Journal of The Electrochemical Society, 165 (9) D321-D327 (2018) D321

0013-4651/2018/165(9)/D321/7/$37.00 © The Electrochemical Society

Electrodeposition of Al, Al-Li Alloy, and Li from an Al-Containing

Solvate Ionic Liquid under Ambient Conditions
Baoguo Zhang, 1,2 Zhongning Shi,1,2,z Lingling Shen, 1,2
Aimin Liu,1 Junli Xu,3
and Xianwei Hu1,2
1 School of Metallurgy, Northeastern University, Shenyang 110819, People’s Republic of China
2 Key Laboratory for Ecological Metallurgy of Multimetallic Mineral (Ministry of Education), Shenyang,
People’s Republic of China
3 Collegeof Science, Northeastern University, Shenyang 110819, People’s Republic of China

Herein, inspired by previous reports on the electrochemical reduction of Al in diverse electrolyte systems, we describe a novel
Al-containing solvate ionic liquid (2:1 (mol/mol) mixture of ethylene carbonate (EC) and AlCl3 ) that allows low-temperature
electrochemical deposition of Al and features the advantages of low cost, ease of preparation, and high electrochemical stability.
Electrodeposition of Al-Li alloy and Li can also be realized in this system. Additionally, the above ionic liquid exhibited a saturated
vapor pressure of 0.0012 kPa and a conductivity of 1.32 mS/cm at 298 K, which was acceptable for practical applications. To
elucidate the electrochemical deposition mechanism, the ionic components of the 2:1 EC/AlCl3 system were characterized by a
range of instrumental analysis techniques and theoretical calculations, and Lewis-acidic cations were identified as the electroactive
species for Al electrodeposition. Notably, an Al-Li alloy could be obtained by co-deposition in the new solvate ionic liquid, and Li
metal could also be electrodeposited on a high-purity Al plate in the form of Al4 Li9 and Li3 Al2 under ambient conditions using LiCl
as a Li source. Al-containing solvate ionic liquids, which to an extent evolved from organic-salts, are of increasing interest. They are
expected to gain more attention in the field of electrochemical metallurgy of active metals, due to their higher tunability and lower
price.
© 2018 The Electrochemical Society. [DOI: 10.1149/2.0211809jes]

Manuscript submitted April 11, 2018; revised manuscript received May 4, 2018. Published May 31, 2018.

The natural abundance, low density, excellent corrosion resistance,
and high electric conductivity of Al make this metal and its alloys,
which are commonly used in aerospace, construction, automotive,
packaging, and electronics industries, strategically important materi-
als for the modern society.1,2 Moreover, Al is an attractive electrode
material for advanced Li-ion and Al/air batteries used in advanced
energy storage systems and conversion technology.3–5
This work deals with the electrochemical extraction of Li and Al-Li
alloys, building on the well-characterized electrodeposition of Al and
requiring a deep understanding of its historical context. Despite the
high melting point of cryolite, no suitable substitute has been found
for this material as a molten salt for the commercial production of Al
in the past 130 years. However, much effort is still being directed at
the development and commercialization of technologies that allow Al
production at temperatures significantly lower than those used in the
Hall-Héroult process and thus result in decreased energy consumption
and lower overall costs.6 From a technical point of view, the simplic-
ity and flexibility of electrodeposition make it an effective method of
extracting primary Al and its alloys.7 In view of the fact that Al cannot
be electrodeposited from aqueous solutions due to the shielding effect
of the hydrogen evolution reaction, Al electrodeposition has so far
been performed utilizing three kinds of non-aqueous baths, namely
inorganic molten salts, organic solvents, and ionic liquids (ILs).8 Con-
sidering the first scenario, although Al can be readily electrodeposited
in an inert gas atmosphere from molten binary AlX3 /MX mixtures
(M = Na, Li, or a K/Na mixture; X = Cl, Br, I),9 the corresponding
process requires very high temperatures, thus unavoidably exhibiting
the drawbacks of high energy consumption, complicated operation,
and volatilization of corrosive AlCl3 gas.10 Conversely, both organic
baths (typically ethers, aromatic hydrocarbons, or sulfones) and ILs
allow Al electrodeposition to be performed at lower temperatures.
In the case of Al electroplating from etheric solvents (e.g., diethyl
ether and tetrahydrofuran (THF)), mixtures of AlCl3 and LiAlH4 are
commonly employed as precursors, whereas aromatic hydrocarbon
baths commonly comprise xylene, toluene, or benzene as the medium
and Al(C2 H5 )3 or AlBr3 as Al sources.11 As can be expected, both
etheric and aromatic hydrocarbon baths are poorly suited for practical
applications because of the high volatility, flammability, and toxicity
of the employed organic media, which hinders the commercialization
of the corresponding electroplating processes.12 In addition, although
z
E-mail: znshi@mail.neu.edu.cn
Al can be electrodeposited from dimethylsulfone (DMSO2 )-AlCl3
systems, temperatures of ≥383 K are commonly employed for this
process, and the obtained coatings typically contain traces of Cl and
S as contaminants.13,14
Compared to inorganic molten salts and organic solvents, IL sys-
tems used for the electrodeposition of Al and its alloys feature the
advantages of low melting points and vapor pressures, excellent chem-
ical/thermal stabilities, and high intrinsic electrical conductivities.15,16
Based on previous reports, the above IL systems can be divided into
two categories, namely first-generation ILs and IL-like systems. Al-
though Al electrodeposition from first-generation ILs has been suc-
cessfully demonstrated and extensively studied, most of these inves-
tigations have dealt with chloroaluminate ILs, which are mixtures
of anhydrous AlCl3 and organic halides such as alkylimidazole and
alkylpyridine chlorides, both of which are hygroscopic and suscep-
tible to decomposition.17–19 Furthermore, the synthesis of conven-
tional ILs is complex, and the resulting products require multi-step
purification and separation, which significantly increases their pro-
duction cost and reduces their green character. Subsequently, the re-
search focus was shifted to air- and water-stable ILs, which, unfortu-
nately, have not yet been extensively used for Al electrodeposition.20,21
Abbott et al. significantly contributed to the development of third-
generation functional ILs, reporting Al electrodeposition from deep
eutectic solvent mixtures of AlCl3 and urea, acetamide or N,N-
dimethylurea.22–25 Li et al. systematically investigated the electrode-
position of Al in AlCl3 /amide (acetamide, propionamide, butyramide)
IL-like systems.26–28 Swadźba-Kwaśny et al. described a range of liq-
uid coordination complexes prepared by mixing donor molecules with
metal chlorides in varying proportions, achieving Al electrodeposition
on a gold plate from a dimethylacetamide-AlCl3 system.29,30 Finally,
Fang et al. reported Al electrodeposition from mixtures of AlCl3 and 4-
propylpyridne or dipropylsulfide.31,32 Notably, the above AlCl3 -donor
systems have already been used (as solutions in organic solvents) as
Lewis-acidic reactants in organic chemistry for a long time.33,34 How-
ever, multinuclear nuclear magnetic resonance (NMR) spectroscopy
analyses demonstrated that most of these mixtures comprise charge-
neutral complexes rather than ionic ones and can thus be described as
pseudo-ILs.29 Nevertheless, IL-like systems not only exhibit physic-
ochemical properties similar to those of conventional ILs but can also
overcome the aforementioned disadvantages of the latter.35,36 There-
fore, the use of the above IL-like systems in catalytic reactions and
for electrochemical deposition has attracted increased attention.23

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 D322 Journal of The Electrochemical Society, 165 (9) D321-D327 (2018)

The discovery of new ligands to extend the family of IL-like sys-

tems for practical applications in various fields is a matter of great
significance.32 In particular, ethylene carbonate (EC) is a polar apro-
tic solvent with low volatility, excellent chemical compatibility, and
significant solubilizing power.37 Although EC is a solid at room tem-
perature (melting point = 35–38◦ C), the liquid state can be mildly
formed upon the admixture of AlCl3 at room temperature, and Al
can be electrodeposited from EC/AlCl3 baths at an EC:AlCl3 mole
ratio of 2:1. Numerous studies on chloroaluminate ILs have identi-
fied Lewis acidic anions [Al2 Cl7 ]– as electroactive species, which,
however, are sensitive to water and corrosive to the equipment.18,38,39
Although some studies demonstrated that the electrodeposition of Al
from IL-like systems can be realized in the absence of [Al2 Cl7 ]– ,
the utilized ligand:AlCl3 molar ratios were approximately equal to
or less than unity, and the sedimentation mechanism has never been
elucidated.25,32,40 Herein, to explore the mechanism of Al electrodepo-
sition at low AlCl3 contents, we employed mass spectrometry (MS),
Raman spectroscopy, 27 Al NMR, and theoretical calculations to an-
alyze an EC/AlCl3 system with an EC:AlCl3 mole ratio of 2:1. The
obtained results showed that the above system belongs to the class of
solvate ILs proposed by Angell et al.41 and satisfies the criteria for
solvate ILs published by Watanabe et al.42 Subsequently, we probed
the conductivity and saturated vapor pressure of the above system
and utilized cyclic voltammetry (CV) to study the electrochemical be-
havior of Al-containing species. Finally, we demonstrated that Al, an
Al-Li alloy, and Li could be electrodeposited from the developed Al-
containing solvate ionic liquid using a potentiostatic technique, and
characterized the deposited materials by X-ray diffraction (XRD),
scanning electron microscopy (SEM), and energy-dispersive X-ray
spectroscopy (EDS) analyses.

Experimental
Reagents and electrolyte system preparation.—EC (99.0%), an-
hydrous AlCl3 (99.0%), and LiCl (99.9%) were purchased from
Shanghai Aladdin biochemical Polytron Technologies, Inc. and used
without any purification. To prepare the IL-like system, the required
amount of AlCl3 was slowly added without any external heating to EC
contained in a sample cell that was held inside a glove box (MBRAUN
MB 200B, Germany) filled with high-purity Ar, with the contents of
water and oxygen maintained below 0.1 ppm. Continuous stirring
over 4 h at 298 K afforded a homogeneous, transparent, colorless
(slightly yellow under fluorescent light), and free-flowing EC/AlCl3
(2:1, mol/mol) IL-like system.
Experimental and theoretical characterization of the EC/AlCl3
system.—Raman spectra were recorded at room temperature using a
LabRAM XploRA Raman spectrometer (Horiba Jobin Yvon, France)
equipped with a 785-nm laser. An Olympus micro objective was used
for observing samples sealed in a capillary. High-resolution mass spec-
tra were acquired using a JEOL AccuTOF-DART mass spectrometer.
Electrical conductivities were measured inside the glove box utilizing
the impedance method (Agilent 4263B LCR impedance meter) at a
fixed frequency of 1000 Hz and a voltage of 1 V. Saturated vapor
pressure was measured employing a fully automatic vapor pressure
meter (MiniVAP VPXpert, Grabner Instruments, Inc., Austria). 27 Al
NMR spectra were recorded on a Bruker Avance 400 spectrometer
(155 MHz, 298 K) using 1.0 M aqueous Al(NO3 )3 as a reference. Sam-
ples were placed in an NMR tube, and the entire apparatus was capped
and sealed with parafilm. Peak intensities and areas were determined
using the MestReNova software package. Density functional theory
calculations were performed using the B3LYP hybrid parameter im-
plemented in Gaussian09. [AlCl2 ]+ , EC, and their binary mixtures
were optimized by B3LYP/6-31G(d) spin non-polarized calculations
in restricted Hartree-Fock mode.43 An isolated AlCl2 + molecule was
simulated in Gaussian09 by setting the charge of the [AlCl2 ]+ cation
to +1. The enthalpy of complexation was obtained at 298.15 K.
Figure 1. (a) Anion- and (b) cation-mode mass spectra of EC/AlCl3
(2:1, mol/mol).
Formation and characterization of electrodeposits.—All electro-
chemical experiments were performed utilizing a three-electrode setup
and a PARSTAT 4000 (Princeton Applied Research, USA) electro-
chemical workstation controlled by VersaStudio software. W (99.9%,
area = 0.24 cm2 ), Pt (99.99%, radius = 1 mm), and Al (99.95%,
radius = 1 mm) wires were used as working, counter, and reference
electrodes, respectively. The W working electrode was polished with
emery papers of increasingly finer grades, washed with deionized
water, and air-dried.
For potentiostatic electrodeposition of Al, a Cu sheet (99.95%,
area = 1 cm2 ) polished with a SiC paper and subsequently cleaned
by sonication in ethanol was used as the cathode, whereas a graphite
sheet (99.99%, area = 1.5 cm2 ) was used for the same purpose for
Al-Li alloy deposition. A high-purity Al (99.99%, area = 1 cm2 )
plate was used as a cathode substrate for Li electrodeposition. To
reduce the influence of the surroundings, all potentiostatic electrolysis
experiments were conducted in a glove box filled with high-purity
Ar. After deposition, samples were cleaned with anhydrous acetone
and air-dried prior to characterization. SEM (Shimadzu SSX-550,
Japan) and EDS were used to visualize the surface morphologies of
as-prepared deposits, and their phase compositions were probed by
XRD (PANalytical MPDDY 2094, Netherlands) using the Cu Kα line
(40 kV, 40 mA).
Results and Discussion
Structural characterization of the EC/AlCl3 IL.—The EC/AlCl3
IL was studied by MS using a specially constructed sample in-
let system. Figures 1a and 1b show direct-analysis real-time mass
spectra recorded to identify the composition of the above elec-
trolyte. It should be noted that the occurrence of fragmentation and

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 Journal of The Electrochemical Society, 165 (9) D321-D327 (2018)
Figure 2. (a) Raman spectra of EC and EC/AlCl3 (2:1, mol/mol) at 298 K
and (b) optimized geometries of EC and [AlCl2 ]+ .
recombination processes during ionization complicated the assign-
ment of some intense peaks. In both cases, despite considerable effort,
we were unable to avoid the formation of these impurity-containing
species, as has also been reported in the literature.31,44 Although MS is
a gas-phase technique and can thus provide results incorrectly reflect-
ing the speciation of the liquid phase (which is characterized by a dense
network of Coulombic and hydrogen bonding interactions),45 both
cationic and anionic species ([AlCl2 (EC)4 ]+ , m/z = 450.2; [AlCl4 ]– ,
m/z = 168.9) were observed. Besides, no Lewis-acidic [Al2 Cl7 ]– ions
(m/z = 302.5) were detected, and their absence was also confirmed by
Raman spectroscopy (Fig. 2a).46 It is generally believed that anionic
species not only travel against the electric field but also compete with
common cations along the electric field, which induces polarization
and reduces the energy efficiency of the electrodeposition process.32
Therefore, the presence of Al-containing cations was concluded to
benefit the electrodeposition of Al.
Moreover, the obtained MS results were similar to those previ-
ously reported for ILs based on complexes of neutral ligands with
AlCl3 ,31 demonstrating that the asymmetric cleavage of AlCl3 gen-
erated [AlCl2 ]+ and [AlCl4 ]– (Eq. 1). Being strongly Lewis-acidic,
[AlCl2 ]+ cations cannot exist in an isolated form and interact with
EC:
2AlCl3 + 4EC ↔ [AlCl2 (EC)4 ]+ + [AlCl4 ]−
The formation of Al-containing cationic species involves either
asymmetric cleavage of a halide-bridged dimer or halide elimina-
tion/redistribution, in which a neutral ligand binds to the cation
for charge compensation.47 To understand the thermodynamics of
the above process, we calculated the enthalpy of complexation be-
tween [AlCl2 ]+ and EC using Gaussian software based on the den-
sity functional theory. Figure 2b shows the optimized geometries
obtained for EC–[AlCl2 ]+ , revealing that a coordination bond is
formed by the overlap of Al and O electron clouds irrespective of
the starting point. The enthalpy of complexation was calculated as
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D323
Figure 3. 27 Al NMR spectrum of EC/AlCl3 (2:1, mol/mol) at 298 K.
H = –287.28 kJ/mol, i.e., the reaction between [AlCl2 ]+ and EC
was spontaneous and exothermic. Actually, if the above cation were
to exist in a non-coordinated state, the corresponding IL should be ex-
tremely Lewis-acidic. However, this cation, [AlCl2 ]+ , has never been
reported in literature, and no direct spectroscopic evidence of its exis-
tence has ever been presented.45 Nevertheless, the above hypothesis is
helpful for understanding and analyzing the investigated system, and
the discovery of the [AlCl2 ]+ cation and confirmation of its existence
are thus of great scientific significance.
The nuclear magnetic resonance behavior of 27 Al (natural abun-
dance = 100%) has been rather well characterized, since its four-pole
distance is not overly wide and the corresponding detection sensitiv-
ity exceeds that of 13 C by three orders of magnitude.48 Unfortunately,
the solvate complexes of Al are often difficult to separate from the
corresponding solutions, which necessitates the use of 27 Al NMR as
an effective means to observe the effects of AlCl3 solvation.49 Herein,
the Al-containing species present in the EC/AlCl3 system were char-
acterized by 27 Al NMR spectroscopy at 298 K. As shown in Fig. 3,
three peaks at 104.23, 58.41, and –15.06 ppm were observed, indi-
cating the existence of three Al species. The [AlCl4 ]– anion observed
in organic halide–based ILs features an Al center four-fold coordi-
nated by chloride ions that effectively prevent further coordination
by other ligands to form five- and six-coordinate complexes and thus
render the anion neutral. Specifically, 27 Al NMR studies of organic
halide–based ILs32 show that no five- and six-coordinate complexes
are found in these systems at AlCl3 molar fraction of ≤ 0.5, with
[AlCl4 ]– being the major anionic species. Moreover, no six-coordinate
Al-containing complexes were observed by 27 Al NMR even in most
of the previously reported IL-like systems such as AlCl3 –urea, –
acetamide, –4-propylpyridine, and –trioctylphosphine.29 However, in
the EC/AlCl3 (2:1, mol/mol) system, a six-coordinate Al-containing
complex ([AlCl2 (EC)4 ]+ , –15.06 ppm) was observed besides the four-
coordinate [AlCl4 ]– (104.23 ppm). The solvation coordination number
is known to be directly related to ligand steric hindrance. In contrast
to previously reported donor molecules, the spatial steric hindrance
of cyclic EC is rather low, allowing the formation of a six-coordinate
[1] complex.
In general, a change from six-fold to five- or four-fold coordination
results in a downfield shift of 27 Al NMR signals.50 Thus, the sharp
resonance observed at 104.23 ppm was attributed to Al-containing
species with tetrahedral coordination, whereas the weak signal at
around –15 ppm was ascribed to Al-containing species with octahedral
coordination, in agreement with the abovementioned MS findings. The
signal at ∼58.41 ppm, featuring a half-width larger than those of the
abovementioned ionic species, was assigned to neutral [AlCl3 (EC)2 ],
in agreement with the previously reported observation of similar five-
coordinate complexes in IL-like systems.29 The increased width of
the pentacoordinate complex signal was ascribed to the fact that the
 D324 Journal of The Electrochemical Society, 165 (9) D321-D327 (2018)
Figure 4. Chemical structure of EC and partial charges (q/e) on constituent
atoms.
electric field gradient in the trigonal bipyramidal structure of such
five-coordinate complexes exceeds that observed for tetrahedral four-
coordinate complexes.
Figure 4 shows the chemical structure and previously determined
atomic charge densities of EC.37,51,52 In the Lewis theory of acid-base
reactions, the base donates a pair of electrons to the acid. Effectively,
in the EC/AlCl3 mixture, the IL is more inclined to generate via Al-O1
coordination interaction due to the most negative charge density of
carbonyl oxygen reconfirmed by theoretical calculation above.
The final open question arising in our structural discussion is the
configuration of six-coordinate complexes. Ironically, in the field
of ILs, the overwhelming majority of Lewis acids correspond to
Lewis-acidic anions such as [Al2 Cl7 ]– ,45 although liquid complexes
of glymes and lithium salts have also been developed to address to-
day’s growing demand for lithium secondary batteries with increased
safety.42 The above mixtures have properties similar to those of ILs and
have been termed solvate ILs with Lewis acidic cations by Angell.41
Following Angell’s categorization of ILs and Watanabe’s criteria for
solvate ILs, the EC/AlCl3 system studied herein can be classified as
a solvate IL, since the [AlCl2 ]+ cation contained therein was sol-
vated by neutral EC molecules. Herein, it should be note that the
amount of neutral molecules [AlCl3 ](EC)2 is very tiny and its pres-
ence is abandoned according to Watanabe’s definition of solvate ILs.
Figure 5 shows the solvate model of [AlCl2 (EC)4 ]+ , revealing that
this species is likely to feature an octahedral configuration and be
weakly Lewis-acidic. Alternatively, the solvate configuration can ef-
fectively shield the Al center, making the solvate IL less sensitive
to water, as confirmed by the implementation of the electrochemical
quartz crystal microbalance technique in air (not shown). Among the
numerous possible formulae reported in literature, the observation of
[AlCl2 (THF)4 ]+ agrees with the above conclusions.53 Moreover, a
similar ionic complex, [FeCl2 (DMSO)4 ]+ , has been reported for Fe.54
Physicochemical properties.—The commercialization of conven-
tional ILs is mainly limited by their toxicity and high cost, whereas
electrodeposition from organic baths is significantly hampered by the
volatility of organic solvents. As we already know, solvate ILs behave
like salt solutions in molecular organic solvents. To investigate the dif-
ferences between the novel solvate IL and traditional organic solvents,
Figure 5. Model of the [AlCl2 (EC)4 ]+ cation.
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Figure 6. Saturated vapor pressure of EC and the EC/AlCl3 (2:1, mol/mol)
system at different temperatures.
the saturated vapor pressure of EC and the EC/AlCl3 (2:1, mol/mol)
system were measured at different temperatures (Fig. 6). The obtained
results revealed that the addition of AlCl3 to EC significantly reduced
the vapor pressure of the whole system. The saturated vapor pressure
of the solvate IL increased with increasing temperature because of
the existence of complex dynamic equilibria in the system, with the
main one corresponding to the competition between cation-anion and
ligand-cation interactions (Eq. 2).55,56
 +
AlCl2 (EC)n (l) + [AlCl4 ]− (l) ↔ EC(l) + [AlCl2 ]+ (l) + [AlCl4 ]− (l)
↔ EC(g) + 2AlCl3(s) [2]
Thus, the rise of the vapor pressure with increasing temperature can
be attributed to the concomitant shift of the above equilibrium to the
right and the appearance of gas-phase EC. However, the vapor pres-
sure of the solvate IL was less than that of EC at any given tempera-
ture because of the interactions between [AlCl4 ]– and [AlCl2 (EC)n ]+ .
Whereas conventional ILs have close-to-zero vapor pressures at ambi-
ent temperature, the vapor pressure of the studied solvate IL at 298 K
was determined as 0.0012 kPa, which was slightly larger than zero but
still low enough to meet the requirements of practical applications.
The electrical conductivity of the EC/AlCl3 system at 298 K was mea-
sured as 1.32 mS/cm, which was of the same order of magnitude as the
values observed for conventional ILs. Therefore, it was concluded that
the Lewis-acidic AlCl3 can modify EC (molecular solvent) to afford
a novel solvate IL having properties similar to those of conventional
ILs and featuring the combined advantages of conventional ILs and
organic baths, e.g., low cost and very low vapor pressure.
Al electrodeposition and its mechanism.—All structural and
physicochemical analyses were performed in view of the fact that Al
can be obtained by electrodeposition from EC/AlCl3 (2:1, mol/mol)
mixtures. Figure 7a shows cyclic voltammograms of EC and the
EC/AlCl3 solvate IL, with the inset showing an enlargement of the
selected area. As expected, the relatively inexpensive EC, often used
as a high-permittivity component of electrolytes in lithium batteries,
had an excellent ability to withstand voltage.57 A pair of redox peaks
appeared after the addition of a stoichiometric amount of Lewis-acidic
AlCl3 , and the gray-white deposit obtained on the copper substrate af-
ter 4-h potentiostatic electrolysis (–0.5 V vs. Al) at room temperature
was confirmed to be metallic Al by XRD (Fig. 7b). All sharp diffrac-
tion peaks in the XRD pattern of the deposit could be indexed to Al and
the Cu substrate, and the absence of other obvious peaks indicated the
suitability of this solvate IL for the electrodeposition of Al. In the case
of conventional chloroaluminate ILs, [AlCl4 ]– is electrochemically in-
active, in contrast to [Al2 Cl7 ]– . However, the confirmed absence of the
latter anion in the investigated solvate IL implied that the electroactive
 Journal of The Electrochemical Society, 165 (9) D321-D327 (2018)
Figure 7. (a) CV curves of EC and EC/AlCl3 recorded at 323 and 298 K,
respectively, at a scan rate of 20 mV/s. Points “p” and “p ” correspond to
reduction and oxidation peaks of metallic Al, respectively. (b) XRD pattern of
the deposit formed on the Cu substrate.
species accounting for the successful Al electrodeposition are cations.
Considering the works of Abbott22,25 and Kitada,58-60 we suggested the
following electrochemical mechanism of Al electrodeposition (Eq. 3):
 +
2 AlCl2 (EC)n + 3e− → Al + [AlCl4 ]− + 2nEC [3]
Thus, during the potentiostatic deposition of Al, cations migrate
to the cathode and release free EC upon discharge, whereas anions
migrate to the anode. Overall, EC is not consumed during electrolysis,
in agreement with the results of Dai et al.61
Figure 8 illustrates the SEM-visualized surface morphology of an
Al layer electrodeposited on the copper substrate, revealing the pres-
ence of a series of spherical nanoclusters in different linear directions
Figure 8. SEM image and EDS spectrum (inset) of the material deposited on
the Cu substrate.
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D325
Figure 9. CV curves of EC and EC/AlCl3 (2:1, mol/mol) containing 10 mol%
LiCl recorded at a scan rate of 50 mV/s. The current plateau at “a” represents
the discharge of Al-containing cations [AlCl2 (EC)n ]+ , and the redox couple
(b, b’) corresponds to the precipitation and stripping of Li metal.
and allowing the average size of Al crystallites to be determined as
∼60 nm. Moreover, the obtained deposit was not dendritic, which
makes the developed methodology suitable for Al plating or Al ion
battery applications. The EDS spectrum of the as-obtained deposit
featured a strong peak of Al, in accordance with the XRD result.
Co-deposition of an Al-Li alloy.—The electrodeposition of Al
and its alloys with non-active metals such as Mn and W has been
extensively characterized.62 Therefore, to have practical value, the
developed EC-based electrolyte should be suitable not only for the
electrodeposition of Al and its alloys with non-active metals, but also
allow the deposition of the widely utilized alloys of Al with reactive
metals such as Li. Notably, the electrodeposition of Al-Li alloys at
room temperature is complicated by the high activity and very negative
redox potential of Li.
The EC-based electrolyte developed herein exhibited a wider elec-
trochemical stability window than electrolytes based on amides, im-
idazolium salts, pyrrole, etc.63,64 and was therefore considered to
be potentially suitable for the electrodeposition of highly active el-
ements. To verify the electrochemical stability and dissolving ability
of this new solvate IL, we tried to obtain an Al-Li alloy by ambient-
temperature electrodeposition using the corresponding metal chlo-
rides as raw materials. Figure 9 shows the cyclic voltammogram of
EC and the EC/AlCl3 solvate IL containing 10 mol% LiCl at 323 K,
demonstrating that EC featured a cathode limit voltage of approxi-
mately –4 V (vs. Al), which theoretically allowed the precipitation of
all elements in the periodic table. Although the electrode potentials of
Al and Li are significantly different, the equilibrium potential of Al
can be greatly changed by the formation of [AlCl2 (EC)n ]+ complex
ions, which allows the co-deposition of Li and Al. Figure 10 shows
the XRD pattern of the deposit formed on a graphite sheet during
2-h potentiostatic electrolysis at –2.8 V (vs. Al), confirming that it
corresponds to an Al-Li alloy of the composition Al4 Li9 . Notably,
deposition was not accompanied by any system deterioration, which
indicated the excellent electrochemical stability of EC as a supporting
electrolyte.
Strategy for Li electrodeposition.—LiCl is not soluble in neutral or
neutral basic ILs, but dissolves in neutral acidic chloroaluminate ILs.
Herein, we utilized 1-ethyl-3-methylimidazole chloride ([EMIm]Cl)
to explain the dissolution mechanism based on the abovementioned
results. At [EMIm]Cl/AlCl3 molar ratios of greater than unity, the
following process is thought to occur (Eq. 4):
[EMIm] Cl + AlCl3 → [EMIm]+ [AlCl4 ]− [4]
 D326 Journal of The Electrochemical Society, 165 (9) D321-D327 (2018)
Figure 10. CV curves of EC/AlCl3 (2:1, mol/mol) with different contents of
LiCl recorded at 323 K and 50 mV/s.
Conversely, a binuclear Al-containing anion is formed if the above
molar ratio is less than unity (Eq. 5):
[EMIm] Cl + AlCl3 → [EMIm]+ [Al2 Cl7 ]−
The addition of a certain amount of LiCl to obtain a neutral ionic
liquid results in the following reaction (Eq. 6):
[EMIm]+ [Al2 Cl7 ]− + LiCl ↔ LiAlCl4 + [EMIm]+ [AlCl4 ]−
Therefore, LiCl dissolves in the neutral acidic chloroaluminate IL
in the presence of [Al2 Cl7 ]– but is also soluble in the newly developed
EC/AlCl3 solvate IL even if there is no [Al2 Cl7 ]– , which is because
the Lewis acidity is reflected in the cations.
Figure 11 shows cyclic voltammograms of the EC/AlCl3 solvate IL
with different LiCl contents, showing that the current plateau signal at
“a” disappeared at an AlCl3 /LiCl molar ratio of unity. This finding was
ascribed to the elimination of electroactive species via the reaction of
Al-containing cations with LiCl (Eq. 7).
 +
[AlCl2 (EC)n ]+ + 2LiCl → 2 Li(EC)n/2 + AlCl4 − [7]
Under these conditions, pure Li deposits could be obtained by
potentiostatic electrodeposition. It should be noted that Li shows
the highest activity among the known elements, as exemplified by
the fact that the Li deposit on the graphite plate caught fire every
time it was removed from the glove box. Therefore, a high-purity
Al plate was used as a cathode substrate for collecting Li via the
formation of Al-Li alloys. Figure 12 shows the XRD pattern of the de-
posit obtained on the Al plate during 1-h potentiostatic electrolysis at
Figure 11. XRD pattern of the material deposited on the graphite sheet.
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Figure 12. XRD pattern of the deposit obtained on the Al plate.
–3 V (vs. Al), revealing that Li could be successfully obtained in the
form of Al4 Li9 and Li3 Al2 . Moreover, no EC was consumed during
[5] electrodeposition, which is an example of atom economy application
in modern electrochemical synthesis and green metallurgy.
Conclusions
[6]
Herein, coordination compounds formed between Lewis-basic EC
and Lewis-acidic AlCl3 at a molar ratio of 2:1 were subjected to struc-
tural investigation utilizing 27 Al NMR, Raman spectroscopy, mass
spectrometry, and theoretical calculations. Besides four-coordinate
[AlCl4 ]– and charge-neutral [AlCl3 (EC)2 ] complexes, a six-coordinate
[AlCl2 (EC)4 ]+ complex was also observed, and its formation was ex-
plained by the asymmetric cleavage of a halide-bridged dimer and the
strong interaction between Al and carbonyl O atoms. The developed
system was classified as a solvate IL, exhibiting properties resem-
bling those of ILs and featuring a very low saturated vapor pressure of
0.0012 kPa and an ionic conductivity of 1.32 mS/cm at room temper-
ature. The solvate octahedral configuration of Al-containing cations
could effectively shield the Al center, making the solvate IL less sen-
sitive to moisture. The EC/AlCl3 system was used for potentiostatic
electrodeposition of Al, and the obtained deposit was characterized
by XRD, SEM, and EDS. Al-containing cations were identified as
electroactive species, and the electrochemical mechanism was repre-
sented as 2[AlCl2 (EC)n ]+ + 3e– → Al + [AlCl4 ]– + 2nEC. More-
over, the newly developed solvate IL allowed the electrodeposition
of Li under ambient conditions and the formation of an Al-Li alloy
by co-deposition, which was ascribed to the excellent electrochemical
stability of EC and the good solubility of Lewis-acidic cations therein.
Acknowledgments
This work was financially supported by the National Key R&D
Program of China (No. 2017YFC0805100), National Natural Science
Foundation of China (No. 50174071), and the Fundamental Research
Funds for the Central Universities (N172502003).
ORCID
Baoguo Zhang https://orcid.org/0000-0001-9986-253X
Lingling Shen https://orcid.org/0000-0001-5862-1836
References
1. E. A. S. Jr and J. T. Staley, Prog. Aerosp. Sci., 131, 32 (1996).
2. G. B. Burger, A. K. Gupta, P. W. Jeffrey, and D. J. Lloyd, Mater. Charact., 23, 35
(1995).
 Journal of The Electrochemical Society, 165 (9) D321-D327 (2018)
3. M. Nestoridi, D. Pletcher, R. J. K. Wood, S. Wang, R. L. Jones, K. R. Stokes, and
I. Wilcock, J. Power Sources, 445, 178 (2008).
4. I. Smoljko, S. Gudić, N. Kuzmanić, and M. Kliškić, J. Appl. Electrochem., 969, 42
(2012).
5. A. Ming, S. Mcwhorter, H. Ajo, T. Adams, Y. Zhao, and J. Gibbs, J. Power Sources,
3333, 195 (2010).
6. J. Thonstad, P. Fellner, G. M. Haarberg, J. Hı́veš, and Å. Sterten, Aluminium Electroly-
sis: Fundamentals of the Hall-Héroult Process, 3rd ed., AluminiumVerlag Marketing
& Kommunikation GmbH, Düsseldorf, Germany (2001).
7. F. Liu, Y. Deng, X. Han, W. Hu, and C. Zhong, J. Alloys Compd., 163, 654 (2015).
8. A. Eftekhari, Y. Liu, and P. Chen, J. Power Sources, 334, 221 (2016).
9. A. Bakkar and V. Neubert, Electrochim. Acta, 211, 103 (2013).
10. J. Fransaer, E. Leunis, T. Hirato, and J. P. Celis, J. Appl. Electrochem., 123, 32 (2002).
11. A. Endo, M. Miyake, and T. Hirato, Electrochim. Acta, 470, 137 (2014).
12. Y. G. Zhao and T. J. Vandernoot, Electrochim. Acta, 3, 42 (1997).
13. T. Jiang, M. J. C. Brym, G. Dubé, A. Lasia, and G. M. Brisard, Surf. Coat. Tech.,
6309, 201 (2007).
14. M. Miyake, H. Motonami, S. Shiomi, and T. Hirato, Surf. Coat. Tech., 4225, 206
(2012).
15. F. Endres and S. Zein El Abedin, Phys. Chem. Chem. Phys., 2101, 18 (2006).
16. R. D. Rogers and K. R. Seddon, Science, 792, 302 (2003).
17. J. Robinson and R. A. Osteryoung, J. Electrochem. Soc., 122, 127 (1980).
18. A. Bakkar and V. Neubert, Electrochim. Acta, 211, 103 (2013).
19. M. Zhang, V. Kamavaram, and R. G. Reddy, JOM, 54, 55 (2003).
20. S. Zein El Abedin, E. M. Moustafa, R. Hempelmann, H. Natter, and F. Endres,
Chemphyschem, 1535, 7 (2006).
21. S. Zein El Abedin, E. M. Moustafa, R. Hempelmann, H. Natter, and F. Endres, Elec-
trochem Commun., 1111, 7 (2005).
22. H. M. Abood, A. P. Abbott, A. D. Ballantyne, and K. S. Ryder, Chem. Commun.,
3523, 47 (2011).
23. E. L. Smith, A. P. Abbott, and K. S. Ryder, Chem. Rev., 11060, 114 (2014).
24. A. P. Abbott, E. I. Ahmed, R. C. Harris, and K. S. Ryder, Green Chem., 4156, 16
(2014).
25. A. P. Abbott, R. C. Harris, Y.-T. Hsieh, K. S. Ryder, and I.-W. Sun, Phys. Chem.
Chem. Phys., 14675, 16 (2014).
26. M. Li, B. Gao, C. Liu, W. Chen, Z. Wang, Z. Shi, and X. Hu, J. Solid State Electr., 1,
20 (2016).
27. M. Li, B. Gao, C. Liu, W. Chen, Z. Shi, X. Hu, and Z. Wang, Electrochim. Acta, 811,
180 (2015).
28. M. Li, B. Gao, W. Chen, C. Liu, Z. Wang, Z. Shi, and X. Hu, Electrochim. Acta, 148,
185 (2015).
29. F. Coleman, G. Srinivasan, and M. Swadźba-Kwaśny, Angew. Chem., Int. Ed., 12582,
52 (2013).
30. J. M. Hogg, L. C. Brown, K. Matuszek, P. Latos, A. Chrobok, and
M. Swadźba-Kwaśny, Dalton Trans., 11561, 46 (2017).
31. Y. Fang, X. Jiang, X. G. Sun, and S. Dai, Chem. Commun, 13286, 51 (2015).
32. Y. Fang, K. Yoshii, X. Jiang, X. G. Sun, T. Tsuda, N. Mehio, and S. Dai, Electrochim.
Acta, 82, 160 (2015).
33. S. Yous, J. H. Poupaert, I. Lesieur, P. Depreux, and D. Lesieur, J. Org. Chem, 1574,
59 (1994).
Downloaded on 2018-06-03 to IP 193.140.239.5 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
D327
34. A. G. Suárez, Tetrahedron Lett., 3523, 40 (1999).
35. Q. H. Zhang, K. D. O. Vigier, S. Royer, and F. Jérôme, Chem. Soc. Rev., 7108, 41
(2012).
36. A. P. Abbott, G. Capper, D. L. Davies, R. K. Rasheed, and V. Tambyrajah, Chem.
Commun., 70, 9 (2003).
37. N. Peruzzi, B. W. Ninham, N. P. Lo, and P. Baglioni, J. Phys. Chem. B, 14398, 116
(2012).
38. C. Du, B. Zhao, X. Chen, N. Birbilis, and H. Yang, Sci. Rep., 29225, 6 (2016).
39. V. S. Protsenko, A. A. Kityk, D. A. Shaiderov, and F. I. Danilov, J. Mol. Liq., 716,
212 (2015).
40. G. Pulletikurthi, B. B. Decker, A. Borodin, B. Weidenfeller, and F. Endres, Progress
in Natural Science: Materials International, 603, 25 (2015).
41. C. A. Angell, Y. Ansari, and Z. Zhao, Faraday Discuss., 9, 154 (2011).
42. T. Mandai, K. Yoshida, K. Ueno, K. Dokko, and M. Watanabe, Phys. Chem. Chem.
Phys., 8761, 16 (2014).
43. M. D. Bhatt and C. O’Dwyer, Curr. Appl. Phys., 349, 14 (2014).
44. A. K. Abdul-Sada, A. M. Greenway, K. R. Seddon, and T. Welton, Org. Mass Spec-
trom., 759, 28 (1993).
45. L. C. Brown, J. M. Hogg, and M. Swadźba-Kwaśny, Top. Curr. Chem., 78, 375
(2017).
46. M. C. Lin, M. Gong, B. Lu, Y. Wu, D. Y. Wang, M. Guan, M. Angell, C. Chen,
J. Yang, B. J. Hwang, and H. Dai, Nature, 324, 520 (2015).
47. D. A. Atwood, Coord. Chem. Rev., 407, 176 (1998).
48. C. Fernandez and J. P. Amoureux, Chem. Phys. Lett., 449, 242 (1995).
49. O. Křı́ž, B. Čásenský, A. Lyčka, J. Fusek, and S. Heřmánek, J. Magn. Reson., 375,
60 (1984).
50. N. M. Rocher, E. I. Izgorodina, T. Rüther, M. Forsyth, D. R. MacFarlane,
T. Rodopoulos, M. D. Horne, and A. M. Bond, Chem. Eur. J., 3435, 15 (2009).
51. L. B. Silva and L. C. G. Freitas, J. Mol. Struct.:THEOCHEM, 806, 23 (2007).
52. J. C. Soetens, C. Millot, and B. Maigret, J. Phys. Chem. A, 102, 1055 (1998).
53. J. Derouault, P. Granger, and M. T. Forel, Inorg. Chem., 3214, 16 (1977).
54. M. J. Bennett, F. A. Cotton, and D. L. Weaver, Acta Crystallogr., 581, 23
(1967).
55. M. J. Earle, J. M. Esperanca, M. A. Gilea, J. N. Canongia Lopes, L. P. N. Rebelo,
J. W. Magee, K. R. Seddon, and J. A. Widegren, Nature, 831, 439 (2006).
56. J. P. Armstrong, C. Hurst, R. G. Jones, P. Licence, K. R. J. Lovelock, C. J. Satterley,
and I. J. Villar-Garcia, Phys. Chem. Chem. Phys., 982, 9 (2007).
57. SS. Zhang, J. Power Sources, 1379, 162 (2006).
58. A. Kitada, K. Nakamura, and K. Fukami, Electrochemistry, 946, 82 (2014).
59. A. Kitada, K. Nakamura, K. Fukami, and K. Murase, Electrochim. Acta, 561, 211
(2016).
60. A. Kitada, S. Takeoka, K. Kintsu, K. Fukami, M. Saimura, T. Nagata, M. Katahira,
and K. Murase, J. Electrochem. Soc., 165, 3 (2018).
61. M. Angell, C. J. Pan, Y. Rong, C. Yuan, M. C. Lin, B. J. Hwang, and H. Dai, P. Natl.
Acad. Sci. USA, 834, 114 (2017).
62. T. Tsuda, Y. Ikeda, T. Arimura, M. Hirogaki, A. Imanishi, S. Kuwabata, G. R. Stafford,
and C. L. Hussey, J. Electrochem. Soc., 16, 19 (2014).
63. Q. Li, J. Jiang, G. Li, W. Zhao, X. Zhao, and T. Mu, Sci. China Chem., 571, 59
(2016).
64. B. Wang, L. Qin, T. Mu, Z. Xue, and G. Gao, Chem. Rev., 7113, 117 (2017).