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Ionics (2013) 19:16991703
DOI 10.1007/s11581-013-0997-8
SHORT COMMUNICATION
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 %).
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: ericmgmg@hotmail.com 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
Electrochemical measurements
ZnOH
aq Haq 2e Zns H2 O 4 h i
ZnOH
aq RT
ic K 3 h i exp 6
The first step (Eq. 3) is the chemistry reaction and does not
H
aq
F
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
F
30mV
33mV 0:5 8
n
RT
lnic lnK3 2 alnCZn2 blnCH 9
a F
lnip
a 10
lnCZn2 CH
lnip
b 11
lnCH CZn2
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.