2084 D. A. Bertuol et al.

Daniel A. Bertuol1,3 Research Article

Franco D. R. Amado2
Hugo Veit3 Recovery of Nickel and Cobalt from Spent
Jane Z. Ferreira3
Andrea M. Bernardes3 NiMH Batteries by Electrowinning
1
Universidade Federal de Santa For nickel and cobalt recovery from spent NiMH batteries by electrowinning, the
Maria, Santa Maria, RS, Brazil. effect of different electrowinning parameters as boric acid concentration, tem-
2 perature, current density, and pH were studied using different synthetic solutions.
Universidade Estadual
de Santa Cruz, Ilhéus, BA, The optimized operational parameters were applied in an electrowinning test
Brazil. with a solution achieved by leaching the electrodes of NiMH batteries. The elec-
3 trowinning tests were performed galvanostatically in a two-compartment cell
Universidade Federal do Rio
separated by an anionic membrane. A platinum/iridium-coated titanium anode
Grande do Sul, Porto Alegre,
RS, Brazil.
and a stainless-steel cathode were used. A sodium sulfate solution served as ano-
lyte. The results demonstrate the technical viability of nickel and cobalt recovery.
The chemical composition of the obtained deposit presented high nickel and
cobalt concentrations.

Keywords: Cobalt recycling, Electrolysis, Electrowinning, Nickel recycling, NiMH batteries

Received: May 16, 2012; revised: July 01, 2012; accepted: August 07, 2012
DOI: 10.1002/ceat.201200283

1 Introduction on the NiCd batteries system, where the Cd electrode is substi-

The fast technological evolution of the electronic industry,
associated with the exacerbated consumption by a part of the
pupulation, is responsible for the major increase in electronic
scrap generation. Recently, an important step was made
regarding the environmental legislation in force in Brazil. In
August 2010, the National Politics of Solid Wastes was insti-
tuted. This regulation, in general terms, establishes the shared
responsibility among the government, industry, sellers, and
final consumers in the management and administration of sol-
id wastes. It institutes the reverse logistics that forces manufac-
turers, importers, distributors, and salespersons of special
wastes where electronics are included, to collect and give the
correct destination for wastes once the products are discarded
by consumers. Among the different types of technological
wastes, which year after year present an increase in their genera-
tion, are batteries since they are a part of portable equipment.
Spent batteries are considered hazardous waste in many
countries due to the potential environmental and human
health risks associated with their content of heavy metals [1].
Regarding NiMH batteries, they are considered environmen-
tally acceptable, since they do not contain highly toxic metals
in their composition [2]. The NiMH operation system is based
–
Correspondence: Prof. D. A. Bertuol (dbertuol@gmail.com), Universi-
dade Federal de Santa Maria, Departamento de Engenharia Química,
Centro de Tecnologia, Av. Roraima n° 1000, Cidade Universitária, Bairro
Camobi, Santa Maria, 97105-900, RS, Brazil.
tuted by the MH (metal hydride). Typical examples of MH
alloys are AB2, which is basically a TiNi2 alloy, and AB5, which
is essentially an LaNi5 alloy [3]. For economic reasons, La is
often replaced by a rare earth alloy [4].
Due to the great increase in spent NiMH battery generation,
the recycling of the metals content present in their composi-
tion should be studied, avoiding the disposal of tons of dan-
gerous waste [5]. The goal of waste minimization, combined
with the economic value of metals such as Ni and Co, requires
the development of efficient recycling processes. Therefore, the
recycling of this kind of waste, besides the benefit in environ-
mental terms, can also bring advantages in economic terms.
Here, Ni and Co from NiMH batteries were recovered by
the galvanostatic technique. The effect of pH, boric acid con-
centration, temperature, and current density in the Ni electro-
winning was investigated. The best operational parameters
evaluated for the Ni electrowinning were employed in the elec-
trowinning of solutions obtained from leaching NiMH batter-
ies. The results demonstrate the technical viability of recover-
ing Ni and Co through electrowinning.
2 Experimental
2.1 Preparation of the Real Solution
2.1.1 Leaching
Cylindrical accumulators type AB5, which weighed on average
18.5 g, where cut in half longitudinally. After removal of the

