial increase in the surface area of the electrode [52], In laboratory scale experiments, the nickel oxide electrode layer is prepared by prior electrolysis of nickel sulphate at a nickel anode [53]. It is used in an undivided cell with a stainless steel cathode and an alkaline electrolyte. 

A completely novel approach to technical electrolysis for anodic oxygen evolution from alkaline solution is the use of amorphous metals, i.e. chilled melts of nickel/cobalt mixtures whose crystallization is prevented by the addition of refractory metals like Ti, Zr, B, Mo, Hf, and P (46-51). For this type of material, enhanced catalytic activity in heterogeneous catalysis of gas-phase reactions has been observed (51). These amorphous metals are shown to be more corrosion resistant than the respective crystallized alloys, and the oxides being formed at their surfaces often exhibit a higher catalytic activity than those formed on ordered alloys, as shown by Kreysa (52-54). 

The analysis of the situation is then quite complex but was worked out by Gilroy et al. (124) and applied to change of coverage by adsorbed oxygen species in the anodic O2 evolution reaction at nickel oxide. A more recent development of their analysis has been given by Lasia (125). 

The electrochemical oxidation is carried out with an electrolyte which is caustic potash (1—4 m) and potassium manganate (100—250 g 1 ) at 60°C at an anode made from nickel or monel (Ni/Cu). The cathode is iron or steel. The anode reaction requires an unusually low current density between 5 and 150 mA cm but usually at the lower end of this range. Even so some oxygen evolution occurs and the current yields are between 60 and 90% the material yield generally exceeds 90%. 

Anode A nickel anode forms in aqueous alkaline solutions a layer of Nickel(IIll-oxide NiOOH. Owing to its application in nickel cadmium and nickel metal hydride accumulators, it is much investigated [20]. It is stable for oxygen evolution and very interesting for selective oxidation reactions ([21] see Chapters 6,15), an industrial application is one step of the vitamin C production [22]). 

A typical example of the application of EIS is the investigation of passive films on Zn, Zn-Co, and Zn-Ni (Fig. 7-18), which were carried out to explain the difference in the corrosion behavior of pure and low-alloyed zinc by the possible formation of electron traps through the incorporation of cobalt or nickel into the oxide film (Vilche et al., 1989). Passive films of zinc in alkaline solutions are known to be n-type semiconductors with a band gap Eg = 3.2 eV (Vilche et al., 1989). The n-type character arises from an excess of zinc atoms in the nonstoichiometric oxide. The impedance measurements in 1 N NaOH solution were carried out at potentials at which Faraday reactions like transpassive dissolution and oxygen evolution do not interfere. The passive layer was formed for 2 h at positive potential before the potential was swept in the negative direction for the impedance meas-... 

Similar size effects have been observed in some other electrochemical systems, but by far not in all of them. At platinized platinum, the rate of hydrogen ionization and evolution is approximately an order of magnitude lower than at smooth platinum. Yet in the literature, examples can be found where such a size effect is absent or where it is in the opposite direction. In cathodic oxygen reduction at platinum and at silver, there is little difference in the reaction rates between smooth and disperse electrodes. In methanol oxidation at nickel electrodes in alkaline solution, the reaction rate increases markedly with increasing degree of dispersion of the nickel powders. Such size effects have been reported in many papers and were the subject of reviews (Kinoshita, 1982 Mukerjee, 1990). 

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