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Silver recovery from spent silver oxide button

cells
Article in Hydrometallurgy July 2010
DOI: 10.1016/j.hydromet.2010.05.004

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Hydrometallurgy 104 (2010) 106111

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Hydrometallurgy
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / h yd r o m e t

Silver recovery from spent silver oxide button cells

Serdar Aktas
Istanbul Technical University, Institute of Science & Technology, Maslak, 34469, Istanbul, Turkey

a r t i c l e

i n f o

Article history:
Received 8 April 2010
Received in revised form 12 May 2010
Accepted 12 May 2010
Available online 25 May 2010
Keywords:
Silver
Spent button cells
Recovery
Leaching

a b s t r a c t
The present work investigates a hydrometallurgical process for silver recovery from spent silver oxide button
cells. The effects of acid concentration, reaction temperature, reaction time and shaking rate on the silver
dissolution are investigated in detail. In addition, an investigation regarding the dissolution kinetics of silver
is undertaken, and the activation energy is found to be 26 kJ/mol. Silver is selectively precipitated as
silver chloride using potassium chloride solution, ensuring that other impurities remain in the solution.
Silver chloride is subsequently reacted with metallic zinc powder in 1.0 M HCl to yield metallic silver of
99.99% purity. The process is proven to be easy, straightforward and environmentally friendly.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Button cells were developed to miniaturize battery packs and to
solve stacking problems. These cells have a high capacity per unit
weight, a long operating life and are currently used in hearing aids,
digital thermometers, insulin pumps, portable medical monitors,
hospital pagers, watches, toys and calculators, among others (Buchchmann, 2001). While battery is in use, the silver oxide is reduced to
metallic silver and the zinc metal is converted to zinc oxide. The overall
reaction is given by Eq. (1) (Compton, 2000).
0

Ag2 Os Zn 2Ag ZnOs

The collection of spent silver oxide batteries due to their economic

value is a widespread trend in global recycling markets (Smith and Gray,
2010; Pistoia et al., 2001). Battery recycling is important due to
environmental issues and for economic reasons (Nan et al., 2006; Wang
et al., 2009; Kang et al., 2010; Pranolo et al., 2010; Sayilgan et al., 2009;
Shin et al., 1983). There are a few battery recycling plants around the
world that apply their own recycling processes to recover valuable
components from spent batteries or to facilitate environmentally
friendly disposal (Krebs, 1999a,b; Grant et al., 1983; David, 1995).
Some processes treat only spent button cells, whereas others involve the
treatment of bulk mixtures containing small cells of different battery
chemistries. Spent silver oxide batteries can be quickly sorted by size.
For instance, at Batrec, a Swiss battery recycling plant, silver oxide
button cells are sorted and used for mercury distillation and the
remaining material is dispatched to a renery for the reclamation of
silver (Batrec Ind. AG, Switzerland).

Tel.: + 90 5337230576.
E-mail address: serdaraktash@yahoo.com.
0304-386X/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2010.05.004

As a noble metal, silver does not dissolve in dilute HCl at room

temperature under moderate conditions, but it readily dissolves in
dilute or concentrated HNO3 to yield a silver nitrate solution
(Holloway et al., 2004). The following reactions (2) and (3) take
place (Svehla, 1987):
0

3Ag 4HNO3aq 3AgNO3aq 2H2 Ol NOg

Ag2 Os 2HNO3aq 2AgNO3aq H2 Ol

According to the process of treating spent silver oxide batteries

developed by the Korea Institute of Geosciences and Mineral
Resources, mercury is recovered from spent silver oxide batteries by
distillation. After the mercury is removed, silver and other fractions
are leached using nitric acid. Silver chloride is then precipitated from
this solution by employing sodium chloride. Silver chloride is then
reduced to metallic silver by employing sodium hydroxide and
dextrose (Sohn, 2003).
The objective of this work was to develop an effective hydrometallurgical process for the recovery of valuable silver from spent silver
oxide button cells.
2. Materials and methods
Maxell SR1120SW spent silver oxide button cells, which were
supplied from a waste collection center in Istanbul, Turkey, were
employed in this work, and their composition is presented in Table 1.
The cells were crushed, dried, ground and nally sieved to produce a
silver-rich-cell powder, and the chemical composition of this cell
powder is presented in Table 2. The direct smelting of button cells using
the appropriate slag-making chemicals is one option for recovering
silver from spent button cells (Sathaiyan et al., 2006). However, this