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external stainless-steel case and the perforated plate from the
negative electrodes plus the fabric separator, the positive and
negative electrodes were manually homogenized and leached
in a 2 M H2SO4 solution at 90 °C under agitation for 4 h [6]. A
1/20 solid/liquid ratio was used. After leaching, the insoluble
residue was filtrated and washed with water. The concentrations
of Ni, Co, Fe, Zn, and Mn in the leaching solutions were mea-
sured by atomic absorption spectroscopy (AAS). The rare earth
concentrations were determined by inductively coupled plasma
(ICP). Total concentrations of the chemical constituents of elec-
trodes were evaluated after their complete dissolution in aqua
regia. Leaching data were compared against this standard.
2.1.2 Precipitation Tests
Prior to electrowinning, the removal of different metals
through selective precipitation was carried out at varying pH
values. The resulting solution of the leaching stage presented a
pH around zero. After the pH increase up to 1.2 through the
addition of sodium hydroxide (5 M), the rare earths were
removed as sulfates. Then, the solution was filtered and the pH
was increased with addition of sodium hydroxide up to 6 and
kept under stirring for 18 h. More details are available in pre-
vious works [7, 8].
2.2 Electrowinning Tests
Aiming to define the ideal conditions for deposition, firstly the
tests were accomplished in a beaker using a Ni solution with a
concentration of 60 g L–1 and pH 4. This pH was selected ac-
cording to the literature [9, 10]. A two-compartment cell was
built to prevent the fast pH variation that was observed during
the tests accomplished in a beaker.
Fig. 1 presents the assembly scheme of a two-compartment
cell used in the different electrowinning tests. The anodic com-
Figure 1. Assembly scheme of the two-compartment cell used in the electrowinning
tests.
Chem. Eng. Technol. 2012, 35, No. 12, 2084–2092 © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Electrolysis 2085
partment consists of the modules 1 and 2 that are connected
for a seal ring, allowing the anolyte to freely circulate in both
modules. The same happens with the cathodic compartment
formed by modules 3 and 4. In this cell, the two compartments
were separated by an anionic membrane (PCacid 60/PCA Ion
Exchange Membranes GmbH) with the dimensions of 7.0 ×
9.0 cm. The membrane utilization leads to a current efficiency
increase by the separation of the cathodic and anodic reactions
[11] and prevents the fast pH variation.
In order to prove the efficiency of the PCAcid 60 membrane
in the pH control, tests were accomplished with a current den-
sity of 250 A m–2, at different temperatures and a pH of 4.0.
The solutions utilized were 60 g L–1 Ni with and without boric
acid addition. The boric acid concentration was 20 g L–1.
According to the literature, the boric acid, besides for acting as
a weak buffer, also improves the ductility and visual appear-
ance of the deposit [12].
The cathode consists of polished stainless steel with a
10-cm2 area and an anode of titanium coated by platinum/
iridium. The solutions were recirculated with the aid of centri-
fugal pumps; the flow was 2 L min–1 in both compartments. In
all tests, a Na2SO4 (1 M) solution was used in the anodic com-
partment. All tests took 2 h.
For the current efficiency determination, the cathode was
weighed before and after each experiment, and the mass differ-
ence represents the deposit mass. However, to ensure that this
mass difference exclusively regarded the deposit, the cathode
as well as the deposit were rinsed with acetone and then evapo-
rated using a jet of air to ensure that any solution drop was
stuck. The current efficiency was then determined by dividing
the theoretical current to produce the deposit by the real sup-
plied one.
The pH was maintained constant through the addition
of concentrated sodium hydroxide and sulfuric acid solu-
tions. The pH measurements as well as the addition of
sodium hydroxide and sulfuric acid were accomplished in
a beaker, where a pump directed the solution to the cell.
After circulation through the cell, the
solution came back to the beaker, where
it was pumped again to the cell in a
closed circuit.
Electrowinning Experiments Using Nickel
Sulfate Solutions
In this step, several parameters for Ni elec-
trowinning were studied in order to obtain
a cohesive deposit with high current effi-
ciency. The studied parameters were pH,
temperature, boric acid concentration, and
current density. The Ni2+ concentration
was 60 g L–1.
Electrowinning Experiments Using Ni, Co,
Mn, and Zn Sulfate Solutions
In order to evaluate the influence of the so-
lution composition in the electrowinning
of Ni and Co, different solutions were em-
ployed as presented in Tab. 1. The electro-
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2086 D. A. Bertuol et al.

