JournalofMetallurgicalEngineering(ME)Volume2Issue3,July2013www.mejournal.

org

EffectsofCurrentDensityandNickelasan
ImpurityonZincElectrowinning
JianmingLu*1,HuajunGuo2,DavidDreisinger3,BruceDowning4
DepartmentofMaterialsEngineering,UniversityofBritishColumbia,3096350StoresRoad,Vancouver,Canada
V6T1Z4
1,3

SchoolofMetallugicalScienceandEngineering,CentralSouthUniversity,Changsa,Hunan,China,410083

MagpowerSystemsInc.,Suite20,1480FosterStreet,WhiteRock,Canada,V4B3X7

*1

Jianming.Lu@ubc.ca;2ghj.csu@163.com;3david.dreisinger@ubc.ca;4bwdowning@shaw.ca

Abstract

cobaltandnickelarenoteasilyremoved.

The effects of current density and nickel as an impurity on

zinc electrowinning has been studied to find an optimum
currentdensitytosolvethezincredissolutionproblemdue
toahighlevelofnickelinelectrolyte.Inthepresenceof0.4
mg/L Ni, with increasing current density from 450 to 550
and650to750Am2,theaverageinductiontimeforzincre
dissolution decreased from 47.2 to 44.62 and 44.41 to 40.28
hours,theaveragecurrentefficiencydecreasedfrom93.74to
93.56 and 93.34 to 92.93%, and the energy consumption
increasedfrom2.916to2.977and2.988to3.077kwh/kgZn.
Thezincdepositmassesat550,650and750Am2were10.6,
32.6 and 35.6% greater than that at 450Am2 respectively.
Consideringtheenergyconsumptionandzincdepositmass,
a current density of 650 Am2 is recommended for zinc
electrowinning. The zinc electrowinning time should be
slightly shorter than the induction time. At this current
density,thezincdepositmasscanbesignificantlyincreased
while the energy consumption increases slightly. In some
plant operations, if the cost for removal of nickel to a
satisfactorylevelistooexpensive,thecurrentdensitycanbe
adjustedtomaximizethezincdepositmass.Thepresenceof
0.4 mg/L Ni has very little effect on cathodic polarizaton
behaviour.

InthepresenceofimpuritiessuchasSb,Co,Ni,As,Ge,
thezinccurrentefficiencywassignificantlydecreased
and the quality of zin deposit was poor [Ault and
Frazer, 1988; Robinson and OKeefe, 1976]. With
regard to cathode deposit behaviour, a general
statement can be made to the effect that the ions of
those impurities with standard potentials more
negative than zinc, such as Al, Mg, Ca and Na, have
littleeffect;ionsofimpuritiesthataremarginallymore
positivethanzinc,suchasCd,andPb,tendtodeposit
at the cathode, decreasing its purity; ions of those
metalsthataremuchmorepositivethanzincandare
characterized with low hydrogen overpotential such
as Pt, Ag, Fe, Co, Ni and Cu decrease current
efficiency[RobinsonandOKeefe,1976].
During zinc electrowinning from sulfate electrolytes
containing nickel, a process of redissolution of
depositedmetaltakesplace[MackinnonandMorrison,
1986; Stefanov and Ivanov, 2002; Mackinnon et al.,
1987; Ivanov, 2004]. The term induction time or
period is used in zinc electrowinning [Turomshina
and Stender, 1955; Fosnach and OKeefe, 1980; Jaksic,
1986]. During this induction time, which coincides
with the beginning of zinc electrodeposition, the zinc
depositsareuniformandadherefirmlytothecathode.
Thetypicalcurrentefficiencyis9395%.Followingthis
induction time, zinc redissolution occurs with
hydrogen evolution. After the zinc is completely
dissolved, deposition restarts. The induction time
depends on several factors such as temperature,
cathodic current density, and the concentrations of
sulfuricacid,zincandimpurities.Thelocalpairmodel
is often used to explain the redissolution of zinc
deposit[Ivanov,2004; Turomshinaand Stender, 1955;
Wang and OKeefe, 1980; Fratesi et al., 1979; Wark,
1979]. The metal impurities codeposited with zinc

