Kinetics of Nucleation at the Electrodeposition of Zinc and Nickel from Ammonium Chloride Electrolytes

Abstract

Zinc–nickel coatings based on the zinc-enriched gamma phase exhibit the maximum corrosion resistance and form the basis of the production of highly electrocatalytically active nanoporous nickel by selective dissolution. The electrodeposition of Zn–Ni alloys is the most widely used method of their preparation which proceeds by the mechanism of anomalous codeposition, where the deposition rate of the electropositive component (nickel) is lower as compared with the electronegative component (zinc). To obtain coatings of the particular morphology, chemical and phase composition, it is necessary to know the kinetics of the cathodic deposition of Zn–Ni alloys in the stage of heterogeneous nucleation, which is the goal of this study. The kinetics of this process is studied in non-stirred ammonium chloride electrolytes using the methods of cyclic voltammetry and chronoamperometry. The mechanism of heterogeneous nucleation at the electrodeposition of zinc and nickel is determined using the approach proposed by Palomar-Pardavé et. al which takes into account the contributions to the total cathodic current made by the parallel reaction of hydrogen reduction and the electric double layer charging. The nucleation mechanism for zinc–nickel coatings is described using the model of Scharifker–Hills for the electrodeposition of binary alloys additionally modified by taking into account the experimentally determined dependence of the composition of zinc–nickel coatings on the time in the stage of cathodic nucleation of the deposit. Using the method of energy-dispersive X-ray spectroscopy, the anomalous character of the deposition of Zn–Ni coatings is confirmed, where the ratio of atomic fractions Ni/Zn turns out to be lower than the ratio of concentrations of ions Ni²⁺/Zn²⁺ in the electrolyte. It is found that both during the electrodeposition of zinc and nickel from their individual solutions and during their anomalous codeposition, the nucleation rate constant increases with an increase in the cathodic potential but in average does not exceed 3 s^–1, which points to the predominantly progressive nucleation. The growth of the new phase, regardless of its chemical composition, is limited by the 3D-diffusion of zinc and nickel ions to the electrode surface. The nucleation site density depends weakly on the deposition potential, decreasing with the transition from zinc to nickel and zinc–nickel alloys. As expected, the contribution of the side reaction of hydrogen reduction is the maximum for nickel electrocrystallization and decreases with the transition to Zn–Ni alloys and zinc, increasing with an increase in the cathodic potential, in agreement with the values of current efficiency.