Hydrometallurgy 157 (2015) 6071

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Production of electrolytic zinc powder from zinc anode casing of spent

dry cell batteries
Ashour Owais a,, Mohamed Abdel Hady Gepreel b, Essam Ahmed a
a
b

Department of Metallurgical and Materials Engineering, Faculty of Petroleum and Mining Engineering, Suez University, 43721 Suez, Egypt
Department of Materials Science and Engineering, EgyptJapan University of Science and Technology (EJUST), 21934 Alexandria, Egypt

a r t i c l e

i n f o

Article history:
Received 11 April 2015
Received in revised form 21 July 2015
Accepted 22 July 2015
Available online 30 July 2015
Keywords:
Zinccarbon batteries
Zinc anode casing
Packed bed electrolysis
Electrolytic zinc powder

a b s t r a c t
This paper aims to study experimentally the packed bed electrolysis of anode particles obtained from zinc casing
of spent secondary batteries, by which electrolytic zinc powder can be produced. Zinc casings of the exhausted
zinccarbon type dry cell batteries were separated from both the internal carbon rods and MnO2 paste materials
and from the external covers then fed into cuboids anode basket made from graphite or titanium. Two stainless
steel permanent cathode sheets together with the anode basket were immersed in a basic solution containing
230 g/L NaOH. Electrolytic zinc powders in the form of nanorods, dendritic and/or a dispersed shape with a purity
of about 99.8% Zn and with an apparent density of 1203.1 to 2085.2 kg/m3 were obtained. The results indicated
that, the graphite basket is better than the titanium one for all studied parameters except for the specic energy
demand factor. The deposited zinc powders are contaminated with about 0.0053% Ti when using titanium basket.
The process was enhanced with increasing current density, electrolyte temperature, electrolyte stirring rate, and
the use of an old electrolyte. The electrolysis process was carried out with cathodic current efciency up to
94.85%, anodic current efciency up to 98.97% and specic energy demand in the range between 0.808 and
2.518 kWh/kg Zn with powder productivity up to 1.150 g/A.h.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Zinccarbon type dry cell batteries are the oldest and most used type
batteries in the world (Khan and Kurny, 2011). In these batteries, anode material is zinc and the cathode is a mixture of manganese dioxide and carbon
(Fig. 1) (Shin et al., 2009). A very large quantity of these batteries is used in
our daily life, but their lives are limited. They are non-rechargeable (primary
cells) which means once discharged, they become useless and are discarded
(Belardi et al., 2011; Rayovac Corp, 2014). The landlling disposal of the
spent batteries, along with other municipal waste, causes not only environmental hazards but also leads to the loss of these valuable metallic elements
and materials (Belardi et al., 2014; Li and Xi, 2005).
Spent zinccarbon type batteries are considered very useful secondary resources of zinc recovery as zinc constitutes almost 22% of the total
weight of these type batteries. However, the zinc anode alone constitutes the maximum portion of zinc in these batteries (Gallegos et al.,
2013; Ma et al., 2014; Nan et al., 2006).
The recovery of zinc from the spent dry cell batteries has been investigated by both pyrometallurgical (Salgado et al., 2003; Xiao et al., 2009)
and hydrometallurgical (Belardi et al., 2011; Buzatu et al., 2013, 2014;
Rcz and Ilea, 2013) processing. A thorough comparison between the
two methodologies is reported in previous works (Espinosa et al., 2004;
Corresponding author.
E-mail address: ashour.owais@suezuniv.edu.eg (A. Owais).

http://dx.doi.org/10.1016/j.hydromet.2015.07.014
0304-386X/ 2015 Elsevier B.V. All rights reserved.

