Electrochimica Acta 115 (2014) 499–503

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Electrodeposition of zinc-cobalt alloys from choline chloride–urea

ionic liquid
Qingwei Chu a,b , Jun Liang a,∗ , Jingcheng Hao a,1
a
State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, PR China
b
Graduate University of Chinese Academy of Sciences, Beijing 100039, PR China

a r t i c l e i n f o a b s t r a c t

Article history: The electrodeposition behavior of zinc-cobalt (Zn-Co) alloy was investigated in choline chloride/urea (1:2
Received 24 August 2013 molar ratio) deep eutectic solvent containing 0.11 M ZnCl2 and 0.01 M CoCl2 . Cyclic voltammetry revealed
Received in revised form 30 October 2013 that Co reduced preferably with respect to Zn and anomalous codeposition of Zn-Co did not occur in this
Accepted 30 October 2013
solvent. Chronoamperometric investigations combined with field emission scanning electron microscopy
Available online 11 November 2013
(FE-SEM) indicated that the electrodeposition of Zn-Co alloys followed the mechanism of instantaneous
nucleation. Energy dispersive spectroscopy (EDS), grazing incidence X-ray diffraction (GI-XRD) and SEM
Keywords:
results showed that the deposition potential influenced the compositions, phase structure and surface
Electrodeposition
Ionic liquid morphology of the Zn-Co alloys.
Zn-Co alloy © 2013 Elsevier Ltd. All rights reserved.
Codeposition mechanism.

1. Introduction the problems associated with hydroxide generation and hydrogen

In recent years, great interest has been shown in the possi-
bilities offered by the electrodeposition of alloys, because they
can improve the mechanical and chemical properties of metals
[1]. Electrodeposition of Zn-Co alloy coatings has drawn a lot of
attention owing to their better anti-corrosion properties than
pure Zn deposits [2–5]. Furthermore, other properties such as
ductility, hardness and weldability of zinc are also improved. The
electrodeposition of Zn-Co alloys has been widely practiced in
aqueous plating systems [3–8]. As characterized by Brenner, the
co-deposition behavior of Zn-Co in aqueous solution is anomalous
process, in which less noble Zn deposits preferably with respect
to the more noble Co, leading to the Zn/Co ratio in the deposit is
higher than that in the solution [9]. This anomalous process can
be explained by the so-called ‘hydroxide suppression mechanism’
[10–12], i.e., a zinc hydroxide layer is formed on the electrode
surface, which can suppress cobalt reduction [13]. In addition, it
would be unavoidable to evolve hydrogen during the electrode-
position process in an aqueous solution electrolyte. Consequently,
the quality of the deposited layers is generally unsatisfactory [14].
Non-aqueous solvents, for example, ionic liquids, provide an ideal
alternative for the electrodeposition of Zn-Co alloys in a practical
sense. Owing to the absence of water in the non-aqueous baths,
∗ Corresponding author. Tel.: +86 931 4968381; fax: +86 931 4968163.
E-mail addresses: jliang@licp.cas.cn (J. Liang), jhao@sdu.edu.cn (J. Hao).
1
Tel.: +86 531 88366074; fax: +86 531 88564464.
evolution that often occur in aqueous baths can in principle be
eliminated during the electrodeposition process [15].
Ionic liquids (ILs) are ionic materials that have a melting point
below 100◦ C. Ionic liquid is a promising electrolyte for electrodepo-
sition of various metals, since it possesses a number of interesting
and advantageous characteristics, such as wide electrochemical
windows, wide working temperature range, high electrical conduc-
tivity, and good thermal and chemical stability [16,17]. Ionic liquids
have generated significant interest in electrochemical studies due
to their remarkable properties.
The electrodeposition of zinc-cobalt alloys has been investi-
gated in a lewis acidic zinc chloride-1-ethyl-3-methylimidazolium
chloride ionic liquids containing cobalt (II) [18]. It was found that
the reduction of cobalt in this ionic liquid occurred at a poten-
tial more positive than the reduction of zinc and the deposits can
be varied from Co-rich to Zn-rich by increasing deposition over-
potential. However, the hygroscopic nature of this ionic liquid
has delayed progress in their practical application [19,20]. Abbott
and co-workers introduced a relatively new class of ionic liquid,
deep eutectic solvent (DES), which is based on eutectic mixtures
of choline chloride (ChCl) with a hydrogen bond donor species
[21]. Eutectic solvent is a powerful and potential media for the
electrodeposition of metals. They are stable in air and water, and
thus electrodeposition is possible in a room atmosphere at ambi-
ent temperatures [22]. Wang et al. [14] prepared Zn-Co alloy from
ChCl-urea ionic liquid and investigated the cathode potential, con-
centration ratio of Zn2+ /Co2+ , temperature and deposition time
on the deposition behavior. However, the nucleation and growth

