Fundamental and Applied Aspects of Nickel Electrowinning from Chloride Electrolytes

Several fundamental aspects related to the nickel electrowinning from chloride electrolytes have been addressed in this paper. The thermodynamic study includes the activity coefficient of the hydrogen ion and the speciation diagram of NiCI2 solutions. The activity coefficient of the hydrogen ion (YH+) was calculated and estimated experimentally using a combination glass pH electrode. It was found that YH+ was greater than one in concentrated NiCl2 solutions and increased significantly with increasing NiCl2 concentration. The speciation diagram for NiCl2 solutions was plotted with YH+ and the effect of the ionic strength on the equilibrium constants being taken into account. It was discovered that the predominant nickel species in the acidic region were Ni2+ and NiCI+ in 0.937 M NiCl2 solution at 25°C. Electrodeposition tests demonstrated that higher Nit' concentration in the electrolyte improved the current efficiency of nickel electrodeposition (CENi). The additions of H3BO3, and NH4Cl increased very little the current efficiency of nickel electrodeposition at pH 1.5 and temperature 60°C. However, the addition of sulfate decreased the current efficiency of nickel electrodeposition. Nickel electrodeposition was also found to be a steady-state process since the amount of acid added to the electrolyte at a constant pH increased linearly with time during galvanostatic electrodeposition. The cathode surface pH during nickel electrodeposition was measured using a flat-bottom combination glass pH electrode and a 500-mesh gold gauze as cathode. The cathode surface pH was found always to be higher than the pH in the bulk electrolyte, and if the current density was sufficiently large, it would eventually reach a level causing precipitation of insoluble Ni(OH)2(s) on the cathode surface. Rotating disc electrode studies revealed that the rate of nickel electrodeposition was first order with respect to the activity of nickel ion and zero order with respect to the activities of chloride and hydrogen ions. The rate of hydrogen evolution was found to be first order with respect to the activity of hydrogen ion and to be zero order with respect to the activities of nickel and chloride ions. These findings indicate that nickel deposition and hydrogen evolution proceed independently.