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Fan Liu, Yida Deng, Xiaopeng Han, Wenbin Hu, Cheng Zhong
PII: S0925-8388(15)31113-0
DOI: 10.1016/j.jallcom.2015.09.137
Reference: JALCOM 35412
Please cite this article as: F. Liu, Y. Deng, X. Han, W. Hu, C. Zhong, Electrodeposition of metals and
alloys from ionic liquids, Journal of Alloys and Compounds (2015), doi: 10.1016/j.jallcom.2015.09.137.
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Fan Liua, Yida Dengc, Xiaopeng Hanb, Wenbin Hua,b,c, Cheng Zhongb,*
a
State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University,
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b
Key Laboratory of Advanced Ceramics and Machining Technology (Ministry of
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Education), Department of Materials Science and Engineering, Tianjin 300072,
China
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c
Tianjin Key Laboratory of Composite and Functional Materials, Department of
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Materials Science and Engineering, Tianjin University, Tianjin 300072, China
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Abstract
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reagents can be overcome by utilizing ionic liquids. This review outlines the current
state of electrodeposition of various types of metals and their alloys in ionic liquids
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with particular focus on the work within the last decade. The metals are categorized
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into four groups and special attention is paid to the reactive metals that cannot
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1. Introduction
The formation of metallic films and coatings is an important technology and has
been applied in many industries. Several methods such as the vapor deposition and
plasma spray have been developed, among which the electrodeposition of metals has
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several distinct advantages such as rapid deposition rates, cost effectiveness, and
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simplicity of high level control over the thickness of the films [1, 2]. The principles
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underpinning the electrodeposition method simply center around Faraday’s original
idea of electrolyzing a metal salt to reduce the metal cation at the cathode. The
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morphology and properties of the coatings can be easily adjusted either by the
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composition of electrolytes (e.g., type of solutions, concentration of metal salts, and
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electrolytes to deposit metals with very negative redox potential due to their narrow
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electrodeposition at high temperature. Over decades, ionic liquids (ILs, also known as
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room temperature or low temperature molten salts) have received considerable and
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ILs are generally defined as those salts composed solely of ions (cations and
anions) with melting points below 100 °C [3]. A typical IL contains a large organic
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makes it difficult for the cations and anions to stack closely with each other, thus
effectively prohibiting IL’s crystallization and lowering its melting point [4, 5].
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properties can be highly tunable due to a large variety of different combinations of
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cations and anions [4, 6].
The history of ILs dates back to 1914 when the first discovered room-temperature
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molten salt was reported by Walden [7], namely ethylammonium nitrate
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([C2H5NH3][NO3]) which possesses a melting point of 12 °C, and it was synthetized
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through the reaction of concentrated nitric acid with ethylamine. Later in the 1970s
and 1980s, a series of studies with regard to AlCl3-based ILs were reported by Chum
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et al. [8] and Wilkes et al. [9]. Such ILs can be categorized as the first generation of
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ILs which are hygroscopic and therefore need to be prepared and used under an inert
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atmosphere. The hygroscopic nature has prevented their applications in many fields
and there has been an urgent need to synthesize the air- and water-stable ILs. In 1992,
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Wilkes and Zaworotko [10] reported the air- and water-stable ILs with the
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anion. These ILs usually are hydrophobic and can be regarded as the second
generation of ILs. Air- and water-stable ILs have attracted great interest among the
researchers, and several hydrophobic anions have been developed so far, especially
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solvents: (1) Known as the “green solvents”, ILs generally have low toxicity, low
vapor pressure and are difficult to volatilize [2]. (2) In most cases ILs are
non-flammable and can be used over a wide temperature range. (3) ILs have wide
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electrochemical windows. The stable electrochemical windows of ILs are within the
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range of 2-6 V, typically around 4.5 V [12]. This allows the deposition of metals with
very negative redox potentials. (4) ILs are good solvents for both organic and
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inorganic materials. ILs can be aprotic, and thus problems with regard to hydrogen
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ions in protic solvents can be solved.
