Accepted Manuscript

Electrodeposition of metals and alloys from ionic liquids

Fan Liu, Yida Deng, Xiaopeng Han, Wenbin Hu, Cheng Zhong

PII: S0925-8388(15)31113-0
DOI: 10.1016/[Link].2015.09.137
Reference: JALCOM 35412

To appear in: Journal of Alloys and Compounds

Received Date: 8 August 2015

Revised Date: 8 September 2015
Accepted Date: 15 September 2015

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/[Link].2015.09.137.

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 ACCEPTED MANUSCRIPT

Electrodeposition of metals and alloys from ionic liquids

Fan Liua, Yida Dengc, Xiaopeng Hanb, Wenbin Hua,b,c, Cheng Zhongb,*

a
State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University,

Shanghai, 200240, China

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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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Electrodeposition of metals and alloys in ionic liquids has been employed in a

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broader range of fields. Issues regarding the evolution of hydrogen, toxicity of

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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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possibly be deposited from traditional aqueous solutions.

Keywords: Electrodeposition; ionic liquids; metals; alloys; redox potential

* Corresponding authors. Tel.: +86 22 22456823; fax: +86 22 22456823.

E-mail address: [Link]@[Link] (C. Zhong).
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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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additives) or by the electrochemical parameters including deposition potential and

current density. However, conventional aqueous solutions cannot be used as

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electrolytes to deposit metals with very negative redox potential due to their narrow
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electrochemical windows. Organic solvents are volatile and inflammable, and

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high-temperature molten salts are generally corrosive and require the

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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increasing interest as non-aqueous electrolytes for the electrodeposition. As

environment-friendly solvents, ILs also have great potential in replacing the

traditional hazardous solvents to meet the growing environmental demands.

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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cation as well as an inorganic or an organic anion. This highly asymmetric structure

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].

Furthermore, ILs are known as “designer solvents” since their physicochemical

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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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1-ethyl-3-methylimidazolium ([EMIM]) as cation and tetrafluoroborate ([BF4]) as

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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

those ILs containing bis(trifluoromethylsulfonyl)imide ([TFSI]) have been widely

used in many applications [11].

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ILs distinguish themselves from traditional molecular liquids in many ways as

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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reviews the latest development of electrodeposition of various types of metals and

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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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2. Electrodeposition of common metals

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2.1. Aluminum (Al)

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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

important issue. Tang et al. [15] used AlCl3/1-ethyl-3-methylimidazolium chloride

([EMIM][Cl]) IL system to electrodeposit Al coating on AZ91D magnesium (Mg)

alloy. Prior to the electrodeposition, a zincate pretreatment was applied so that a Zn

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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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AlCl3/[EMIM][Cl] IL system for the electrodeposition of Al on the AZ91D Mg alloy.

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Before the electrodeposition, a novel electrolytic etching pretreatment at 25 mA cm–2

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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electrolytic etching pretreatment [16]. Ueda and co-workers have systematically

investigated the electrodeposition of Al and its alloys in room temperature ILs and

AlCl3-based molten salts [20-24]. For example, they [22] successfully

electrodeposited an Al layer on the AZ121 Mg alloy from the same IL system

(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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electrodeposition of Al-based alloys [25-28]. In terms of the binary system, they

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electrodeposited Al–W [26] and Al–Hf [27] alloy. They added K3[W2Cl9] into the
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AlCl3/[EMIM][Cl] IL system to serve as the source for W, through controlling

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

provides a holistic view of the electrodeposition of Al-based alloys.

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2.2. Zinc (Zn)

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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different acidity by adding different percentage of ZnCl2, the morphology of Zn

deposits could be controlled by adjusting the deposition temperature and potential.