Keywords
ZincElectrowinning;InductionTime;SulfateSolution;Nickel

Introduction
Zinc electrowinning which is generally conducted in
acidicsulfatesolutionhasbeenextensivelystudiedto
improvethezinccurrentefficiencyandreduceenergy
consumption [Alfantazi and Dreisinger, 2001;
Recendiz etal., 2007; Tripathy et al., 2004]. The zinc
current efficiency and deposit quality are affected by
zinc and sulfuric acid concentrations, current density,
temperature and impurities. Some of the harmful
impurities such as copper and iron can be easily
removed to such an extent that they virtually do not
affectzincdeposition.However,someofthemsuchas

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www.mejournal.orgJournalofMetallurgicalEngineering(ME)Volume2Issue3,July2013

behave as a cathode with respect to the zinc deposit

and catalyzes the hydrogen discharge. However, the
induction time is only observed in the presence of
irongroup metal impurities. The overpotential of
hydrogenevolutiononnickelisabout0.6Vlowerthan
that on zinc [Sharma, 1998]. Nickel can dramatically
depolarize the discharge of hydrogen ions. The
induction time is related to the hydrogen bubble
formation stage on the active regions of the cathode
surface,containingcodepositednickel[Majaetal.,1982;
Wiart et al., 1990; Cachet et al., 1993; Bozhkov et al.,
1990].

electrochemically conditioned for 3 weeks. The

objective of sandblasting and electrochemical
conditioningwastobuildadensePbO2layerandalso
adenselayerofMnO2,bothofwhichfirmlyadhereto
the lead substrate. These two layers prevent the
significant dissolution of lead and contamination of
the zinc deposit. If the anodes were not used for a
certain time, they were electrochemically re
conditioned. The electrolyte was prepared using
neutral zinc electrolyte, deionized water, reagent
grade sulfuric acid and highly pure metallic
manganesewiththecompositionof70g/LZn,140g/L
H2SO4 and 5 g/L Mn. Seven cycles (23 day for one
cycle) of zinc electrowinning were applied. At the
beginning of each cycle, 5 mg/L of animal bone glue
was added to each cell. The electrolyte was not
changed foreach cycle. The cells were connectedin a
series for a constant electrical current that was
supplied by a PAR273A electrochemical interface. All
cellswereplacedinawaterbathandthetemperature
was controlled at 38 0.1C. The cell voltage and
current were measured using an OMBPDQ2 data
acquisition module from OMEGA Inc. and a Model
90000999 DC Ammeter shunt from Canadian Shunt
IndustriesLtd.

Ahighcurrentefficiencyandhighqualityzincdeposit
can be obtained from highly purified electrolyte.
However, rigorous electrolyte purification can be
economically nonviable. Alternative ways to reduce
the harmful effects of impurities are: (1) the use of
suitable additives, (2) the optimization of zinc
electrowinning operating conditions, or (3) the
combinationof(1)and(2).
The objective of this study was to find an optimum
current density and zinc deposition time to suppress
oravoidtheharmfuleffectofnickelandoptimizezinc
electrowinningoperationbystudyingtheinfluenceof
nickel ions and current density on current efficiency
and induction time for zinc electrowinning from
sulfateelectrolytes.

ElectrowinningTests
Thecompositionoftheelectrolytewas:55g/LZn,160
g/L H2SO4, 2 g/L Mn, 2.5 mg/L Arabic gum and
variable amounts of additives. The experiment setup
wasthesameasthatforelectrochemicalconditioning
oftheleadanodes

Experimental
MiniCellsforZincElectrowinning
The anodes and cathodes were manufactured using
leadsilveralloyandanindustrialaluminiumsheetfor
zinc electrowinning. The nonworking areas of the
anodes and cathodes were surrounded with a cold
mount epoxy resin. A copper wire was connected to
an anode or cathode using a silverrich conductive
cement for the electrical connection. The sizes of the
anodes and cathodes were 11 cm2. The electrolysis
cell was a 600mL Pyrex beaker fitted with a lid in
whichspacersweredrilledtomaintainafixedanode
cathodedistance(20mm).Theelectrolytevolumewas
set at 500 mL. After each test, the zinc deposit was
stripped and the aluminum cathode was brushed
usinganabrasivecleaningpad.Boththecathodeand
anode were rinsed with deionized water and stored
inadry,cleanplaceforthenexttest.

