Chinese Journal of Chemical Engineering, 20(1) 130—139 (2012)

Low-temperature Electrodeposition of Aluminium from Lewis Acidic

1-Allyl-3-methylimidazolium Chloroaluminate Ionic Liquids*

ZHENG Yong (郑勇)1,2, ZHANG Suojiang (张锁江)1,**, LÜ Xingmei (吕兴梅)1, WANG Qian
(王倩)1, ZUO Yong (左勇)1 and LIU Lian (刘恋)1,2
1
Beijing Key Laboratory of Ionic Liquids Clean Process, State Key Laboratory of Multiphase Complex Systems,
Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
2
College of Chemistry and Chemical Engineering, Graduate University of Chinese Academy of Sciences, Beijing
100049, China

Abstract Lewis acidic 1-allyl-3-methylimidazolium chloroaluminate ionic liquids were used as promising elec-
trolytes in the low-temperature electrodeposition of aluminium. Systematic studies on deposition process have been
performed by cyclic voltammetry and chronoamperometry. The surface morphology and X-ray diffraction (XRD)
patterns of deposits prepared at different experimental conditions were also investigated. It was shown that the nu-
cleation density and growth rate of crystallites had a great effect on the structure of aluminium deposited. The crys-
tallographic orientation of deposits was mainly influenced by temperature and current density. Smooth, dense and
well adherent aluminium coatings were obtained on copper substrates at 10-25 mA·cm−2 and 313.2-353.2 K. More-
over, the current efficiency of deposition and purity of aluminium have been significantly improved, demonstrating
that the ionic liquids tested have a prospectful potential in electroplating and electrorefining of aluminium.
Keywords ionic liquid, low temperature, electroplating, electrodeposition, deposits

1 INTRODUCTION properties [11, 12]. Nevertheless, the high experimental

temperature always results in hard operation and high
As the most abundant metallic element in the energy consumption. From the practical applications
earth crust, aluminium has been widely used in the point of view, it is still needed to develop novel elec-
preparation of corrosion-resistant coating owing to its trolytes with improved physicochemical features and
excellent physicochemical properties and decorative- mild operating conditions.
ness. The conventional methods for aluminium coat- Labeled as room-temperature molten salts, ionic
ing include mainly thermal spraying, hot dipping, liquids (IL) are composed entirely of organic cations
sputter deposition, vapor deposition and electrodeposi- and organic/inorganic anions [13-15]. Over the past
tion [1-6]. Among these techniques, the electrodeposi- decades, the research on IL has received extensive
tion method has more favorable features, such as low attention and significant progress in a wide range of
energy consumption, high reaction efficiency, mild research fields [16, 17]. Many studies demonstrate that
experimental conditions and easy control of alumin- ILs are promising electrolyte in the electrodeposition
ium deposit structure [7]. However, the conventional of reactive metals [18-20]. The excellent properties of
Hall-Héroult electrolysis process is not applicable to ILs can overcome effectively the drawbacks of tradi-
the electrodeposition of aluminium due to the high tional electrolytes.
operating temperature (above the melting point of alu- Early in 1950s, Hurley and Wier [21] first found
minium). Moreover, since the highly negative standard that aluminium could be electrodeposited from the IL
potential of Al/Al(III) couple vs. normal hydrogen consisting of N-ethylpyridinium chloride and AlCl3 at
electrode (NHE), aluminium cannot be electrodeposited low temperature. From then on, extensive and system-
from aqueous solutions. Consequently, it is necessary atical research on the electrodeposition of aluminium
to find more appropriate and efficient electrolytes. and aluminium alloy in ILs has been reported in the
In the past century, some organic aprotic solvents literature [22-28]. It shows that improved quality of
were first developed for the electrodeposition of alu- aluminium deposits and current efficiency can be ex-
minium and high-quality aluminium coatings have been pected due to the high conductivities and broad elec-
obtained [8-10]. However, these systems suffer from a trochemical windows of ILs. The most frequently
lot of inherent disadvantages: low electrical conductivi- studied systems are the chloroaluminate ILs generated
ties, narrow electrochemical window, low dissolving by the combination of organic chloride salts and AlCl3.
capability of aluminium salts, high volatility and flam- Aluminium can be deposited from Lewis acidic
mability, which restrict the application of this technique. chloroaluminate ILs in which the molar percentage of
By contrast, the inorganic electrolytes used show AlCl3 is higher than 50%. Among the Al-containing
higher chemical stability and better electrochemical species in these ILs, only [Al2Cl7]− anion is reducible

Received 2011-11-18, accepted 2011-12-12.