Sayilgan et al., 2009). Baba et al. (2009) proposed a combined pyro- and
hydro-metallurgical process. However, using the pyrometallurgical processing or the use of critical treatment conditions for Zn recovery has
bad effects on the environment by means of emissions, secondary waste
streams and hazardous work environments. Therefore, the development
of intensied hydrometallurgical, zero-waste (Toro et al., 2006) treatment
routes is highly recommended. The hydrometallurgical process generally
includes; dissolving the zinc anode in sulfuric or hydrochloric acid
media, sometimes with prior water washing treatment and recovering
the zinc from solution by electrowinning technique (Sayilgan et al., 2009).
Another efcient method to recover metal powders from spent raw
materials without application of both leaching and electrowinning techniques is the packed bed electrolysis process (Owais, 2012, 2015; Owais
and Friedrich, 2003; Owais and Gepreel, 2013). By applying this method,
high-quality electrolytic metal powders can be produced through the direct electrolytic rening of exhausted materials. This technique combines
the leaching step and the metal recovery by electrowinning in one process. This process depends on utilizing anode particles which are put in
a basket made from titanium to collect the particles and to conduct the
electricity to them. One of the main advantages of this technique is the
continuous feeding of the anode particles into the basket, also there is
no need for adding an external source of metal ions to the electrolytic
cell as usually done in the case of electrowinning technique.
The current efciency of an electrolytic process can be expressed as
the ratio of the amount of material actually deposited on the electrode

A. Owais et al. / Hydrometallurgy 157 (2015) 6071

61

Fig. 1. Schematic diagram of a typical zinccarbon battery cross section (Shin et al., 2009).

to that which should have deposited on the basis of Faraday's law, by

the passage of the same charge, assuming that no side reactions take
place at the electrode. In general, the current efciency depends on
many factors such as the current density, the presence of additives
and/or impurities in the electrolyte, the composition and the properties
of the electrolyte, the electrolysis temperature, and the nature of the
electrodes and of the electrodeposit. The current efciency also depends
on the presence of additives and/or of impurities which may co-deposit
or may inuence the electrochemical reaction or may affect the overvoltages of the desirable and the undesirable reactions (Gupta, 2003).
The produced zinc powder can be employed in both chemical industries such as preparation of benzidine, hydrosulphite and rongalite, and
also in metallurgical industries such as production of precious metals
e.g., gold and silver by application of cementation process, in addition
to purifying zinc electrolytic baths. Moreover, it can be used for the production of amalgam alloy which is used in dental llings. It can be used
in different applications in electronic industries as well. Zinc powder can
be also used as paint for a heavy-duty coating for large-scale structures
such as offshore oil rigs, sea containers and other marine equipment and
bridges. Besides, it is used in alkaline batteries, rocket fuel and cosmetics
(Shari et al., 2009).
The main aim of this research work is to study, experimentally, the effect of different parameters on the packed bed electrolysis of the zinc
anode casing of the spent dry cell secondary batteries to produce electrolytic zinc powders (see owchart in Fig. 2). The studied parameters are
electrolyte temperature, electrolyte stirring rate, current density, the material of anode basket (graphite or titanium), and the state of the electrolyte (new or old). To accomplish this target, the zinc anode casing of the
spent batteries was separated from both internal cathode materials (carbon and MnO2) and from the external plastic covers. Zinc casing sheets
were placed in an anode basket, which acts as the carrier and the current
feeder to the anode particles in the employed electrolytic cell. Two stainless steel sheets used as starting cathodes together with anode basket
were put in an electrolytic cell containing 230 g/L NaOH as a basic electrolytic solution. The used materials and the produced powders were characterized using XRD, XRF, and SEM analyzers.

Fig. 2. Flowchart of production of electrolytic zinc powder from spent secondary batteries.

was separated from the internal paste material in the battery, cut to
smaller sizes by shredder and washed with distilled water. Zinc sheets
in the size range of 2030 mm length, 1020 mm width and 1 mm

2. Experimental details
2.1. Materials
Spent zinc batteries were broken and separated from the external
papers and non-zinc metal protecting covers. Zinc anode casing sheet

Fig. 3. Casing of secondary batteries as zinc anode sheets.