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http://dx.doi.org/10.1016/j.electacta.2013.10.204
500 Q. Chu et al. / Electrochimica Acta 115 (2014) 499–503

mechanism of Zn-Co alloy from ChCl-Urea ionic liquid has not been
systematically investigated and well understood.
In the present study, we explored the electrochemical depo-
sition of Zn-Co alloys from a 1:2 ChCl–urea eutectic-based ionic
liquid. Cyclic voltammetry and chronoamperometry were used
to investigate the electrochemical mechanism and the nucle-
ation/growth process of Zn-Co alloys from the ionic liquid. Zn-Co
alloys electrodeposited by potentiostatic methods on Cu substrates
were characterized. The effect of deposition potential on the com-
position, phase structure and morphology of the deposits was
examined.

2. Experimental

Choline chloride (ChCl) [HOC2 H4 N(CH3 )3 Cl, AR, ≥99.0%], urea

[CON2 H4 , AR, ≥99.0%] and zinc chloride [ZnCl2 , AR, ≥98.0%] were
used as received. Cobalt chloride [CoCl2 ·6H2 O, AR, ≥99.0%] was
dried at 80◦ C for 24 h under vacuum. The ChCl-based ionic liquid
was prepared by mixing the ChCl and urea with a molar ratio of 1:2
in a beaker at 80◦ C until a homogeneous, colorless liquid formed.
Then 0.11 M ZnCl2 and 0.01 M CoCl2 was added to the liquid with
gentle stirring to obtain navy-blue solutions.
Cyclic voltammetry (CV) and chronoamperometry (CA) were
carried out using an Autolab electrochemical workstation. Elec-
trochemical experiments were performed using a three-electrode
cell. A platinum disk (1.0 mm diameter) was assembled as working
electrode, and a zinc plate (10mm × 10 mm) was used as counter
electrode and reference electrode. The working electrode was pol-
ished with 0.3 mm alumina paste, cleaned in an ultrasonic acetone
bath, rinsed with distilled water and dried before each measure-
ment. The cyclic voltammetry experiment was performed at 80◦ C
and scan rates of 50 mV/s.
The deposition of Zn-Co alloy was carried out potentiostatically
on an Autolab electrochemical workstation. The working elec-
trode was a Cu plate with a working surface area of 126 mm2
(7mm × 18 mm). The counter electrode and reference electrode
were Zn plate (100 mm2 , 10mm × 10 mm). All the electrodes were
rinsed with acetone, cleaned with distilled water and then dried in
air before all measurements. The electrodeposition of Zn-Co alloy
was performed using a constant potential mode at 80◦ C for 20 min
under stirring.
A field emission scanning electron microscope (FESEM, JSM-
6701F) and a scanning electron microscopy (SEM, JSM-5600LV)
were employed for the observations of the deposits morphology.
Elemental compositions of the Zn-Co deposits were observed by
energy dispersive spectroscopy (EDS, Kevex). Phase structure of the
deposits was determined by Rigaku D/MAX2400 grazing incidence
X-ray diffraction (GI-XRD, incident angle 2◦ ) using Cu-K␣ radiation
Fig. 1. Cyclic voltammograms for Pt disk electrode in 1ChCl/2urea ionic liquid con-
taining 0.11 M ZnCl2 + 0.01 M CoCl2 at scan rate of 50 mV/s under 80 ◦ C.
in the 2␪=30◦ -60◦ range with a scanning rate of 15◦ /min and a step
of 0.02◦ .
3. Results and discussion
3.1. Voltammetric studies
Typical cyclic voltammograms in 1:2 ChCl–urea ionic liquid con-
taining 0.11 M ZnCl2 and 0.01 M CoCl2 on a Pt electrode at 80 ◦ C are
shown in Fig. 1. There are two reduction peaks on the cathodic
branch of the voltammogram. The small peak at 0.06 V (noted as
“a”) is attributed to the Co2+ to Co reduction process, while the evi-
dent reduction peak at–0.37 V (noted as “b”) can be assigned to the
Zn2+ to Zn reduction process. EDS analysis shows that the deposit
potentiostatically plating at 0.06 V (reduction peak “a”) for 20 min
on Cu plate is composed of 36.1wt% Zn and 63.9wt% Co (Fig. 2a).
Zn-Co codeposition is achieved through the deposition of Zn upon
(deposited) Co at a potential more negative than that of Co deposi-
tion. This necessarily results in Zn content lower than that of Co. The
deposit potentiostatically plating at −0.37 V (reduction peak “b”)
for 20 min on Cu plate is composed of 93.5wt% Zn and 6.50wt% Co
(Fig. 2b). Combined with the result of CV and component analysis,
it can be found that the electrodeposition of Zn-Co in 1:2 ChCl–urea
solution is not an anomalous codeposition, i.e. more noble metal Co
depositing preferentially with respect to the less noble one Zn.
As suggested by Gómez and Vallés [6], the detection of multiple
peaks during the electrochemical oxidation of Zn-Co alloys can be