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Deng et al. [30] investigated the electrochemical reaction of Zn(II)/Zn on Mg alloy

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substrates in N-butyl-N-methyl-pyrrolidinium dicyanamide ([BMP][DCA]) IL. ZnCl2

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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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anions, which later could be reduced to Zn metal through a single-step electron

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transfer process. The electrodeposition of Zn involved three-dimensional

instantaneous nucleation under diffusion control. Pan et al. [32] added 1 wt.% ZnCl2

into the AlCl3/[EMIM][Cl] IL system and successfully co-deposited Al and Zn on

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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crystalline structure, the kinetics parameters of Cu ions and the corresponding

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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

electrochemical behavior of copper in trimethyl-N-hexylammonium

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bis(trifluoromethylsulfonyl)imide ([TMHA][TFSI]) IL. They added Cu(II) salts and

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Cu metal into the IL and found that Cu(I) was stable while Cu metal was oxidized.
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Brettholle et al. [33] dissolved the Cu wire in two ILs

(1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([Py1,4][TFSI]) and

[EMIM][TFSI]) to produce Cu(I). Cu nanoparticles were electrodeposited from this

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.

[37] calculated the electrochemical parameters including the standard heterogeneous

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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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also proposed ( ). Mohan et al. [41] successfully

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electrodeposited a dense and adhesive Cu layer on mild steel in [EMIM][Cl]/ethylene

glycol IL electrolyte containing CuCl2. The three-dimensional instantaneous

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nucleation mechanism of Cu was also revealed. Rousse et al. [42] reported the
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research of electrodeposition of Cu-Zn thin films from [Py1,4][TFSI] IL, 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

the formation of Ni–Cu deposits followed the three-dimensional instantaneous

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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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Fe could be reversibly deposited on W and glassy carbon electrodes in the

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AlCl3-based IL system. Pye et al. [44] investigated in detail the electrochemical

behavior of Fe in AlCl3/1-methyl-3-ethylimidazolium chloride ([MEIC]) IL system

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with different pH. It was found that pH affected the solubility of Fe(II) and the
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kinetics of the reduction. In the acid solution, quasi-reversible reduction of Fe(II)

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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

AlCl3/[BMIM][Cl] IL system and successfully deposited Fe nanoparticles with the

average size of about 64 nm. There have been several reports about the

electrodeposition of Co and Ni in the AlCl3-based IL system. Yang et al. [46]

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employed the anodic aluminum oxide (AAO) to grow Co nanowires. The cobalt

nanowires were obtained through the direct current electrodeposition in the

[EMIM][Cl] IL with the addition of ethylene glycol. Scanning electron microscopy

(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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nanowires fabricated from IL system were of a polycrystalline structure. Deng et al.

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[47] investigated the electrodeposition behavior of Ni on polycrystalline Cu and

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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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of alloys based on iron-group metals including Co–Cr and Fe–Ni–Cr in ChCl-based

ILs [48, 49].

3. Electrodeposition of light metals

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].

Endres and co-workers investigated the electrodeposition of Li in ILs [53, 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

(UPD) of Li on Au(111), which followed a layer-by-layer mechanism with the

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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

showed that there was only Cu framework left.

Wibowo et al. [54] conducted CV experiments to study the electrochemical

behavior of Na/Na(I) redox couple in 12 different ILs, and the results indicated that

except for [BMP][TFSI], N-ethyldimethylpropylammonium

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bis(trifluoromethylsulfonyl)imide ([N2,1,1,3][TFSI]) and N-hexyltriethylammonium

bis(trifluoromethylsulfonyl)imide ([N6,2,2,2][TFSI]), in most of the ILs the potential

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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of metal substrates (Ag, Cu and Ni) on Mg deposition-dissolution processes. The

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results showed that the Ag substrate could react with the deposited Mg to form Ag-Mg
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alloy, which decreased the overpotential of electrochemical deposition-dissolution of

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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magnesium. The authors tried to electrodeposite Mg in [EMIM][BF4],

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1-butyl-1-methylpyrrolidinium triflate ([BMP][TfO]) and [BMP][TFSI] ILs. It turned

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

electrodeposition of Mg in these ILs. Shimamura et al. [55] investigated the

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co-deposition of Mg with Li in the N,N-diethyl-N-methyl-N-(2-methoxyethyl)

ammonium bis(trifluoromethylsulfonyl)imide ([DEME][TFSI]) IL. The reversible

reduction and oxidation of Mg accompanied by the co-deposition/co-dissolution of Li

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

binary metal deposition process [58, 59].

