Minerals Engineering, Vol. 14, No. I, pp.

115-183, 2001
Pergamon 0 2001 Publishedby Elsevier Science Ltd
All rights resermi
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ELECTROWINNING OF COBALT FROM ACIDIC

SULPHATE SOLUTIONS-EFFECT OF CHLORIDE ION

N. PRADHANq, P. SINGH*, B.C. TRIPATHY* and S.C. DASq

1 Regional Research Laboratory (CSIR), Bhubaneswar 751013, India

$ Department of Chemistry, Murdoch University, Murdoch, WA 6150, Australia
* Author for correspondence. Email: singh@chem.murdoch.edu.au
(Received 3 December 2000; accepted 10 April 2001)

ABSTRACT

Cobalt electrowinningfrom acidic sulphate solution was carried out in the presence and absence of
chloride ion in the electrolyte. The effect of current density, electrolyteflow rate and temperature on
cobalt electrowinning was studied from pure cobalt sulphate solutions and solutions containing
2000 mg dm chloride ion. It was found that presence of chloride ion did not have any significant
effect on cobalt deposition potential, current efJiciency and preferred crystal orientation of the
electrowon cobalt. However, the surface morphology of the cobalt electrodeposits was affected quite
strongly which may be attributed to the variation of the intensity of the crystal planes during the
electrodeposition process. 0 2001 Published by Elsevier Science Ltd. All rights reserved.

Keywords
Electrometallurgy; electrowinning

INTRODUCTION

Cobalt is one of the most strategic metals among the less common metals because of its high demand for
making magnetic alloys, cutting and wear-resistant alloys and mostly superalloys (Hodge, 1990). About
70% of the worlds cobalt is recovered by hydrometallurgical route, where electrowinning is the final step
(Vemey, 1988). Most of the cobalt metal produced today by electrowinning is either from pure cobalt
sulphate solutions (Bouchat and Sauet, 1960; Mantell, 1960, Das and Subbaiah, 1984; Lenthall and Bryson,
1997) or from sulphate solutions containing inorganic/organic additives (Mantell, 1960; Lenthall and
Bryson, 1997, Bray, 1947; Liddell, 1945; Das and Subbaiah, 1987). Even though electrowinning of metals
from chloride solution has many advantages over the sulphate media (Ji et al, 1993), this process has not
found commercial application generally on the grounds of economy (Verney, 1988) and corrosion problem
of the plant.

Halide ions are known for their activating effect on both cathodic and anodic reactions in many
electrochemical systems (e.g. Libby, 1952; Antropove, 1972). The favourable influence of chloride ions
(Cl-) in the electrodeposition of heavy non-ferrous metals (zinc, cadmium, copper, nickel) is well
documented (Levin, 1982; Bobov et al., 1996; Fang et al., 1993; Lakshmanan et al., 1977). The effects of
Cl- as an additive on electrodeposition of various non-ferrous metals from their sulphate solutions have

115
716 N. Pradhan et al.

also been studied (Fang et al., 1993; Lakshmanan et al., 1977). For example the presence of Cl- in the
electrolyte has been found to increase cathodic current efficiency (Fang et al., 1993) and improve the
quality of the metal electrodeposit (Lakshmanan et al., 1977). However, not much is reported in the
literature on the influence of Cl- on cobalt electrodeposition from acidic sulphate solutions. This paper
reports the effect of Cl- on cathode potential (CP), cathodic current efficiency (CE), crystal orientation and
deposit morphology of the electrowon cobalt from acidic sulphate solutions. The effects of electrolyte flow
rate, current density and temperature, in the presence and absence of Cl-, are also reported.

EXPERIMENTAL
Flow cell

A flow cell consisting of two identical circular compartments (Figure l), cathodic and anodic, each of 9 cm
diameter was made from perspex of thickness 3.2 cm with a groove of lcm depth. Each groove
accommodated an electrode of 5 cm diameter. The two compartments were separated by a micro porous
Daramic separator placed between the two halves and clamped together using Viton O-rings. The catholyte
and anolyte were circulated through their respective compartments by using peristaltic pumps [Cole-Parmer
Instrument Company, Australia, Model No. 7553-751 through inlet and outlet ports made from Teflon.
Apart from this, one extra port was provided in each compartment to connect a reference electrode for
measuring the cathode and anode potentials.

Fig.1 Cathodic and anodic compartments of the circular flow cell with a cobalt electrodeposit.