Table 1. Composition of the solutions employed in the electro- impregnated [8, 13]. The nonleached material obtained after
winning tests. filtration consisted basically of this fine metallic screen.
Electrolytes Concentration [g L–1]
Ni Co Mn Zn 3.2 Precipitation of Rare Earths
Ni/Co 60 10 – –
Tab. 3 presents the recovery yield of rare earths and others
Ni/Co/Mn 60 10 3 – metals after precipitation at pH 1.2. It was determined by the
ratio of concentration in solution before and after precipita-
Ni/Co/Mn/Zn 60 10 3 2
tion and indicates that more than 98 wt % of rare earths are
Ni/Co/Zn 60 10 – 2 recovered. It also demonstrates that Fe followed by Zn are the
contaminants with a higher rate of precipitation.

winning parameters were: 50 °C, 30 g L–1 of boric acid, pH 4, Table 3. Yields obtained through precipitation at pH 1.2.
and 250 A m–2.
Element Recovery yield [%]
Electrowinning Experiment Using Real Solutions
Ce 98.57
The parameters used were those considered the optimum ones
for Ni electrowinning, i.e., 50 °C, 30 g L–1 of boric acid, and La 97.17
pH 4. Nd 97.83
Pr 99.00
3 Results and Discussion Ni 1.84
Co 3.33
3.1 Leaching
Zn 5.91
Tab. 2 summarizes the results obtained in the electrode leach- Fe 9.89
ing. The use of sulfuric acid led to a poor extraction of Fe.
Another important factor contributing to this low Fe concen- Mn 1.48
tration was that the external cases as well as the perforated
plates from the negative electrode were removed before leach-
ing. The metallic alloy that these parts are made of contains a
high Fe concentration. Previous results indicated that in real 3.3 Purification of Ni-Co Solution
situations the external cases as well as the perforated plate
could be removed by magnetic separation [8]. After recovery of the rare earths, a precipitation test at pH 6
was accomplished aiming at the removal of Fe, Zn, and Mn,
leaving Ni and Co in solution. The results indicated in Tab. 4
Table 2. Leaching yields obtained using a 2 M sulfuric acid solu- demonstrated that Fe could be completely removed. Concern-
tion, at 90 °C for 4 h.
ing Mn, only a poor removal efficiency around 2.3 % could be
Element [g L–1] Extraction [%] achieved. For complete Mn precipitation, a pH value of about
10 was required [14]. Zn could be removed by around 24.0 %.
Ce 3 83.33 The Ni precipitation usually starts around pH 6.5 but in this
La 2.1 84.00 case, probably due to a greater amount of Ni compared to
other metals, it was observed that already at pH 6 around
Nd 0.76 86.36
0.5 % Ni was coprecipitated. In relation of Co, around 2.2 %
Pr 0.63 79.75 was lost in the precipitation.
Ni 22.3 82.59
Co 2.4 92.31 Table 4. Precipitation yields obtained through precipitation at
pH 6.
Zn 0.76 95.72
Element Precipitation [%]
Fe 0.046 53.33
Ni 0.00
Mn 1.22 91.04
Co 2.23
Zn 24.01
For Ni, a higher dissolution was not achieved probably due
to the poor dissolution of Ni from the positive electrodes. The Fe 100.00
positive electrodes utilized in this work consist of a highly
Mn 2.31
porous metallic screen into which the Ni compounds are

