Kinetics of nucleation during electrodeposition of zinc and nickel from ammonium chloride electrolytes

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Abstract

Zinc-nickel coatings based on the zinc-enriched gamma phase are characterized by maximum corrosion resistance and are the basis for the production of electrocatalytically highly active nanoporous nickel by selective dissolution. Electrodeposition of Zn–Ni alloys is the most common method of their preparation and proceeds by the mechanism of anomalous co-deposition, in which the rate of an electropositive component (nickel) deposition is lower than of an electronegative component (zinc). To obtain coatings with certain morphology, chemical and phase composition, it is necessary to know the kinetic regularities of cathodic deposition of Zn–Ni alloy at the stage of heterogeneous nucleation, the determination of which is the purpose of this work. The kinetics of the process was studied in non-stirred ammonium chloride electrolytes using the methods of cyclic voltammetry and chronoamperometry. The mechanism of heterogeneous nucleation during electrodeposition of zinc and nickel was determined within the framework of the approach by Palomar-Pardave et al., taking into account the contributions of the hydrogen reduction reaction and charging of the double electric layer to the total cathodic current, and for zinc-nickel coatings using the model by Scharifker et al. for electrodeposition of a binary alloy, additionally modified taking into account the experimentally determined dependence the composition of zinc-nickel coatings on time at the nucleation stage of the cathodic deposit formation. Using the method of X-ray spectral analysis, the anomalous nature of deposition of Zn–Ni coatings was confirmed, the ratio of atomic fractions of Ni/Zn in which turned out to be lower than the ratio of concentrations of Ni2+/Zn2+ ions in the electrolyte. It was found that both during electrodeposition of zinc and nickel from their individual solutions and during their anomalous co-deposition, the nucleation rate constant increases with the cathodic potential, but on average does not exceed 3 s–1, which indicates predominantly progressive nucleation. The growth of a new phase, regardless of the chemical composition of the resulting deposit, is limited by the 3D-diffusion of zinc and nickel ions to the electrode surface. The density of nucleation active sites is weakly dependent on the deposition potential, decreasing during the transition from zinc to nickel and zinc-nickel alloys. The contribution of the side reaction of hydrogen reduction as expected is maximum in the case of nickel electrocrystallization. It decreases during the transition to alloys and zinc, increasing with the cathodic potential, which is consistent with the current efficiency of the electrodeposition process.

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A. E. Tinaeva

Voronezh State University

Email: ok@chem.vsu.ru
Russian Federation, Voronezh

O. A. Kozaderov

Voronezh State University

Author for correspondence.
Email: ok@chem.vsu.ru
Russian Federation, Voronezh

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2. Fig. 1. (a) Cathodic voltammograms obtained on the Au electrode in 0.08 M NiCl2 + 0.04 M ZnCl2 + 2 M NH4Cl (1–5), 0.04 M ZnCl2 + 2 M NH4Cl (3ʹ), and 0.08 M NiCl2 + 2 M NH4Cl (3ʺ) at different potential scan rates: 2 (1), 5 (2), 10 (3, 3ʹ, 3ʺ), 25 (4), 50 (5) mV/s. (b) Dependence of the maximum current density on the square root of the potential scan rate. (c) Dependence of the maximum potential on the logarithm of the potential scan rate.

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3. Fig. 2. (a) Cathode chronoamperograms obtained on the Au electrode in 0.08 M NiCl2 + 0.04 M ZnCl2 + 2 M NH4Cl at different deposition potentials Edep = –860 (1), –880 (2), –900 (3), –1000 (4) mV. Empty markers are experimental data, solid lines are the result of nonlinear regression analysis using formula (15). (b) Chronoamperograms reconstructed in Cottrel coordinates.

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4. Fig. 3. Cathode chronoamperograms obtained on the Au electrode in 0.04 M ZnCl2 + 2 M NH4Cl (a) and 0.08 M NiCl2 + 2 M NH4Cl (b) at deposition potentials E = –860 (1), –880 (2), –900 (3), –1000 (4) mV. Empty markers are experimental data, solid lines are the result of nonlinear regression analysis using formula (14).

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5. Fig. 4. Change in the atomic fraction of nickel in the coating deposited from 0.08 M NiCl2 + 0.04 M ZnCl2 + 2 M NH4Cl at potentials Edep = –860 (), –880 (), –900 (), –1000 () mV. The dotted line is the result of nonlinear regression analysis using formula (1). The CRL (composition reference line) level corresponds to the atomic fraction of nickel in the case of normal deposition, when the ratio of metal concentrations in the alloy and ions in the solution coincides.

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6. Fig. 5. Partial current transients of electrocrystallization (1), hydrogen reduction reaction (2) and charging of the double electric layer (3), obtained from the results of nonlinear regression analysis of experimental chronoamperograms on the Au electrode in 0.08 M NiCl2 + 0.04 M ZnCl2 + 2 M NH4Cl (a), 0.04 M ZnCl2 + 2 M NH4Cl (b) and 0.08 M NiCl2 + 2 M NH4Cl (c) at a potential of E = –880 mV.

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7. Fig. 6. Dependences of the rate constant of the hydrogen reduction reaction (a), the rate constant of the nucleation process (b) and the density of nucleation centers (c) on the cathode potential, found from the results of nonlinear regression analysis of experimental chronoamperograms on the Au electrode obtained in 0.04 M ZnCl2 + 2 M NH4Cl (1), 0.08 M NiCl2 + 2 M NH4Cl (2) and 0.08 M NiCl2 + 0.04 M ZnCl2 + 2 M NH4Cl (3).

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