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Electrochemical recycling of Zn from spent Zn

MnO2 batteries

Article in Ionics November 2013

DOI: 10.1007/s11581-013-0997-8


2 104

5 authors, including:

Eric M. Garcia Hosane A. Tarco

Federal University of So Joo del-Rei Federal University of So Joo del-Rei


Ione Maria Ferreira de Oliveira

Federal University of Minas Gerais


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Ionics (2013) 19:16991703
DOI 10.1007/s11581-013-0997-8


Electrochemical recycling of Zn from spent ZnMnO2

Eric M. Garcia & Hosane A. Tarco & Jlio O. F. Melo &
Ana Paula C. M. Silva & Ione M. F. Oliveira

Received: 28 June 2013 / Revised: 21 August 2013 / Accepted: 26 August 2013 / Published online: 10 September 2013
# Springer-Verlag Berlin Heidelberg 2013

Abstract Scientific scene has increased the environmental Several processes for the recycling of batteries were proposed,
studies about battery recycling. Following this tendency, this mainly in Europe, both pyrometallurgical and hydrometallur-
paper aims to study the electrochemical recycling of zinc from gical [7] processes. The waste generated by ZnMnO2 batte-
ZnMnO2 batteries. The electrodeposition of zinc was ries is basically constituted Zn and Mn metals [311]. Thus,
performed on carbon steel. In pH=4.6, the zinc electrodepo- the electrochemical recycling is preferable since the electro-
sition occurs via chemistry and electrochemistry steps. For deposition can be perfectly applied in this case [2]. Freitas and
determinant step reaction, the order was (lnip/lnCH+)0 and Pietre [7, 8] studied the recycling of ZnMnO2 batteries using
(lnip/lnCZn+2)1. electrodeposition. In this work, the authors present the recov-
ery of zinc by galvanostatic electrodeposition (Eq. 1) with
Keywords Anode . Zinc recycling . ZnMnO2 batteries high efficiency (~80 %).

ZnSO4aq 2e Zns SO42

aq 1

The battery arrangement represents the major current problem Although this has been a valuable work, the authors did not
of modern society. Nevertheless, few papers have been inter- provide sufficient measures to characterize the zinc electrode-
ested in studying the recycling of these materials [14]. One of position mechanism. Buzatu et al. [10] studied the metallic
most problematic batteries is the ZnMnO2 batteries [35]. electrodeposition as strategy for recycling the ZnMnO2 bat-
The amount these batteries consumed worldwide is very large; teries. This paper was focused in optimization of the electro-
however, the Zn and Mn compounds do not have high eco- deposition process for obtaining the simultaneous deposition
nomic value [3, 4]. Around 60 billion of ZnMnO2 batteries of zinc and manganese. Brito et al. [10] also reported a
are produced annually [5, 6]. For this reason, a solution for simultaneous recovery of Zn and MnO2 from spent batteries.
spent batteries waste is very important. It is no coincidence The current efficiency for zinc and manganese electrodeposi-
that recycling is the method most widely used for this purpose. tion reaches 94.02 % [11]. Although the current efficiency
showed a high value, few information about mechanism are
discussed. Metallic zinc is more used in applications as gal-
vanized steels, sacrifices metals and batteries applications.
E. M. Garcia (*) : H. A. Tarco : J. O. F. Melo : A. P. C. M. Silva Many papers that study the electrochemical recycling of Zn
Universidade Federal de So Joo Del ReiUFSJ/Campus de Sete
MnO2 batteries consider the Mn and Zn electrodeposition
Lagoas Laboratrio de Sntese Orgnica e Eletroqumica(LaSOEL),
Rodovia MG 424, Km 47, Minas Gerais 35701-970 Belo Horizonte, simultaneously [311]. Although both ions are very important
Brazil economically and environmentally for better compression of
e-mail: electrodeposition mechanism in this paper, only anode was
researched. Thus, this paper aims to study the recycling of
I. M. F. Oliveira
Chemistry Department, Federal University of Minas Gerais, Belo zinc, from spent ZnMnO2 batteries, by electrodeposition in
Horizonte, Minas Gerais, Brazil acid medium. The principal aspect focused in this paper is the
1700 Ionics (2013) 19:16991703