S. Aktas / Hydrometallurgy 104 (2010) 106111

Table 1
Composition of Maxell SR1120SW silver oxide button cells.
Component

Weight %

Steel case
Battery paste
Membrane and plastics
Electrolyte
Remainder

55.25
37.1
4.25
3.1
0.3

Table 2
Chemical composition of cell powder.
Elements

Weight %

Ag
Zn
Hg
C
S
Fe
Pb
Cd
Ni

62.09
13.55
0.54
2.48
0.0088
0.0040
b 0.0100
N.D.
N.D.

Not detected

method was not used in the present study because it causes

environmental problems. The owchart for the silver recovery from
spent silver oxide button cells is shown in Fig. 1.
All of the chemicals used in this study were of analytical grade. The
spent silver oxide button cells were crushed, and the cases
were dismantled. The obtained cell powder was dried in an oven at
100 C, ground and then sieved to remove non-metallic fractions,
prior to homogenization using a three-dimensional shaker. After

107

these treatments, a homogeneous silver-containing cell powder

weighing 131.1 g was obtained and used for the leaching experiments. The establishment of optimal dissolution parameters was
performed by examining the following factors: time, temperature,
amount of cell powder, shaking rate and molarity of the nitric acid. For
each experiment, 5 mL of various nitric acid solutions of 0.52.0 M
was employed to dissolve the silver incorporated in the spent button
cells. The experiments were conducted inside a falcon tube placed in a
temperature-controlled shaking bath to ensure uniform heat convection at the surface of the falcon tube.
To determine the silver content (Mo) of the cell powder, ve samples
were subjected to dissolution in concentrated nitric acid (Merck Extra
Pure 65%) to ensure that they were completely dissolved. Next, the
silver content was measured using a Titroline Easy Silver Titrator, and
the average silver content was calculated to be 62.09% 0.01. However,
33.5% of this silver content is in the form of silver oxide (Ag2O). This is
because all spent button cells employed in this work were found to be
not completely consumed.
Solid/Liquid separation was performed following each dissolution
experiment. For the AAS (Perkin Elmer AAnalyst 800) analyses, 5 mL
of the ltered solution was introduced into the instrument at an
appropriate dilution. The efciency of this leaching process was
calculated from the percentage of silver recovery using the following
formula:
Leaching Efficiency% = Mt = W Mo  100

where W is the weight of the cell powder taken for each experiment,
Mo is the silver content (62.09%) of the cell powder and Mt is the silver
quantity at the end of the leaching process.
To investigate the dissolution behavior of the silver from the spent
button cells, a kinetic study was undertaken. In the recovery step, silver
was selectively precipitated as silver chloride using stoichiometric
amount of KCl solution. The silver chloride was then reacted with
metallic zinc powder (b150 ) with a purity of 99.9% (Aldrich) in
various acidic media inside a falcon tube placed in a temperaturecontrolled shaking bath to obtain metallic silver. For each experiment,
100 mg of silver chloride and 5 mL of acidic solutions were employed
using various temperatures and quantities of zinc powder. After the
replacement reaction, excess zinc was digested in 1.0 M HCl (pH = 0.01)
to clean the product thoroughly. The morphology of the silver produced
was investigated using a JEOL JSM-5800 LV scanning microscope (SEM).
The samples were also examined by XRD analysis using a Philips X'Pert
PW3020 (theta/2theta, 2 motors) X-ray diffractometer. The oxygen
content of the samples was measured with a NOH-2000 analyzer.
3. Results and discussion
The process outlined in this paper can be used to recover almost all
of the silver present in the spent button cells employed in this study.
3.1. Dissolution of silver incorporated in spent silver oxide button cells

Fig. 1. Flowchart for the silver recovery from spent silver oxide button cells.