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A. Owais et al. / Hydrometallurgy 157 (2015) 6071

Table 1
XRF analysis of zinc anode casing.
Components

Zn

Pb

Cd

Fe

Cu

Sn

Hg

Ni

Tc

Wt.%

99.000

0.7960

0.0597

0.0274

0.0166

0.0111

0.0198

0.0119

0.0170

Fig. 4. XRD analysis of zinc casing anode sheets.

thickness (Fig. 3) were put in an anode basket made from graphite or titanium and employed as the anode in the electrolytic cell. The different
components contained in the casing sheets before the experiments
were examined by X-ray uorescence (XRF) (Rigaku XRF-NEXCG,
Japan) and illustrated in Table 1. The phases which exist in these zinc
sheets were examined by X-ray diffractometer (XRD-6100, Shimadzu,
Japan) and are presented in Fig. 4. A sodium hydroxide salt was dissolved in a distilled water to give 230 g/L and used as an electrolyte in
the electrolytic cell (Calusaru, 1979).

The electrodeposited powders were extensively washed in distilled

water, dried in a vacuum drying oven (JSR, JSVO-30T, Korea) in an
argon gas as inert atmosphere to avoid the oxidation of the produced
powder, then weighed, and nally characterized using XRF, XRD, scanning electron microscopy (SEM) (JEOL JSM-6360LA, Japan) and particle
size analyzer (Malvern mastersizer 2000, UK) equipped with Hydro
2000SM unit.

2.2. Experimental apparatus and procedure

The sketch of the bench scale experimental setup used for the electrolysis experiments is shown in Fig. 5, while the actual view of the different applied devices is illustrated in Fig. 6-a. Zinc anode sheets were
put in a graphite or a titanium basket, which has the dimension of
100 mm width, 100 mm active height, and 50 or 30 mm thickness respectively with 5 mm net openings average size (Fig. 6-b and -c). Two
stainless steel sheets with the dimensions of 100 mm width, 100 mm
active height and 3 mm thickness were used as permanent cathodes.
Both anode baskets lled with zinc sheets and stainless steel cathode
sheets were inserted in a 5 L beaker glass, which was lled with the previously prepared NaOH basic electrolyte. The alkaline electrolytes are
more appropriate than acidic electrolytes. The energy consumption of
an acid process is about 35% of the cost of zinc powder production
(Habashi, 1991; Shari et al., 2009), whereas the alkaline process consumes less energy due to the lower overpotential. Alkaline processes
are also friendlier to the environment because they avoid the problem
of iron dissolution and removal as jarosite in the acid processes (Lee
and Piron, 1997). The electrodes were suspended in the cell with an
anode/cathode separating distance of 25 mm. A hot plate with magnetic
stirrer (KRH basic IKA LABORTECHNIK, Germany) was used for
heating up and stirring the electrolyte. The direct current was supplied
to the electrodes by a power supply (GW Instek, DC Power supply
sps-1820, Taiwan). The output cell voltage was directly recorded to
the computer using digital multimeter VA18B with PC-Link computer
software.

Fig. 5. Sketch of bench scale experimental setup. 1 Hot plate with magnetic stirrer, 2
rotating sh, 3 stainless steel sheet 1 (), 4 anode basket lled with zinc casing (+),
5 stand & cell cover, 6 thermometer, and 7 stainless steel sheet 2 ().

A. Owais et al. / Hydrometallurgy 157 (2015) 6071

63

Fig. 6. Views of the used electrolytic cell (a), the Ti anode basket lled with zinc sheets (b) and the graphite anode basket (c). 1 Hot plate with magnetic stirrer, 2 a 5 L backer glass lled
with 3 L electrolyte, 3 Ti anode basket, 4 digital multimeter connected to laptop, 5 two stainless steel cathode sheets, and 6 DC supplier.

From the results shown in Figs. 7 and 8, it is obvious that the increase
of electrolyte temperature from 30 to 50 C has a positive effect on all
parameters of the electrolysis process. Both the anodic and cathodic current efciencies and powder productivity were increased from 88.88%
to 95.80% and from 78.21% to 89.98% and from 0.948 to 1.091 g/Ah respectively, while the specic energy demand was decreased from 2.52
to 2.10 kWh/kg Zn. This can be due to the increase of dissolution rate
of zinc anode particles (Ren et al., 2010) which cause a good feeding
of the zinc ions to the electrolyte bulk solution (Zn Zn2 + + 2e)