* Supported by the National Basic Research Program of China (2009CB219901), the National Key Technology Research and Devel-
opment Program of the Ministry of Science and Technology of China (2012BAF03B01), the National Natural Science Foundation
of China (20906096, 20873152) and the Open-end Fund of State Key Laboratory of Multiphase Complex Systems (MPCS-2011-D-06).
** To whom correspondence should be addressed. E-mail: [email protected]
 Chin. J. Chem. Eng., Vol. 20, No. 1, February 2012 131

and responsible for the deposition. In recent years, an amber liquid at room temperature. Melting point:
many authors [29-31] reported that the structure of 290 K. Yield: 96.3%.
aluminium deposits was greatly influenced by the sur- 1-Butyl-3-methylimidazolium chloride ([Bmim]Cl)
face interaction in the interfacial solvation layer. The It was prepared according to Huddleston et al.’s work
cation type of IL had a vital effect on the interaction [36]. The final product was obtained as a white wax-like
strength of the interfacial layer. In recent years, some solid at room temperature. Melting point: 338 K. Yield:
bis(trifluoromethylsulfonyl)imide ([NTf2]−) ILs were 87.4%.
found to be capable of dissolving AlCl3 and nanocrys- Lewis acidic [Amim]Cl/AlCl3 and [Bmim]Cl/
talline aluminium could be electrodeposited from these AlCl3 ILs 1︰1.5 [Amim]Cl/AlCl3, 1︰1.8 [Amim]Cl/
solutions [32-34]. Nevertheless, these electrolytes are AlCl3, 1︰2.0 [Amim]Cl/AlCl3 and 1︰2.0 [Bmim]Cl/
inferior to the chloroaluminate ones in many key prop- AlCl3 were prepared by mixing precise molar quanti-
erties, such as conductivity, viscosity and liquid range ties of [Amim]Cl or [Bmim]Cl with anhydrous AlCl3
when they contain the same molar concentration of under dry argon atmosphere at room temperature. The
AlCl3. Moreover, the limited dissolving power of resulting liquids were filtered through G4 glass frit
AlCl3 and high costs of [NTf2]− ILs hinder their ad- and purified by pre-electrolysis before use. The final
vancement to an industrialization process. Consider- products were obtained as pale yellow liquids.
ing the properties and costs, chloroaluminate ILs have [Bmim][NTf2] (1-butyl-3-methylimidazolium
wide application potential and are worth of further bis(trifluoromethylsulfonyl)imide) The IL was
investigation. prepared and purified as a yellow liquid via an early
In this work, Lewis acidic 1-allyl-3-methylimi- method [37]. Yield: 95.5%.
dazolium chloroaluminate ILs ([Amim]Cl/AlCl3) were All ILs prepared have been characterized by nu-
first synthesized and used as electrolyte in the clear magnetic resonance (NMR). The peaks and cor-
low-temperature electrodeposition of aluminium. The responding chemical shifts obtained confirmed the
properties of [Amim]Cl/AlCl3 ILs, especially electri- structures of these ILs, and no impurity peaks were
cal conductivities have been discussed. Based on elec- found in the NMR spectra.