PolarizationMeasurement
Cyclic voltammetry and linear polarization were
carried out in a three electrode system using a
PAR273A electrochemical interface, where the cell
consisted of a lead anode (1x1 cm2) covered with
MnO2, an Al cathode (1x1 cm2) and an Ag/AgCl
referenceelectrode.Theanodecathodedistancewas5
cm. Before cathodic polarization, the cathodes were
first electrodeposited with an 18 m thick zinc layer
from the same electrolyte used for polarization
measurements.
SolutionPreparation
Highly pure zinc oxide, reagent grade sulfuric acid
and highly pure metallic manganese were used to
prepare synthetic electrolyte. The composition of the
zincoxidefromUSZincwas:99.87%ZnO,0.0001%Cd,

ElectrochemicalConditioningofLeadAnodes
Newleadanodeswerefirstsandblastedtoachievean
average roughness of 30 m, and then

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JournalofMetallurgicalEngineering(ME)Volume2Issue3,July2013www.mejournal.org

0.0001%Fe,0.125%water,0.0008%Pband0.00001%As.
The contents of other heavy metal impurities are not
expectedtoexist(lessthan0.0001%).Thepuremetallic
manganese was from Manganese Metal Company,
SouthAfrica.Reagentgradenickelsulfatewasadded
as an impurity. The Arabic gum from Sigma Aldrich
and bone animal glue from Teck Corporation were
usedasadditives.

Voltage noise appeared for Cells B and C. The cell

voltage sharply droped for Cells B and D, indicating
theoccuranceofzincredissolution.
AsshowninFig.2,thecathodepotentialvstimecurve
was smooth and the cell voltage noise resulted from
the anode potential noise. The anode potential noise
was probably primarily caused by the poor contact
between the loosely connected manganese dioxide
particles, and that between the manganese dioxide
layer and lead substrate. Oxygen evolution in the
porous manganese dioxide layer exerted varying
forces on the manganese dioxide particles and causes
the fluctuation in the contact resistence and thus
potential drop. Since the electrolyte contained 2 g/L
manganese ions, manganese dioxide accumulated on
the anode during zinc electrowinning. As more
manganese dioxide was deposited, the manganese
dioxide layer became loose and finally fell off the
anode.

Neutral mother electrolyte (160180 g/L Zn and 510

g/LH2SO4)wasfirstpreparedusingsulfuricacidand
zinc oxide. The zinc mother solution was prepared
usingthefollowingprocedures:(1)slowlyaddsulfuric
acid to deionzed water, (2) gradually add zinc oxide
intocooledsulfuricacidsolutionwithstirring,(3)after
thesolutioncoolsdown,strontiumcarbonate(0.1g/L)
is added to remove lead through coprecipitation of
lead sulfate with strontium sulfate with stirring (over
one hour), (4) let the solid settle over night, and (5)
filter the mother solution to remove the precipitate
(SrSO4).

The electrolyte was prepared by mixing mother

solution,deionizedwater,sulfuricacidandadditives.

3.1

ChemicalAnalyis

The concentration of zinc was analyzed by titration

withEDTA.InthepresenceofMn2+,thetitrationwas
calibrated due to the interference of Mn2+. The free
acidwastitratedusing1NNaOH.

3.0
Cell Voltage / V

Results and Discussion

AnodeConditioningandReproducibleTests

Before the electrowinning tests, the anodes were

conditioned several times and reproducibility tests
were conducted. The zinc current efficiencies for all
twenty cells in the final anode conditioning test were
greater than 96.50.4%, and those in the
reproducibility test were greater than 95.70.15%,
suggesting the cells were well conditioned and
demonstratedgooduniformity.

2.9
A

2.8

Cell A
Cell B
Cell C
Cell D

2.7
2.6

12

24

36

48

60

72

Time / hour
FIG. 1 TYPICAL CELL VOLTAGE VS TIME AT 450 Am-2

Voltage vs Ag/AgCl / V

3.0

TypicalCellVoltagesofZincElectrowinning
Fig. 1 shows typical cell voltage vs time curves
obtained from the electrolyte containing nickel. The
cell voltage first rose rapidly at the beginning due to
the larger cathodic polarization on zinc than that on
the aluminum substrate. Then it gradually decreased
due to the increase in the cathode surface area and
hydrogen ion concentration, and the decrease in the
cathodeanode distance as more zinc was deposited.

Cell Voltage

2.8
2.6

Cell Voltage
Cathode/Anode Potential

2.4
2.2
2.0
1.8
-1.0
-1.2

Anode Potential
Cathode Potential

12

Time / hour

16

20

FIG.2CELLVOLTAGE,ANDANODEANDCATHODE
POTENTIALSVSTIMEFORTHECELLWITHVOLTAGENOISE
AT450Am2.

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www.mejournal.orgJournalofMetallurgicalEngineering(ME)Volume2Issue3,July2013

A rescaled cell voltage vs time curve with zinc re

dissolution is shown in Fig. 3. During the induction
time,thecellvoltagedecreasedveryslowly.Whenthe
nickelrich area increased to a critical value, the
discharge of hydrogen ions was depolarized so
significantly that the cathode potential was mainly
determinedbythedischargeofhydrogenions.Asthe
nickelrich area increased, the cathode potential
increased quickly while the cell voltage decreased.
When most of zinc deposit was dissolved, the nickel
rich area shrank and the cathode potential began to
decrease. The cell voltage increased until the cathode
was completely covered with zinc. The time for zinc
redissolution and recovering the cathode with zinc
was about two hours. The cell voltage changed by
about 0.2 V. The development of zinc redissolution
differedforeachcell,resultinginvariousvoltagetime
curves. For some cells, the zinc redissolution was
slower (Figure 4). The cell voltage changed to a less
extentduringthezincredissolution.

the cell voltage was close to its minimum (Fig. 6). By

comparison with other cell voltage curves, the cell
voltagewouldincreaseafter10to20minutes.Thezinc
redissolution started at one site and developed
radially.

2.95

FIG.5ZINCDEPOSITHALFREDISSOLVED

2.90

2.90
2.88

2.80

2.86
Cell voltage / V

Cell Voltage/V

Induction time
2.85

2.75
2.70
2.65
47

48

49

50

51

52

53

2.80
2.78
2.76
2.72

2.70

FIG.3CELLVOLTAGEVSTIMEFORTYPICALZINCRE
DISSOLUTION

60

62

64

66

Tim e / h

2.95
Induction time

FIG.6CELLVOLTAGEVSTIMEFORTHEZINCDEPOSITHALF
REDISSOLVED

2.90
Cell Voltage/V

2.82

2.74

Time / hour

2.85

Effect of Nickel Concentration on Zinc Electrowinning

2.80

The effects of nickel concentration on zinc

electrowinning were investigated at 0, 0.2 and 0.4
mg/L Ni. The experimental design and results are
summarized in Table 1. In Runs 1 and 2, a
electrowinning time of 66 hours was used to ensure
that zinc redissolution occurred for all cells and to
study the effect of nickel concentration on the
inductiontime.Zincdepositshadalargerprobability
of redissolution, shorter induction time, and lower
currentefficiencyatahighernickelconcentration.