and also due to the increase of the diffusion rate of zinc ions in the electrolyte bath, where the viscosity of the electrolyte is decreased with increasing the electrolyte temperature (Owais, 2009; Sadiku-Agboola
et al., 2011). This is beside the enhancement of the reduction reaction rate of zinc ions at the cathode surface to produce zinc metal
(Zn2 + + 2e Zn). Moreover, increasing the temperature has a
good effect on the electrolyte conductivity which decreases the
cell voltage and consequently decreases the specic energy demand.
This helps the electrolysis process to be more effective from the cost
point of view as well.
SEM micrographs of the electrodeposited zinc powder are illustrated
in Fig. 9 and indicated that the deposited powders are in a dispersive
shape while the ner particle size was obtained with powders which
electrodeposited at 30 C as shown in Fig. 10. A low temperature is anticipated to promote grain renement. A decrease in the temperature is
expected to result in a higher overpotential, which should increase the
nucleation rate (Youcai et al., 2013).
The apparent density of the deposited powders was increased with
increasing the temperature of the electrolyte as shown in Fig. 11. The
apparent density is a function of particle shape, particle size distribution, particle arrangement and the degree of particles porosity (Angelo
and Subramanian, 2008). The apparent density decreases with decreasing particle size and with increasing surface roughness. An increase in
the irregularity and porous texture of the powder grain decreases the
apparent density.

Fig. 7. Cell voltage against duration of the electrolysis of zinc anode casing of spent zinc
carbon type batteries in a graphite basket at different electrolyte temperatures, (1000 A/
m2, 250 rpm).

Fig. 8. Effect of electrolyte temperature on different electrolysis parameters.

3. Results and discussion

Different factors were extensively studied to show their effect on the
electrolysis of zinc anode casing of spent secondary batteries to obtain
electrolytic zinc powder using a basic electrolyte solution containing
230 g/L NaOH. The main factors studied are electrolyte temperature
(3050 C), electrolyte stirring rate (250350 rpm), current density
(5001000 A/m2), the material of the anode basket (graphite or titanium), and the state of the electrolyte (old or new). Fresh (new) electrolyte solutions were used in all experiments (Sections 3.13.4) while old
and fresh (new) solutions were used when the state of the electrolyte
(old or fresh) was investigated (Section 3.5).

3.1. Effect of electrolyte temperature

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A. Owais et al. / Hydrometallurgy 157 (2015) 6071

Fig. 9. SEM micrographs of the deposited zinc powders from electrolysis of zinc anode casing of secondary batteries at 1000 A/m2 and 250 rpm (magnication 200), (a) 30 C, (b) 40 C,
and (c) 50 C.

3.2. Effect of electrolyte stirring rate

As shown in Figs. 12 and 13, it is cleared that the increase of electrolyte stirring rate has a good effect on both anodic and cathodic current
efciencies, and also powder productivity when the stirring rate is increased from 250 to 300 rpm; while a further increase of the rate from
300 to 350 rpm has a bad effect on all parameters instead of anodic current efciency. The former case can be due to the increase of both dissolution rate of zinc anode particles and diffusion rate of zinc ions from the
anode surface to the cathode area; which consequently increase the
amount of the electrodeposited zinc metal. The latter case can be attributed to some zinc particles washed away from the stainless steel
cathodes because of turbulent ow in the bath (Bansal et al., 2011;
Ghorbani et al., 2001). So the moderate stirring rate of 300 rpm is the
best rate which can be used effectively. On the other side, the increasing
of electrolyte stirring rate causes a decrease in the specic energy demand from 2.105 to 1.638 kWh/kg. This can be due to the decrease in
the average cell voltage from 2.333 V to 1.60 V which resulted from
the decrease of the electrical resistance of the electrolyte with increasing the electrolyte stirring rate.
As shown from SEM micrographs in Fig. 14, the shape and size of the
deposited powders were strongly affected by the electrolyte stirring.
Nanorods from zinc powders appeared when high stirring rate of
350 rpm was applied (Fig. 14-d). The size of the deposited powders is
signicantly inuenced by stirring rate as shown in Fig. 15. The use of
bath stirring (300 rpm) is intended to improve the mass transport in
the electrolyte and therefore enhance the rate of deposition and nucleation results in ne particles. However, further increase of the stirring
rate (350 rpm) led to a reduction of the cathodic current efciency.
Since the main reactions at the cathode during electrodeposition is a
competition between zinc reduction and hydrogen evolution, as the
limiting current density is approached during zinc deposition, the zinc
ion concentration near the cathode is quickly depleted and the cathode

Fig. 10. Effect of electrolyte temperature on particle size distribution of the electrodeposited
zinc powder in a graphite basket.

reaction shifts from zinc deposition to hydrogen evolution (Rajkumar

and Alagar, 2014; Tuaweri et al., 2013). An improvement in cathode current efciency with stirring (at 300 rpm) helps to prevent the adsorption of evolved hydrogen, which regularly sits on the surface of the
cathode The deposition of a mixture of zinc and zinc hydroxide or zinc
oxide results in a pH increase in the vicinity of the cathode and also
the stirring could depolarize the hydrogen evolution reaction and possibly reduce the nucleation rate of zinc on the surface of the cathode. This
means, stirring rate may have been inauspicious to the zinc nucleation
process conditions. The highest apparent density was obtained at
300 rpm as shown in Fig. 16.

Fig. 11. Effect of electrolyte temperature on the apparent density of the electrodeposited
zinc powder in a graphite basket.

Fig. 12. Cell voltage against duration of the electrolysis of zinc anode casing of spent
zinc carbon type batteries in a graphite basket at different electrolyte stirring rates,
(1000 A/m2, 50 C).

A. Owais et al. / Hydrometallurgy 157 (2015) 6071

65

Fig. 13. Effect of electrolyte stirring rate on different electrolysis parameters.

Fig. 14. SEM micrographs of the deposited zinc powders from electrolysis of zinc anode casing of secondary batteries at 1000 A/m2 and 50 C, (a) 250 rpm, (b) 300 rpm, (c) 350 rpm at
magnication 200, and (d) 350 rpm at magnication 15000.

Fig. 15. Effect of electrolyte stirring rate on particle size distribution of the electrodeposited zinc powder in a graphite basket.

Fig. 16. Effect of electrolyte stirring rate on the apparent density of the electrodeposited
zinc powder in a graphite basket.

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A. Owais et al. / Hydrometallurgy 157 (2015) 6071

Fig. 20. Effect of current density on particle size distribution of the electrodeposited zinc
powder in a graphite basket: a) 500, b) 750 and c) 1000 A/m2.
Fig. 17. Cell voltage against duration of the electrolysis of zinc anode casing of spent zinc
carbon type batteries in a graphite basket at different current densities, (300 rpm, 50 C).

3.3. Effect of current density

A sharp difference was observed between the cell voltages of the different experiments carried out at different current densities (Fig. 17).
The lowest current density at 500 A/m2 showed a lower cell voltage
(0.710 V) while that at 1000 A/m2 showed a higher value of 1.990 V.

This can be interpreted from Ohm's law (V = I R), where a direct proportional effect between voltage (V) & current (I) is taken place. From
Fig. 18, it is cleared that, the increase of current density from 500 to
1000 A/m2 has a positive effect on cathodic current efciency (increased
from 74.23% to 94.85%), anodic current efciency (increased from 78.35%
to 96.91%) and powder productivity (increased from 0.900 g/Ah to
1.150 g/Ah). These results are in agreement with those of Chaim
et al. (1994), Shari et al. (2009) and Diggle et al. (1973). This can

Fig. 18. Effect of current density on different electrolysis parameters.

Fig. 19. SEM micrographs of the deposited zinc powders from electrolysis of zinc anode casing of secondary batteries at 300 rpm and 50 C (magnication 200), (a) 500 A/m2, (b) 750 A/m2,
and (c) 1000 A/m2.

A. Owais et al. / Hydrometallurgy 157 (2015) 6071

Fig. 21. Effect of current density on the apparent density of the electrodeposited zinc
powder in a graphite basket.