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 Electrolysis 2087

3.4 Preliminary Electrowinning Tests 5

60°C
The first tests were performed in a beaker but,
due to the great pH variation during the ex- 4 50°C
periments, this one-compartment cell was dis- 40°C
carded. Seeking to obtain higher current effi- 3

pH
ciency and an easy way to control the pH, a 24°C
cell of two compartments was built. In this cell,
2 60°C Without
the compartments are divided by an anionic
membrane [15, 16]. Two anionic membranes Membrane
were tested, PCAcid 400 D and PCAcid 60. 1
The membrane PCAcid 400 D was quickly dis- 0 30 60 90 120
carded since Ni seemed to be passing by diffu- Time (min)
sion to the anodic compartment.
Fig. 2 demonstrates the pH variation of the Figure 3. Cathodic pH value variation as a function of the experimental time, for a
catholyte solution during the course of the ex- solution with 60 g L–1 of nickel and 20 g L–1 of boric acid with a current density of
250 A m–2.
periment. It can be observed that, except for
the curve relative to the temperature of 24 °C,
the pH tends to decline during the experiment. These results solution. It also presents the results obtained in a test accom-
possibly indicate that an increase in the solution temperature plished without the membrane, where, due to the absence of
causes an increase in the rate of the proton migration through the membrane, NaSO4 was not used. In the respective curve, at
the membrane, from the anodic to the cathodic compartment. 60 °C, it was observed that the pH falls in a rate much more
This happens because the small ionic diameter of the protons, accentuated than when the membrane is used. This effect con-
associated to the applied potential difference in the cell, possi- firms the membrane utilization efficiency in the pH control
bly turns the proton migration through the anionic mem- and, therefore, it also contributes to cost reduction, since it
brane. In the anionic compartment, a pH decrease from aver- reduces the amount of chemical reactants necessary for the pH
age values > 5 to average values < 3 was observed. This adjustment. In these tests, the solutions of both compartments
possibly occurs due to the oxygen evolution on the anode and were also changed after each test. Obviously, boric acid addi-
in this way the resulting H+ ions of this reaction tend to tion brought improvements regarding the pH variation for the
migrate through the membrane in the cathode direction. results obtained at 24 °C acting as a buffer. Concerning the
Thus, the pH increase for the test accomplished at 24 °C higher temperatures, no change could be observed in the pH
could be explained as a function of the reduction rate of H+ variation when boric acid was added.
ions present in the solution due to the evolution of H2(g) in
the cathode, since at lower temperatures the rate of the proton
migration through the membrane from anolyte to catholyte is 3.5 Determination of the Ideal Conditions
reduced. However, for the higher temperatures, the H+ migra- for Ni Electrowinning
tion was significantly increased, compensating for the effect of
the pH increase due to hydrogen evolution, making the pH 3.5.1 Current Efficiency as a Function of Temperature
value decrease during the course of the tests. The solutions of
both compartments were substituted after each test. Fig. 4 presents the current efficiencies achieved in the experi-
Fig. 3 illustrates the variation of the pH values during the ments with different temperatures. Except for the deposit
electrowinning tests when 20 g L–1 of boric acid is added to the obtained at 21 °C without boric acid addition and without pH
control (the initial pH value was 4),
all others presented current effi-
7
ciencies > 95 % reaching 99.8 % for
the deposit obtained at 61 °C
6 (without pH control and without
60°C boric acid addition). However, the
50°C quality of the deposits attained
pH

5
40°C with boric acid addition is quite
24°C superior to the others. When the
4 pH was maintained constant at 4,
neither an improvement in the cur-
3
rent efficiency nor in the quality of
0 30 60 90 120 the deposit were observed.
The deposits obtained without
Time (min)
boric acid addition presented low
Figure 2. Cathodic pH value variation as a function of the experimental time, for a solution with or no ductility. A temperature de-
60 g L–1 of nickel without addition of boric acid and a current density of 250 A m–2. crease also contributes to the re-

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 2088 D. A. Bertuol et al.

Current efficiency (%) 100

95 Without pH control
and Boric Acid

Without pH control,
90
Boric Acid 20 g/L

pH 4.0, Boric Acid 20

85 g/L

Figure 4. Current efficiency ob-

80 tained for Ni deposition as func-
0 10 20 30 40 50 60 70 tion of the temperature, using
different solutions and a current
Temperature (°C) density of 250 A m–2.

duction on the deposits’ cohesion; the lower the temperature
the worse was the deposit quality. At 21 °C the deposit was re-
duced to powder. A temperature increase, besides resulting in
an increment of the current efficiency, also improved the qual-
ity of the formed deposit [12]. However, even the ones ob-
tained at 61 °C did not present good ductility and also
exhibited a lot of perforations, probably due to the hydrogen
evolution associated to an inefficient stirring. Small gas bub-
bles formed due to the hydrogen reduction on the cathode
stuck on the deposit surface [17] and stayed on the surface
during the test, resulting in surface perforation.
All results obtained with boric acid addition indicated a
great quality improvement and an enhancement in ductility.
Even for 20 °C, the deposit obtained with the boric acid addi-
tion consists of several overlapping layers while the one
attained without boric acid consisted basically of a powder.
Another advantage regarding boric acid utilization was the fact
that the resulting deposits are easily removed from the cath-
ode.
The obtaining of high-quality deposits using nickel sulfate
electrolytes poses some difficulties, as there is a competition
with the reaction of hydrogen reduction, which causes a
decrease in the current efficiency. Another fact to be consid-
ered, together with the current efficiency, is the simultaneous
pH increase close to the cathode due to the reduction of the
ion hydrogen concentration. A high pH value on the cathode
surface will result in nickel hydroxide precipitation [18]. The
presence of this pH gradient can result in the degradation of
the deposit appearance as well as in the reduction of ductility
[12].
The best deposits with high current efficiency of > 99 % and
good ductility were the ones obtained at 50 °C. This current
efficiency value is higher than the average values found in the
literature when typical Ni electroplating systems (systems
without solution separation by the membrane and using an Ni
anode) are applied. In these systems, the efficiency is around
96 % [17]. Thus, the temperature of 50 °C was selected for the
tests performed for the definition of other parameters like pH,
boric acid concentration, and current density for Ni deposi-
tion.
3.5.2 Current Efficiency as a Function of pH
Fig. 5 demonstrates the current efficiency variation as a func-
tion of pH under a constant temperature of 50 °C and a cur-
rent density of 250 A m–2. The efficiency increases with the
increase of the pH up to 4, where the maximum efficiency is
reached, and above this pH value the current efficiency de-
creases again.

100
Current efficiency (%)

95

90

85

Figure 5. Current efficiency in

80 the Ni deposition as a function
2 3 4 5 6 of pH for tests done at 50 °C,
250 A m–2, in solutions contain-
pH ing 20 g L–1 of boric acid.

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 Electrolysis 2089

Regarding the deposits’ quality, the deposit obtained at pH 6
presented the worst properties, since it is constituted from very
brittle overlapping sheets. The one obtained at pH 2 was stuck
on the cathode and in this way it was not possible to remove
it. The deposit obtained in pH 4, besides for maximal current
efficiency, exhibited also the best physical properties as high
ductility. This fact makes pH 4 the ideal selection for electro-
winning. This result corroborates the pH value found in the
literature regarding Ni deposition [9, 19]
3.5.3 Current Efficiency as a Function of Acid Boric
Concentration
Fig. 6 presents the results obtained for the current efficiency
as a function of boric acid concentration. The current efficien-
cy stays practically constant for all the boric acid concentra-
tions tested. However, the one obtained with 30 g L–1 exhibits a
value a little higher than the others. This concentration is in
agreement with the concentration range suggested in the lit-
erature for the production of Ni deposits, when sulfamate or
Ni watts baths are used. For both baths, the suggested concen-
tration is among 30–45 g L–1 [17]. Regarding the deposits’
quality, those obtained with 20, 30, and 40 g L–1 presented very
close morphology and ductility while those achieved using 5
and 10 g L–1 were very fragile.

Boric acid is an important component of a typical Ni electro-
plating bath [17]. It is cheap and nonvolatile and brings no
additional problems for effluent regulation [18]. Another
important fact is that boric acid prevents the formation of
nickel hydroxide due to the pH increase close to the cathode.
Among the possible mechanisms related to the boric acid effect
is that it acts as a buffer. It has been confirmed that the cath-
ode surface pH is lower in its presence. Another possible
mechanism is that boric acid forms a weak nickel borate com-
plex, Ni(H2BO3)2, which acts as a homogeneous catalyst to re-
duce the overpotential for the Ni deposition [12].
3.5.4 Current Efficiency as a Function of Current Density
In this stage, the deposits were obtained using different current
densities with the objective of verifying the influence of current
density on the current efficiency as well as on the coating me-
chanical properties. Fig. 7 indicates that the current efficiency
stays almost stable when the current density is varied, however,
the highest value was achieved with a current density of
250 A m–2. This value was also used in different works where
Ni is recovered from Li-ion batteries [19] as well as in the Co-
and Ni-Co alloys plating [20].

100

99,8
Current Efficiency (%)

99,6

99,4

99,2

99 Figure 6. Current efficiency as a

0 5 10 15 20 25 30 35 40 45 function of acid boric concen-
tration for tests done at 50 °C,
Boric acid [g/L] pH 4, and 250 A m–2.

100
Current efficiency (%)

99

98

97

96

Figure 7. Current efficiency as a

95
100 150 200 250 300 350 400
function of current density for a
solution with 30 g L–1 of boric
Current density (A/m²) acid at pH 4 and 50 °C.

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2090
Fig. 8 presents the values regarding the specific energy con-
sumption for the Ni deposits. Despite the current, the efficiency
stayed almost constant (Fig. 7) and the specific energy consump-
tion increased with the increase of the current density, since the
applied cell voltage also increased with the increment in cur-
rent density. All of the deposits presented excellent ductility.
In order to investigate the morphology of the deposit ob-
tained with 250 A m–2, micrographics were generated using a
scanning electronic microscope (SEM). It can be observed in
Fig. 9 that a homogeneous and compact deposit formed by
spherical particles.
3.5.5 Electrowinning Experiments Using Ni, Co, Mn, and Zn
Sulfate Solutions
Tab. 4 lists the current efficiency results obtained in different
tests done to verify the effect of solution compositions in the
recovery of Ni and Co by electrowinning. Initially, an Ni/Co
solution was tested and a deposit of good quality was obtained,
then a Ni/Co/Mn solution was examined, resulting also in a
good-quality deposit. The current efficiency remains unsteady
for both deposits as indicated in Tab. 5.
Once again, a new electrolyte was added to the solution (Ni/
Co/Mn/Zn). The obtained deposit was in a form of a powder,
turning impossible to calculate the current efficiency since part
of the deposit loosened from the cathode. In order to verify if
Zn was responsible for the deposit degradation, a new solution
was prepared containing Ni/Co/Zn and again the deposit was
in a form a powder indicating that Zn was the reason for the
degradation of the deposit.
3.6 Electrowinning Test with a Real Purified Solution
After finishing the tests with synthetic solutions, which aimed
at the determination of ideal electrowinning conditions
(250 A m–2, 50 °C, 30 g L–1 of acid boric, pH 4), new tests were
performed using a solution obtained through the batteries’
leaching with sulfuric acid, after steps of precipitation for Fe
and removal of rare earth metals.
The obtained deposit did not exhibit a good quality, and a
great part of it loosened from the cathode, therefore, it was not
3,5
Specific energy consumption
3
2,5
(kWh/kg)
2 process was possibly not effective in pro-
1,5
1 perhaps related to the tape used to fix
0,5
0 trations of the nonmetals are rejected,
100 150 200 250 300
Current density (A/m²)
Figure 8. Specific energy consumption as a function of the current density for Ni deposits.
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D. A. Bertuol et al.
Figure 9. Micrographs of the Ni deposit, obtained with 250 A m–2,
50 °C, 30 g L–1 of boric acid, and pH 4.
Table 5. Current efficiency obtained using different solution com-
positions.
Electrolytes Current efficiency
Ni-Co 99.20
Ni-Co-Mn 99.28
Ni-Co-Mn-Zn n. d.
Ni-Co-Zn n. d.
n. d. = not determined
possible to calculate the current efficiency. Tab. 6 presents the
deposit chemical composition obtained by atomic absorption
spectroscopy (AAS); it can be observed that the deposit com-
position is largely formed by Ni and Co (91.92 wt %). How-
ever, the presence of Fe is still detected, despite the purification
stage previously accomplished. This fact is possibly associated
with contaminations in the cell or in the pumps. As expected,
Zn was deposited and possibly the deposit’s bad quality was
caused by its presence. The presence of Mn was also detected.
In order to confirm if the deposit was formed only by the
metals listed in Tab. 6, an analysis by microprobe (EDX), pre-
sented in Fig. 10, was performed. The results are summarized
in Tab. 7 and demonstrate that no other metal was detected,
however, they indicate the presence of other elements such as
oxygen, sulfur, and carbon.
The presence of oxygen and sulfur are
probably associated with the contamina-
tion by the mother solution. Despite the
deposit, as presented in Fig. 9, is rinsed
and dried before the analysis, the cleaning
moting the total removal of the solution
contaminants. The presence of carbon is
the sample on the support for analysis
accomplishment. When the concen-
350 400 the Ni plus Co concentration reached
84.18 wt %. However, the result obtained
by atomic absorption (91.92 wt %) is
more reliable.
Chem. Eng. Technol. 2012, 35, No. 12, 2084–2092
 Electrolysis 2091