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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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(Sm), europium (Eu), and ytterbium (Yb) [60-73].

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Tsuda et al. [71] studied the electrochemical behavior of La in AlCl3/[EMIM][Cl]

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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anions. The La metal could be irreversibly electrodeposited at around –1.95 V in the

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LaCl3 saturated melt with the addition of SOCl2 and excessive LiCl. Legeai et al. [67]

reported the electrodeposition of La in the ambient atmosphere in

1-octyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide ([OMP][TFSI]) IL.

The thickness of the La film was about 350 nm after the potentiostatic

electrodeposition for 2 h. Bhatt et al. [60] investigated the electrochemical behavior of

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La, Sm and Eu in N,N,N-Trimethyl-n-butylammonium

bis(trifluoromethanesulfonyl)amide ([Me3NnBu][TFSI]) IL. The reduction from La(III)

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.

Kurachi et al. [65] investigated the electrochemical behavior and diffusion

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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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of La. The electrodeposition of Dy was controlled by diffusion and the authors

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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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processes of Dy in [P2,2,2,5][TFSI] IL through chronoamperometry, the nucleation

mechanism of Dy changed from instantaneous nucleation to progressive nucleation

when the applied overpotential became more negative than the deposition peak

potential of Dy. And the electrodeposited Dy particles had a diameter of around

800–900 nm.

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Lair et al. [66] employed the [BMIM][TFSI]/ethanol IL to electrodeposit a

uniform, adherent cerium oxide thin layer on stainless steel. The content of this

hydrophobic IL ([BMIM][TFSI]) in the deposition electrolyte greatly affected the Ce

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

respectively. The deposition of Ce species at all three electrodes took place at

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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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introduction of Ce could effectively improve the corrosion resistance of AA2024

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aluminum alloy, however the content of Ce in the coating was low, the process should
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be optimized to obtain higher concentration of Ce in the coating in the future.

Tachikawa et al. [69] studied the electrochemical behavior of Eu(II) and Eu(III)
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in the hydrophobic [BMP][TFSI] IL and calculated the diffusion coefficient of Eu(II)

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and Eu(III). Nagaishi et al. [73] examined the spectroscopic and electrochemical
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properties of Eu(III) in the hydrophobic [DEME][TFSI] IL with different water

content. Electrochemical parameters such as redox potential of Eu(III)/Eu(II) and

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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Yb(III) in the [BMP][TFSI] and [EMIM][TFSI] ILs. The redox reactions of

Eu(III)/Eu(II), Sm(III)/Sm(II) and Yb(III)/Yb(II) occurred at –0.3 V, –1.6 V and –1.0

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

deposition temperature was 70 °C in order to stimulate mass transfer and lower

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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
M

electrodeposit rare-earth metals and their alloys, and the BMP+-based ILs had wider
D

electrochemical windows and were more suitable for the electrodeposition of

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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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studied the electrochemical behavior and diffusional behavior of Nd(III) in

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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].

5. Electrodeposition of noble metals

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

research on the electrodeposition of noble metal-based alloys in ILs [74-76]. The

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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]

and 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) ILs, the

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electrodeposition behavior of Pt in HClO4 aqueous solution was also presented as

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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

proved that these nanoclusters were Pt metal. The electrodeposition process of Pt in

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ILs followed three-dimensional progressive nucleation with diffusion-controlled

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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

electrochemistry of Pt(IV)-Pt(II)-Pt redox system in [DEME][BF4] IL. Fig. 5 shows

the schematic illustration of Pt deposition. The reduction from Pt(IV) to Pt consisted

of Pt(IV)-Pt(II) and Pt(II)-Pt two processes depending on the applied potential. The

deposition potential greatly affected the size and morphology of Pt nanoparticles as

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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

[BMP][TFSI] ILs, respectively. It was found that [BMP][Cl] should be introduced

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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

reduction reaction (ORR).