67

like Cu which passivated strongly when a higher current density is

applied.
The effect of increasing current density on the specic energy required for the electrolysis process showed that the highest value is
1.771 g/Ah when the highest current density at 1000 A/m2 is applied.
This can be attributed to the increase of cell voltage at higher current
density and consequently the increase of the calculated energy demand.
From the previous obtained results, it is concluded that the application
of higher current densities is favorable and higher values more than
1000 A/m2 must be studied extensively to obtain the best current
density which give the best results of the process parameters.
SEM micrographs of the electrodeposited powders (Fig. 19) indicated that, zinc powders with dispersed shape were obtained at low and
high values of current density while at a moderate value (750 A/m2),
a dendritic shape was formed. Particle size distribution analysis was
performed to gain further knowledge of the dependence of ultrane
powder electrowinning on current density. The particle size distribution
depending on the current density was shown in Fig. 20. The deposit
powder obtained during zinc electrowinning in NaOH solution decreases considerably the real current density as a consequence of the
large increase in surface area. As a result, the cathodic overpotential is
also decreased (St-Pierre and Piron 1990). In other words, the number
of smaller particles present in the mixture increased with increasing
current density. This observation may be explained by the easy formation of stable nuclei due to a large number of ions discharged in the
cathode. The hydrogen evolution overpotential on the cathode also is
high when the current density is high, favoring the discharge of the
zinc ions (Guillaume et al., 2007; Hewaidy et al., 1979; Youcai et al.,
2013). The apparent density of the deposited powders was increased
gradually with increasing current density as shown in Fig. 21.
3.4. Effect of the material of anode basket

Fig. 22. Cell voltage against duration of the electrolysis of zinc anode casing of spent zinc
carbon type batteries in different anode basket materials, (1000 A/m2, 300 rpm, 50 C).

be attributed to the increase of the deposition rate of zinc powder on

the cathode surface when the current density is higher, and no fear
from the passivation of zinc anode particles at the higher current
densities as happened in electrolysis of the other nonferrous metals,

As shown in Fig. 22, the cell voltage of the electrolysis process carried
out in a titanium basket is lower than that which was carried out in a
graphite basket, because the electrical conductivity of the titanium
metal is better than that of graphite. Fig. 23 shows the effect of both basket materials on the different process parameters and indicates that the
graphite basket is better than titanium for the all process parameters instead of the specic energy demand which is better when titanium basket was used. The big process problem when the titanium basket is

Fig. 23. Effect of anode basket material on different electrolysis parameters.

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A. Owais et al. / Hydrometallurgy 157 (2015) 6071

Fig. 24. SEM micrographs of the deposited zinc powders from electrolysis of zinc anode casing of secondary batteries at 1000 A/m2, 300 rpm and 50 C (magnication 200), (a) graphite
basket, and (b) titanium basket.

utilized is its serious corrosion at the applied experimental conditions.

This of course will lower the age of the basket beside its bad effect on
the purity of the electrolyte solution after a long period of the electrolysis process, due to the gradual accumulation of titanium ions in the solution, which consequently will cause a contamination of the deposited
zinc powder due to its penetration in the deposited powders.
When graphite and/or titanium baskets were used, the electrodeposited powders showed a dispersive shape as indicated from SEM micrographs which presented in Fig. 24 with a somewhat ner particle
size when titanium basket was utilized as indicated from the size analyzer curves in Fig. 25. The deposited powders have a higher apparent
density when graphite basket was used (Fig. 26).

effect of the initial concentrations of both NaOH and zinc ions on the
electrolysis process.
The microstructure of the deposited zinc powders in an old or new
electrolyte is illustrated in Fig. 29 and indicated that dispersive zinc
powders were obtained in old electrolyte while nanorod shape powders
were obtained in new electrolyte with a ner particle size as shown
in Fig. 30. The apparent density of the produced powders in an old electrolyte is higher than that which obtained from a fresh electrolyte as
shown in Fig. 31.

3.5. Effect of the electrolyte state

To study the possibility of re-application of the pre-used electrolyte
in the electrolysis process or the reproducibility of the electrolyte, two
different age electrolytes (new and/or old) were tested and the resulted
electrolysis curves were illustrated in Fig. 27. It was observed that, the
cell voltage of the electrolysis process is higher when a new electrolyte
is utilized in the electrolytic cell. The effect of the age of the electrolyte
solution on the different process parameters was illustrated in Fig. 28
and showed that the pre-used old electrolyte for 3 h is better for all parameters compared to the anodic current efciency which showed a
lower value. This can be due to the accumulation of zinc ions in the
pre-used electrolyte from the previous experiments and also due to
the change in the concentration of NaOH in the electrolyte solution.
The rise of anodic current efciency with new electrolyte may be due
to the utilization of a fresh solution which is empty from any previous
concentration of zinc ions and causes a good dissolution of anode particles, beside an effective diffusion of zinc ions in the electrolyte bulk solution. Further experiments should be done extensively to show the

Fig. 25. Effect of an anode basket material on the particle size distribution of the electrodeposited zinc powder: a) graphite basket and b) titanium basket.