trochemical measurements, the electrodeposition
process of aluminium from [Amim]Cl/AlCl3 was 2.3 The measurement of physicochemical properties
studied in detail. The effects of deposition parameters,
including temperature, current density and molar ratio
of [Amim]Cl/AlCl3, on the surface morphology, X-ray The NMR experiments of ILs were performed on
diffraction (XRD) pattern and purity of deposits were a NMR spectrometer (av-400 MHz, Bruker, Switzer-
also investigated. These results were analyzed from land) at 298.2 K. In the measurement of NMR for
the perspective of microcrystalline nucleation and Lewis acidic [Amim]Cl/AlCl3 and [Bmim]Cl/AlCl3
growth. According to above studies, the optimum ex- ILs, acetone-D6 was used as an external standard to
perimental conditions for aluminium electrodeposition suppress the interference from other solvents. The
were finally determined. surface morphology and compositional analysis of
aluminium deposits were examined with emission
scanning electron microscope (SEM) (JSM-6700F,
2 EXPERIMENTAL JEOL Ltd., Japan) and energy dispersive analysis
2.1 Chemicals X-ray (EDAX) (XL30 S-FEG, FEI Co., USA) respec-
tively. And the X-ray diffraction (XRD) patterns of
aluminium deposits were collected on a X-ray dif-
All the chemicals used in this work were fractometer (X’Pert Pro MPD, PANalytical Co., Neth-
purchased commercially with analytic grade from erlands) with Cu Kα radiation (λ = 0.15405 nm). A
Alfa Aesar and Sinopharm Chemical Reagent Co. density meter (Anton Paar DMA5000, Anton Paar Co.,
N-methylimidazolium, allyl chloride, acetonitrile, Austria) with a resolution of 1 µg was employed to
1-chlorobutane and acetone were purified by distilla- determine the densities of ILs.
tion. Anhydrous aluminium chloride was used without
further purification. Prior to use, aluminium plate
(99.95%), aluminium wire (99.99%), platinum plate 2.4 Electrochemical experiments
(99.95%) and copper foil (99.95%) were polished with
emery paper, cleaned with acetone, treated with a di- All the electrochemical experiments were carried
lute hydrochloric acid/sulfuric acid mixture, finally out in an argon-filled glove box (Universal, MIK-
rinsed with deionized water and dried in air. ROUNA Co., China) where water and oxygen content
was both kept below 1×10−6. The data of electrical
2.2 Preparation and characterization of ILs conductivities were obtained through a conductivity
meter (DDS-307, Shanghai Precision & Scientific
Instrument Co., China) from 298.2 to 373.2 K. The
1-Allyl-3-methylimidazolium chloride ([Amim]Cl) other electrochemical measurements were performed
This IL was synthesized according to method described using an electrochemical workstation (CHI1140A, CH
in the literature [35]. The final product was obtained as Instrument, USA) controlled by CHI1140A software
132 Chin. J. Chem. Eng., Vol. 20, No. 1, February 2012