Reagents

The electrolytes were prepared by using ultra pure water [Millipore MilliQ System] along with the
following analytical grade reagents : cobalt sulphate (CoS04.7H20), sulphuric acid (H$04) and cobalt
chloride (CoC12.6HzO). The pH of the electrolyte was adjusted by adding sulphuric, acid. Addition of
different concentrations of Cl- to the cobalt electrolyte was made by adding appropriate amounts from a
stock solution of cobalt chloride.
 Electrowinningof cobalt from acidic sulphatesolutions--effect of chloride ion 777

Electrode preparation

For the electrowinning studies the surface of the stainless steel electrode was polished with 1200 grade
to mirror finish. The surface was then roughened by using 360 grade emery paper
silicon carbide paper
following which the electrode was cleaned with 1 M HCl and then thoroughly washed with ultra pure
water.

Electrolysis

All the electrowinning experiments were conducted from 1.0 M COSOJ electrolytes for two hours by
applying constant current from a regulated power supplier [0-3OV, 5A, DC Power Supply, Dicksmith
Electronics, China]. A precision voltmeter and an ammeter were placed in the cell circuit to record the
potential and current. A thermostat [Grant (Selbys), Australia] was used to maintain the electrolyte
temperature. The pH of the electrolyte was kept at 3. The cathode and anode were made from stainless steel
(Austentic grade 316) and lead-antimony (Sb, l-5%) respectively. A saturated calomel electrode (SCE)
was used as the reference electrode and all the potentials were measured against it and reported as such.
The surface to surface cathode to anode distance was. kept at 3 cm. After electrolysis, the cathode was
removed from the cell, washed thoroughly with water followed by acetone and then dried. The cathodic
current efficiency was calculated from the weight gained by the cathode at the end of the electrolysis.

The effect of change in chloride concentration in the range O-5000 mg drnm3on the cobalt electrowinning
was studied at 250 A m-, electrolyte flow rate 4.6 dm3 h-i and 60C.

The effect of variation of current density (250 -750 A me2), electrolyte flow rate (1 - 4.6 dm3 h-l) and
temperature (20-6OC) on cobalt electrowinning from acidic sulphate electrolytes containing 2000 mg dmm3
Cl- was also investigated.

Deposit examination

A Philips PW 1050X-ray diffractometer was used to examine nickel deposits to determine their preferred
crystal orientations. The surface morphology of the electrowon metal was examined by scanning electron
microscopy (SEM) using a Phillips SE 1OlB microscope.

RESULTS AND DISCUSSION

The cobalt electrowinning from cobalt sulphate electrolyte at 250 A mT2,4.6 dm3 h- electrolyte flow rate
and 60C occurred at 0.81 V with a current efficiency of 97 %. The electrowon cobalt had a smooth and
compact deposit morphology consisting of fibrous crystallites (Figure 2a) with the preferred crystal
orientation (100) (101) (110).

The addition of Cl- in the range O-5000 mg dmm3to the electrolyte did not have any effect on the CP, CE
and preferred crystal orientation. This is not surprising because Cl- form only very weak complexes with
Ni2+in aqueous solutions. However, the adsorption of Cl on the surface of the electrode does seem to have
a significant effect on the deposit morphology even though all the deposits looked compact and smooth.
This is probably related to the effect of Cl- on the variation of the intensity of growth of the crystal planes.
The addition of 100 mg dmm3of Cl- promoted the formation of large sized crystallites having hexagonal
shape but poorly developed boundaries (Figure 2b). Increasing the Cl- concentration to 500 mg dm-3
decreased the size of the crystallites. At 2000 mg dmm3the cobalt deposit consisted of angular crystals
together with some thin plate-like crystals perpendicular to the substrate (Figure 2~). Further increase of
Cl- concentration up to 5000 mg dmm3,resulted in triangular crystallites distributed randomly throughout
the deposit surface (Figure 2d).
 N. Pradhan et al.

Fig.2 SE micrographs of electrodeposited cobalt from acidic sulphate solutions at 250 A rne2, 4.6 dm3
h- and 60C;
(a) Addition free; (b) 100 mg drne3 Cl- ; (c) 2000 mg dme3 Cl- ; (d) 5000 mg dmm3 Cl-.

Current density

As one would expect from the usual i vs V relationships, increase in current density shifted the CP of cobalt
electrodeposition to more negative potentials. For example in the chloride free electrolyte, when the current
density was increased from 250 to 750 A me2, the CP increased by 260 mV. However, a slight decrease in
the CE was observed (Table 1). Similar observations have been made by Lenthall and Bryson (1997). The
X-ray diffractograms of the electrodeposited cobalt showed that the change in current density did not affect
the order of preferred crystal orientation significantly and the order of preferred crystal orientation
remained either (100) (101) (110) or (110) (100) (101) (Table 1). All the cobalt electrodeposits were
visually bright and smooth. But under SEM, there were significant differences in the morphology of the
deposits. The surface morphology of the electrodeposited cobalt obtained from pure cobalt sulphate
solution at 250 Ame was smooth and compact and consisted of fibrous crystallites (Figure 2a). By
increasing the current density to 450 Amm2 polyhedral growth was seen (Figure 3a) which remained almost
unchanged even at 550 Amm2. But at 750 Amm2 dendritic growth developed over the polyhedral crystals
(Figure 3b).
 Electrowinning of cobalt from acidic sulphate solutions--Sxt of chloride ion 779

TABLE 1 Effect of electrolytic parameters on CP, CE and crystal orientation of the

electrowon cobalt from acidic sulphate solutions in the presence and absence of
chloride ion

Electrolytic parameters [Chloride] CP CE Crvstal orientation (hkl)

/mgdme3 IV I% Relative peak intensity (I/I_) / %
(100) (101) (110)
Current density / A mm2
250 0 -0.81 97 100 13 6
450 0 -0.96 96 26 4 100
550 0 -1.00 95 8 47 100
650 0 -1.07 94 8 2 100
750 0 -1.09 92 12 4 100
250 2000 -0.82 97 100 55 54
450 . 2000 -0.98 95 100 17 73
550 2000 -0.99 95 3 2 100
650 2000 -1.05 94 3 1 100
750 2000 -1.08 93 17 4 100
Electrolyte flow rate /
dm3 h-
1 0 -0.82 97 78 37 100
1.8 0 -0.82 98 100 23 36
3 0 -0.81 98 100 27 18
4.6 0 -0.81 97 100 13 6
1 2000 -0.81 95 30 6 100
1.8 2000 -0.82 96 100 34 76
3 2000 -0.83 96 100 59 47
4.6 2000 -0.83 97 100 55 54
Temperature / C
20 0 -0.97 84 15 5 100
40 0 -0.89 95 64 12 100
50 0 -0.84 95 92 10 100
60 0 -0.81 97 100 13 6
20 2000 -0.95 85 70 36 100
40 2000 -0.88 96 34 12 100
50 2000 -0.84 96 100 60 35
60 2000 -0.81 97 100 55 54

In the presence of 2000 mg dme3 Cl- in the electrolyte the effect of variation of current density on CP, CE
and crystal orientations was similar to that observed in the absence of Cl-. Thus Cl had no significant
effect on these characteristics of the cobalt electrodeposition process. However, as noted earlier the
presence of Cl- did have an effect on the deposit morphology which varied with the changing current
density. For example the addition of 2000 mg dme3 Cl- to the electrolyte resulted in a cobalt deposit
consisting of a mixture of angular and thin plate like crystals perpendicular to the substrate (Figure 2c) as
compared to the fibrous deposit obtained in its absence as noted earlier. Increasing the current density to
450 Amm2resulted in sharp elongated crystals showing different deposit morphology (Figure 3~). 550 Ame
produced polyhedral crystals of size 2-4 pm with dendritic appearance at the top of each crystal (Figure
3d). Further increase in current density to 750 Amm2increased the size of the crystals resulting in crystal
growth with cabbage like appearance through out the deposit (Figure 3e).

Electrolyte flow rate

As can be seen from Table 1 the electrolyte flow rate (l-4.6 dm3 h-) did not have any effect on the CP and
CE of the cobalt electrodeposition. However, the change of flow rate did affect the crystal orientations as a
result of varying mass transport characteristics. The order of preferred crystal orientation at a flow rate of 1
dm3 h-i was (110) (100) (101) with (110) plane being the most preferred. At 1.8 dm3 h- flow rate the
780 N. Pradhan et al.

crystal orientations changed to (100) (110) (101) and at higher flow rates, the orientation (100) (101) (110)
became predominant. The (110) plane was found to be the most preferred plane at flow rates > 1 dm3 h-t.
The cobalt deposit morphology was affected significantly by the electrolyte flow rate. At 1 dm3 h- the
surface morphology consisted of nodular crystals of sizes 2-6 urn (Figure 4a). Increasing the flow rate to
1.8 dm3 he resulted in a mixture of nodular and elongated crystals (Figure 4b). At 3 dm3 h-t flow rate the
deposit consisted of bundles of elongated crystals randomly distributed throughout the deposit (Figure 4~).
At a still higher flow rate of 4.6 dm3 h- a fibrous but relatively compact deposit was seen as reported
before (Figure 2a).