Fig. 26. Effect of anode basket material on the apparent density of the electrodeposited
zinc powder.

Fig. 27. Cell voltage against duration of the electrolysis of zinc anode casing of spent zinc
carbon type batteries in different electrolyte states in a titanium basket, (1000 A/m2,
300 rpm, 50 C).

A. Owais et al. / Hydrometallurgy 157 (2015) 6071

69

Fig. 28. Effect of the electrolyte state on different electrolysis parameters.

Fig. 29. SEM micrographs of the deposited zinc powders from electrolysis of zinc anode casing of secondary batteries in a titanium basket at 1000 A/m2, 300 rpm and 50 C (magnication
15000), (a) old electrolyte, and (b) new electrolyte.

XRF analyses of the electrodeposited zinc powders from both graphite and/or titanium baskets are illustrated in Table 2 and indicate that
zinc powders with an average composition of about 99.8% Zn were obtained during the electrolysis process. The deposited powders were
contaminated with about 0.0053% Ti when the titanium anode basket

was utilized. The source of titanium in the produced powders can be

due to the serious corrosion of the basket and entrapment of the dissolved Ti ions to the deposited zinc powders. This value can be increased
over a long period of electrolysis process. The severe corrosion of the

Fig. 30. Effect of the electrolyte state on the particle size distribution of the electrodeposited zinc powder in a titanium basket: a) old electrolyte and b) new electrolyte.

Fig. 31. Effect of electrolyte state on the apparent density of the electrodeposited zinc
powder in a titanium basket.

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A. Owais et al. / Hydrometallurgy 157 (2015) 6071

Table 2
XRF analysis of the deposited Zn powder.
Component

Zn

Pb

Cd

Fe

Sn

Tc

Ni

Ti

Wt.%, in a graphite basket

Wt.%, in a titanium basket

99.8000
99.8000

0.0895
0.0912

0.0139
0.0073

0.0460
0.0288

0.0240
0.0235

0.0142
0.0186

0.0147
0.0151

0.0053

titanium basket causes also a rapid failure of the basket beside a lot of
money losses.
The produced zinc phase appeared in XRD analysis as shown in
Fig. 32 is in the metallic form without any zinc oxides. This can be due
to the utilization of an inert gas drying furnace for drying the produced
powders.
4. Conclusions
Packed bed electrolysis process was successfully applied on zinc
anode casing of secondary dry cell batteries to produce high quality
electrolytic zinc powders (about 99.8% Zn). The following conclusions
can be drawn from this investigation:
1. The produced zinc powders have different shapes (nanorods, dendritic and/or dispersive), different sizes and different densities
(from 1203.1 to 2085.2 kg/m3) depending on the applied process
conditions.
2. The graphite basket was more efcient than titanium one in terms of
all the studied parameters including; cathodic and anodic current efciencies and powder productivity, except for the specic energy demand due to the better electrical conductivity of the titanium basket.
3. The process is enhanced by increasing both the current density, electrolyte temperature, electrolyte stirring rate (up to 300 rpm) and
when an old electrolyte was utilized.
4. The proposed electrolysis process is a promising recycling technique
since it was carried out with cathodic current efciency up to 94.85%,
anodic current efciency up to 98.97% and specic electrical energy
demand in the range from 0.808 to 2.518 kWh/kg Zn with powder
productivity up to 1.150 g/A.h.

Acknowledgments
The authors would like to thank Eng. Alaa Dardeir (Department of
Metallurgical and Materials Engineering, Faculty of Petroleum and

Mining Engineering, Suez University) for his assistance in conducting

the experimental work.

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