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Journal of Electroanalytical Chemistry 599 (2007) 288294
www.elsevier.com/locate/jelechem
Abstract
Here we describe the electrolytic deposition of Zn, Sn and Zn/Sn alloys from a solution of the metal chloride salts separately in urea
and ethylene glycol/choline chloride based ionic liquids. We show that the deposition kinetics and thermodynamics dier from the aqueous processes and that qualitatively dierent phases, compositions and morphologies are obtained for the metal coatings in the dierent
ionic liquid systems. We have quantied the electrochemical stripping responses using cyclic voltammetry together with compositional
analysis using SEM/EDAX and X-ray diraction. The dierences in electrochemical responses are rationalised in terms of the speciation
of both Zn and Sn chlorides in the ionic liquids that have been identied using FAB mass spectrometry. Also we demonstrate that composite metal coatings, e.g. containing Al2O3 particles, can be obtained from these liquid systems by virtue of the stable liquid suspensions.
This novel feature of these liquids is a function of their relatively high viscosity.
2006 Elsevier B.V. All rights reserved.
Keywords: Electrodeposition; Zinc; Alloy; Ionic liquid; Eutectic
1. Introduction
Ionic liquids are classed as salts that are liquid at below
100 C [1]. They have been extensively studied primarily for
synthetic and electrochemical applications [2]. The majority of investigations have concentrated on imidazolium
cations with discrete anions such as BF
and
4 ; PF6
(F3CSO2)2N . These ionic liquids have large potential windows and exhibit relatively high conductivities and low viscosities. Two recent reviews by Endres [3,4] cover all
aspects of electrodeposition from these liquids, Compton
and coworkers [5] have reviewed fundamental aspects of
electrochemistry in ionic liquids and a book by Ohno [6]
describes other electrochemical aspects. While ionic liquids
with discrete anions show signicant potential for the electrodeposition of electronegative metals such as aluminium
*
0022-0728/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jelechem.2006.04.024
have been carried out using Type 3 based liquids, which use
hydrogen bond donors as the complexing agents [11,12].
The use of simple amides, acids and alcohols as complexing
agents makes the liquids very versatile and to distinguish
them from other ionic liquids the term deep eutectic solvents (DES) has been coined. DESs have been used for
electropolishing [13], polymer synthesis [14] and metal
oxide processing [15]. Most of our previous studies have
concentrated on choline chloride as the quaternary ammonium salt as it is non-toxic, biodegradable and is already
used as a common component to numerous household
and industrial products. Hence it can be applied economically to large-scale processes. In the current work we show
how DESs formed with choline chloride and either urea or
ethylene glycol can be used for the electrodeposition of
zinc, tin, and zinctin alloys. We also show that the choice
of hydrogen bond donor aects the type of alloy and the
electrochemistry of the components in solution.
Zinctin alloys have been deposited from a variety of
aqueous baths including sulphate [16], gluconate [17] and
pyrophosphate baths [18]. The alloys are found to have
better corrosion resistance than pure zinc, particularly in
high humidity conditions and are also reported to be superior to cadmium deposits in marine environments.
2. Experimental
289
290
0.450x10 -4
0.075x10-4
0.350x10 -4
0.050x10-4
0.250x10 -4
0.025x10-4
0.150x10 -4
0.050x10
i/A
i/A
-4
0
-0.025x10
-4
-0.050x10 -4
-0.050x10 -4
-0.150x10 -4
-1.500 -1.000 -0.500
291
-0.075x10 -4
0
0.500
1.000
1.500
E/V
Fig. 2. Voltammograms (scan rate 20 mV s1) for a Pt microdisc electrode
(0.5 mm diameter) immersed in a 1:2 ChCl:EG DES containing 0.05 M
SnCl2 and 0.5 M ZnCl2.
-0.100x10 -4
-1.250
-0.750
-0.250
0.250
E/V
0.750
1.250
292
with 3 wt% SnCl2 [10]. The issue associated with the use of
these Type 1 zinc eutectics is the low conductivity
(36 lS cm1 at 40 C) whereas the two Type 3 eutectic mixtures used in this work have much higher conductivities
(ChCl:2urea = 1.8 mS cm1 and ChCl:2EG = 11 mS cm1
both at 40 C) [11,13].
Alternatively the deposition of tin, reported here, produced more dendritic clusters. The dendrites are built up
of simple cubic crystals as can be seen from Fig. 5. The
deposition of whisker-like deposits, which is common for
the deposition of tin from aqueous solutions, was not
observed in either ionic liquid when the current density
applied was 10 mA cm2.
Electrolysis of the mixed SnCl2/ZnCl2 solutions produced deposits with dierent morphologies depending on
the hydrogen bond donor used. With urea based liquids
the deposit was made up of cubic crystallites, which look
similar to those found in Fig. 4 (not shown). Energy Dispersive Analysis by X-rays (EDAX) showed that they are
predominantly zinc (ca. 89%) with the remainder being
1600
Intensity / cps
EG
Urea
1200
800
400
0
20
40
60
2 / degrees
80
100
60
50
Wt %
40
30
20
10
0
80
100
120
-2
Current density / mA cm
140
293
Fig. 11. Scanning electron micrograph showing dierent regions of a hull cell panel coated with an alloy deposit grown from the solution of 0.5 M
Zn:0.05 M Sn in 1ChCl:2urea containing 3 wt% Al2O3 (shown in Fig. 3) at various current densities for 30 min. A = 85 mA cm2; B = 97; C = 110;
D = 148.
294