role of zinc and proton concentration on electrodeposition agitation at 60 C for 2 h. After, the Zn metal was dissolved in
mechanism. Thus, we used cyclic and linear voltammetry with H2SO4 0.5 mol L1 (Eq. 2).
variation of H+ and Zn+2 concentrations. In this work, com-
plement tests will be done to determine the mechanism of Zns H2 SO4aq ZnSO4aq H2g 2
electrodeposition of recycled Zn from ZnMnO2 batteries on
carbon steel. The composition of the solution obtained in the process was
carried out by atomic absorption spectrophotometry. It is impor-
tant to know the concentrations of manganese and iron. In spite
Experimental of the laundering made, such leaching is likely to have significant
quantities of these metals that may influence decisively the
Preparation of zinc electrodeposition solutions discussion of the results. The value found for concentration of
both Mn and Fe was below of the detection limit (less than
Figure 1a represents the illustration of a ZnMnO2 battery and 0.1 mol L 1 ). The value for zinc concentration was
its components. The ZnMnO2 batteries were manually dis- 0.112 mol L1
mantled and physically separated into their different parts: The pH of ZnSO4 solutions was adjusted with NaOH(s). To
anode, cathode, steel, separators, and current collectors. The study the effect of Zn+2 concentration, solutions were pre-
Zn anode was washed with diluted solution of H 2SO4 pared with different concentrations of Zn+2 at pH=4.60. The
0.01 mol L1. The process was done under constant magnetic same was made for H+ ions using the solution ZnSO4

Fig. 1 a The illustration of Zn

MnO2 battery and its
components. b The scheme for
obtaining of ZnSO4 solution in
different concentration of Zn+2
and H+
Ionics (2013) 19:16991703 1701

100 mmol L1. The scheme for obtaining of ZnSO4 a

solution at different pH and concentrations are showed
in Fig. 1b.

Electrochemical measurements

Electrochemical measurements were made using an

AUTOLAB PGSTAT 30 power supply. The working
electrode was made of commercial carbon steel. The
samples were prepared as rectangular foils with a geo-
metric area of 1.00 cm2. The auxiliary electrode, with an
area of 3.75 cm2, was made of platinum. A saturated Ag/
AgCl reference electrode was used. The working elec-
trodes were sanded with 600-grit sandpaper before each
measurement and washed with distilled water. All the electro- b
chemical measurements were performed without solution ag-
itation at 25 C.

Results and discussion

The zinc electrodeposition was studied using cyclic and linear

voltammetry. Figure 2a shows the resultant cyclic voltammo-
gram for zinc electrodeposition on carbon steel electrode at pH=
4.60. A solution without zinc was prepared with 0.10 M Na2SO4
in same pH value (pH=4.60). From cyclic voltammetry, it is
observed that zinc electrodeposition happens in potentials more
negative than 1.1 V. The crossover in 1.20 V is typical of a
new phase formation involving the nucleation process [2, 816].
Fig. 2 a Cyclic voltammogram for zinc deposition onto a steel electrode
In anodic zone, the peak B around 0.91 V is related with zinc
at pH=4.60 and [Zn+2]=0.10 mol L1. For comparison purposes, a
dissolution. The anodic (Qa) and cathodic charge (Qc) with solution with 0.1 M Na2SO4 replaced the zinc solution. b The anodic
variation of zinc concentration is given in Fig. 2b. The Qa/Qc (Qa) and cathodic charge (Qc) for cyclic voltammogram with variation of
value when [Zn +2]=0.10 mol L1 is 0.82. This value would be zinc concentration
characteristic of quasi-reversible process [16]. However, it was
verified that the current peak is constant with scan rate1/2 and the
potential peak (Ep) shifts for more cathodic region with increase and its concentration can be obtained considering the first step
of scan rate. This can be an evidence of irreversibility of zinc in quasi-equilibrium condition (Eq. 5).
electrodeposition [16]. The shift in cathodic current for irrevers- h ih i
ible electrochemical reaction is 30 mV/n for decade, where n is ZnOH aq H
K1 h i 5
the stoichiometric coefficient for electrons and is the symmetry 2
coefficient [16]. The value found for shift in Ep was 33 mV/dec.
For discovery, the symmetry coefficient () value is necessary to The second step (Eq. 4) is the reduction of ZnOH(aq)+
reflect about the mechanism of zinc electrodeposition. Thus, species in metallic zinc. Considering this step as the reaction
we can consider the metallic electrodeposition in more than determinant step (rds) for zinc electrodeposition, the cathodic
one step. The zinc electrodeposition at pH~4 is given by current is given by Eq. 6. Substituting Eq. 5 into Eq. 6, the rds
Eqs. 3 and 4 [68]. is reformulated (Eq. 7). Taking into account the shift in ca-
thodic current with increase in scan rate (33 mV/dec) and
aq H2 O ZnOHaq Haq 3 n =2, the value is approximately 0.5 (Eq. 8).