Table 6. Chemical composition of the deposit obtained in the observed that the obtained product is also in the form of a
electrowinning of the solution purified at pH 6, determined by powder that should be subjected to a subsequent treatment
AAS. stage [21]. The powder that formed on the cathode could be
easily separated by filtration and directed to a pyrometallurgi-
Element [wt %]
cal process to produce a Ni-Co alloy. As almost 6 wt % of the
Fe 0.8 deposit is composed of Zn, when the powder is molten Zn, it
can be easily recovered by vaporization and thus, the composi-
Ni 73.92
tion of the ingot obtained will be close to 100 wt % of Ni and
Zn 5.68 Co.
Co 18.00
Mn 1.6 4 Conclusions
Table 7. Chemical composition from the deposit obtained in The obtained results demonstrate the usefulness of a two-com-
electrowinning using the solution purified at pH 6, determined partment cell separated by an anionic membrane regarding
by EDX. current efficiency improvement. The application of the mem-
brane reduces the pH variation, diminishes the hydrogen evo-
Element [wt %]
lution, and in this way increases the current efficiency. Another
C 3.63 important factor is the decrease of pH fluctuation, thus contri-
O 14.36
buting to the reduction of reagent consumption that should be
added to the bath to maintain the pH steady.
S 1.52 The results also indicate that boric acid addition improves
Mn 1.15 in a substantial way the deposits’ cohesion as well as the flex-
ibility. The optimum conditions in terms of best current effi-
Fe 3.04 ciency and deposit cohesion for Ni deposition were: 30 g L–1 of
Co 13.63 boric acid, 50 °C, 250 A m–2, and pH 4.
After several tests with synthetic solutions, electrowinning
Ni 53.9
was accomplished using a purified solution obtained after the
Zn 8.77 leaching of NiMH batteries. The best parameters for deposi-
tion were defined in the Ni electrowinning. However, as the
purification stage was not effective in in the removal of con-
Despite the fact that the deposit did not present a good taminants, especially of Zn, the obtained deposit was of low
quality, the main objective of recovering Ni and Co was quality; it constituted basically of a powder. The main objec-
reached. When the obtained results are compared to those tive of this work, Ni and Co recovery, was successfully reached,
found in the literature for the processes of Ni production, as since the deposit chemical composition presents a rather high
the ones that use carbonyl or hydrogen reduction, it is concentration of Ni and Co, i.e., 91.92 wt %.

a) b)

Figure 10. a) EDX spectrum of the deposit obtained from the real solution purified at pH 6. b) Micrograph of the deposit obtained from
the real solution purified at pH 6.

Chem. Eng. Technol. 2012, 35, No. 12, 2084–2092 © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
2092
Acknowledgment
The authors would like to thank CAPES, CNPq, and
FAPERGS, Brazil for their financial support.
The authors have declared no conflict of interest.
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