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The excellent properties of ILs have aroused great interest among researchers and
ILs have been widely used in the deposition of metals and their alloys. This article
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alloys in ILs with a particular focus on the reactive metals with very negative redox
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potentials.
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Aluminum (Al) has a large negative redox potential of –1.67 V (vs. normal
hydrogen electrode) [13], and it is also water-sensitive and can easily form a
passivation oxide layer on the surface [14], which makes its electrodeposition difficult
to proceed in aqueous solutions. ILs have become the ideal solvents to solve this
problem. AlCl3-based ILs have been widely used for the electrodeposition of Al and
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its alloys. The adhesive strength between the Al coating and the substrate is an
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layer was successfully coated on the substrate. An Al coating was then
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electrodeposited by bipolar current pulse polarization on this zincated substrate. The
adhesive strength of the Al coating to the substrate was better than 11 MPa [15]. Ling
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and co-workers have done considerable in-depth research on the electrodeposition of
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Al and its alloys including Al–Cr and Al–Mn [16-19] in AlCl3-based ILs. Apart from
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studying the composition, morphology and properties (e.g., hardness and corrosion
resistance) of the coating, they particularly focus on the investigation of the adhesion
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strength between the coating and the substrate. For example, Ling et al. [16] chose the
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was employed for 10 min on the substrate. The adhesion strength of subsequently
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electrodeposited Al coating on the substrate was higher than 4 MPa, and the authors
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also gave a detailed illustration of the mechanism of the improved adhesion through
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investigated the electrodeposition of Al and its alloys in room temperature ILs and
(AlCl3/[EMIM][Cl]) at 10 °C. The authors added ethylene glycol into the electrolyte
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and studied its effect on the morphology of Al coating. As it can be seen from Fig. 1,
ethylene glycol could effectively reduce the formation of cavities and help to improve
the surface flatness in Al electroplating. IL containing 0.1 M ethylene glycol was the
better concentration to prepare a mirror-like surface and a dense Al layer. Zhang et al.
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[13] investigated the effect of nicotinamide on the electrodeposition of Al in the
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AlCl3/1-butyl-3-methylimidazolium chloride ([BMIM][Cl]) IL system. It was
indicated that nicotinamide could inhibit the deposition of Al, which could be
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attributed to the adsorption of nicotinamide on the electrode surface. Nicotinamide
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also played the role of a leveling agent which helped to form highly homogeneous and
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smooth Al deposits. The AlCl3-based ILs can also be employed to electrodeposit Al
alloys. Hussey and co-workers carried out a series of research associated with the
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electrodeposited Al–W [26] and Al–Hf [27] alloy. They added K3[W2Cl9] into the
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deposition potential and deposition current Al-W alloys with a W content approaching
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96 at.% could be prepared. However, as the W content of the alloys increased above
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30 at.%, the deposits became powdery and brittle. Alloys composed of nearly 3 at.%
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W were dense and compact. X-ray photoelectron spectroscopy (XPS) revealed that Al
and W existed in the form of metal instead of oxides after Ar+ etching, indicating the
formation of Al–W alloys. They also investigated the ternary systems including
Al–W–Mn [25] and Al–Mo–Ti [28] in the lewis acidic AlCl3/[EMIM][Cl] IL which
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Zn can be used as a protective layer to prevent the substrates from corrosion, and
there already have been many reports about the electrodeposition of Zn from ILs
[29-31]. Using choline chloride (ChCl)/urea mixture, Bakkar et al. [29] deposited a
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smooth Zn layer onto Mg substrate with greatly improved corrosion resistance. They
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particularly investigated the deposition behavior of Mg in five different ChCl-based
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ILs. As shown in Fig. 2, the lowest corrosion rates of Mg were achieved in ChCl/urea
and ChCl/Gl systems, but Mg suffered pitting in ChCl/Gl. Therefore ChCl/urea would
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be the most suitable solvent for the deposition of Zn onto Mg substrates.
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Hsiu et al. [31] electrodeposited Zn particles in ZnCl2/[EMIM][Cl] IL with
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was added into the IL and the temperature was 50 °C. The results suggested that
[Zn(DCA)3]– complex anion was formed through the reaction of Zn(II) with DCA–
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instantaneous nucleation under diffusion control. Pan et al. [32] added 1 wt.% ZnCl2
AZ91D Mg alloy at room temperature. The effect of the deposition potential on the
microstructure, the deposition rate and the chemical composition of the deposit was
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also studied. The results showed that as the deposition potential became more
negative, the deposition rate increased and the content of Zn in the coating decreased.
When the deposition potential was –0.2 V (vs. Al), a homogeneous chemical
composition of the coating was obtained. However, the composition was non-uniform
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as the potential became more negative, which could possibly be attributed to the fast
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reduction of Al at a more negative potential and the relatively low ZnCl2
concentration in IL.
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2.3. Copper (Cu)
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The electrodeposition of Cu is common in the aqueous solutions as well as in the
ILs, the research associated with the deposition of Cu in ILs is focused on the
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nucleation mechanism. Endres and co-workers have done plenty research on the
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electrodeposition of Cu and its alloys [33-35]. Murase et al. [36] studied the
Cu metal into the IL and found that Cu(I) was stable while Cu metal was oxidized.
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IL. The size of the nanoparticles obtained from [Py1,4][TFSI] was about 20 nm, which
was bigger than that obtained from [EMIM][TFSI] (about 10 nm). XPS
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characterizations showed that Cu nanoparticles formed from both ILs were partly
oxidized, resulting in a CuO shell. Tsuda et al. [37] and Zhang et al. [38] studied the
electrochemical behavior of Cu2O and CuO in the ChCl-based IL system. Tsuda et al.
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rate constant, the Cu(I) diffusion coefficient and the transfer coefficient of the
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Cu(I)/Cu(II) reaction in the ChCl/urea IL. The authors also proved that ChCl/urea IL
system shares the same physicochemical properties with other common room
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temperature ILs such as tri-1-butylmethylammonium
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bis[(trifluoromethyl)sulfonyl]imide ([Bu3MeN][TFSI]) [39]. Similarly, Lloyd et al.
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[40] reported the similar study associated with the kinetics of the Cu(I)/Cu(II) reaction.
Zhang et al. [38] investigated the electrochemical reduction of CuO to copper in the
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ChCl/ethylene glycol IL at 80 °C, and the mechanism for this reduction process was
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nucleation mechanism of Cu was also revealed. Rousse et al. [42] reported the
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relationship between the deposition potential and the composition of Cu-Zn alloy was
also investigated. As the reduction of Zn begins around –1.6 V (vs. Ag), an increase of
Zn percentage can be observed, between –1.6 V (vs. Ag) and –2.25 V (vs. Ag), the Zn
content decreases whereas the Zn content increases again when the potential is more
negative than –2.25 V (vs. Ag). Wang et al. [43] co-deposited Ni–Cu alloy coatings on
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Cu substrates in the ChCl-urea IL. The onset reduction potentials for Cu (–0.32 V)
and Ni (–0.47 V) were close, suggesting that the co-deposition of Ni–Cu could be
easily achieved. As shown in Fig. 3, the typical current-time transients revealed that
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nucleation/growth mechanism. The coating containing about 17.6 at.% Cu exhibited
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the best corrosion resistance.
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2.4. Iron (Fe), Cobalt (Co) and Nickel (Ni)
Due to their unique magnetic and thermophysical properties, there has been
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considerable interest in the electrodeposition of iron-group metals (Fe, Co, and Ni)
and their alloys. ILs have become an ideal solvent for their electrodeposition since
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they benefit the formation of high quality deposited layers. Chum et al. [8] found that
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with different pH. It was found that pH affected the solubility of Fe(II) and the
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could be observed whereas in the alkaline solution, Fe(II) was difficult to be reduced.
Endres et al. [45] added anhydrous FeCl3 and 2 wt.% of nicotinic acid into
average size of about 64 nm. There have been several reports about the
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employed the anodic aluminum oxide (AAO) to grow Co nanowires. The cobalt
(SEM) photos of Co nanowires are shown in Fig. 4. It was found that the average
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diameter of cobalt nanowires was nearly 45 nm, which corresponded well with the
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diameter of pores on the porous anodic alumina template. In terms of the morphology
and property, the cobalt nanowires electrodeposited from IL system had a smoother
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surface and better magnetic properties than the ones electrodeposited from an aqueous
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solution, which could be attributed to the different crystalline structures of nanowire,
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the crystalline grain size, and the defects in nanowires. The cobalt nanowires showed
good squareness and the X-ray diffraction (XRD) patterns revealed that the Co
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glassy carbon electrodes in the air- and water-stable [EMIM][DCA] IL. SEM photos
indicated that the morphology of the nickel deposits depended on the deposition
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potential. XRD spectroscopy results showed that the nickel deposits had crystalline
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nature. Apart from Cu, Mohan and co-workers also investigated the electrodeposition
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Light metals (such as lithium (Li), sodium (Na), magnesium (Mg), etc.) are very
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reactive and have very negative redox potentials, therefore the electrodeposition of
such metals cannot be achieved in the traditional aqueous solutions due to the
hydrogen evolution before the reduction of the metals. ILs with their supreme
properties such as wide electrochemical window and good thermal stability become
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the ideal electrolytes for the electrodeposition of such metals. A variety of ionic
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liquids have been used for the deposition of Mg and group I metals [50-57].
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Gasparotto et al. [53] studied the electrochemical behavior of Li on the Au(111) in the
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air- and water-stable [Py1,4][TFSI] IL with 0.5 M Li[TFSI]. Cyclic voltammetry (CV)
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and scanning tunneling microscopy (STM) indicated the underpotential deposition
formation of at least two monolayers, and eventually Li-Au alloy was formed. Yan et
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al. [56] added N-methyl-2-pyrrolidone (NMP) into [EMIM][TFSI] and studied the
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electrodeposition of Cu and Li. It was found that NMP could effectively increase the
solubility of Cu(II) in the IL. The UPD of Li was observed at about –2 V (vs. Pt), and
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as the deposition potential became more negative, Li–Cu coatings with higher Li
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content could be obtained. The obtained Li–Cu coatings were dense and adherent, and
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after dissolving the Li–Cu deposits in distilled water for 5 min, the SEM images
behavior of Na/Na(I) redox couple in 12 different ILs, and the results indicated that
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window was insufficient enough to observe the formation and removal of bulk Na.
The authors also calculated the diffusion coefficients of Na+ in the aforementioned
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ILs.
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Nuli et al. [51] added 1 M Mg(CF3SO3)2 into [BMIM][BF4] and firstly
investigated the electrodeposition and dissolution processes of Mg on Ag, Pt, Ni, and
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stainless-steel substrates. Ag substrate had a higher deposition/dissolution efficiency
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and a less overpotential than Pt, Ni, and stainless-steel electrodes. Energy dispersive
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spectroscopy (EDS) results indicated that Mg existed in the deposited film and the
deposits were dense. Feng et al. [50] conducted the similar research to study the effect
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results showed that the Ag substrate could react with the deposited Mg to form Ag-Mg
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Mg and promoted the cycling efficiency. Cheek et al. [52] used the procedures
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described in previous work [50, 51] but failed to reproduce the electrodeposition of
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out that the electrochemical window of the imidazolium IL was insufficient for the
reduction of Mg, whereas the BMP-based ILs could be used for the reduction of
several Mg salts. Besides, the elevated temperature was indispensable for the
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occurred in the IL-based electrolyte containing both Mg and Li salts. However, the
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reduction of Mg would be difficult to proceed in the IL-based electrolyte containing
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Mg only. This phenomenon could be attributed to a kind of “induced deposition” for
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4. Electrodeposition of rare-earth metals
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As the reactive light metals, rare-earth metals also have very negative redox
potentials. To date, there have been many reports regarding the electrodeposition of
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rare-earth metals such as lanthanum (La), dysprosium (Dy), cerium (Ce), Samarium
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IL, they found that the solubility of LaCl3 in the IL increased with the increasing
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acidity of the electrolytes. Raman spectra indicated the presence of AlCl −4 and Al 2 Cl 7−
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LaCl3 saturated melt with the addition of SOCl2 and excessive LiCl. Legeai et al. [67]
The thickness of the La film was about 350 nm after the potentiostatic
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to La was irreversible which agreed well with the conclusion from Tsuda et al. [71]. A
grey Eu deposit could be obtained at –3.1 V, after washing with acetone the deposits
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quickly oxidized in the air and formed a white layered substance, which could
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possibly indicate the formation of Eu metal.
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behavior of Dy in trimethyl-pentylphosphonium bis(trifluoromethanesulfonyl)imide
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([P2,2,2,5][TFSI]) IL. CV showed that the reduction of Dy(III) to Dy included just one
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step and no anodic peak ascribed to the oxidation of Dy metal was observed. This
result indicated that the reduction of Dy was irreversible and it agreed well with the
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conclusion from Bhatt [60] and Tsuda [71] who studied the electrochemical behavior
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calculated the diffusion coefficient and the activation energy for diffusion of Dy in
[P2,2,2,5][TFSI]. After etching with Ar+ to remove the affect from the oxidation for the
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surface layer of Dy, it was found that the deposit was Dy metal according to XPS
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results [65]. Kazama et al. [64] continued to study the the nucleation and growth
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when the applied overpotential became more negative than the deposition peak
800–900 nm.
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uniform, adherent cerium oxide thin layer on stainless steel. The content of this
growth rate and crystallinity, thus controlling the morphology of the deposited layer.
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Hatchett et al. [63] used [Me3NBu][TFSI] IL to dissolve Ce2(CO3)3 and investigated
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the electrochemical behavior of Ce on Au, Pt and glassy carbon electrodes
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potentials more positive than the reduction potential in aqueous solutions. Lisenkov et
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al. [68] added CeCl3 into AlCl3/[BMIM][Cl] IL system and successfully co-deposited
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Al-Ce metallic protective coating on surface of Pt and AA2024 Al alloy. The formed
coating exhibited a globular microstructure and had a thickness of nearly 75 µm. The
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aluminum alloy, however the content of Ce in the coating was low, the process should
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Tachikawa et al. [69] studied the electrochemical behavior of Eu(II) and Eu(III)
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and Eu(III). Nagaishi et al. [73] examined the spectroscopic and electrochemical
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diffusion coefficient of Eu(III) were determined. It was found that the redox potential
in the dehydrated IL was shifted to 0.75 V more positive than that in aqueous solution.
Yamagata et al. [72] investigated the electrochemical behavior of Eu(III), Sm(III) and
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V respectively (vs. Ag/Ag(I)). The mobility of these ions was very low and their
estimated diffusion coefficients were around 10–8 cm2 s–1, which could be attributed to
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the complex formation or the strong coulombic interaction with TFSI–. Gomez et al.
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[62] investigated the co-deposition of Sm and Co in the ChCl-urea IL system, the
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solution viscosity. The content of Sm increased as the deposition potential became
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more negative.
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Glukhov et al. [61] investigated the electrochemical behavior of Y, Gd and Yb in
[Bu3MeN][OTf] and [BMP][OTf] ILs, the CF3SO3− -based ILs could be used to
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electrodeposit rare-earth metals and their alloys, and the BMP+-based ILs had wider
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rare-earth metals and their alloys. This result matched well with the conclusion from
Cheek et al. [52] who studied the electrodeposition of Mg in ILs. Tsuda et al. [70]
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[P2,2,2,5][TFSI] IL, the diffusion coefficient of Nd(III) was about 10–8 cm2 s–1, Raman
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spectroscopy revealed that the interaction between Nd(III) and TFSI– was strong,
which corresponded well with the results from Yamagata et al. [72].
Noble metals such as platinum (Pt), palladium (Pd), silver (Ag), ruthenium (Ru),
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rhodium (Rh) are resistant to corrosion and oxidation and they have been widely used
as important catalysts. The electrodeposition of this type of metals and alloys in the
ILs have been reported a lot. For example, Sun and his co-workers have done plenty
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authors started early from studying the electrodeposition of Zn [31] and then they
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continued to investigate the electrodeposition of Pt-Zn alloys [76]. They also studied
the electrochemical behavior of Cu at first [77] and later carried out a great deal of
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research regarding the electrodeposition of Pd-based alloys including Pd-Cu and
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Pd-Sn [74, 75].
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He et al. [78] investigated the electrodeposition behavior of Pt in [BMIM][BF4]
comparison. Atomic force microscopy (AFM) indicated that fairly dense and separate
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spherical Pt nanoclusters with a diameter of nearly 100 nm were obtained in ILs. XPS
hemispherical growth. The Pt films prepared in both ILs showed high electrocatalytic
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performance for the electro-oxidation of methanol. Zhang et al. [79] investigated the
of Pt(IV)-Pt(II) and Pt(II)-Pt two processes depending on the applied potential. The
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well as the fraction of Pt(110) and Pt(100) crystalline orientation domains. Huang et
al. [76] added PtCl2 into the ZnCl2/[EMIM][Cl] IL for electrodeposition of Pt-Zn
alloy at 90 °C. Pt(II) was found to be reduced at a potential slightly more positive than
Zn(II), and the morphology and composition of the electrodeposits were dependent on
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the deposition potential and the concentration of Pt(II). Guillamat et al. [80] obtained
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the Pt–Co alloy with different composition from the ChCl/urea IL. XPS indicated that
Pt and Co elements were in the metallic state without the formation of metal oxides.
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The electrodeposits were uniformly distributed and showed nodular morphology. In
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order to investigate the co-deposition of Pt–Fe alloy, Huang et al. [81] added Pt(II)
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and Fe(II) into [BMP][DCA], [BMP][TFSI] and a mixture of [BMP][DCA] and
into the [BMP][TFSI] IL to increase the solubility of PtCl2 and FeCl2. The Pt–Fe alloy
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coatings with various atomic ratios of Pt/Fe were obtained and the coating with equal
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content of Pt and Fe exhibited the largest reductive current density for oxygen
PdCl42– in [BMP][TFSI] IL. Pd(II) could be irreversibly reduced to Pd, and the
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diffusion coefficient of PdBr42– was also calculated. XRD and XPS indicated that the
three-dimensional progressive nucleation under the diffusion control. Jou et al. added
Pd–Sn [74] at 120 °C. The presence of Pd(II) in the deposition electrolytes decreased
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the overpotential required for the Cu electrodeposition. The deposits showed nodular
morphology and the crystal size of the deposit decreased with increasing deposition
deposits increased as the deposition potential became more negative, the morphology
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of Pd–rich Pd–Sn deposits was featured by compact nodules whereas the Sn-rich
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deposits were polyhedral crystals [74].
The electrodeposition of other noble metals such as Ru, Ag, Rh have also been
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reported. Mann et al. [83] studied the electrodeposition behavior of Ru on Au(111) in
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[BMIM][DCA] IL. It was found that the formation of Ru(IV)-complex was a key
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prerequisite for the deposition of Ru. Thin Ru films with the thickness of
results indicated the metallic state of these films. Raz et al. [84] investigated the
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that the deposition and dissolution of Ru took place at –2.1 and 0.2 V (vs. Pt),
Au-Ag nanoparticles with the crystal size of 16-30 nm. Jayakumar et al. [86] also
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surface morphologies and metal compositions of the deposits varied with the
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types of metals and their alloys in ILs with a particular focus on the reactive metals
metals and their alloys are discussed. ILs become an appealing alternative to aqueous
solvents due to their widened electrochemical window which enables the deposition
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of certain metals that are difficult to be electrodeposited in aqueous solutions.
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Moreover, deposits with high quality and various morphologies can be achieved
owing to the absence of the hydrogen evolution which is more likely to occur in
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aqueous electrolytes. In addition to the chloroaluminate ILs which is defined as the
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first generation of ILs, an increasing percentage of the electrodeposition of metals
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have been performed in air- and water-stable ILs, especially those reactive metals
including light metals and rare-earth metals. Apart from studying the surface
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morphology and adhesion strength of deposits, more attention is paid on the kinetic
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parameters of metal ions and their corresponding nucleation and growth mechanisms.
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slow rates of diffusion which is ascribed to the high viscosity of ILs. The typical
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potentials leading to nanoscale deposits. The key advantage of using ILs centers
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around the ability to tailor the redox potentials through metal speciation when
depositing the metals, and this tunability of redox properties allows for the
aqueous solvents. In a word, the unique properties of ILs enable the formation of
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Although ILs are promising electrolytes, there remain many aspects that require
urgent investigations for better application of ILs. In terms of the inherent properties,
ILs have high viscosity which leads to the low mobility and diffusion coefficient of
metal ions. The high concentration of ions doesn’t necessarily result in high
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conductivities. The conductivity of IL is largely influenced by the low viscosity and
the conductivity values are generally smaller than 10 mS cm–1. The solubility of metal
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salts in ILs varies and the thermodynamics underpinning this variability are poorly
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understood. Fundamental electrochemical issues such as the mass transport of the
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species in ILs, the speciation of metal ions, the double-layer structure at the electrode,
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the local solubility in the diffusion layer region and the adsorption of ionic species on
uneconomical compared with traditional aqueous and organic solvents, the cost of ILs
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Corresponding measures should be taken to tackle the problems mentioned above and
a key objective of future research will be focused on reducing the cost of the ILs. As
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research will help to explore the mechanism and rules underpinning the
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electrodeposition process. The efforts will also be made to design and prepare ILs
with specific composition according to user’s needs and hopefully the desired
physical and chemical properties (e.g., high conductivity, high stability, suitable
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[EMIM][Cl] 1-ethyl-3-methylimidazolium chloride
[BMIM][Cl] 1-butyl-3-methylimidazolium chloride
XPS X-ray photoelectron spectroscopy
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ChCl choline chloride
[BMP][DCA] N-butyl-N-methyl-pyrrolidinium dicyanamide
[TMHA][TFSI] trimethyl-N-hexylammonium
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bis(trifluoromethylsulfonyl)imide
[Py1,4][TFSI] 1-butyl-1-methylpyrrolidinium
bis(trifluoromethylsulfonyl)imide
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[Bu3MeN][TFSI] tri-1-butylmethylammonium
bis(trifluoromethylsulfonyl)imide
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MEIC 1-methyl-3-ethylimidazolium chloride
AAO anodic aluminum oxide
SEM scanning electron microscopy
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NMP N-methyl-2-pyrrolidone
[N2,1,1,3][TFSI] N-ethyldimethylpropylammonium
bis(trifluoromethylsulfonyl)imide
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[OMP][TFSI] 1-octyl-1-methyl-pyrrolidinium
bis(trifluoromethylsulfonyl)imide
[Me3NnBu][TFSI] N,N,N-Trimethyl-n-butylammonium
bis(trifluoromethanesulfonyl)imide
[P2,2,2,5][TFSI] trimethyl-pentylphosphonium
bis(trifluoromethanesulfonyl)imide
[BMIM][PF6] 1-butyl-3-methylimidazolium hexafluorophosphate
AFM atomic force microscopy
ORR oxygen reduction reaction
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Acknowledgements
(51374005), Research Fund for the Doctoral Program of Higher Education of China
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Education Commission and Education Development Foundation-China (11CG12),
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National Key Technology R&D Program (2011BAE13B08).
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Figure captions:
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33 mol% EMIC-AlCl3 ionic liquid, (b) the melt containing 0.1 M ethylene glycol, and
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(c) the ionic liquid containing 0.2 M ethylene glycol. Reprinted from ref. 22, with
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theoretical models for three-dimensional nucleation. Reprinted from ref. 43, with
Fig. 4. (a) FE-SEM images of surface (a) and cross-sectional (b) morphology of Co
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nanowires with alumina partially removed using 0.5 M NaOH solution. Reprinted
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from ref. 46, with permission from Elsevier.
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of PtCl42– to PtCl62– and Pt and (B) the four-electron electroreduction of PtCl62– to Pt.
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Reprinted with permission from ref. 79. Copyright 2011 American Chemical Society.
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