aq Haq 2e Zns H2 O 4 h i
aq RT
ic K 3 h i exp 6
The first step (Eq. 3) is the chemistry reaction and does not
depend on potential. The specie ZnOH(aq)+ is the intermediary,
1702 Ionics (2013) 19:16991703

h i  RT

ic K3 Zn2
aq exp 2 7

33mV 0:5 8

To verify the validity of this mechanism, linear voltammetry

was performed in cathodic region in different concentrations of
Zn+2 and H+. This result can be observed in Fig. 3a, b. In fact,
the peak current increases with increasing of Zn+2 concentration
(Fig. 3a). However, the same was not true for H+ ions. With the
pH variation, the peak current remains practically constant.
Assuming that the peak current for rds depends on H+ and
Zn+2 concentration, we can apply the ln on Eq. 7 to obtain
Eq. 9. Differentiating Eq. 9 with respect to Zn+2 and H+ con-
centration, two coefficients are described as shown in Eqs. 10 Fig. 4 Representation of (lnip/lnCH+) and (lnip/lnCZn+2) obtained from
linear voltammetry
and 11, respectively. This can be best visualized in Fig. 4.

lnic lnK3 2 alnCZn2 blnCH 9
a F
a 10
lnCZn2 CH

b 11
lnCH CZn2

According to Fig. 4, the coefficient a is around one and

the coefficient b is around zero. These results indicate that
the reaction represented by Eq. 4 is the rds for zinc electrode-
position. Figure 5 shows the simulation and experimental
curve for zinc electrodeposition. For simulation curve, Eq. 7
was used and was considered =0.50, R =3.14 Jmol1 K1,

Fig. 3 a Linear voltammograms for zinc electrodeposition onto a steel

electrode at pH=4.60 in different concentration of Zn+2. b Linear Fig. 5 The simulation and experimental linear voltammetry for zinc
voltammograms for zinc electrodeposition onto carbon steel electrode electrodeposition on carbon steel with [Zn+2]=0.10 mol L1 and pH=
with [Zn+2]=0.10 mol L1 in different pH values 4.60
Ionics (2013) 19:16991703 1703

F =96.500 Cmol1, and T=298 K. The generic equation uti- Acknowledgments The authors acknowledge Universidade Federal de
lized for simulation was i Pl eP2 where P 1 is the ex- So Joo Del ReiUFSJ/Campus de Sete Lagoas.

change current and P2 2aFRT . Until the process was controlled

by activation energy, the simulation and experimental data are
in agreement with each other a good approximation. After the
limit that corresponds to diffusion control, the simulation
has failed as expected. The theoretical value of P 2 was 1. Yao JT, Chen FY, Chien KC (2013) J Hazard Mater 258:102
2. Innocenzi V, Veglio F (2012) Hydrometallurgy 129:50
38.90 V 1 , and the experimental value of P 2 was 3. Garcia EM, Hosane AT, Tulio M, Rosana ZD, Jacqueline AFS, Eudes
37.8 V1. The error of 2.82 % shows that the model proposed L, Diana QL, Marcos BJGF (2012) J Appl Electrochem 46:361
for zinc electrodeposition is acceptable. The error of 2.82 % 4. Komilis D, Bandi D, Kakoronis G (2011) Sci Total Environ 409:2555
shows that the model proposed for zinc electrodeposition is 5. Freitas MBJG, Garcia EM (2007) J Power Sources 171:953
6. Freitas MBJG, Garcia EM, Celante VG (2009) J Appl Electrochem
acceptable. 39:601
7. Freitas MBJG, Pietre MK (2004) J Power Sources 128:343
8. Freitas MBJG, Pegoretti VC, Pietre MK (2007) J Power Sources 164:
Conclusion 947
9. Buzatu M, Sceanu S, Ghica VG, Iacob G, Buzatu T (2013) Waste
Manage 33:1764
In this paper, the electrochemical recycling of ZnMnO2 10. Brito PSD, Patrcio S, Rodrigues LF, Csar ACS (2012) Surf Coat
anode was performed. Under our experimental conditions, Tech 206:3036
the electrodeposition of zinc on carbon steel occurs under 11. Ferella F, Michelis I, Veglio F (2008) J Power Sources 183:805
12. Salles YCM, Oliveira GCG, Daz SL, Barcia OE, Mattos OR (2011)
irreversible control. From cyclic voltammetry, zinc electrode-
Electrochim Acta 56:7931
position is observed that occurs for potentials more negative 13. Beltowska-Lehman E, Ozga P, Swiatek Z, Lupi C (2002) Surf Coat
than 1.1 V. In pH=4.60, the zinc electrodeposition occurs via Tech 151:444
two steps (chemistry and electrochemistry). The reaction order 14. Hegde AC, Venkatakrishna K, Eliaz N (2010) Surf Coat Tech 205:2031
15. Garcia EM, Taroco HA, Matencio T, Domingues ZR, Santos FAJ,
in relation to Zn+2 is one and in relation the H+ is zero. The
Freitas MBJG (2011) J Appl Electrochem 41:1373
simulation of zinc electrodeposition with proposed mecha- 16. Bard AJ, Faulkner LR (2000) Electrochemical methods, fundamen-
nism presented only 2.82 % of error. tals and applications. Wiley, New York

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