in a three-electrode cell. In the determination of cyclic relatively weak cation-anion interaction, high struc-
voltammograms, platinum working electrode and plati- tural symmetry of [Amim]+ cation and high molar
num plate counter electrode were used. A non-aqueous concentration of ions (8.89 mol·L−1, 298.2 K) [38, 39].
Ag+/Ag electrode (CHI112, CH Instrument, USA) Besides, [Amim]Cl and [Amim]Cl/AlCl3 are much
containing the 0.1 mol·L−1 solution of AgNO3 in easier to prepare and purify. The final IL products
[Bmim][NTf2]/acetonitrile (298.2 K) was employed as were obtained with good purity, which paved the way
reference electrode. As for the electrodeposition ex- for low-temperature electrodeposition of aluminium.
periments, the working, counter and reference elec- In the following work, Lewis acidic [Amim]Cl/AlCl3
trodes were copper foil, aluminium plate and alumin- ILs with molar ratio of 1︰2.0, 1︰1.8 and 1︰1.5
ium wire, respectively. And the electrodeposition of were used as electrolytes.
aluminium on copper substrates was conducted by
galvanostatic method. All the ILs were heated in an oil 3.1 Results of cyclic voltammetry
bath and the accuracy of temperature was ±0.5 K
(RET basic, IKA, Germany). After electrodeposition,
all the deposits were washed by acetonitrile, deionized To probe into the eletrodeposition behavior of
water and finally dried in air. aluminium, cyclic voltammetry has been used in this
work. Fig. 2 shows the cyclic voltammograms of
Lewis acidic [Amim]Cl/AlCl3 ILs recorded on a Pt
2.5 Calculation of current efficiency electrode at 303.2 K. The potential range was con-
trolled between −2.0 and 0.2 V to avoid the interfer-
The current efficiency (CE) in electrodeposition ence from the oxidation of [AlCl4]− anions and reduc-
was calculated by tion of [Amim]+ cations. It can be seen that a pair of
3 × 96485 × m peaks is obtained between −0.1 and −2.0 V in each
CE (%) = × 100 (1) sample. The reduction peaks at −2.0 V on the negative
27 × I × t scan are ascribed to the bulk electrodeposition of alu-
where the yield of aluminium (m) was determined minium, while the oxidation peaks around −0.4 V on
from the mass difference of cathode before and after the reverse scan reflect the stripping process of depos-
deposition. ited aluminium:
4[Al2 Cl7 ]− + 3e− ⎯⎯
→ Al + 7[AlCl4 ]− (2)
3 RESULTS AND DISCUSSION
7[AlCl4 ]− + Al ⎯⎯
→ 4[Al2 Cl7 ]− + 3e− (3)
Compared with the conventional ILs applied in In these ILs, the reduction of Al(III) begins to
the low-temperature electrodeposition of aluminium, occur around −1.2 V, which is much more positive
[Amim]Cl/AlCl3 and [Amim]Cl have more attractive than the standard potential of Al/Al(III) couple in
properties. As Fig. 1 illustrates, the electrical conduc- aqueous solutions (−2.47 V, vs. Ag+/Ag). The differ-
tivity of 1 ︰ 2.0 [Amim]Cl/AlCl3 is significantly ence in deposition potential of aluminium is probably
higher than that determined in the well-known 1︰2.0 attributed to the different coordination pattern of
[Bmim]Cl/AlCl3 [22]. It indicates that lower cell volt- Al(III) in [Amim]Cl/AlCl3 and aqueous solutions. As
age, higher current efficiency and higher deposition Fig. 2 shows, it can also be found that the reduction
rate can be expected in [Amim]Cl/AlCl3. Considering potential of Al(III) in ILs decreases in the order 1︰2.0
the relationship between ionic conduction and mo- [Amim]Cl/AlCl3>1 ︰ 1.8 [Amim]Cl/AlCl3>1 ︰ 1.5
lecular features of ILs, the high electrical conductivi-
ties of [Amim]Cl/AlCl3 are probably ascribed to the

