Direct electroreduction of solid cuprous chloride to prepare copper powder in a"neutral"ambient-temperature ionic liquid,1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid(BMIMBF4)was investigated.Cyclic voltammetry of the CuCl powder in a Pt-powder cavity microelectrode exhibited that solid CuCl can be electrochemical reduced in the ionic liquid.Chronoamperometry of the salt powder filled Mo-cavity electrode(current collector)in the ionic liquid further demonstrated the conversion of chloride to metal inside the cavity,as confirmed by scanning electron microscopy,energy-dispersive X-ray,and X-ray diffraction spectra.
The effect of two alkylpyridinium ionic liquids （py-iLs） including N-butylpyridinium hydrogen sulfate （BpyHSO4） and N-hexylpyridinium hydrogen sulfate （HpyHSO4） on the kinetics of copper electrodeposition from acidic sulfate solution was investigated by cyclic voltammetry and potentiodynamic polarization measurements. Results from cyclic voltammetry indicate that these py-iLs have a pronounced inhibiting effect on CuE＋ electroreduction and there exists a typical nucleation and growth process. Kinetic parameters such as Tafel slope, transfer coefficient and exchange current density obtained from Tafel plots, lead to the conclusion that py-iLs inhibit the charge transfer by slightly changing the copper electrodeposition mechanism through their adsorption on the cathodic surface. In addition, scanning electron microscope （SEM） and X-ray diffraction analyses reveal that the presence of these additives leads to more leveled and fine-grained cathodic deposits without changing the crystal structure of the electrodeposited copper but strongly affects the crystallographic orientation by significantly inhibiting the growth of （111）, （200） and （311） planes.
The electrodeposition behavior of nickel at glassy carbon(GC)and stainless steel(SS)electrodes in low temperature urea-acetamide-NaBr-KBr melt was investigated using cyclic voltammetry,chrono-amperometric current-time transients and scanning electron microscopy.Cyclic voltammograms and dimensionless chronoamperometric current-time transients analysis show that the electrodeposition of nickel is an irreversible process and proceeds via three-dimensional progressive nucleation with diffusion-controlled growth on both GC and SS substrates.Scanning electron microscopic analysis indicates the nickel deposits obtained on SS electrode are generally uniform,dense,and adherent to the substrate with rounded crystallites in the nanometer size regime.It is also found that the crystal structure of the electrodeposited nickel is independent on the deposition potential.The nickel deposits produced from the melt at higher cathodic potential exhibit larger grain size.
The effect of two alklpyridinium hydrosulfate based ionic liquids(ILs)including N-butylpyridinium hydrogen sulfate(BpyHSO4)and N-hexylpyridinium hydrogen sulfate(HpyHSO4)as additives on the nucleation and growth of copper from acidic sulfate bath was investigated using cyclic voltammetry,chronoamperometric and scanning electron microscopy techniques.Results from cyclic voltammetry indicated that the two studied additives had a blocking effect on copper electrodeposition process and this effect initiated by HpyHSO4was more pronounced in comparison to BpyHSO4.Dimensionless chronoamperometric current-time transients for the electrodeposition of copper from the bath free of additives were in good accord with the theoretical transients for the limiting case of instantaneous three-dimensional nucleation with diffusion-controlled growth of the nuclei.However,the instantaneous nucleation mechanism observed in the additive-free bath was changed to a more progressive one when additives were present in the bath.Surface morphology analysis indicated that alklpyridinium hydrosulfate ILs can induce the formation of leveled and finer grained deposits by the adsorption of additive at the first stages of deposition process,leading to decrease of the nucleation and growth rate of nuclei.
The stability of ionic liquid additive 1-butyl-3-methylimidazolium hydrogen sulfate （[BMIM]HSO4） during zinc electrowinning from acidic sulfate solution was investigated by cyclic voltammetry, electrochemical impedance spectroscopy and scanning electron microscopy. Compared with the traditional industrial additives, gelatine and gum arabic, [BMIM]HSO4 has more excellent chemical and thermal stabilities. The inhibition effects of gelatine and gum arabic on the zinc electrocrystallization are observed to markedly weaken due to their part degradation after 12 h longtime successive electrolysis and high temperature （90 ℃） treatments. In contrast, the activity of [BMIM]HSO4 is practically unaffected after 24 h longtime successive electrolysis and high temperature treatments. These results are corroborated with the corresponding morphological analysis of the cathodic deposits.