Fig. 2 shows that the silver dissolution increased with an increased

nitric acid molarity of the solution, which is in agreement with the
study by Ozmetin et al. (1998). At 1.0 M and higher molarities of nitric
acid the dissolution increased with an increased quantity of cell
powder. However, at a nitric acid molarity of 0.5 M, the dissolution
decreased with an increased quantity of cell powder, because the
amount of nitric acid present at 0.5 M is not sufcient to leach all of
the silver from the cell powder.
To determine the effect of temperature more accurately, a 0.5 M
nitric acid solution was selected. Fig. 3 displays the effect of temperature
on the dissolution of silver at a nitric acid molarity of 0.5 M.
As shown in Fig. 3, temperature played an important role in the
dissolution of silver from spent button cells. At 25 C with 50 mg of

108

S. Aktas / Hydrometallurgy 104 (2010) 106111

Fig. 2. Effect of nitric acid molarity on the dissolution of silver, depending on the
quantity of the cell powder (1 h, 25 C, 5 cc solution, 200 rpm).

Fig. 4. Effect of temperature on the dissolution of silver (1 h, 5 cc solution, 1.0 M HNO3,

200 rpm).

the cell powder, dissolution of 47% was obtained, whereas at 65 C,

dissolution of 95% was observed. The dissolution clearly increased
with increasing temperature. However, the dissolution decreased
with an increased quantity of the cell powder because at a nitric acid
molarity of 0.5 M, the amount of nitric acid present was not sufcient
to leach all of the silver from the cell powder. Interestingly, a different
dissolution behavior was observed when a 1.0 M nitric acid solution was employed. Fig. 4 shows the variation of silver dissolution at
1.0 M nitric acid solution with changing quantities of cell powder and
temperature.
As shown in Fig. 4, the silver was entirely dissolved at 45 C. Thus,
temperatures of 55 C or 65 C were not investigated. Based on these
results, it is clear that increasing temperature results in higher
dissolution efciencies.
The effect of time on the dissolution of silver was shown in Fig. 5. As
shown in this gure, the reaction time had an important role in the
dissolution of silver from spent button cells. For instance, dissolution of
38% was observed after 15 min in a 0.5 M nitric acid solution. However,
under the same conditions, when the leaching time was extended to 1 h,
dissolution of 48% was achieved. Dissolution of 85% was observed after
15 min using 2.0 M nitric acid solution. Under the same conditions,
when the leaching time was extended to 45 min or 1 h, dissolution of
99% was achieved. With the exception of the 0.5 M nitric acid solution,

after 45 min of reaction time, no appreciable increase in the dissolution

was observed.
Fig. 6 shows the effect of shaking rate on the dissolution of silver.
As shown in the gure, the shaking rate was an important
parameter affecting the dissolution of silver from spent button cells.
When 50 mg of cell powder was used at a shaking rate of 10 rpm, a
dissolution of 44% was obtained. However, when the shaking rate was
increased to 200 rpm, a dissolution of 69% was achieved. This nding
indicates that silver dissolution is affected by diffusion-controlled
kinetic factors as well as chemical-controlled factors (Habashi, 1976).

Fig. 3. Effect of temperature on the dissolution of silver (1 h, 5 cc solution, 0.5 M HNO3,

200 rpm).