Figure 2 Cyclic voltammograms recorded on a Pt elec-

trode in Lewis acidic [Amim]Cl/AlCl3 ILs at 303.2 K (po-
Figure 1 The electrical conductivities of 1︰2.0 [Amim]Cl/ tential scan rate: 0.1 V·s−1)
AlCl3 and 1︰2.0 [Bmim]Cl/AlCl3 from 298.2 to 373.2 K 1︰1.5 [Amin]Cl/AlCl3; 1︰1.8 [Amin]Cl/AlCl3;
■ 1︰2.0 [Amin]Cl/AlCl3; ● 1︰2.0 [Bmin]Cl/AlCl3
1︰2.0 [Amin] Cl/AlCl3
 Chin. J. Chem. Eng., Vol. 20, No. 1, February 2012 133

[Amim]Cl/AlCl3. According to the values of molar It can be inferred that the electrodeposition of alu-
ratio and density, the molar concentration of [Al2Cl7]− minium from 1︰2.0 [Amim]Cl/AlCl3 is mainly in-
in above systems follows the same order. The predomi- fluenced by mass diffusion and kinetic limitations,
nant presence of anion can be expressed as [Al2Cl7]− such as electron transfer or surface chemical reaction
in 1 ︰ 2.0 [Amim]Cl/AlCl3 and 1 ︰ 2.0 [Bmim]Cl/ steps [23]. Similar conclusion has also been drawn
AlCl3 based on the analysis of 27Al NMR results (see from other Lewis acidic [Amim]Cl/AlCl3 ILs.
Table 1) [29]. Therefore, it is proper to state that alu-
minium is more prone to be electrodeposited from 3.2 Nucleation/growth process for electrodeposi-
Lewis acidic [Amim]Cl/AlCl3 ILs with higher molar tion of aluminium
concentration of [Al2Cl7]− anions under the same con-
ditions.
Chronoamperometric experiments have been
conducted to investigate the nucleation/growth proc-
Table 1 27Al NMR chemical shifts of 1︰2.0 ess of aluminium, which is critical to the study of
[Amim]Cl/AlCl3 and 1︰2.0 [Bmim]Cl/AlCl3 electrocrystallization mechanism and surface mor-
27
Al NMR chemical shift δ/ppm phology of aluminium deposits on copper substrates.
T/K For each experiment, the potential of working elec-
1︰2.0 [Amim]Cl/AlCl3 1︰2.0 [Bmim]Cl/AlCl3 trode was stepped from an initial value without reduc-
298.2 103.960 106.626 tion of Al(III) taking place to sufficiently negative
potentials to initiate the nucleation/growth process. A
series of typical current-time transients derived from
Additionally, cyclic voltammograms of [Amim]Cl/ different step potentials for the electrodeposition of
AlCl3 ILs at different scan rates have been determined. aluminium from Lewis acidic [Amim]Cl/AlCl3 ILs at
The cathodic limit was set to −2.1 V so that the current 313.2 K are shown in Figs. 4 and 5. Apparently, all the
density (ipc) of bulk deposition peak could be achieved. transients exhibit typical shape for a nucleation proc-
The experimental results for 1︰2.0 [Amim]Cl/AlCl3 ess. Owing to the charging of electrode double layer, a
are presented in Fig. 3. It is evident that both ipc and sharp decay of current can be observed after the ap-
the corresponding deposition peak potential ( ϕ pc ) of plication of step potential, especially at higher poten-
aluminium shift more negative when the scan rate (v) tials. The following increase in current is attributed to
increases. As shown in the inset of Fig. 3, the plots of the nucleation and growth of aluminium nuclei on
ipc against the square root of scan rate (v1/2) display copper electrode. The rising current finally reaches a
good linearity. However, the straight line obtained by maximum (im) at time (tm), when the discrete diffusion
plotting ipc vs. v1/2 does not pass through the origin as zones of growing crystallites start to overlap [22]. Af-
expected for a simple linear diffusion controlled process. ter that, the current transients decay as the deposited

Figure 3 Cyclic voltammograms recorded on a Pt electrode in 1︰2.0 [Amim]Cl/AlCl3 at 303.2 K

potential scan rate/V·s−1: 1—0.02; 2—0.04; 3—0.06; 4—0.08; 5—0.10; 6—0.12
134 Chin. J. Chem. Eng., Vol. 20, No. 1, February 2012

( i / im )2 = 1.2254 ( t / tm )−1 {1 − exp ⎡⎣ −2.3367 ( t / tm )2 ⎤⎦}

2

(5)
To identify the nucleation model, a common
method is applied by the comparison between dimen-
sionless experimental current-time experiments and
dimensionless theoretical transients for each nuclea-
tion mechanism. Before an effective comparison can
be made, the experimental time has been corrected for
the potential-dependent induction time (t0), by refining
the time axis as t ′ = t − t0 and tm′ = tm − t0 . Estimation
Figure 4 Current-time transients resulting from potential
step experiments on Cu electrodes in 1︰2.0 [Amim]Cl/AlCl3 of t0 can be made according to the method described
at 313.2 K in [42]. The dimensionless plots of (i / im )2 vs. (t ′ / tm′ ) 2 ,
deposition potential/V: 1—−0.25; 2—−0.20; 3—−0.15; 4—
−0.10; 5—−0.05 along with theoretical curves obtained from Eqs. (4)
and (5) are presented in Fig. 6. As can be seen, the
electrodeposition of aluminium on copper substrates
fits well to the theoretical model for three-dimensional
instantaneous nucleation with diffusion-controlled
growth.

Figure 5 Current-time transients resulting from potential

step experiments on Cu electrodes in 1︰2.0, 1︰1.8, 1︰1.5
[Amim]Cl/AlCl3 ILs at −0.2 V and 313.2 K

layer becomes thicker. The time required to reach im is Figure 6 Comparison of the dimensionless experimental
shorten when the applied potential is more negative in current-time transients, derived from the results in Fig. 4,
the same IL (see Fig. 4). Meanwhile, Fig. 5 indicates with the theoretical curves for instantaneous nucleation and
progressive nucleation
that im increases in the order 1 ︰ 1.5 [Amim]Cl/ instantaneous; progressive; ● −0.15 V; ▽ −0.20 V;
AlCl3<1 ︰ 1.8 [Amim]Cl/AlCl3<1 ︰ 2.0 [Amim]Cl/ ◆ −0.25 V
AlCl3, while tm changes in an opposite trend. These
results suggest that the nucleation density and rate of
aluminium are enhanced as the molar concentration of 3.3 Surface morphology of aluminium deposits
Al(III) increases in Lewis acidic [Amim]Cl/AlCl3 ILs.
The bulk electrodeposition of aluminium on for- It is necessary to explore optimum experimental
eign substrates often involves a three-dimensional conditions of aluminium deposition on copper substrates
nucleation/growth process. Some classic models have for industrial application. Consequently, the effects of
been proposed to describe this process, typically as main experimental parameters, including temperature
hemispherical diffusion-controlled growth of the nuclei (313.2-373.2 K), current density (5-25 mA·cm−2) and
[40]. This model has two limiting cases: instantaneous molar ratio of [Amim]Cl to AlCl3 [(1︰1.5)- (1︰2.0)]
nucleation and progressive nucleation. In the first lim- on the surface morphology of aluminium deposits and
iting case, all the nuclei are instantaneously formed at current efficiency have been investigated. The deposi-
the beginning of chronoamperometric experiments. tion time and stirring speed were kept as 30 min and
The second case refers to a situation where the nuclei 300 r·min−1, respectively.
are generated gradually as the deposition experiment In this work, it is found that temperature has a
proceeds. They are expressed respectively by [41] significant impact on the surface morphology of alu-
minium coatings. Bright, smooth and dense deposits
( i / im )2 = 1.9542 ( t / tm )−1 {1 − exp ⎡⎣ −1.2564 ( t / tm )⎤⎦}
2
were obtained in the temperature range from 313.2 to
353.2 K. However, the deposits turned dark and poorly
(4) adherent at the temperature higher than 353.2 K,
 Chin. J. Chem. Eng., Vol. 20, No. 1, February 2012 135

particularly at 373.2 K. For illustration, the SEM nuclei were generated so that the deposits displayed
micrographs of aluminium deposits prepared from finer microstructures. After the nucleation density
1︰2.0 [Amim]Cl/AlCl3 under different temperatures reached a maximum value, the crystallites experienced
are shown in Fig. 7. When the temperature rises, the a rapid overlapping growth at 25 mA·cm−2, which
average grain size of crystallites increases from 1 to eventually resulted in larger grain size and rougher
10 µm approximately. The deposits produced at 313.2, deposits.
333.2 and 353.2 K all display dense and homogeneous As is well-known, the content of AlCl3 in chloro-
microstructures with spherical particles. By contrast, a aluminate ILs is another important parameter in elec-
relatively rough and incompact surface with large trodeposition of aluminium. Herein, experimental re-
clusters of platy-shaped crystals is observed on the sults reveal that the deposits increase in grain size and
sample obtained at 373.2 K. The difference in micro- become less compact when the molar ratio of
structures of aluminium deposits probably results [Amim]Cl to AlCl3 [(1︰1.5)- (1︰2.0)] rises under
from the variation of electrical conductivities and dif- the same conditions. For example, the particle size of
fusion rate of ions in IL at different temperatures. A resulting deposits in the studied ILs follows the order
higher temperature followed by nonuniform distribu- 1 ︰ 1.5 [Amim]Cl/AlCl3>1 ︰ 1.8 [Amim]Cl/AlCl3>
tion of current density and high deposition rate is 1︰2.0 [Amim]Cl/AlCl3 at 20 mA·cm−2 and 313.2 K.
prone to promote the dendritic growth, which often This trend of variation of surface morphology can be
leads to rough coatings. seen clearly from the SEM micrographs of aluminium
Searching for appropriate current density is key deposits shown in Figs. 9 and 7 (a). Based on the dis-
to the electrodeposition of aluminium. Figs. 8 and 7 (a) cussion above, it is proposed that the molar concentra-
show the SEM images of deposits prepared from tion of reducible [Al2Cl7]− anions and corresponding
1︰2.0 [Amim]Cl/AlCl3 with different current densi- nucleation density of aluminium on copper surface
ties at 313.2 K. It is apparent that the grain size of decrease as the molar content of AlCl3 increases in
aluminium crystallites decreases from about 3 to 1 µm [Amim]Cl/AlCl3 ILs. Consequently, uniform, compact
as current density increases in the range of 5-20 and dense aluminium coatings have been obtained
mA·cm−2. Nevertheless, the deposited crystals grow to from 1︰2.0 [Amim]Cl/AlCl3 more easily than 1︰1.5
a larger size when the current density increases to 25 and 1︰1.8 [Amim]Cl/AlCl3.
mA·cm−2. Among these samples, the deposits obtained In summary, the aluminium deposits prepared
at 15 and 20 mA·cm−2 have the most smooth and from Lewis acidic [Amim]Cl/AlCl3 ILs have finer
compact structures. It can be inferred from above microstructures than those produced in many conven-
phenomena that the nucleation density on copper elec- tional chloroaluminate-based ILs at the studied ex-
trode surface increased with current density rising perimental conditions [22-24]. Moreover, most of the
between 5 and 20 mA·cm−2. As a result, more aluminium deposited films adhered well to the substrates without

(a) 313.2 K (b) 333.2 K

(c) 353.2 K (d) 373.2 K

Figure 7 SEM micrographs of aluminium electrodeposits prepared from 1︰2.0 [Amim]Cl/AlCl3 at 20 mA·cm−2 and dif-
ferent deposition temperatures (The inset images show the higher magnification micrographs of deposits)
136 Chin. J. Chem. Eng., Vol. 20, No. 1, February 2012

(a) 5 mA·cm−2 (b) 10 mA·cm−2

(c) 15 mA·cm−2 (d) 25 mA·cm−2

Figure 8 SEM micrographs of aluminium electrodeposits prepared from 1︰2.0 [Amim]Cl/AlCl3 at 313.2 K and different
deposition current densities (The inset images show the higher magnification micrographs of deposits)

(a) 1︰1.5 [Amin]Cl/AlCl3 IL (b) 1︰1.8 [Amin]Cl/AlCl3 IL

Figure 9 SEM micrographs of aluminium electrodeposits obtained at 313.2 K and 20 mA·cm−2 from different
[Amim]Cl/AlCl3 ILs (The inset images show the higher magnification micrographs of deposits)

obvious crevices in between (see Fig. 10). The alu-

minium coatings with optimum surface morphology
were obtained from 1︰2.0 [Amim]Cl/AlCl3 at 313.2-
353.2 K and 10-20 mA·cm−2. It can be concluded that
the morphology of deposits changes as a function of
experimental parameters (temperature, current density
and molar ratio of [Amim]Cl/AlCl3), which have a
significant effect on the nucleation and crystal growth
process of aluminium. Therefore, appropriate nuclea-
tion density and growth rate of crystallites are critical
to the generation of favorable coatings. Figure 10 SEM micrograph of the cross section for an
about 20 µm aluminium coating (bright region) obtained
3.4 Current efficiency in the electrodeposition of from 1︰2.0 [Amim]Cl/AlCl3 at 20 mA·cm−2 and 313.2 K
on Cu substrate (underneath the bright region)
aluminium