Fig. 2. EDS spectra of Zn-Co deposits obtained by potentiostatic deposition from 1ChCl/2urea ionic liquid containing 0.11 M ZnCl2 + 0.01 M CoCl2 at 0.06 V (a) and -0.37 V (b).
 Q. Chu et al. / Electrochimica Acta 115 (2014) 499–503 501

Fig. 3. Linear sweep voltammetry for Pt disk electrode in 1ChCl/2urea ionic liquid Fig. 4. Current-time transients resulting from chronoamperometric experiments
containing 0.11 M ZnCl2 (dotted line); 0.01 M CoCl2 (solid line). that were performed at a Pt electrode in 1ChCl/2urea ionic liquid containing 0.11 M
ZnCl2 and 0.01 M CoCl2 at different applied potentials from -0.3 V to -0.5 V at 80 ◦ C.

attributed to the dissolution of the metals in the alloy via different

cobalt contents. Thus, the information regarding the characteristics
of the components of the alloy and the structure of the deposited
phases can be got from the voltammetric response. When the scan
reversed, three oxidation peaks (I, II and III), as shown in Fig. 1, are
observed in the potential range of 0.32 to 0.68 V. The dissolution
peaks for pure Zn and pure Co are at 0.24 V and 0.82 V, respectively
(Fig. 3), and dissolution peaks for Zn–Co deposits are somewhere
in between those two potentials. Based on the results, as well as
on the data reported by other authors for the Zn–Co alloys having
similar characteristics [4,23], the three anodic dissolution peaks
correspond to the dissolution of the constituents of two phases,
i.e, Zn-rich and Co-rich Zn-Co alloy. The anodic peaks (I) and (II)
correspond to the dissolution of zinc from different phases of Zn–Co
alloys. The peak (III) corresponds to the dissolution of Co from their
phases.
Chronoamperometry is widely used to study nucleation
phenomena in aqueous or molten media [24]. Deposition of met-
als/alloys onto a foreign substrate generally involves some type Fig. 5. Comparison of experimental data obtained from chronocurrent transients
with instantaneous and progressive nucleation models in 1ChCl/2urea ionic liquid
of three dimensional nucleation process accompanied with hemi-
containing 0.11 M ZnCl2 and 0.01 M CoCl2 .
spherical growth of the developing nuclei. Three-dimensional
nucleation/growth can be described as either ‘instantaneous’ or
‘progressive’ [19]. Instantaneous nucleation tends to lead to for- and growth of Zn/Co nuclei, until a peak appeared. This rise in cur-
mation of an alloy phase (a solid solution), whereas progressive rent culminates in a broad maximum, im , at the position of which on
nucleation to a phase which has a small amount of one species the time axis, tm , depends upon the magnitude of the potential step.
inserted in the matrix of the other major species [25]. Finally the current converge to the limiting current corresponding
Current transients of chronoamperometric experiments for var- to linear diffusion to a planar electrode as per the Cottrell’s law. The
ious potentials are shown in Fig. 4. The initial regime of each im increases while the tm shortens with an increase in the applied
transient is characterized by a sharp decrease in current which potential. This can be explained by the decrease in the time required
corresponds to the formation of the first nuclei on the electrode. for the diffusion layer to overlap, owing to an increased nucleation
Then the current increases which is attributed to the formation density [19].

Fig. 6. SEM micrographs of the Zn-Co alloy deposited from 1ChCl/2urea ionic liquid containing 0.11 M ZnCl2 and 0.01 M CoCl2 at (a) -0.3 V, (b) -0.40 V and (c) -0.50 V for 10s.
502 Q. Chu et al. / Electrochimica Acta 115 (2014) 499–503
Fig. 7. Composition of the electrodeposited Zn-Co alloys, determined with EDS, as a
function of the deposition potential from 1ChCl/2urea ionic liquid 0.11 M ZnCl2 and
0.01 M CoCl2 at 80 ◦ C.
Scharifker and Hills proposed a convenient method to identify
the nucleation mechanism [26]. The most commonly used models
for describing the current-time transient are progressive and
instantaneous nucleation models. The theoretical transients for
limiting cases of instantaneous (Eq. (1)), in which all the Zn/Co
nuclei are created at the same moment at the beginning of the
Fig. 8. XRD full pattern of the Zn-Co deposits plated at different potentials for 20 min (a) and XRD fitting patterns of Zn-Co deposits plated at -0.3 V (b), -0.4 V (c) and -0.5 V
(d) for 20 min.
electrolysis, and progressive (Eq. (2)) nucleation, that new crystals
are continuously created throughout electrolysis, are represented,
by
(1)(i/im )2 = 1.9542 (t/tm )−1 {1 - exp[− 1.2564(t/tm )]} 2
2 −1 2 2
(2)(i/im ) = 1.2254 (t/tm ) {1 − exp[−2.3367(t/tm ) ]} where
im and tm are the current and the time, as respective peak
coordinates.
Fig. 5 shows the experimental current transients plotted in
current-time coordinates, along with the lines for instantaneous
and progressive nucleation (black and blue lines), described by
Eq. (1) and (2). It is clear that the Zn-Co nucleation follows the
instantaneous three-dimensional nucleation. Combined with the
cyclic voltammetry results, it reveals that the Zn-Co codeposition
produces solid solutions in ChCl-Urea ionic liquid.
The SEM micrographs of the Zn-Co alloy deposited on the Cu
electrode surface at short depositing time are used to further
investigate the nucleation mechanism (Fig. 6). The presence of
growth centers with similar sizes can be observed at different
applied potential, which is consistent with instantaneous three-
dimensional nucleation.
3.2. Characterization of deposits
The composition and microstructure of the Zn-Co alloy elec-
trodeposited onto copper plate from 1:2 ChCl–urea ionic liquid
 Q. Chu et al. / Electrochimica Acta 115 (2014) 499–503
Fig. 9. SEM micrographs of the Zn-Co deposits obtained from 1:2 ChCl-urea ionic liquid containing 0.11 M ZnCl2 and 0.01 M CoCl2 at (a) -0.3 V, (b) -0.4 V and (c) -0.5 V for
20 min.
containing 0.11 M ZnCl2 and 0.01 M CoCl2 using different potentials
for 20 min were characterized.
An abridged summary of the composition of the electrode-
posited Zn-Co alloy, determined with EDS, as a function of the
deposition potential is shown in Fig. 7. It can be seen that the Co
content decreases when the deposition potential becomes more
negative. This is mainly ascribed to that the Zn deposition rate
increases with more negative potential. The composition reference
line (CRL), representing the percentage of Co in the deposits equals
to that in the bath [10], is also shown in Fig. 7. It is obvious that the
Co content in deposits is always above the CRL, which means that
the codeposition of Zn and Co is a normal type in 1:2 ChCl–urea
ionic liquid, consistent with the results of the voltammetric study.
Fig. 8 shows the GI-XRD patterns of Zn-Co alloy electrodeposited
plated onto copper plate at different potential for 20 min. It can be
seen from Fig. 8a that two diffraction peaks, viz., a broad peak at 2␪
in the range between 41 to 44◦ and a peak at 2␪=50◦ , are observed
for all deposits. The peak at 2␪=50◦ is the diffraction peak from
copper substrate. The broad diffraction peak at 2␪ in the range
of 41 to 44◦ can be fitted to a Zn-rich ␩-phase and a cubic Zn-Co
␥-phase by a profile-fitting procedure as shown in Fig. 8b-d. Consid-
ering the fitting results, an increase of the ␩-phase and decrease of
the ␥-phase are observed when the potential becomes more neg-
ative. The increase of the ␩-phase means that the Co content in
the deposit decreases with the potential becoming more negative.
This observation is in good agreement with the aforementioned
EDS analysis.
The surface morphologies of Zn-Co alloys electrodeposited in
the 0.11 M ZnCl2 and 0.01 M CoCl2 plating bath for 20 min at the
potential of −0.3 V, -0.4 V and −0.5 V are shown in Fig. 9. The Zn-Co
deposit obtained from −0.3 V is made up of spherical clusters with
diameter ranging from 1 to 2 ␮m (Fig. 9a). The clusters distribute
independently each other, making the surface of the deposit highly
porous. The grain clusters with size of 2 to 3 ␮m appear on the
coating surface at the potential of −0.40 V (Fig. 9b). With further
increasing the potential to -0.5 V, the diameter of the grain clusters
increases to 3 to 4 ␮m (Fig. 9c). With the potential increasing, the
growth rate increases and thus the diameter of the grain clusters
increases.
Based on the EDS, XRD and SEM results, it is clear that the
composition, phase structure and surface morphology of the Zn-
Co alloys prepared in ChCl-Urea ionic liquid can be controlled by
varying the deposition potential.
4. Conclusions
The electrodeposition behavior of Zn-Co alloys from 1:2
ChCl–urea ionic liquid containing 0.11 M ZnCl2 and 0.01 M CoCl2
was studied. Cyclic voltammogram and chronoamperometry anal-
ysis show that the electrodeposition of Zn-Co alloy is a normal
503
codeposition and the nucleation mechanism of Zn-Co alloy is an
instantaneous process. EDS and XRD studies clearly demonstrate
that the compositions and phase structure of the Zn-Co alloys are
significantly dependent on the deposition potentials. It is found