3.2. Dissolution kinetics of silver from spent silver oxide button cells
To determine the rate constant (k) of silver dissolution in the
temperature range of 298328 K, 1 (1 X)1/3 (Dickinson and Heal,
1999; Markus et al., 2004; Ekinci et al., 1998) was plotted over time, as
shown in Fig. 7.
Fig. 8 shows the Arrhenius plot of ln k vs. 1000/T for silver
dissolution. The activation energy for silver dissolution was calculated
to be 26 kJ/mol, which indicates that this is an intermediatecontrolled process (Habashi, 1976).
In the light of the results obtained through dissolution experiments, optimum leaching condition is as follows: 5 mL, 1.0 M HNO3,

Fig. 5. Effect of time on the dissolution of silver (25 C, 5 cc solution, 200 rpm, 50 mg).

S. Aktas / Hydrometallurgy 104 (2010) 106111

109

Fig. 6. Effect of shaking rate on the dissolution of silver (1 h, 25 C, 5 cc solution, 1.0 M HNO3).

Fig. 8. Arrhenius plot of ln (k) vs. 1000/T.

45 C, 1 h, 200 rpm, 250 mg cell powder. It was observed that mercury

is entirely converted to Hg+ 2 ions under this condition, and did not
precipitate as mercury (II) chloride. Even though silver could be
dissolved more than 99% at 25 C using 2.0 M nitric acid solution
mercury was observed to be converted to mercury (I) ions, which coprecipitates as mercury (I) chloride with the silver chloride during the
precipitation process. This precipitate would present an undesirable
impurity in the nal product. A subsequent paper will examine the
observation regarding the valence of mercury and its recovery process
in detail.

(NO3)2 (Petrucci and Harwood, 1997), which made it possible to

precipitate silver selectively.

At room temperature, a silver precipitation efciency of 99.9% was

obtained after 60 min at 200 rpm. It is worth mentioning that mercury
remained in the solution because mercury was in the form of Hg

3.3.1. Replacement reaction of silver chloride with zinc powder

In order to decide what medium is suitable for replacement reaction
of silver chloride with zinc powder, various solutions (distilled water,
1.0 M HCl and 1.0 M H2SO4) were tested, as shown in Fig. 9.
As seen from the gure that HCl medium was found to be most
efcient among the tested media for this reason HCl solution was
chosen for the optimization of this replacement reaction.
To see the effect of the molarity of hydrochloric acid, various acid
concentrations (0.52.0 M HCl) were examined, as shown in Fig. 10.
Whereas using 1.0 M HCl solution a conversion of 96% was achieved,
using other concentrations lower conversion efciencies were
obtained.
According to the study conducted by J.A. Murphy et al. (1991), silver
chloride/silver conversion by zinc powder was conducted at 7080 C.
Thus, various temperatures were tried to observe their effect on the
conversion of silver chloride to silver, as shown in Fig. 11. According to
this gure, higher temperatures resulted in less conversion efciencies
due to the possible acceleration of zinc digestion in HCl medium.
To determine the exact amount of zinc powder to complete this
conversion, various zinc powder quantities were employed for
replacement reaction, as shown in Fig. 12. As seen from the gure

Fig. 7. Plot of 1 (1 X)1/3 with respect to time.

Fig. 9. Effect of reaction medium on the conversion of AgCl to Ag (1 h, 25 C, 5 cc

solution, 200 rpm, 1.0 M HCl, 1.0 M H2SO4, 100 mg AgCl).

3.3. Selective precipitation of silver as silver chloride using potassium

chloride
A freshly prepared KCl solution of stoichiometric amount was
added to the solution to precipitate silver selectively as silver chloride
based on the low solubility product constant of AgCl (Petrucci and
Harwood, 1997) as shown in Eq. (5).

10

AgCls Agaq Claq Ksp 1:8  10

110

S. Aktas / Hydrometallurgy 104 (2010) 106111

Fig. 10. Effect of hydrochloric acid molarity on the conversion of AgCl to Ag (1 h, 25 C,5 cc
solution, 200 rpm, 100 mg AgCl).