In this work, more than 95% current efficiency optimal efficiency was obtained as 99.6% from 1︰2.0
has been achieved for all the aluminium deposits. The [Amim]Cl/AlCl3 at 313.2 K and 20 mA·cm−2, while
 Chin. J. Chem. Eng., Vol. 20, No. 1, February 2012 137

the minimum value was 95.3% for the deposition

conducted in 1︰1.5 [Amim]Cl/AlCl3 at 373.2 K and
5 mA·cm−2. Generally speaking, the current efficiency
decreased to the range of 95.3%-99.6% when the tem-
perature increased from 313.2 to 373.2 K. With the
increase of current density, the current efficiency first
increased to a maximum at 10-20 mA·cm−2 and then
slightly decreased in each IL. Moreover, the current
efficiency were raised as the molar ratio of
[Amim]Cl/AlCl3 changed from 1︰1.5 to 1︰2.0.
The current efficiency in electrodeposition of
aluminium reflects the yield of deposits under differ-
ent experimental conditions. To the best of our knowl- Figure 12 XRD pattern of the aluminium deposits ob-
edge, the yield of aluminium is mainly affected by tained from 1︰2.0 [Amim]Cl/AlCl3 at 313.2 K
cathodic side reactions and crystal growth process. deposition current density/mA·cm−2: 1—25; 2—20; 3—10
The cathodic side reactions, including the reduction of
[Amim]+ cations and oxidation of deposited alumin-
ium are more likely to take place as temperature and
current density increases. Meanwhile, part of the
rough and poorly adherent coatings which has been
derived from nonuniform crystal growth is prone to
fall off the substrates. The lower temperature and cur-
rent density followed by favorable surface morphol-
ogy of deposits often result in higher yield of alumin-
ium and current efficiency.

3.5 Crystal structures and composition analysis

of aluminium deposits
Figure 13 XRD pattern of the aluminium deposits obtained
at 313.2 K and 20 mA·cm−2 from 1︰2.0, 1︰1.8, 1︰1.5
The relationship between crystal structures and [Amim]Cl/AlCl3 ILs
surface morphology of aluminium deposits was fur-
ther explored by XRD. In order to facilitate the fol-
lowing analysis, the peaks resulting from copper sub- and high current density usually increases the peak
strates have been corrected and removed from the intensity of (200) plane, thus promoting the crystal
spectra. As expected, the XRD patterns of all the sam- growth in this direction on copper substrates. Fur-
ples match well with the standard values for alumin- thermore, the changes in crystal patterns can also re-
ium in JCPDS cards. It is found that the crystallo- flect the surface morphology of deposits. According to
graphic orientations of deposits change along with the measurement of SEM micrographs, the bright,
experimental conditions (see Figs. 11, 12 and 13). smooth and well adherent deposits almost exhibit a
These results indicate that the influence of experimental preferred crystallographic orientation of (200).
parameters on the crystal growth of aluminium depos- The compositions of aluminium deposits pre-
its follows the order temperature>current density> pared at different conditions have been characterized
molar ratio of [Amim]Cl to AlCl3. The low temperature by EDAX. The results show that mass content of alu-
minium in these samples is more than 98%. As Fig. 14
illustrates, a strong peak of aluminium and an ex-
tremely weak peak of oxygen can be seen from the
EDAX spectrum of the deposits shown in Fig. 7 (a).
The detected oxygen may probably result from the
oxidation of aluminium in the atmosphere, and the
mass content of aluminium is as high as 99.6%. It is
demonstrated that the high-purity deposits generally
show a smooth and compact surface, which has effec-
tively prevented the further oxidation of aluminium.

4 CONCLUSIONS

Figure 11 XRD pattern of the aluminium deposits ob- A systematic research on the low-temperature
tained from 1︰2.0 [Amim]Cl/AlCl3 at 20 mA·cm−2 electrodeposition of aluminium from Lewis acidic
deposition temperature/K: 1—313.2; 2—353.2; 3—373.2
[Amim]Cl/AlCl3 ILs is presented. These electrolytes
138 Chin. J. Chem. Eng., Vol. 20, No. 1, February 2012

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