2.75
2.70
2.65
12

13

14

15

16

17

18

Time / hour
FIG.4CELLVOLTAGEVSTIMEFORSLOWERZINCRE
DISSOLUTION

When the zinc deposit was half redissolved (Fig. 5),

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JournalofMetallurgicalEngineering(ME)Volume2Issue3,July2013www.mejournal.org

TABLE1RESULTSOFZINCELECTROWINNINGFROMSULFATESOLUTIONWITHDIFFERENTNICKELCONTENTS
0mg/LNi(Run1)

0.2mg/LNi(Run2)

Current
efficiency
(%)

Cell
No

3.3625

92.71

3.3635

92.74

3.3644

0.4mg/LNi(Run3)

Current Induction
Zincmass
efficiency
time
(g)
(%)
(hour)

Cell
No

3.3429

92.68

0.4902

13.59

54.79

0.0097

0.27

63.74

0.834

23.12

47.94

92.76

3.3387

92.57

0.9391

26.03

45.94

3.3673

92.84

3.3407

92.62

1.0293

28.54

44.32

3.3657

92.80

10

0.6827

18.93

50.52

1.2013

33.3

40.84

11

3.3555

92.51

12

63.27

11

0.6203

17.2

52.17

13

3.3515

92.40

14

1.7223

47.75

28.93

13

3.3776

93.64

15

3.3415

92.13

16

3.3676

93.37

15

1.0433

28.92

44.32

17

3.3546

92.49

18

3.3404

92.61

17

2.7395

75.95

19

3.347

92.28

20

3.3258

92.21

19

0.98

27.17

47.19

Average

3.3574

92.57

Average

2.2471

62.30

51.62

Average

1.3255

36.75

47.19

Cell

Zincmass

No

(g)

Current Induction
Zincmass
efficiency
time
(g)
(%)
(hours)

*Electrowinningtime:66hours.TheinductiontimeforCell17inRun3wasnotdeterminedbecauseoftheconnectionproblemwithitsanode.

The effect of nickel concentration on the current

efficiency was investigated in Run 3. Compared with
theelectrowinningtimeneededinRun1andRun2,a
shorterelectrowinningtime(20hours)wasrequiredto
avoid zinc redissolution. This was designed to study
the effect of the nickel concentration on current
efficiencybeforeredissolutionoccured.FromTable2,
the zinc current efficiency was not affected in the
nickelconcentrationrangingfrom0to0.4mg/L.

basedonthecellvoltagevstimecurves,andthenthe
theoretical zinc mass at the induction time was
determined according to the current density. The
resultsaregiveninFig.7.Itshouldbenotedthatthe
redissolutiondidnotoccurfortwocellsat550Am2
andonecellat450Am2.Therefore,theinductiontime
for these three cells was assumed to be 66 hours in
order to calculate the average induction time and
theoreticalzincmass.

TABLE2EFFECTSOFNICKELCONCENTRACTIONONZINC

Bytheincreasingcurrentdensityfrom450to550and
650to750Am2,theaverageinductiontimedecreased
from 49.28 to 44.62 and 44.41 to 40.28 hours (Fig. 7a)
while the theoretical zinc mass at the average
inductiontimeincreasedfrom2.693to2.983and3.586
to3.682g(Fig.7b),indicatingthatalargermassofzinc
deposit per unit area was able to be obtained at a
higher current density. Zinc redissolution was
primarily caused by the enrichment of nickel on a
cathode [Wiart et al., 1990; Cachet et al., 1993]. Since
the nickel concentration (0.4mg/L) was much lower
than that of zinc (55g/L), and the standard electrode
potential of Ni2+/Ni (0.23V vs SHE) is much higher
than that of Zn2+/Zn(0.76V vs SHE), nickel was
electrodeposited at a limiting current when zinc
started electrodepostion. The zinc deposition rate
increased with increasing current density while the
nickel deposition rate did not change. Therefore, at a
higher current density, the nickel content in the
deposit was lower and the induction time decreased

CURRENTEFFICECYINRUN3
Ni
(mg/L)

Currentefficiencyforeach
cell(%)

Average
current
efficiecny(%)