Fig. 12. Effect of zinc quantity on the conversion of AgCl to Ag (1 h, 25 C, 5 cc solution,

200 rpm, 1.0 M HCl, 100 mg AgCl).

that 30% more than stoichiometric amount of zinc powder was found
to convert all silver chloride to metallic silver which is in agreement
with a study conducted by J.A. Murphy et al. (1991). Thus, 29.6 mg of
zinc powder is observed to be enough to convert 100 mg of silver
chloride to metallic silver at room temperature after 1 h at a shaking
rate of 200 rpm. The replacement reaction is shown in Eq. (6).

10 ppm, although oxygen was not detected. According to the SEM

images shown in Fig. 13, a porous powder was produced via the
replacement reaction. The particles were sub-micron in size and had a
dendrite-type structure. Similar images were also obtained in a study
conducted by E.A. Abdel-Aal and F.E. Farghaly (2007).

2AgCls Zns 2Ags ZnCl2aq

Similar to cementation reactions, zinc is oxidized through the process

of acquiring chloride from silver chloride, resulting in the production of
silver powder. The remaining zinc powder was then reacted with dilute
1.0 M HCl. This treatment generated a silver powder of 99.99% purity.
Table 3 displays mass balance based on 360 pieces of button cells
employed in the present study.
3.3.2. Characterization of the obtained powders
Following the metallic silver powder was produced, it was washed
with fresh 1.0 M HCl (pH = 0.01), distilled water, then acetone and
subsequently dried under a vacuum at 80 C for 1 h.
To determine the purity of the produced powder, potentiometric
titration was performed. The sample produced by zinc was found to
contain 99.99% silver. Zinc content of the sample was found to be

4. Conclusion
In the present work, a hydrometallurgical process was developed
to recover silver metal from spent silver oxide button cells. It was
demonstrated that the silver metal incorporated in spent button cells
could be dissolved more than 99%, with the use of dilute nitric acid
solutions (0.5 M2.0 M) even under moderate experimental conditions. The activation energy of silver dissolution was calculated to be
26 kJ/mol, which indicates that this is an intermediate-controlled
process. These results were conrmed in the experiments used to
investigate the effects of shaking rate and temperature. The dissolved
silver was selectively precipitated with KCl solution as AgCl with an
efciency of more than 99% ensuring that mercury and zinc remained
in the solution. Mercury can be recovered selectively using an
appropriate resin. The silver chloride was shown to be reduced to
metallic silver by the help of metallic zinc powder in 1.0 M HCl
medium at room temperature at 200 rpm with an efciency of more
than 99%. Using this method, a ne silver powder with a purity of
99.99% was produced. This powder can be used directly in various
applications, including the production of silver nitrate, which is used
in anti-bacterial and pharmacological applications; the production of
silver cyanide, which is the main component of silver plating baths in
jewelry and as an alloy element.

Table 3
Mass balance based on 360 pieces of button cells.

Fig. 11. Effect of temperature on the conversion of AgCl to Ag (1 h, 5 cc solution,

200 rpm, 1.0 M HCl, 100 mg AgCl).

Substance

Quantity (g)

Total button cells

Cell powder amount
Total silver amount
HNO3 consumption for leaching
KCl consumption for precipitation
AgCl amount
HCl consumption for replacement reaction
Zn consumption (30% more than stoichiometric amount)
Silver (99.99% purity nal product)

353.5
131.1
81.4
165.2
56.2
107.9
196.9
32.0
80.4

S. Aktas / Hydrometallurgy 104 (2010) 106111

111

Fig. 13. Scanning electron micrographs of silver powders (1300, 10,000).

Zinc nitrate solution from the initial leaching process, and zinc
chloride solution from the replacement reaction can be put together
for zinc precipitation by the help of sodium hydroxide.
The proposed process avoids environmental problems and allows
for the non-hazardous hydrometallurgical recovery of valuable silver
from spent silver oxide button cells.
Acknowledgments
The author wishes to thank TUBITAK for nancial support under
project 109M365. Special thanks are due to Gnta Zorlu MSc student
and Raife Deniz Toker PhD student, for their invaluable discussions.
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