that the Co content in the deposits and the ␥-phase of Zn–Co alloys
decrease while the Zn content and the ␩-phase increase with the
deposition potential becomes more negative. The morphology of
the Zn-Co deposits is also potential dependent and the diameter
of the grain clusters increases for increasingly negative values of
potential.
Acknowledgments
The financial support from National Natural Science Foundation
of China (Grant No. 51305432) and the “Hundred Talents Program”
of Chinese Academy of Sciences (J. Liang) was gratefully acknowl-
edged.
References
[1] S. Basavanna, Y. Arthoba Naik, J. Appl. Electrochem. 39 (2009) 1975–1982.
[2] C.N. Panagopoulos, D.A. Lagaris, P.C. Vatista, Mater. Chem. Phys. 126 (2011)
398–403.
[3] E. Gómez, X. Alcobe, E. Vallés, J. Electroanal. Chem. 505 (2001) 54–61.
[4] J.B. Bajat, S. Stanković, B.M. Jokić, S.I. Stevanović, Surf. Coat. Tech. 204 (2010)
2745–2753.
[5] J.B. Bajat, V.B. Miskovic-Stankovic, M.D. Maksimovic, D.M. Drazic, S. Zec, Elec-
trochim, Acta 47 (2002) 4101–4112.
[6] E. Gómez, E. Vallés, J. Electroanal. Chem. 397 (1995) 177–184.
[7] M. Mouanga, L. Ricq, P. Berçot, J. Appl. Electrochem. 38 (2007) 231–238.
[8] M. Mouanga, L. Ricq, P. Bercot, Surf. Coat. Tech. 202 (2008) 1645–1651.
[9] A. Brenner, Electrodeposition of Alloys, Principles and Practice, Academic Press,
New York, 1963, pp. 194, Ch. 30.
[10] K. Higashi, H. Fukushima, T. Urakawa, J. Electrochem. Soc. 128 (1981) 2081.
[11] T. Tsuru, S. Kobayashi, T. Akyama, H. Fukushima, S.K. Gogia, R. Kammel, J. Appl.
Electrochem. 27 (1997) 209–214.
[12] Z.F. Lodhi, J.M.C. Mol, W.J. Hamer, H.A. Terryn, J.H.W. De Wit, Electrochim. Acta
52 (2007) 5444–5452.
[13] J.L. Ortiz-Aparicio, Y. Meas, G. Trejo, R. Ortega, T.W. Chapman, E. Chainet, P. Ozil,
Electrochim. Acta 52 (2007) 4742–4751.
[14] X. Wang, H. Li, J. Wang, X. Fu, J. Gu, Mater. Protection 43 (2010) 30–33.
[15] M.Z. An, P.X. Yang, C.N. Su, A. Nishikata, T. Tsuru, Chin. J. Chem. 26 (2008)
1219–1224.
[16] C.N. Su, M.Z. An, P.X. Yang, H.W. Gu, X.H. Guo, Appl. Surf. Sci. 256 (2010)
4888–4893.
[17] C.D. Gu, Y.H. You, Y.L. Yu, S.X. Qu, J.P. Tu, Surf. Coat. Tech. 205 (2011)
4928–4933.
[18] P.Y. Chen, I.W. Sun, Electrochim. Acta 46 (2001) 1169–1177.
[19] H.Y. Yang, X.W. Guo, X.B. Chen, S.H. Wang, G.H. Wu, W.J. Ding, N. Birbilis,
Electrochim. Acta 63 (2012) 131–138.
[20] F. Endres, Chem. Phys. Chem. 3 (2002) 144–154.
[21] A.P. Abbott, D. Boothby, G. Capper, D.L. Davies, R.K. Rasheed, J. Am. Chem. Soc.
126 (2004) 9142–9147.
[22] A. Bakkar, V. Neubert, Electrochem. Commun. 9 (2007) 2428–2435.
[23] G. Trejo, R. Ortega, Y. Meas, E. Chainet, P. Ozil, J. Appl. Electrochem. 33 (2003)
373–379.
[24] K. Serrano, P. Taxil, J. Appl. Electrochem. 29 (1999) 505–510.
[25] Y.P. Lin, J.R. Selman, J. Electrochem. Soc. 140 (1993) 1304–1311.
[26] B. Scharifker, G. Hills, Electrochim. Acta 28 (1983) 879–889.