Fig.3 SE micrographs of electrodeposited cobalt from acidic sulphate solutions at 4.6 dm3 h-i and 60C;
(a) 450 A mm2 ; (b) 750 A me2 ; (c) 250 A mm2and 2000 mg dmW3Cl- ; (d) 450 A me2 and 2000
mg dme3 Cl ; (e) 750 A mm2and 2000 mg dmm3 Cl.

The presence of 2000 mg dmW3 Cl- in the electrolytic bath did not have any effect on the cobalt
electrodeposition characteristics (CP, CE and crystal orientattion) as a function of the electrolyte flow rate.
However, the presence of Cl- did have an effect on the morphology of the electrowon cobalt. At 1 dm3 h-
the deposit morphology consisted of elongated thin plate-like crystals distributed randomly over the deposit
 Electrowinningof cobalt from acidic sulphate solutions--effect of chloride ion 781

(Figure 4d). Increasing the flow rate to 1.8 dm3 h- resulted in similar morphology but with larger sized
crystals [Figure 4e]. Further increase in the flow rate to 4.6 dm3 h- produced a deposit morphology
consisting of a combination of angular crystals and thin plate-like crystals perpendicular to the substrate
(Figure 2~).

Fig.4 SE micrographs of electrodeposited cobalt from acidic sulphate solutions at 250 A mm2 and 60C;
(a) 1 dm3 h- ; (b) 1.8 dm3 h-i ;(c) 3 dm3 h-; (d) 1 dm3 h- and 2000 mg dmw3Cl- (e) 1.8 dm3 h-
and 2000 mg drnm3Cl-.

Temperature

Temperature is an important factor during electrodeposition of metals. In the present study, the influence of
temperature was studied in the range 20-6OC. As one would expect, a decrease in the cathode potential for
cobalt electrodeposition was observed with increase in temperature. For example the CP changed from -
782 N. Pradhan et al.

0.97 V at 20C to - 0.81 V at 60C. The temperature had a significant,effect on the CE. The CE increased
from 85% to 95% when the temperature was raised from 20 to 40C but then remained almost the same at
higher temperatures up to 60C as noted in Table 1. Normally hydrogen evolution should occur prior to the
cobalt electrodeposition. However, because the hydrogen evolution overpotential on cobalt is high, the
electrodeposition of cobalt from aqueous solution is possible. Furthermore with increase in temperature the
cobalt electrodeposition overpotential decreases by more than does the hydrogen overpotential (Louis et al,
1988). Thus high CE for the metal deposition is obtained at high temperatures (60-70C). It is interesting to
note that the variation of temperature in the range 2060C had virtually no effect on the cobalt crystal
orientations, which remained predominantly as (110) (100) (101). The (110) plane was the most preferred
plane. The electrodeposits obtained from pure cobalt sulphate solution in the temperature range 20-50C
were dull, non-smooth and non-uniform. These deposits had nodular morphology. A typical example is
shown in Figure 5. At 6OC, bright, smooth and relatively compact deposits with fibrous crystallites were
obtained. This could be related to the deposition of metal at a potential where hydrogen evolution is less of
a problem.

Fig.5 SE micrograph of electrodeposited cobalt from acidic sulphate solution at 250 A mm2,4,6.dm3 h-i
and 40C.

Even though the addition of 2000 mg dme3 of Cl- in the electrolyte at 20-60C had no effect on CP, CE
and cobalt crystal orientations (Table l), the temperature did affect the cobalt deposit morphology at
>50C. At 60C the deposit morphology consisted of a mixture of angular crystals and thin plate like
crystals perpendicular to the substrate as compared to the fibrous deposit as noted in the absence of Cl- at
the same temperature.

CONCLUSIONS

The effect of Cl- on the electrowinning of cobalt from acidic sulphate solutions has been investigated as a
function of varying electrolytic bath parameters including current density, electrolyte flow rate and
temperature. It is found that the presence of Cl- has no significant effect on cathode potential, current
efficiency and crystal orientations. However, the presence of Cl does affect the morphology of the
electrodeposited metal under conditions of all the investigated parameters.
 Electrowinning of cobalt from acidic sulphate solutions-effect of chloride ion 783

ACKNOWLEDGMENTS

The authors thank P. Fallon for assistance in SEM, K. Seymour for XRD and T.B. Issa for general
assistance throughout the work. The authors (Pradhan, Tripathy and Das) thank Dr. R.P. Das for
encouragement. The financial support of the Australian Government in carrying out a part of this work is
also acknowledged.

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