94.14

94.3

94.21

94.25

94.23

0.2

93.57

93.83

94.36

94.08

93.96

0.4

94.37

93.9

94.38

94.25

94.23

*electrowinningtime:20hours

EffectofCurrentDensityonInductionTimeand
CurrentEfficiency
Theeffectsofcurrentdensityoncurrentefficiencyand
induction time were investigated in the current
density ranging from 450 to 750 Am2. Ten cells were
usedforeachcurrentdensity.Theelectrowinningtime
was set to be 66 hours to ensure that redissolution
tookplaceinallcells.
The induction time for redissolution were obtained

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muchlessthanthatexpectedininverseproportionto
current density. More zinc was able to be deposited
beforetheredissolutionatahighercurrentdensity.

greater than that at 450 A m2, respectively. The zinc

deposit mass increased significantly with increasing
current density from 450 to 650 A m2 while it
increased very little with further increasing current
density to 650 A m2. Hydrogen evolution was the
main cathodic side reaction. In the current density
rangingfrom450to750Am2,thecurrentefficiencyof
hydrogen evolutionincreased with increasing current
density. At a higher cathodic current density,
hydrogen evolution was facilitated more than zinc
deposition,resultinginalowerzinccurrentefficiency.

70
(a)

50
40
30
20

Initial induction time for each cell

Average induction time

10
0
400

500

600

700

95
800

Current density (A/m )

Current Efficiency (%)

Induction time / hour

60

6
Theoretical zinc mass at tIn / g

(b)

5
4
3

93
92
91

Current efficiency for each cell

Average current efficiency

90
400

500

600

700

800

-2

0
400

Current density / A m )
FIG.8CURRENTEFFICIENCYASAFUNCTIONOFCURRENT
DENSITYAT0.4m/LNi

Mass at the induction time for each cell

Average mass at the induction time
500

600

700

3.2

800

-2

Current density / A/m

3.1
Cell Voltage / %

(b)
FIG.7(a)INDUCTIONTIMEAND(b)THEORETICALZINC
MASSATTHEINDUCTIONTIMEASAFUNCTIONOF
CURRENTDENSITYAT0.4m/LNi

Since the electrolyte in a cell was not changed, the

zincconcentrationdecreasedfasteratalargercurrent
density, resulting in a decrease in the current
efficiencyiftheelectrowinningtimewascloseforeach
current density. Therefore, the amount of electricity
passedwassetatthesameforallcurrentdensitiesand
the corresponding electrowinning time was 24, 19.64,
16.62, 14.4 hours for 450, 550, 650 and 750 Am2,
respectively.

3.0
2.9
2.8
2.7

Cell voltage for each cell

Average cell voltage

2.6
400

500

600

700

800

-2

Current density / A m )
FIG.9AVERAGECELLVOLTAGEASAFUNCTIONOF
CURRENTDENSITYAT0.4m/LNi

With increasing current density from 450 to 550 and

650 to 750 Am2, the average cell voltage increased
from2.916to2.977and2.988to3.077V(Fig.9),i.e.the
average cell voltages at 550, 650 and 750 A m2 were
2.09%, 2.81% and 5.52 higher than that at 450 A m2,
respectively, due to the larger cathodic, anodic
polarization and IR drop at a higher current density.
The energy consumption increased from 2.55 to 2.61
and2.62to2.71kwh/kgZn.

The current efficiencies were determined based on

themassesofzincdepositsandsummarizedinFig.8.
With the increasing current density from 450 to 550
and 650 to 750 Am2, the average current efficiency
decreased from 93.74 to 93.56 and 93.34 to 92.93%,
while the zinc deposit mass increased from 2.524 to
2.791and3.347to3.422g,i.e.thezincdepositmasses
at550,650and750Am2were10.6%,32.6%and35.6%

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JournalofMetallurgicalEngineering(ME)Volume2Issue3,July2013www.mejournal.org

A recommended current density was 650 Am2 since

the zinc mass deposit can significantly be increased
and the energy consumption increases slightly. At a
highercurrentdensity,thezincdepositmasscanonly
increase slightly while the energy consumption
increases significantly. Further evaluation needs to
consider the following factors: cell temperature,
electrolytecoolingandacidevaporation.

thedepositionofmorenickel.
The cathodic polarization curves on the aluminum
cathodeatdifferentnickelconcentrationsareshownin
Fig.11.Theyweresimilartothoseattheforwardscan
in the cyclic voltammograms shown in Fig. 10. With
decreasingcathodepotentialfrom1.15Vto1.23Vvs
Ag/AgCl,acurrentshoulderappeared.
0.15

PolarizationInvestgation

(a)

To further understand the effects of nickel

concentration and current density on zinc
electrowinning, cyclic voltammetry and linear
polarizationwereconducted.

0.05
I/A

0.00

2
1

-0.05

The cylic voltammograms on aluminum cathodes at

different nickel concentrations are shown in Fig. 10a.
The peaks around 0.9 and 1.0 V vs Ag/AgCl were
rescaled in Yaxis and shown in Fig. 10b to further
depict the difference between these curves. The
forwardscanintheelectrolytewithoutnickelrevealed
a flattened peak around 1.02V due to the hydrogen
evolution. It was stimulated by the iron impurities
contained in the aluminum substrate on which the
potential of hydrogen evolution was lower than the
potential on pure aluminum since there was no such
peak on pure aluminium [Brennon et al., 1987;
StenfanovandIvanov,2002].Zincdepositionbeganat
1.12VvsAg/AgClandthelargeanodicpeakshowed
that this was the predominant process. After the
complete zinc dissolution, a peakappearedat 0.89V
vsAg/AgCl,duetothehydrogenevolutionontheiron
aggregatescoveredwithnickel.

-0.10
-0.15

-0.7

-0.8

-0.9

-1.0

-1.1

-1.2

Potential vs Ag/AgCl / V

0.020

(b)
1: 0 mg/L Ni 3
2: 0.4 mg/L Ni
3: 4.0 mg/L Ni

I/A

0.015
0.010

0.005

3
2
1

0.000

-0.7

-0.8

-0.9

-1.0

-1.1

-1.2

Potential vs Ag/AgCl / V

Thepeaksat1.02VvsAg/AgClintheforwardscanin
the electrolyte containing 0.4 and 4.0 mg/L Ni were
slightly higher than that without nickel due to the
faster hydrogen evolution on the nickel deposited on
the cathode. The potential of hydrogen evolution on
nickelisabout0.10Vlowerthanthatonironand0.40
V lower than that on aluminium [Sharma, 1998]. The
zinc deposition began at 1.12 V vs Ag/AgCl. The
smaller anodic peak for the electrolyte containing 4.0
mg/L Ni indicated that the zinc deposition was
accompanied with hydrogen evolution. After the
completezincdissolution,cathodicpeaksoccurredat
0.89 V due to the hydrogen evolution on the iron
aggregates covered with nickel. The peak for the
electrolytecontaining0.4mg/LNiwasslightlyhigher
thanthatintheelectrolytewithoutNiwhilethepeak
in the electrolyte containing 4.0 mg/L Ni was much
higherduetothefasterhydrogenevolutionbecauseof

1: 0 mg/L Ni
2: 0.4 mg/L Ni
3: 4.0 mg/L Ni

0.10

FIG.10.(a)VOTLTAMMOGRAMAND(b)RESCALEDINYAXIS
OF(a)FORALUMINUMCATHODESATDIFFERENTNICKEL
CONCENTRATIONSATASWEEPRATEOF0.5mVs1

Fig. 12 shows the cathodic polarization curves on the

zincdepositsobtainedat450Am2.Comparedwiththe
polarizationcurvesinFig.11,theZn(II)reductionon
the zinc deposit started at a potential about 50 mV
more positive than that on the aluminum substrate,
suggesting lower polarization of Zn(II) reduction on
zinc. There was no current shoulder like that on the
aluminiumsubstrateshowninFig.11.
ComparisonofFigs.11and12,atapotentialwherea
current shoulder appeared, indicated that the current
densityonthealuminiumsubstratewasmuchhigher
thanthatonthezincdepositduetoahigherhydrogen
evolution current density on the former. The
aluminiumsubstratehadbettercatalyticpropertiesor

85

www.mejournal.orgJournalofMetallurgicalEngineering(ME)Volume2Issue3,July2013

activesitesforhydrogenevolution.Astheactivesites
for hydrogen evolution on the alumium substrate
were gradually covered with zinc, the hydrogen
evolution was progressively inhibited, resulting in a
slowincreaseinthecurrentdensityandthenacurrent
shoulder.

0.4

I/A

At a potential below 1.3 V vs Ag/AgCl, the current

density on the aluminium substrate was close to that
on the zinc deposit as the active sites for hydrogem
evolutionwascompletelycoveredbyzinc.

0.0
-0.7

0.3

I/A

2
1: 0 mg/l Ni
2: 0.4 mg/L Ni
3: 4.0 mg/L Ni

-1.0

-1.1

-1.2

-1.3

-1.4

0.030

(b)
0.025

I/A

0.020

0.010

1: 0 mg/L Ni
2: 0.4 mg/L Ni
3: 4.0 mg/L Ni

0.000
-0.7

-0.8

-0.9

-1.0

-1.1

-1.2

Potential vs Ag/AgCl / V
Fig.11.(a)CATHODICPOLARIZATIONCURVESAND(b)
RESCALEDINYAXISOF(a)ONALUMINUMCATHODESIN
ELECTROLYTESWITHDIFFERENTNICKELCONTENTSATA
SWEEPRATEOF0.5mVs1

-1.3

-1.4

Thepresenceofupto0.4mg/Lnickelhadalittleeffect
onthecathodicpolarizationbehaviour.

The polarization measurements were also conducted

onthezincdepositspreparedathighercurrents(550,
650 and 750 Am2). The current density for the
preparation of the zinc deposits practically has very
little effect on the polarization behaviour on the zinc
deposit.

86

-1.2

By comparison of zinc deposit masses prior to re

dissolutionandenergyconsumption,acurrentdensity
of 650 Am2 is recommended for zinc electrowinning
since at this current density, and the zinc deposit
masse can be increasedsignificantly while the energy
consumption is increased slightly. The zinc
electrowinning time should be controlled slightly
belowtheaverageinductiontime.Insomecases,ifthe
nickel can not be removed to a satifactory level
economically, the current density can be adjusted to
maximizezincdepositmasses.

3 12
2 3
1

0.005

-1.1

Inthepresenceof0.4mg/LNi,withincreasingcurrent
density from 450 to 550 and 650 to 750 Am2, the
average induction time decreased from 49.3 to 44.62
and 44.41 to 40.3 hours, the zinc current efficiency
decreasedfrom93.74to93.56and93.34to92.93%,and
the energy consumption increased from 2.55 to 2.61
and2.62to2.71kwh/kgZn.Theaveragezincdeposit
mass prior to zinc redissolution at 550, 650 and 750
Am2were10.6,32.6and35.6%greaterthanthatat450
Am2,respectively.

Potential vs Ag/AgCl / V

0.015

-1.0

The induction time for zinc deposit redissolution

decreased with increasing nickel concentration.
However, the zinc current efficiency prior to
redissolutionwasnotaffectedinthepresenceofupto
0.4mg/Lnickel.

-0.9

-0.9

Conclusions

-0.8

-0.8

F
IG. 12. CATHODIC POLARIZATION CURVES ON THE ZINC
DEPOSITS IN THE ELECTROLYTE CONTAINING 0, 0.4 and 4.0
mg/LNi.

(a)

0.0
-0.7

1: 0 mg/L Ni
2: 0.4 mg/L Ni
3: 4.0 mg/L Ni

Potential vs Ag/AgCl / V

0.4

0.1

0.2
0.1

From the above discussion, the addition of 0 to 0.4

mg/L Ni had very little effect on the cathodic
polarizationbehaviour.

0.2

1
3 2

0.3

ACKNOWLEDGMENT

The authors would like to thank MagPower Systems

Inc. for permission to publish this work, and also
thankAngloAmericanfortheirsupport.

JournalofMetallurgicalEngineering(ME)Volume2Issue3,July2013www.mejournal.org

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