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Bando et al. [82] investigated the electrochemical behavior of PdBr42– and

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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

deposit was crystalline Pd metal, and the electrodeposition of Pd involved

three-dimensional progressive nucleation under the diffusion control. Jou et al. added

[EMIM][Cl] into [EMIM][BF4] and investigated the electrodeposition of Pd–Cu [75],

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

overpotential [75]. In the Pd–Sn co-deposition, the content of Sn in the Pd–Sn

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

approximately 5 nm and a relatively homogeneous morphology were obtained. XPS

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results indicated the metallic state of these films. Raz et al. [84] investigated the
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electrodeposition behavior of Ru on silicon in [BMIM][PF6] IL. CV results indicated

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that the deposition and dissolution of Ru took place at –2.1 and 0.2 V (vs. Pt),

respectively. Tsai et al. [85] employed [BMIM][BF4] IL for the electrodeposition of

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Au-Ag nanoparticles with the crystal size of 16-30 nm. Jayakumar et al. [86] also
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investigated the electrochemical behavior of Ru, Rh and Pd in [BMIM][Cl] IL. The

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surface morphologies and metal compositions of the deposits varied with the

composition of the electrolytes as well as the electrodeposition potential.

6. Summary and Outlook

This article reviews the latest development of the electrodeposition of different

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types of metals and their alloys in ILs with a particular focus on the reactive metals

with very negative redox potentials. Voltammetric investigations of four groups of

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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However, the voltammetry of a number of simple redox couples are characterized by

slow rates of diffusion which is ascribed to the high viscosity of ILs. The typical
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instantaneous nucleation is seen in the majority of metals with negative redox

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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

co-deposition of metals that would have large difference in redox potentials in

aqueous solvents. In a word, the unique properties of ILs enable the formation of

novel alloys and make it easier to create nanoscale deposits.

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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

the substrate or deposit remain to be thoroughly illustrated. Moreover, ILs are

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uneconomical compared with traditional aqueous and organic solvents, the cost of ILs
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is still high which greatly prohibited their applicability on a large scale.

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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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ILs progressively become more inexpensive and available, an increasing amount of

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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

viscosity, and wide electrochemical window) can be achieved.

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Appendix List of symbols

ILs ionic liquids

[C2H5NH3][NO3] ethylammonium nitrate
[EMIM] 1-ethyl-3-methylimidazolium
[BF4] tetrafluoroborate
[TFSI] bis(trifluoromethylsulfonyl)imide

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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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XRD X-ray diffraction

CV cyclic voltammetry
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STM scanning tunneling microscopy

UPD underpotential deposition
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NMP N-methyl-2-pyrrolidone
[N2,1,1,3][TFSI] N-ethyldimethylpropylammonium
bis(trifluoromethylsulfonyl)imide
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[N6,2,2,2][TFSI] N-hexyltriethylammonium bis(trifluoromethylsulfonyl)imide

EDS energy dispersive spectroscopy
[BMP][TfO] 1-butyl-1-methylpyrrolidinium triflate
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[DEME][TFSI] N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium

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

This work was supported by National Nature Science Foundation of China

(51374005), Research Fund for the Doctoral Program of Higher Education of China

(20100073120109), “Chen Guang” project supported by Shanghai Municipal

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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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Fig. 1. SEM images of Al electroplating on a AZ121 alloy obtained at 10 °C from (a)

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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permission from Springer.

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Fig. 2. Potentiodynamic polarisation curves of Cp Mg in different ILs at 60 °C.

Reprinted from ref. 29, with permission from Elsevier.

Fig. 3. (a) Current-time transients resulting from chronoamperometric experiments

that were performed on a Cu microelectrode in the 1:2 ChCl-urea IL containing 0.6 M

NiCl2·6H2O and 0.01 M CuCl2·2H2O by stepping the potential at 70 °C. (b)

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Comparison of the dimensionless experimental current-time transients with the

theoretical models for three-dimensional nucleation. Reprinted from ref. 43, with

permission from Elsevier.

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.

Fig. 5. Schematic illustration of Pt deposition via (A) the disproportionation reaction

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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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PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC