Electrochimica Acta 54 (2009) 53075319

Contents lists available at ScienceDirect

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

Review

Electrodeposition of metals from non-aqueous solutions

Wojciech Simka , Dagmara Puszczyk, Ginter Nawrat
Department of Inorganic Chemistry and Technology, Faculty of Chemistry, Silesian University of Technology, B. Krzywoustego Street 6, 44-100 Gliwice, Poland

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

Article history: Electrodeposition of metals from non-aqueous solutions is reviewed. Attention is paid mainly to sur-
Received 26 September 2008 face morphology of deposits and their adhesion. The major reasons for carrying out electrodeposition in
Received in revised form 6 April 2009 non-aqueous electrolytes (such as conventional organic solvents, ionic liquids and molten salts) are the
Accepted 11 April 2009
water and air stability and the wide electrochemical window of these media. The following metals have
Available online 21 April 2009
been electrodeposited and investigated for the last 15 years: aluminum, zinc, silver, palladium, tantalum,
zirconium, gadolinium, plutonium, nickel, cobalt, and other alloys.
Keywords:
2009 Elsevier Ltd. All rights reserved.
Electrodeposition
Room temperature ionic liquids
Molten salts
Conventional organic solvents

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5308
2. Non-aqueous media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5308
2.1. Molten salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5308
2.2. Ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5308
3. Electrodeposition from the non-aqueous media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5309
3.1. Electrodeposition from conventional organic solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5309
3.1.1. Group 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5309
3.1.2. Group 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5309
3.1.3. Group 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5310
3.1.4. Group 8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5310
3.1.5. Group 10 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5310
3.1.6. Group 12 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5310
3.1.7. Group 13 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5310
3.1.8. Group 15 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5310
3.2. Electrodeposition from ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5310
3.2.1. Group 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5310
3.2.2. Group 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5311
3.2.3. Group 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5311
3.2.4. Group 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5311
3.2.5. Group 7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5311
3.2.6. Group 8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5311
3.2.7. Group 9 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5311
3.2.8. Group 10 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5311
3.2.9. Group 11 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5312
3.2.10. Group 12 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5312
3.2.11. Group 13 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5312
3.2.12. Group 14 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5313
3.2.13. Group 15 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5313

Corresponding author. Tel.: +48 32 237 26 05; fax: +48 32 237 22 77.
E-mail address: wojciech.simka@polsl.pl (W. Simka).

0013-4686/$ see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2009.04.028
5308 W. Simka et al. / Electrochimica Acta 54 (2009) 53075319

3.3. Electrodeposition from molten salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5314

3.3.1. Group 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5314
3.3.2. Group 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5314
3.3.3. Group 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5314
3.3.4. Group 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5315
3.3.5. Group 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5315
3.3.6. Group 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5316
3.3.7. Group 9 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5316
3.3.8. Group 10 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5316
3.3.9. Group 11 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5316
3.3.10. Group 12 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5316
3.3.11. Group 13 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5316
3.3.12. Group 14 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5317
3.3.13. Group 15 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5317
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5317
Appendix A. List of symbols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5317
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5317

1. Introduction ture ionic liquids, but the practical aspects of their maintenance
and handling are different enough to make them distinct from one
Electrodeposition of metals from non-aqueous solutions has another. The room temperature ionic liquids are usually quaternary
attracted attention in the last few years. Conventional aqueous solu- ammonium salts, such as tetraalkylammonium, [R4 N]+ , or are based
tions cannot be always used as electrolytes due to the liberation on cyclic amines: aromatic (pyridinium, imidazolium) and satu-
of hydrogen molecule during electrolysis, narrow electrochemical rated (piperidinium, pyrrolidinium) ones. Also the low temperature
windows, low thermal stability, and evaporation. These are the rea- molten salts based on sulfonium [R3 S]+ and phosphonium [R3 P]+
sons why scientists have searched for new non-aqueous solutions cations are well-established. Anions can be based on cyano groups,
to electrodeposit metals. The role of non-aqueous electrolytes in such as [Ag(CN)2 ] , [C(CN)3 ] or [N(CN)2 ] [1]. The early history
technology has become more and more important. Facing seri- of ILs starts in 1914, when the rst report on a room-temperature
ous problems concerning the environment and energy scientists molten salt was published by Walden [2]. He reported the physical
have found out new possibilities in electrochemical applications properties of ethylammonium nitrate, [C2 H5 NH3 ]NO3 , which has a
using non-aqueous electrolytes. However, there are technical issues melting point of 12 C and is formed by the reaction of concentrated
that make their commercialization hard, such as cell heat bal- nitric acid with ethylamine. In the 1970s and 1980s, Osteryoung and
ance, corrosion of cell components, low current efciency, dendritic co-workers, and also Hussey and co-workers carried out research
deposition, and similar difculties. To overcome these problems on organic chloride/aluminum chloride ambient-temperature ionic
intensive and systematic studies (scientic and technological) of liquids [39]. The ionic liquids based on AlCl3 can be considered
new electrolytes are required. as the rst generation of ionic liquids. AlCl3 -based ILs have hygro-
scopic nature, so they must be prepared and handled under an
2. Non-aqueous media inert-gas atmosphere. This has delayed progress in their use in
many applications. The synthesis of air- and water-stable ionic
2.1. Molten salts liquids, which are regarded as the second generation of ILs, has
attracted interest in their utilization in various elds. In 1992,
A classical solution of an electrolyte is obtained by dissolution Wilkes and Zaworotko reported the rst air- and moisture-stable
of a salt in a molecular solvent. Such a system consists of solvated ILs based on the 1-ethyl-3-methylimidazolium cation, [EMIM], with
ions, their charged or neutral combinations and solvent molecules. tetrauoroborate or hexauorophosphate as anions [10]. These
On the other hand, a salt may be melted down (liquied) by pro- ionic liquids can be prepared and safely stored outside the inert
viding heat to the system, to counterbalance the salt lattice energy. atmosphere. Generally, they are water insensitive, but exposure to
Such a system called molten salt or ionic liquid (abbreviated as moisture for a long time sometimes causes changes in their phys-
IL, list of the symbols is placed at the end of article) consists of ical and chemical properties [11]. Within the last few years ionic
ions and their combinations and is free of any solvent molecules. liquids based on more hydrophobic anions have been developed,
General features of molten salts are as follows: they can function especially those containing bis(triuoromethylsulfonyl)imide [12].
as solvents, liquids (like water), have good heat capacity, can attain Ionic liquids behave very differently to traditional molecular liq-
very high temperatures (red heat, >700 C), and conduct electricity. uids when they are used as solvents. ILs are usually non-volatile,
Typical application temperatures are 4501025 C but can be as low in most cases non-ammable, less toxic, good solvents for both
as 70 C. The most common molten systems are LiClKCl, NaClKCl, organic and inorganic materials, and can be used over a wide tem-
Flinak, LiFCaF2 , but also other mixtures are used and investigated. perature range. Moreover, ILs show good electrical conductivity and
have wide electrochemical windows. Their another virtue is that the
2.2. Ionic liquids problems associated with hydrogen ions in protic solvents can be
eliminated, because ionic liquids are usually aprotic [11]. Generally
Salts having low melting points are liquid at room temperature the greatest advantages of ILs are:
and form a new class of liquids called room temperature ionic liq-
uids (RTILs). The information about RTILs can be found in the eld non-volatility,
literature with such key words as room-temperature molten salt, inammability,
ambient-temperature molten salt, low-temperature molten salt, low toxicity,
liquid organic salt or ionic liquid. Generally, the physicochemical good solubility,
properties of RTILs are the same as those of the high tempera- high thermal stability,
 W. Simka et al. / Electrochimica Acta 54 (2009) 53075319
wide electrochemical windows,
high polarity,
high purity.
Of course, there exist some exceptions to the above-mentioned
features. For instance, it was reported that some ILs may be evap-
orated and then re-condensed. The assumed non-volatility of ILs
had been the base of their common reputation of green solvents
[1]. In electrochemistry the stability window of a solvent is of great
importance. Any solvent is suitable for conducting a range of elec-
trochemical experiments on species dissolved within it, if only
these species are more easily oxidized or reduced than the solvent
itself. In RTILs, it is found that the constituent anions are oxidized
at sufciently large potentials and organic cations undergo reduc-
tion at sufciently low ones. The potentials, at which these bulk
processes appear, determine the accessible electrochemical win-
dow for each liquid [12]. The stability windows for ILs remain in
the broad range from 2 to 6 V, but typically are 4.5 V [1]. The next
outstanding property of ILs is their high thermal stability. It results
from the difference between reported melting and solidication
points that may be as high as 200 C, as it is observed in the case of
1-propyl-3-methylimidazolium chloride, [PrMeIm][Cl]. The melt-
ing point of this salt is above the room temperature (60 C), but the
solidication point is 140 C [1].
Additives, present intentionally or unintentionally, such as
halide ions or molecular solvents can extremely inuence the
results of an electrochemical investigation. Thus, where their pres-
ence is unwanted, it is important to identify and eliminate those
components. The most prevalent impurity affecting RTILs is water.
Solvating properties of RTILs vary depending on the nature of the
constituent ions; anions possessing high charge density and organic
cations with short alkyl chains stabilize more polar molecules,
whereas more lipophilic RTILs may be generated by using charge-
diffuse anions. Considering Brnsted acidity/basicity, ionic liquids
are almost always aprotic [12]. The main drawbacks of ionic liquids
are:
low conductivity,
high viscosity,
high density,
cost of production.
The density of the ionic liquids is typically within 1.21.5 g cm3 ,
but there are ILs showing the density lower than 1 g cm3 , such as
those based on the dicyanoamide anion, [N(CN)2 ] . The viscosity of
the ionic liquids is much higher than that of water (H2 O = 0.89 cP
at 25 C). Typically it is at the level of 3050 cP, but in some cases
much higher viscosities, even as high as 500600 cP have been
reported. The high viscosity of ILs causes some difculties in their
handling. Viscosity plays an important role in conductivity and
self-diffusion because conductivity is inversely proportional to the
medium viscosity, so as viscosity increases, the conductivity falls.
The self-diffusion coefcients of ILs are of the order of 1010 to
1011 m2 s1 . These relatively low values are due to high viscosity.
Room temperature conductivities, , for ILs are within a broad
range of 0.118 mS cm1 , but even the highest conductivity is
much lower in comparison to the conventional aqueous electrolyte
solutions applied in electrochemistry. For example, the specic
conductivity of an aqueous KOH (29.4 wt%) solution, applied in
alkaline batteries, reaches 540 mS cm1 . A dilution of neat ILs with
solvents (molecular liquids) also brings an increase in the conduc-
tivity. For instance, the specic conductivity of neat [EMIM][BF4 ] is
14 mS cm1 , but its 2 mol dm3 solution in acetonitrile shows the
conductivity of 47 mS cm1 . Dilution of the viscous neat ILs with
a molecular diluent reduces also the viscosity of the mixture [1].
Ionic liquids are applied in [1,1118]:
5309
a) electrochemistry as:
electrolytes for: double-layer electrochemical capacitors, in
electrolysis of aluminum (electrodeposition process) and
recovery, electrodeposition of metals and semiconductors, like
Zn and its alloys, Ag, PdAu alloy, InSb, CdTe, Ge, Ta, Cr, in
electrodeposition of elements that are inaccessible otherwise,
in a thermogalvanic cell, in lithium batteries, in a thermally
regenerative fuel cell,
b) powder and materials production:
to produce ne spherical particles of silver, nickel, iron and
carbon,
c) nuclear applications:
as fuel salt in the thorium molten salt nuclear reactor,
d) analytical chemistry as:
media for detection of gases and development of stable and
robust sensors, sensing materials for organic vapors in a quartz
crystal microbalance device,
medium in GC, HPLC,
solvents for extraction of metals,
matrixes for UVMALDI mass spectrometry,
e) nanotechnology as:
electrolytes for production of nanoscale materials like Al,
AlMn alloys, Fe, Pd,
f) other:
mono- and biphasic studies (organic synthesis),
as micro-media and a catalysts (in oxidation of methanol).
3. Electrodeposition from the non-aqueous media
3.1. Electrodeposition from conventional organic solvents
In this and in the following sections metals are divided in accor-
dance with periodic groups.
Electrodeposition of metals and alloys from non-aqueous solu-
tions (such as aromatic, dimethylsulfone, acetone and acetates)
provides cost-effective and easy to control technique to fabricate
thin lms and intermetallic compounds.
3.1.1. Group 3
Lutetiumcobalt thin lms were electrodeposited from anhy-
drous dimethylsulfoxide (DMSO) solution, containing LiCl, LuCl3
and CoCl3 , at room temperature. The surface of LuCo lm
was uniform, adhesive, had metallic luster and the lm was
amorphous [19]. From DMSO solution LuNi alloys were also elec-
trodeposited potentiostatically on the copper substrate. Deposited
lms were amorphous and deposits having up to 28.77 at.%
lutetium showed cracks. Solutions with low lutetium concentra-
tion (<0.05 M) presented ne-grained deposits without cracks, with
lutetium concentration lower than 13 at.%. The alloy phase of LuNi
adhered rmly to the substrate after heating at 520 C [20].
3.1.2. Group 4
Zirconia lms (ZrO2 ) were deposited on the stainless steel SS
316 L in a non-aqueous electrolyte based on absolute ethyl alco-
hol and ZrCl4 . The lm consisted of crystallites with a spheroidal
shape (open macroporous structure), forming agglomerates of a
very large surface area. The layer composition was very close to
the stoichiometric zirconia [21]. The preparation of lanthanum
and uranium metals at high temperatures was done in dimethyl-
formamide (DMF) and in the -butyrolactone/tetrahydrofuran
mixture (-BL/THF). The deposit of lanthanum was contaminated
by conducting salt cations (Li). The experimental results demon-
strated that uranium could be electrochemically prepared in the
organic medium at room temperature [22]. The electrochemical
behavior of titanium and Ti4+ compounds was examined in THF
solutions. Tetrabutylammonium chloride (TBACl) and LiCl were
5310 W. Simka et al. / Electrochimica Acta 54 (2009) 53075319
used as supporting electrolytes. The product of pure titanium oxi-
dation was Ti4+ . The reason for deposition of pure Ti was not
accomplished [23]. A TiO2 lm was obtained by an electrochem-
ical method using a sacricial titanium anode as a cation source in
iodine-dissolved acetone bath. Under the inuence of iodide ions
TiO2+ was produced as the result of dissolution of the oxide lms
and then it was deposited on the cathode. The lm thickness was
determined by the voltage applied during electrolysis [24].
3.1.3. Group 5
Tantalum(V) and niobium(V) oxide lms were easily fabricated
in acetone bath using Ta and Nb anodes as the metal sources and
a metal-free solvent, containing halide ions as the supporting elec-
trolyte. The resulting lms had to be annealed at high temperature
to effect crystallization. The coatings prepared on stainless steel
substrates acted as effective barrier against electrolytic corrosion
[25].
3.1.4. Group 8
The processes of iron(II) and neodymium(III) reduction in the
metal chlorideacetamideureaNaBrKBr melt were investigated
at 70 C. NdFe could be codeposited by induced codeposition
and the composition of the lm varied with Nd(III)/Fe(II) molar
ratio. NdFe lms comprised of nanoparticles with the size of
100200 nm and the lm was amorphous [26].
3.1.5. Group 10
Gadoliniumcobalt lm was electrodeposited from gadolinium
toluenesulfonate (salt of rare earth) dissolved in dimethylfor-
mamide (DMF). As a supporting electrolyte (n-Bu)4 NBF4 was used.
Copper sheet was used as a substrate. The results revealed that an
amorphous GdCo lm can be obtained by potentiostatic electroly-
sis in the CoCl2 -(p-CH3 C6 H4 SO3 )3 GdureaDMF solution. The lm
was dense and homogeneous and the content of Gd increased with
the increasing cathodic potential. Co3 Gd alloy phase was rmly
adhering to the substrate [27]. The mixed system of a molten salt
and an organic solvent can be also utilized as an electrolyte. For
instance, in the preparation of perpendicular magnetic Gdx (FeCo)y
thin lm, by the pulse potential mode, such electrolyte was used.
The system consisted of ZnCl2 DMSO2 melt at 70 C. A Pt/Si sub-
strate was utilized for electrodepositing a Gdx (FeCo)y thin lm.
The pulse potential mode for electrodepositing a perpendicular
Gd13.3 (FeCo)86.7 magnetic thin lm in the electrolyte was suc-
cessfully utilized [28]. The electroplating of nickeltungsten alloys
from acetate solution was studied, since the acetate nickel-plating
electrolyte has some advantages over other known nickel-plating
electrolytes. The electrolyte had a composition of nickel acetate,
sodium tungstate, sodium acetate and saccharin. The increase in
tungsten(VI) concentration in the electrolyte has resulted in crack-
ing of coating, but its luster has been improved. Saccharin presence
in the electrolyte decreased the internal stresses in the alloy coating
[29].
3.1.6. Group 12
Methanol, acetonitrile and propylene carbonate baths were
used to electrodeposit zinc telluride. The solutions contained a
given solvent and also TeCl4 , ZnCl2 , NaClO4 as a supporting elec-
trolyte. Propylene carbonate was successfully demonstrated to
be an effective aprotic organic solvent. The underpotential depo-
sition of Zn (UPD) occurred only in acetonitrile and propylene
carbonate baths. Finely crystalline lms cannot be obtained in
methanol or acetonitrile. The lms obtained from propylene car-
bonate bath showed a stoichiometric ratio of ZnTe [30]. CdS lms
were prepared from a non-aqueous solvent using the electrode-
position technique. Na2 S2 O3 , CdSO4 and EDTA were dissolved in
ethylene glycol (EG). The quality of the deposits was found to
be independent of sulfur and cadmium ion concentrations, but
the deposit characteristics were dependent on the bath temper-
ature. Generally a rise in temperature had increased the grain size
[31].
3.1.7. Group 13
Aluminum was electrodeposited from different aromatic sol-
vents. The solutions of aluminum bromide in solvents like benzene,
toluene, p-xylene and ethylbenzene were investigated. The idea
of this electrodeposition was to develop a technological line for
electroplating workpieces. It was discovered that aluminum would
not have been deposited from benzene solution. From toluene
solution Al was deposited in the form of individual crystals.
The authors managed to obtain high-quality aluminum coatings
from xylene, ethylbenzene and xylenedurene electrolytes. The
main disadvantage of applying organic solutions was the cre-
ation of radical alkyls with carbon chain length of four and
longer that hampered the generation of electroactive species [32].
Also, adherent aluminum coatings were deposited on various alu-
minum alloys, titanium and copper alloys as well as steel, from
AlCl3 LiAlH4 diethyl ether baths (the NBS baths). Those baths had
few drawbacks such as high ammability, variation of the com-
position and limited lifetime. Another bath used to deposit Al
was the THFbenzeneAlCl3 LiAlH4 bath. Obtained deposits were
satisfactory. Solvents in non-complexed AlBr3 electrolytes (bro-
mide baths) were benzene, toluene, xylene and their mixtures and
derivatives. The bath life was also excellent (1 year of operation
with unchanged composition). Organoaluminum compounds like
alkylaluminum as well as quaternary ammonium salts dissolved
in aromatic solvents created good electrolytes for Al renement
[33]. The cathodic and anodic behavior of aluminum had been
studied again in AlCl3 /DMSO2 electrolyte at 130 C. The reaction
between Al and the electrolyte had led to the formation of a pas-
sivating layer by accumulation of the resulting corrosion products
on the metal surface. In that region suldes were found, mean-
ing that the corrosion was associated with the reduction of DMSO2
[34]. In [35] aluminum deposition processes in DMSO2 -based elec-
trolytes were investigated. AlCl3 /DMSO2 electrolytes were very
stable in the temperature range of 80150 C. Dense, bright and
adherent Al coatings were obtained over a wide range of tem-
peratures. The results from Al rening experiments showed that
Al alloy could be puried via electrolysis in 0.2:1 AlCl3 /DMSO2 at
130 C.
3.1.8. Group 15
The electrochemical behavior of Tm3+ ions was investigated in a
system consisting of Tm(NO3 )3 , LiClO4 and DMSO at room tempera-
ture. The rare earth surfaces and their alloy lms were prepared for
the rst time and TmCo alloy lms were uniform, adhesive, com-
pact and showed a metallic luster. The size of metal grains obtained
was of about 20 nm [36].
3.2. Electrodeposition from ionic liquids
3.2.1. Group 2
NuLi and co-workers reported for the rst time the magnesium
electrodeposition and dissolution processes in the ionic liquid of
[BMIM][BF4 ] with Mg(CF3 SO3 )2 at room temperature. Magnesium
was found in the deposited lm and the deposits were dense. Also,
magnesium deposition on silver substrate in [BMIM][BF4 ] with
Mg(CF3 SO3 )2 was examined at room temperature. Porous Mg depo-
sition became compact and crystalline and deposited Mg could be
completely dissolved electrochemically, leaving a clean and lm
free surface. Pyramidal-shaped magnesium deposits of microsize
were formed [3739].
 W. Simka et al. / Electrochimica Acta 54 (2009) 53075319
3.2.2. Group 3
The electrochemical behavior of uranium in 1-butyl-3-
methylimidazolium chloride (BMIC) at a glassy carbon electrode
was studied in the temperature range 70100 C. UO2 was
deposited at the electrode and some electrolyte was also
entrapped during the electrodeposition [40]. In [41] the lan-
thanum electrodeposition in ambient atmosphere, using 1-octyl-
1-methyl-pyrrolidinium bis(triuoromethylsulfonyl)imide ionic
liquid (OMPTf2 N), was reported for the rst time.
3.2.3. Group 4
Titanium was electrodeposited from TiCl4 -1-methyl-3-
butylimidazolium bis(triuoromethylsulfone)imide at room
temperature on Au(1 1 1) substrate. A dense layer of three-
dimensional clusters of Ti, having 12 nm thickness, was formed.
Also AuTi surface alloying was observed [42]. The electro-
chemical production of TiAl alloys was investigated using
TiCl4 AlCl3 1-butyl-3-methyl imidazolium chloride electrolytes.
The experiments were conducted at different temperatures
between 70 and 125 3 C and at various cell voltages between
1.5 and 3.0 V. The optimized condition for producing ner particle
size and high Ti content in TiAl alloys was obtained for the
applied voltages of 1.52.0 V, and temperature ranges from 70 to
100 C. The low current efciency is due to the formation of a TiCl3
passive layer on the electrodes, which retards the kinetics of redox
reactions and reduces the cathode current density as well as the
current efciency of the process [43].
3.2.4. Group 5
The electroplating of tantalum on NiTi alloy in RTIL, 1-
butyl-1-methylpyrrolidinium bis(triuoromethylsulfonyl)imide,
[BMP]Tf2 N, was investigated. Adherent, dense and uniform layers
of Ta, of about 500-nm thickness, can be electrodeposited at 200 C.
The coated sample showed a better corrosion resistance than the
uncoated one [44]. The electrodeposition of tantalum was carried
out in the same IL also at 200 C. The optimization of tantalum
electrodeposition process in IL allowed the achievement of an
adherent, homogeneous and protective lm of tantalum oxidized
on its surface (Ta2 O5 ) [45]. The electroreduction of TaF5 on Au(1 1 1)
and on polycrystalline gold substrates was investigated at room
temperature in the ionic liquid 1-butyl-1-methylpyrrolidinium
bis(triuoromethylsulfonyl)amide, [Py1,4 ]TFSA. Attempts to
deposit micrometer thick tantalum layers at room temperature
fail, presumably because of kinetic reasons [46].
3.2.5. Group 7
The electrochemistry of manganese in a hydrophobic RTIL,
[BMP]Tf2 N, was examined. Manganese coatings were pre-
pared by electrodeposition at several substrates. Mn coatings
were amorphous [47]. Zinc, manganese and zincmanganese
alloys had been electrodeposited from the hydrophobic tri-
1-butylmethylammonium bis(triuoromethane)imide. Zn(II) and
Mn(II) species were introduced into IL by the anodic dissolution of
metallic electrodes. Zn electrodeposits were very stable and exhib-
ited good adhesion [48].
3.2.6. Group 8
The rst investigation of ruthenium electrodeposition on
Au(1 1 1) from an ionic liquid, 1-butyl-3-methylimidazolium
dicyanamide, which exhibits sufcient solubility of RuCl3 at room
temperature, was reported in [49]. Also the electrochemical depo-
sition of ruthenium on n-type silicon from an ionic liquid was
reported for the rst time in [50]. The study was performed by dis-
solving ruthenium(III) chloride in a 1-butyl-3-methyl imidazolium
hexauorophosphate (BMIPF6 ) room temperature ionic liquid at
90 C. Metallic Ru lms have been deposited.
5311
3.2.7. Group 9
The electrochemical behavior of rhodium(III) chloride in BMIC
was studied at a glassy carbon (GC) working electrode at tem-
peratures 70100 C. The electrowinning of rhodium resulted in a
deposition of metallic rhodium [51]. The electrocrystallization of
cobalt and its alloys (containing Ni) with Al was investigated in the
AlCl3 BMIC and [BMIM][PF6 ] ionic liquids [52]. The electrodepo-
sition of cobalt and zinccobalt alloys on nickel, tungsten, copper
and GC electrodes was examined in 4060 mol% zinc chlorideEMIC
molten salt, containing cobalt(II), at 80 C. The zinc content of ZnCo
alloys was found to vary nonlinearly with the deposition poten-
tial. Zn-Co deposits with a low zinc content were amorphous and
the crystalline nature of ZnCo electrodeposits increased as zinc
content of the deposits rose. An addition of propylene carbon-
ate co-solvent to the melt decreased the melting temperature of
the solution and enabled the electrodeposition to be performed
at a lower temperature (40 C) [53]. An CoZn alloy deposit was
obtained from an ambient-temperature molten salt electrolyte,
CoCl2 ZnCl2 1-butylpyridinium chloride (BPC) system, and from
the bath containing an organic solvent. The morphology and the
current efciency of the alloy were improved by an addition of
organic solvent, i.e. propylene carbonate or ethyl alcohol, to the
bath. The bath temperature could be decreased from 130 to 25 C
by the addition of these organic solvents. The crystal structure of
the CoZn alloy deposit changed from the binary phase of Zn and an
intermetallic compound, Co5 Zn21 , to that of Co and the intermetal-
lic compound, as a function of the Co content in the deposit [54].
Cobaltaluminum alloys of different composition (up to 60 at.% Al)
were electrodeposited onto a copper cathode from the AlCl3 BPC
melt saturated with CoCl2 at room temperature. The deposited sur-
face obtained was very smooth and also had a bright metallic color
[55]. A porous anodic alumina template was synthesized by the
electrochemical anodization of aluminum and was used to grow
cobalt nanowires. The cobalt nanowires were produced by direct
current electrodeposition. The results of tests indicated that the
average diameter of cobalt nanowires was about 45 nm, which is
generally the same as the pore diameter of the porous anodic alu-
mina template, and the cobalt nanowires electrodeposited from a
mixture of 1-ethyl-3-methylimidazolium chloride ionic liquid and
ethylene glycol had a smoother surface and better magnetic prop-
erties than the cobalt nanowires electrodeposited from an aqueous
solution, and they showed a better squareness. X-ray diffraction
patterns showed that the Co nanowires fabricated from a mixture
of EMIC ionic liquid and ethylene glycol were of a polycrystalline
structure [56].
3.2.8. Group 10
The electrochemical reduction of palladium halide complexes
was examined in a hydrophobic [BMP]Tf2 N [57]. The electrode-
position of PdAg alloys was examined in a basic EMIC/BF4 ionic
liquid, containing Pd(II) and Ag(I), within a temperature range from
35 to 120 C. The composition of the PdAg alloys could be var-
ied by the deposition potential and concentrations of metal species
in the solution. The alloys were nodular and became more com-
pact upon increasing the temperature up to 120 C [58]. Platinum
nanoparticles were cost-effectively electrodeposited from a droplet
of water-immiscible ionic liquid ([BMIM][PF6 ]) that contained
metallic precursor-chloroplatinic acid hexahydrate (H2 PtCl6 ). The
electrodeposition was carried out in the aqueous solution of KPF6
with the H2 PtCl6 -containing ionic liquid droplet-conned GC elec-
trode. The method demonstrated here required much less amount
of IL, for example, only 5 l. The IL droplets could form micro-
media. The water-immiscible IL droplet (the micro-media) was also
suitable for the cost-effective electrodeposition of bimetal nanopar-
ticles, like PtRu [17]. The electrodeposition of PtZn from a Lewis
acidic 4060 mol% zinc chlorideEMIC ionic liquid, containing
5312 W. Simka et al. / Electrochimica Acta 54 (2009) 53075319
PtCl2 , was investigated at 90 C. PtZn deposit was amorphous or
nanocrystalline and the formed lm was thick or compact. The com-
position and morphology of PtZn electrodeposits could be varied
by the deposition potential and Pt(II) concentration [18]. Codepo-
sition of palladiumindium alloy from a chloride-rich EMIC/[BF4 ]
ionic liquid was studied at 120 C [59]. The electrodeposition of
nickel and nickelzinc alloys was examined at polycrystalline tung-
sten electrode in a zinc chlorideEMIC molten salt. Dense and
compact nickel deposits with good adherence could be prepared
by controlling the deposition potential. The presence of crystalline
nickel deposits was indicated. The electrodeposition of NiZn alloys
was achieved through the underpotential deposition of zinc on the
deposited nickel. The electrodeposits composition was indicated
and the phase types of nickelzinc alloys were dependent on the
deposition potential. For the NiZn alloys prepared by the UPD of Zn
on Ni, the zinc content in NiZn was always less than 50 at.%. Results
revealed that UPD is an interesting route for the electrochemical
preparation of NiZn alloys [60]. The electrodeposition behavior of
nickel was investigated at glassy carbon and polycrystalline cop-
per electrodes in the 1-ethyl-3-methylimidazolium dicyanamide
(EMI-DCA) room temperature ionic liquid. SEM images of the nickel
deposits indicated that the morphology of the nickel electrode-
posits was dependent on the deposition potential. The crystalline
nature of the nickel deposits was revealed by the powder X-ray
diffraction spectroscopy results [61].
3.2.9. Group 11
The deposition of silver nanowires in a commercial nuclear
track-etched polycarbonate template from the ionic liquid
[BMIM][PF6 ] was studied. Nanowires had a very high aspect ratio
with an average diameter of 80 nm and length of 5 m [62]. The
reduction of Ag+ to Ag0 has been studied electrochemically at
glassy carbon electrodes using the techniques of cyclic voltam-
metry and chronoamperometry. Ag+ is known to be chemically
reduced to form Ag0 nanoparticles by species present in the distil-
lable room temperature ionic liquid, DIMCARB (synthesized from
Me2 NH and CO2 in a 1.8:1 ratio). A compact lm of Ag also was
deposited onto glassy carbon in the presence of nanoparticles [63].
Silver and gold nanoparticles were produced during the electrolysis
of imidazolium liquid crystals containing dicyanoargentate(I) and
dicyanoaurate(I) anions. Gold particles were nanodots, aggregated
into spheres or multiglobular shapes (100 nm). The electrodepo-
sition of silver led to the formation of hexagonal platelets in the
amorphous silver gangue [64]. The electrodeposition of copper in
[BMP]Tf2 N was studied at variable temperatures. Nanocrystalline
copper was formed in that ionic liquid at room temperature [65].
3.2.10. Group 12
Ionic liquids were used as electrolytes for electrodeposition of
metals onto Mg and its alloys. ChCl:2 urea mixture was found to be
the most feasible liquid for successful electrodeposition. Smooth,
sealed and more corrosion-resistant Zn layers were formed [66].
Also crystalline Zn deposits could be prepared from various acidic
ZnCl2 EMIC ILs by proper control of the temperature and depo-
sition potential [67]. Zn can also be nanostructured on Au(1 1 1)
surfaces in [BMIM][BF4 ]. Patterned Zn nanoclusters and large-scale
arrays of Zn nanoclusters were obtained and described in [68]. The
electrolytic deposition of Zn, Sn and ZnSn alloys from a solution of
metal chloride salts in urea and ethylene glycol/choline chloride
based ionic liquids was investigated. Zinc and tin can be elec-
trodeposited individually or as alloys from these liquids. The alloy
morphology and composition can be changed by rational choice of
the IL [69]. The electrocrystallization of semiconductor ZnSb was
also studied at the electried ionic liquid/Au(1 1 1) interface, using
ZnCl2 [C4 mim]+ Cl (1-butyl-3-methylimidazolium chloride), at
50 C. A homogeneous distribution of ZnSb clusters of spherical
shape with diameters up to 15 nm was found [70]. The elec-
trodeposition of zinc on GC and nickel substrates was studied in
5050 mol% zinc chlorideEMIC molten salt. The quality of the zinc
deposits was greatly increased by the addition of propylene car-
bonate as a co-solvent. The deposits produced from the plating
baths with higher propylene carbonate concentrations or at higher
temperatures exhibited larger grain size. Well-adhering bulk zinc
electrodeposits on nickel substrate were obtained from these media
[71]. The deposition of ZnNi alloy from the ambient-temperature
molten salts ZnCl2 NiCl2 EMIC and ZnCl2 NiCl2 EMICethyl alco-
hol was investigated. The Ni content in the deposits could be
controlled from 12.3 to 98.6 mol% by changing the bath compo-
sition, temperature and current densities. The formation of the
amorphous structure in the deposit of the Ni content varying from
40 to 70 mol% was conrmed [72]. The electrochemical deposi-
tion of CdTe from a Lewis basic EMIC/[BF4 ] was examined in the
temperature range 80140 C. The CdTe electrodeposits could be
obtained by the UPD of Cd on the deposited Te. To prepare CdTe
codeposits an excess amount of Cd(II) was required. The polycrys-
talline CdTe was formed through direct electrodeposition without
subsequent annealing [73].
3.2.11. Group 13
The nanocrystalline aluminum was electrodeposited without
any additives in the [BMP]Tf2 N saturated with AlCl3 . The bulk
deposition of Al at room temperature on gold was studied. The
obtained deposits were uniform, dense, shining and adherent to
the substrate, with crystallites in the nanosize regime. At 100 C
the quality of the deposit was better with an average size of
crystallites of 34 nm [74]. A dense and adhesive Al layer was also
electrodeposited on a Mg alloy in the AlCl3 EMIC ionic liquid at
25 C. The protective Al layer reduced the corrosion rate of the
Mg alloy [75]. In the same electrolyte the electrodeposition and
surface morphology of Al on W and Al electrodes was studied
by Jiang and co-workers. The electrodeposits obtained on both
electrodes were dense, continuous and well adherent. Dense Al
deposits were also obtained on Al substrate using continuous cur-
rent deposition [76]. The electroplating of mild steel by aluminum
in the rst generation ionic liquid EMICAlCl3 was investigated.
Pretreatment of substrates played a key role in the adhesion of
the coating. Al coating made on a conventionally pretreated mild
steel was of high quality but it did not exhibit good adherence
to the substrate. The authors have found that the in situ electro-
chemical etching of the substrate by anodic polarization prior to
the electrodeposition led to well adherent Al coatings of the good
resistance to mechanical scratching. That was due to dissolution
of the pre-formed iron oxide layer and re-deposition of iron or the
formation of a FeAl alloy that resulted in the excellent adhesion
[77]. Al electrodeposition in AlCl3 trimethylphenylammonium
chloride (TMPAC) was performed on W and Al electrodes. Dense
aluminum electrodeposits were obtained on both substrates
[78]. A nanoscale electrodeposition of Al on Si(1 1 1):H sub-
strates was investigated at room temperature, applying the
AlCl3 [C4 mim]+ Cl ionic liquid. The bulk Al deposition exhibited
features similar to Al deposits on metal substrates, for instance
Au(1 1 1) [79]. The recycling of aluminum metal matrix composite
via electrolysis in the same ionic liquid was examined at 103 C.
Pure aluminum was deposited on a copper electrode. The deposit
microstructure ranged from columnar to spherical one [80]. The
electrodeposition of Al in three different water- and air-stable
ionic liquids, [BMP]Tf2 N, [EMIM]Tf2 N and trihexyl-tetradecyl-
phosphoniumbis(triuoromethylsulfonyl)imide (P14,6,6,6 Tf2 N),
was studied. A nanocrystalline Al can be electrodeposited in
[BMP]Tf2 N saturated with AlCl3 . The deposits obtained were uni-
form, dense, shining and adherent, with very ne crystallites in the
nanometer size regime. Coarse cubic-shaped aluminum particles
 W. Simka et al. / Electrochimica Acta 54 (2009) 53075319
in the micrometer range were obtained in [EMIM]Tf2 N. In this ionic
liquid the particle size increased with temperature. A very thin,
mirror-like Al lm containing very ne crystallites of about 20 nm
was obtained in P14,6,6,6 Tf2 N at room temperature [81]. Al and Al/Pt
alloys could be deposited from the room temperature ionic liquids
of AlCl3 and benzyltrimethyl ammonium chloride (BTMAC) on
Pt, Al and Fe electrodes. Uniform, adherent, crack-free aluminum
deposits were obtained. Co-electrodeposition of Al with Pt was
also studied [82]. The protective action of thin layers of aluminum
electroplated on a carbon steel has been studied. The coatings
were obtained via electroreduction, at room temperature, from
an ionic liquid constituted by 1-butyl-3-methyl-imidazolium hep-
tachloroaluminate ([BMIM]Al2 Cl7 ). Coatings of different thickness,
ranging from 10 to 40 m, were obtained. It was found that the alu-
minum layers deposited from ionic liquids signicantly protected
the substrate from the general corrosion and this action increased
with the thickness of the coating. Already the present results show
the possibility of utilizing ionic liquids as electrochemical media
for coating processes of industrial relevance [83]. Also galvano-
static electrodeposition was used to electrodeposit aluminum
on mild steel in AlCl3 /[bmim]Cl (1-butyl-3-methylimidazolium
chloride) ionic liquid at variable temperatures (581601 C).
Effects of variations in current density and temperature on surface
morphology and crystal orientations were systematically studied.
Results showed that the current density certainly caused changes
in the morphology and microstructure of the deposit, and the
type of deposit microstructure was changing rapidly as a function
of temperature, especially at higher current densities. It was
indicated that all of the electrodeposits exhibited mainly the
(2 0 0) crystallographic orientation [84]. The electrodeposition of
AlIn, AlSb, and AlInSb alloys was examined at the copper rotating
wire electrodes in the Lewis acidic aluminum chloride-1-ethyl-3-
methylimidazolium chloride room temperature ionic liquid. The
behavior of the partial current densities for In and Sb observed dur-
ing the electrodeposition process indicated that at higher applied
current densities a phase rich in In and Sb was deposited in parallel
with the ternary Alx Iny Sb100xy alloys [85]. The electrodeposition
of Al, Mn, Ni, Zn, Sn, and Cu was successfully demonstrated in
the ionic liquids (ILs) composed of 1-methyl-3-alkylimidazolium
or N-methyl-N-alkylpyrrolidinium cations with dicyanamide
anions. The 1-ethyl-3-methylimidazolium dicyanamide (EMI-
DCA), 1-butyl-3-methylimidazolium dicyanamide (BMI-DCA), and
N-butyl-N-methyl pyrrolidinium dicyanamide (BMP-DCA) ILs were
used. The ability of electrodepositing Al from the BMP-DCA IL is
of importance because according to the previous literature data
aluminum can be electrodeposited almost exclusively from the
highly water-sensitive Lewis acidic chloroaluminate ILs and the
water-stable TFSA-based ILs. In this work, EMI-DCA was examined
for electrodeposition of various metals, including Sn, Zn, Ni and
Cu. It is found that SnCl2 , ZnCl2 , NiCl2 , and CuCl dissolve readily
in the EMI-DCA IL. While Ni and Zn could not be electrodeposited
from most Lewis basic or neutral ILs reported in literature, they
can be obtained from the DCA-based ILs. Moreover, the ability to
electrodeposit reactive metals such as Al and Mn is of signicance
[86]. The electrodeposition of indium and copper in 1-butyl-
1-methylpyrrolidinium bis(triuoromethylsulfonyl)amide was
studied at variable temperatures. The nanocrystalline In with grain
size between 100 and 200 nm was formed at room temperature
[65]. Aluminum deposition process on tungsten electrodes was
conducted in a room temperature molten salt, AlCl3 TMPAC. The
underpotential deposition of Al, in the form of several monolayers,
was observed [87]. The interfacial reactions of MoSiB with AlSi
metallic coatings during processing to achieve high-temperature
corrosion protective mullite coating for advanced turbine mate-
rials were discussed in the reference [88]. AlSi was deposited
on MoSiB substrate material by a molten salt (AlCl3 with an
5313
organic electrolyte, SiO2 and mullite particles) cathodic deposi-
tion. The interfacial region during the AlSi deposition was the
precursor to the formation of compositionally graded mullite by
annealing and subsequent oxidation. This research suggested that
the metallic precursor should be deposited by organic electrolysis
rather than by molten salt electrolysis, to minimize the effects
of the process temperature. An aluminiumlanthanum alloy was
electrodeposited in the LaCl3 saturated AlCl3 EMIC melt at 25 C.
It was concluded that the addition of LaCl3 into the melts led to
the increase in deposition overpotential affecting the orientation
and improving the surface morphology [89]. The electrodeposition
of aluminiumnickel intermetallic compounds was carried out
onto platinum and mild steel cathodes from the AlCl3 BPC molten
bath saturated with nickel(II) chloride at room temperature. The
deposited surfaces were very smooth and had a bright metallic
color [90]. Binary aluminiumchromium alloys were deposited
from 2:1 AlCl3 N-(n-butyl)pyridinium chloride room temperature
molten salt. The electrodeposition was carried out on platinum and
mild steel cathodes. The chromium content of the electrodeposit
varied from 0 to 94 at.%. The deposit microstructure consisted of
both, Cr-rich and Al-rich solid solutions and intermetallic com-
pounds. The excellent high temperature oxidation resistance of a
series of AlCr alloys on the mild steel, containing 2050 at.% Cr, was
revealed between 600 and 800 C [91]. Also some codeposition of Al
with Co, Cr, Zn or Mn from AlBr3 dimethylethylphenylammonium
bromide (DMEPAB) solutions in toluene, containing acetylace-
tonate of a corresponding metal, was examined. Here only the
electrochemistry of deposits was investigated [92]. The application
of ionic liquid electrolytes succeeded in the electrodeposition of
light and transition metals as well as compound semiconductors
on metal and semiconductor substrates at room temperature,
with nanometer or atomic resolution. In the Ga, Cd and Ni elec-
trodeposition experiments a Lewis acidic room temperature ionic
liquid, 1-methyl-3-butylimidazolium chloride/aluminum chloride
mixture was used. In the case of ZnSb deposition, the AlCl3 was
replaced by ZnCl2 . The formation of metal monolayers (Ga, Ni) has
been contrasted with the occurrence of surface alloying (CdAu)
[93].
3.2.12. Group 14
The electrodeposition of germanium on Au(1 1 1) and Si(1 1 1):H
was investigated in AlCl3 BMIC and [BMIM][PF6 ]. Ultrathin Ge
lms with varying thickness were obtained at relatively low
temperatures [52]. The electrochemical reaction of Sn(II)/Sn
was investigated in a room temperature ionic liquid, 1-n-
butyl-1-methylpyrrolidinium bis(triuoromethyl-sulfonyl)imide
(BMPTFSI) at 25 C. The electrodeposition of Sn on a Cu substrate
was possible in BMPTFSI containing Sn(II). The morphology of the
obtained tin deposit was a smooth and dense facet. The oxidation
of Sn(II) to Sn(IV) was not observed [94].
3.2.13. Group 15
The electrodeposition of antimony was performed on GC and
nickel electrodes in a basic EMIC/[BF4 ] RTIL. Dense deposits were
obtained within a deposition temperature range between 30 and
120 C. Deposits obtained at 30 C had a nodular appearance
whereas those obtained at 80 and 120 C consisted of ne polygonal
crystals. The fact that good Sb electrodeposits can be obtained from
this RTIL suggests that such liquids may be useful for the deposi-
tion of InSb semiconductors [95]. The electrodeposition of bismuth
on Au(1 1 1) in an acidic chloroaluminate ionic liquid, 1-methyl-3-
butylimidazolium chloridealuminum chloride, was investigated.
Different morphologies of Bi crystals were obtained: needle-like
structures and ultrathin Bi lms [96]. The deposition of super-
conductor alloy precursors (BiSrCaCu) was studied in a room
temperature molten salt medium based on EMICAlCl3 system at
5314 W. Simka et al. / Electrochimica Acta 54 (2009) 53075319
120 C. Pt, Al, Ti, Cu and Ag were used as substrates for deposition
of the alloy and Al was found to be the best for depositing alkaline
earth metal alloys. The compositions of the electrodeposits were
in close agreement with the mole ratios of BiSrCaCu supercon-
ductor alloy precursors [97].
3.3. Electrodeposition from molten salts
3.3.1. Group 1
The electrochemical reduction behavior of lithium at a graphite
electrode in a molten lithium chloride and a molten mixture
of lithium chloride and tin(II) chloride was examined at 625 C.
Lithium intercalation into graphite had occurred before deposition
of metallic lithium started [98]. The behavior of Li+ was studied
at the inert and active electrodes in the molten LiClKCl eutectic.
The Mg-Li alloy lms with -Mg and -Li phases were obtained
by potentiostatic electrolysis at 2.35 and 2.55 V, respectively
[99]. In Ref. [100] it was mentioned that liquid calciumlithium
alloy deposits were formed in the LiClKClCaCl2 eutectic melt at
450600 C. Also some experiments were carried out on lithium
deposition from 2MeTHFethylene carbonate (EC)LiAsF6 on a
stainless steel substrate. A ber-like lithium was deposited which
had a diameter of 0.1 m and was 1 m long [101]. The electro-
chemical insertion of sodium into graphite was examined in a
molten sodium uoride at 1025 C in [102].
3.3.2. Group 2
The electrodeposition of magnesium from molten MgCl2 and
MgCl2 MgF2 mixtures was studied at 780 C. The nucleation pro-
cess on a magnesium electrode showed that probably a very thin
oxide layer was formed at these conditions [103]. In Ref. [104] the
electrodeposition of magnesium ions was examined in a molten
CaCl2 NaCl system at 550 C. The electrochemical reduction of
Mg(II) occurred to solid magnesium. An electroplating technique
of the superconductive boride, MgB2 , onto graphite substrates was
reported in [105]. The electrochemical codeposition of Mg, Li and
Zn on a molybdenum electrode in LiClKClMgCl2 ZnCl2 melts at
1216 C to form MgLiZn alloys was investigated. MgLiZn alloys
with different phases were prepared via galvanostatic electrolysis
[106]. Films of MgB2 with a thickness of tens of micrometer were
fabricated on graphite substrates by means of electrolysis in a mix-
ture of magnesium chloride, potassium chloride, sodium chloride
and magnesium borate, fused at 600 C. The electroplating of MgB2
is easy to scale up because of the simple and low-priced instal-
lations. The method is applicable to the industrial fabrication of
magnesium boride lms on large-scaled surfaces of various shapes.
Metallic calcium can be produced electrolytically by dissociating
calcium oxide in a molten calcium chloride electrolyte at 900 C. It
was essential to use a porous ceramic diaphragm around the anode
to separate the anolyte and catholyte in order to deposit calcium.
The cathodically deposited calcium can be used to reduce most of
the other metals, e.g. actinides, lanthanides, refractory metals, rare
earths and other precious metals (titanium, lead, silver, tin) in an in
situ hybrid process [107].
3.3.3. Group 3
A pyrochemical separation of actinides from the rare earths in
LiClKCl eutectic-liquid metal systems has been examined. It was
shown that actinide metals were recovered on the cathodes and
americium was the most difcult to separate [108]. The electrode-
position of uranium and plutonium in the LiClKCl eutectic salt on
W and Mo working electrodes was studied at 450, 500 and 550 C
in [109]. The electrode reactions of U and Pu were complicated by
the formation of an alloy. The properties of thorium chloride ions
were investigated on a W electrode in a molten eutectic LiClKCl
in the temperature range 420550 C. Here the electrochemistry
of thorium was only examined [110]. Electrorening experiments
of uranium were successfully carried out in the LiClKCl eutectic
molten salt at 500 C with a graphite cathode. The formation of
U-graphite intercalation compound (GIC) helped the self-scraping
mechanism of uranium dendrite [111]. Also uranium deposits were
prepared by the electrolysis in a fused chloride melt (NaClKCl)
at 670710 C [112]. Uranium and uraniumzirconium electrode-
posits were produced in the molten LiClKCl eutectic. Pure U
deposits were built of chains of uranium crystals with a rhomboidal
shape and complex internal porosity structure, while samples from
deposits containing Zr showed polycrystalline features. The surface
of UZr electrodeposit was dendritic with aggregates of ne grains
[113]. Features of neptunium dissolved in the LiClKCl eutectic
were investigated on tungsten electrodes. Electrochemical proper-
ties were only studied, without surface analysis [114]. The behavior
of plutonium and proper conditions for plutonium recovery at
the liquid cadmium cathode (LCC) were examined. Plutonium was
successfully collected up to 7.75 wt.% without the disturbance by
solid phase formation at the surface. Plutonium formed the inter-
metallic compound PuCd6 [115]. Also the electrode reaction of
Pu3+/ Pu couple at the surface of a liquid Cd electrode was inves-
tigated at 450, 500 and 550 C in the LiClKCl eutectic melt. The
formation of the alloy PuCd6 was observed as well as other inter-
metallic compounds, PuCd2 and PuCd4 [116]. The electrochemical
behavior of neodymium was studied in several molten media, par-
ticularly in LiFCaF2 at 810 C [117]. The electrodeposition of Nd in
a LiFNdF3 Nd2 O3 melt was possible. Depending on the electrode
substrate the co-reduction of Li+ occurred [118]. The electrodeposi-
tion of samarium and cobalt on copper substrate was investigated
in a molten LiClKClSmCl3 CoCl2 system at 450 C. SmCo3 was
formed on Cu substrate by potentiostatic electrolysis [119]. The
electrochemical formation of SmCo alloy lms at Co cathode was
studied in a LiClKClSmCl3 system at 450 C. A very thin lm of
SmCo2 alloy was obtained. Much thicker alloy lm was formed
by Li codeposition method [120]. The electrochemical formation
of SmNi alloys was performed in LiClKClSmCl3 at 450 C. The
formation of SmNi2 phase was conrmed and the thickness of
the lm was estimated to be 100 nm. A much thicker SmNi2 lm
(20 m) was obtained by cathodic galvanostatic electrolysis [121]. A
possibility of gadolinium boride synthesis in the chlorideuoride
melt (NaClKClNaFGdF3 KBF4 ) was examined in the tempera-
ture range 700750 C. For the rst time gadolinium hexaboride
nanotubes were synthesized on a molybdenum cathode [122]. Also
the electrochemistry of Gd(III) was studied at W and Al electrodes
in the LiClKCl eutectic at temperatures ranging from 400 to 550 C.
On Al electrode a stable GdAl alloy was formed [123]. The behav-
ior of erbium(III) was investigated in the molten LiClKCl eutectic
for temperatures ranging from 380 to 550 C. Erbium formed some
alloys with solid Al electrodes [124]. As an example of terbium elec-
trodeposition some terbiumiron intermetallic compound, TbFe2 ,
was prepared by the electrochemical reduction of thermally com-
pounded powders of Tb4 O7 and Fe2 O3 in a molten CaCl2 at 900 C
[125]. The electrochemical formation of dysprosiumiron alloy
lms was done in a molten LiClKClDyCl3 system at 500 C. The
alloy lm was thin and not adhesive. An adhesive DyFe2 lm was
obtained at the activated Fe electrode after cathodic electrodeposi-
tion of Dy metal [126]. The electrochemical behavior of DyCl3 was
examined in LiClKCl at different temperatures. The SEMEDX anal-
ysis of the deposits conrmed the formation of DyAl3 alloy [127].
The electrochemical behavior of praseodymium was investigated
in two molten chlorides, the eutectic LiClKCl and the equimolar
CaCl2 NaCl melt, at different temperatures. At the aluminum elec-
trode a stable PrAl alloy was formed [128]. The electrochemistry of
europium on GC was studied in the temperature range 400550 C.
For the extraction of Eu from a molten salt the use of a reactive
electrode made of aluminum led to Al4 Eu alloy formation [129].
 W. Simka et al. / Electrochimica Acta 54 (2009) 53075319
The electrochemical formation of ytterbiumnickel alloy lms at
Ni cathode was carried out in a molten system, LiClKClYbCl3 , at
450 C. A very thin YbNi2 lm was formed by potentiostatic electrol-
ysis, but a much thicker alloy lm was formed by the Li codeposition
method [130]. The electrodeposition of lutetium on inert electrodes
and the formation of lutetiumaluminum alloys were investigated
in the eutectic LiClKCl in the temperature range 9461096 C.
Al3 Lu and mixtures of Al3 Lu and Al2 Lu, were obtained from the
LiClKCl melt containing Lu(III) by potentiostatic electrolysis using
an Al electrode [131].
3.3.4. Group 4
In Ref. [132] an attempt was described to propose an electroplat-
ing method for producing a thin titanium layer on iron surface by
galvanic contact deposition, in which pure titanium and iron elec-
trode were immersed into a molten salt (NaClTiCl2 ) at 900 and
930 C. A pure titanium layer could not have been obtained by this
method. Under high temperature conditions the improvement of
the oxidation resistance of TiAl alloy was investigated by elec-
troplating the aluminiumchromium alloys in a AlCl3 NaClKCl
molten salt containing CrCl2 at 150 C. On TiAl specimen, cov-
ered with -Al8 Cr5 , uniform AlCr2 layer was formed during the
oxidation at 900 C for 24 h. An AlCr2 layer was covered by a thin
dense Al2 O3 . Both layers acted as a superior protection barrier
against the high temperature oxidation of TiAl alloy. The plat-
ing of -Al8 Cr5 deposit reduced the oxide thickness to 1/40 of that
on TiAl alloy without the deposit [133]. The examination of the
electrodeposition of titanium diboride, TiB2 , was carried out using
continuous current plating (CCP) and pulse current plating (PCP)
to produce a uniform and of very low porosity coating. The sol-
vent used was a uoride mixture (LiFNaFKF, known as Flinak)
containing K2 TiF6 and KBF4 in a mass relation of one to four. The
temperature of the process was 600 C and all the results were
obtained on graphite electrodes as the substrates. The electrode-
position with PCP produced coatings with better quality, showing
fewer cracks and better adhesion to the substrate when compared
to those obtained by CCP [134]. TiB2 coatings over a molybdenum
substrate were examined by comparing the electrochemical tech-
niques of CCP and periodically interrupted current (PIC) at 700 C
for 30 min. The solvent used was an eutectic Flinak mixture contain-
ing K2 TiF6 and KBF4 (1:5 molar ratio). The metallic, bright coatings
produced by PIC showed improvements in the morphology and
microstructure such as a better adhesion and reduction of the num-
ber of pores [135]. Niobiumtitanium alloys can be prepared by
codeposition (galvanostatic electrolysis) in NaClKClNaF melts at
600 C. The obtained alloys showed poor appearance of a pow-
dery deposit [136]. Ref. [137] was focused on the preparation of
titanium diboride coatings by electroplating in uoridechloride
electrolytes (KFKCl, 946 mol%), containing K2 TiF6 and KBF4 (in
the molar ratio 1:5, respectively) as the electroactive components.
The electroplating was carried out at 800 C for 60 min. As a result
the high-quality TiB2 coatings were prepared by CCP and PIC. Com-
pared with CCP, the gram size of the TiB2 coatings prepared by the
PIC was smaller. Electrochemical studies on zirconium chloride in
the molten LiClKCl eutectic were carried out in the presence and
absence of Zr metal, in the temperature range 10461121 C. It was
noticed that it was one of the very few molten salt systems showing
crossovers of the forward and reverse sweeps at different potential
regions in convolutive potential sweep voltammetry indicative of
presence of an insoluble species in the melt [138]. To investigate
the electrodeposition mechanism of Zr(IV), the electrochemistry of
a LiClKClK2 ZrF6 melt at molybdenum and tungsten electrodes
was studied at the temperature ranging between 1046 and 1246 C.
The intermediate product was ZrCl2 , and the ratio between Zr(II)
and Zr(IV) became larger with the increase of temperature. The
MgZr alloy was prepared at the liquid magnesium electrode at
5315
1.3 V (versus Ag/AgCl) by potentiostatic electrolysis. The content
of zirconium was about 9.91 mass% of the erogeneous nucleus and
the zirconium concentration of the whole MgZr alloy was about
0.8 mass% [139]. For electroforming zirconium metal, ZrAl alloy
and carbon lm on ceramic substrates had been introduced. Zr
metal and alloy lm were formed in the LiClKCl melt contain-
ing Zr(II) at 410550 C, whereas a carbon lm was formed in a
molten carbonate. A working electrode consisted of a metal part and
a ceramic substrate. The conclusion was that it was possible to coat
ceramic substrates of complicated structures. Also ceramics can be
coated with other metals when using appropriate baths [140]. The
formation of a coating layer consisting of Nialuminide containing
Hf on a Ni10 at.%Cr8 at.%Al alloy substrate was attempted by the
electrodeposition of Hf, Ni, and Al. Ni was deposited by the elec-
trolysis in an aqueous solution. Hf and Al were deposited by the
molten-salt electrolysis. For the sample rst treated with the Hf-
deposition, subsequently treated with the Ni-deposition, followed
by the Al-deposition, a coating consisting of Ni2 Al3 of about 40-m
thickness was uniformly formed on the alloy. At the center region
of this coating, a Hf-concentration layer was formed. The alloy cov-
ered with the Ni2 Al3 coating containing the Hf-concentrated layer
showed a high cyclic-oxidation resistance. On this alloy after the
oxidation test an adhesive scale having a spiked shape was formed.
This scale mainly consisted of -Al2 O3 , and contained HfO2 parti-
cles [141].
3.3.5. Group 5
The electrodeposition of metallic niobium on a surface of car-
bon electrode in fused electrolytes (NaClKCl, 50:50 mol%) at 720 C
was studied. The formation of niobium carbide occurred before the
metal deposition. The metallic coating could not prevent the for-
mation of the rst layer of preliminary carbide. A niobium carbide
coating, having few atomic layers of thickness, was rapidly gener-
ated. This study showed the feasibility of niobium electrodeposition
on carbon substrates and the quality of them could be improved by
monitoring other parameters [142]. Also, some niobium deposits
were prepared from alkali chloride melts on Ni and AISI316 stain-
less steel substrates by the constant current and by pulse current
methods. The melts used were the LiClKCl (eutectic) and NaClKCl
(equimolar) mixtures. The inuence of electrolysis conditions on
the nature, morphology and purity of the deposits was studied.
No metallic niobium was obtained at temperatures below 500 C.
The LiClKCl melt was an inconvenient electrolyte for perform-
ing niobium electrodeposition. At temperatures between 550 and
650 C the deposits were dendritic and non-adherent. Pure Nb lay-
ers could be prepared at 750 C. The presence of suboxides like Nb6 O
in the metallic phase was caused by a high negative overpotential
during the pulse current period. A thin layer of NbNi alloy such
as NbNi3 was formed at the interface of the nickel substrate. At
the niobiumstainless steel interface no alloys were detected but
homogenous adherent layers of 50-m thickness were obtained.
Generally all chloride electrolytes can be used to produce high-
quality Nb deposits when the temperature is equal or exceeds
700 C [143]. The nucleation of tantalum in molten alkaline uoride
media was investigated in the 670750 C temperature range. The
aim of this work was to prepare tantalum coatings for anode materi-
als, such as silver and copper. An eutectic LiFNaF melt (60/40 mol%)
was used and tantalum ions were introduced to the system as
potassium heptauorotantalate, K2 TaF7 . The tantalum nuclei were
hemispherical and their growth was three-dimensional and limited
by the diffusion of tantalum ions. The increase of the current density
and temperature enhanced the nucleation rate and nuclei density
[144]. The electrodeposition of tantalum in the same molten u-
orides as in the ref. [144] was conducted at 800 C. After addition
of both K2 TaF7 and Na2 O, tantalum deposition was observed. The
electrodeposition had been run on copper cathodes and showed
5316 W. Simka et al. / Electrochimica Acta 54 (2009) 53075319
that pure and coherent Ta coatings were obtained at a lower oxide
content (Ro < 0.5 where Ro is the molar ratio of OTa). At higher Ro
values the coatings were powdery and contained Na3 TaO4 , NaTaO3
together with traces of Ta metal from the deposition of TaO [145].
The behavior of molten salt systems, where CsCl was used as a sol-
vent for potassium and cesium oxyuorotantalates, was examined.
The molten systems were CsClK3 TaOF6 and CsClCs3 TaOF6 . Mul-
tiphase deposits crystallized and the number of phases inherent in
one deposit could be as more as six. The low-valency tantalum com-
pound, CsTa2+z 5x O5+y F1y , hitherto rarely mentioned in the led
literature, was present in almost all obtained cathodic deposits. The
conditions for the electrodeposition of pure Ta metal from oxygen-
containing melts were also found [146].
3.3.6. Group 6
An attempt was made to apply the electroplating of refrac-
tory metals in molten salts to the LIGA process or to the surface
coating of conventional LIGA (Lithographic Galvanoforming Abfor-
mung) microparts to give higher strength and heat resistance for the
microparts. The characteristics of tungsten lm electrodeposited
from ZnCl2 NaClKCl melt at 250 C were reported. WCl4 was
added as a source of tungsten ion. The electrolysis gave a smooth
W lm without incorporated melts and impurities. The coating of
microparts with an adhesive and smooth W lm was successfully
demonstrated [147]. The electrodeposition of metallic tungsten
was studied also in the similar ZnCl2 NaClKCl (0.6:0.2:0.2 mole
fraction) melt at 250 C. WO3 hardly dissolved in this medium,
so the solubility was increased by the addition of KF. A smooth
and ne lm of metallic tungsten was obtained on a nickel sub-
strate by the potentiostatic electrolysis. The surface of Ni contact
probe pin was successfully coated with a smooth and adhesive
tungsten lm by using this method at low temperature [148]. The
behavior of chromium ions in the equimolar CaCl2 NaCl mixture
at 550 C was investigated using various substrates like Mo, W
and GC. In the work only electrochemical properties of Cr were
studied [149]. Molybdenum silicide was coated in the molten salt
(NaClKClNaFNa2 SiF6 SiO2 ) and Si powder for obtaining the oxi-
dation resistance of molybdenum in air. A hexagonal MoSi2 was
formed as a single phase with homogeneous thickness of tens of
micrometer above 800 C. The tetragonal MoSi2 phase was addi-
tionally formed at 700 C [150]. Also, molybdenum metal lm was
electrodeposited in the ZnCl2 NaClKCl melt containing MoCl3 at
250 C. The addition of KF to the melt gave a dense, adhesive and
thicker metal lm under the same electrolysis conditions. The pre-
sented process was regarded as a new method for molybdenum
coating at low temperatures [151]. The formation of the UAl alloy
has been studied in the temperature range of 400550 C by electro-
chemical techniques in the molten LiClKCl eutectic. Galvanostatic
electrolyses were carried out both on solid Al rods and plates. Sta-
ble and dense UAl deposits were obtained with high faradic yields
and the possibility to load the whole bulk of a thin Al plate was
demonstrated. The analyses of the deposits indicated the formation
of different intermetallic phases (UAl2 , UAl3 and UAl4 ), depending
on the experimental conditions [152].
3.3.7. Group 9
The electrochemical formation of GdCo alloys was investi-
gated in a molten LiClKClGdCl3 system at 450 C. CoGd3 lm was
formed on Co substrate by cathodic electrolysis [153].
3.3.8. Group 10
The electrochemical reduction of lanthanum ion and forma-
tion of palladiumlanthanum alloy lm were studied in the
LiFNaFKFLaF3 melt at 500 C. The formation of Pd3 La alloy lms
was conrmed for both samples electrolyzed at 0.45 V for 2 h and
0.25 V for 1 h. For the latter case, a dense and uniform Pd3 La alloy
lm of 30 m in thickness was obtained. Lanthanum metal cannot
be electrodeposited in this melt [154].
3.3.9. Group 11
In LiFNaFKF eutectic melt the formation of Au2 Na alloy phase
was investigated at 500 C. The working electrode was an Au
wire. The (Au2 Na + Au) electrode showed excellent stability and
can be used as a good reference electrode for further electro-
chemical works in that melt [155]. The behavior of copper ions in
ZnCl2 2NaCl mixture was examined at 450 C. Instantaneous and
three-dimensional nucleation and crystal growth of copper was
showed. The nucleation of metallic Cu on tungsten electrode had
dominated the deposition process [156].
3.3.10. Group 12
The electrodeposition of the semiconductor ZnSe was per-
formed in a molten CaCl2 NaCl mixture at 550 C. ZnSe was
electrodeposited on glass sheets covered with SnO2 . Yellow, trans-
parent and adherent thin lms were obtained, containing up to 90%
of well crystallized ZnSe and of 1-mm grain size [157].
3.3.11. Group 13
The electrochemical deposition of aluminum from a basic and
an acidic molten AlCl3 NaClKCl mixture on a graphite electrode
at 140 C was examined. It was shown that depending on the cur-
rent density and AlCl3 concentration (acidic or basic melt) different
Al morphologies were evident, but a silver-bright, compact, non-
porous and very stable metallic form of Al was deposited in the
acidic melt with KI addition as a surfactant. In the basic solution
the deposit morphology was dull grey, spongy and non-compact
[158]. Also a similar investigation was reported in [159], where
the electrocrystallization of Al was studied in the AlCl3 NaClKCl
molten salt onto a polished graphite electrode at 140 C. The electro-
chemical formation of aluminum nitride was examined in molten
LiClKClLi3 N systems at 450 C. The oxidation of nitride ions pro-
ceeded to form adsorbed nitrogen atoms which reacted with the
surface to form an AlN lm. The obtained nitride lm had a thick-
ness of sub-micron order. The obtained nitride layer consisted of
two regions: the outer layer containing AlN and aluminum oxyni-
tride and the inner layer containing metallic Al and AlN. Also AlN
particles of wurtzite structure were produced, having 15 m of
diameter. This process was expected to become a new process
of the AlN powder formation [160]. The electrochemical behavior
of niobium in an AlCl3 NaCl molten salt electrolyte was investi-
gated by linear sweep voltammetry at 190 C. Low Nb deposits
were fcc aluminum. As the Nb content had increased an amorphous
phase was introduced into the structure [161]. Niobiumaluminum
alloys were formed in the LiClKCl eutectic melt at tungsten and
niobium electrodes. This melt was suitable for the electrowin-
ning of NbAl alloys [162]. AlMn amorphous plating layers were
electrodeposited in AlCl3 NaClMnCl2 . The structure of a deposit
was the fcc aluminum solution, when the manganese content was
smaller than 17%, and amorphous phase when the manganese
content was between 25 and 45%. A mixture of amorphous and
intermetallic Al8 Mn5 was obtained when the manganese content
was larger than 45%. The corrosion resistance of AlMn amorphous
plating layer was about four times that of aluminum layers [163].
The AlMn alloy coatings were electrodeposited on the AZ31B Mg
alloy in AlCl3 NaClKClMnCl2 molten salts at 170 C, aiming to
improve the corrosion resistance. The severe corrosion of Mg alloy
resulting in a loose and layered product on its surface during elec-
trodeposition of AlMn alloy on Mg alloy from molten salts was
obviously an obstacle for adhesion of the deposited AlMn alloy
coating. However, it may be overcome by pre-deposition of a thin
zinc layer on the substrate before the electrodeposition in molten
salts. The amorphous phase AlMn alloy coating with compact
 W. Simka et al. / Electrochimica Acta 54 (2009) 53075319 5317

tumor-like morphology exhibited much higher corrosion resistance electrodeposition of metals is denitely more economic than the
than the solid solution AlMn alloy coating with loose faceted mor- formation of coatings with methods such as plasma spray, PVD, or
phology. The increase of the Mn content in the alloy coating can CVD.
also improve the corrosion resistance by reducing the corrosion
current density and enhancing the breakdown potential [164]. The Appendix A. List of symbols
cathodic codeposition of AlCr and AlNi alloys was carried out in
the AlCl3 NaClKCl molten salt containing CrCl2 and/or NiCl2 at
150 C. A mixture of intermetallic compounds of Cr2 Al, Ni3 Al, and H2 O viscosity of water (cP)
Al3 Ni was formed [165].  conductivity (mS cm1 )
A surface area (cm2 )
3.3.12. Group 14 -BL -butyrolactone
The electrochemistry of tin(II) was studied at tungsten and [BF4 ] tetrauoroborate anion
GC electrodes in acidic and basic molten salts (ZnCl2 + 2NaCl, BMIC 1-butyl-3-methylimidazolium chloride
2ZnCl2 + 3NaCl, ZnCl2 + NaCl) at 450 C. The electrodeposition of [BMIM] 1-butyl-3-methylimidazolium
Sn was uncomplicated at W but on GC it was complicated by the [BMP]Tf2 N 1-butyl-1-methylpyrrolidinium
nucleation. Good adherence of liquid tin, formed in the reduction bis(triuoromethylsulfonyl)imide
process, to the electrode materials was observed [166]. The elec- BPC 1-butylpyridinium chloride
trochemical reduction behavior of tin at the graphite electrode in BTMAC benzyltrimethyl ammonium chloride
a molten lithium chloride and a molten mixture of lithium chlo- CCP continuous current plating
ride and tin(II) chloride was examined at 625 C. During cathodic ChCl choline chloride
polarization the deposition of metallic tin from the chloride mixture [C4 mim]+ Cl 1-butyl-3-methylimidazolium chloride
onto the graphite surface occurred, while no intercalation of tin into CVD chemical vapour deposition
the graphite bulk took place. The reduction of tin at the graphite DMEPAB dimethylethylphenylammonium bromide
electrode did not lead to the formation of signicant amounts of DMF dimethylformamide
nano-sized materials [98]. The electrochemical deposition of alu- DMSO2 dimethyl sulfone
minum and lead from the basic molten AlCl3 NaClKCl mixture DMSO dimethyl sulfoxide
on an aluminum electrode at 180 C was studied by voltammetry, EC ethylene carbonate
as well as the potential and current transient and constant current EDTA ethylene-diaminetetra-acetic acid tetrasodium salt
deposition. In basic solutions the deposit morphology was dull grey, EG ethylene glycol
spongy and non-compact, while in the presence of PbCl2 smoother EMIC 1-ethyl-3-methylimidazolium chloride
and non-porous aluminum was formed [167]. EMI-DCA 1-ethyl-3-methylimidazolium dicyanamide
[EMIM] 1-ethyl-3-methylimidazolium cation
3.3.13. Group 15 GC glassy carbon
The electrochemistry of antimony and bismuth in the GIC graphite intercalation compound
AlCl3 NaClKCl molten salt containing SbCl3 , BiCl3 , TeCl4 at 150 C IL ionic liquid(s)
was investigated. Stable deposit layers of pure Bi were not obtained ITO indium tin oxide
under the constant potential control. The deposition of a binary LCC liquid cadmium cathode
alloy was possible in the melt containing BiCl3 and SbCl3 and also LIGA Lithographic Galvanoforming Abformung Process
with TeCl4 and BiCl3 . A stable BiSb alloy deposit of metallic Sb and NBS National Bureau of Standards
BiSb solid solution was obtained. Also a stable Bi-Te alloy deposit [N(CN)2 ] dicyanoamide anion
was obtained with the molten salt containing BiCl3 and TeCl4 ; the OMPTf2 N 1-octyl-1-methyl-pyrrolidinium
alloy had good crystallinity [168]. bis(triuoromethylsulfonyl)imide
PCP pulse current plating
4. Conclusions [PF6 ] hexauorophosphate anion
PIC periodically interrupted current
The electrodeposition of metals from non-aqueous solutions, [PrMeIm][Cl] 1-propyl-3-methylimidazolium chloride
such as conventional organic solvents, ionic liquids and molten P14,6,6,6 Tf2 N trihexyl-tetradecyl-phosphonium
salts, is presented. The application of the above-mentioned solu- bis(triuoromethylsulfonyl)imide
tions makes possible obtaining the cathodic deposits of metals or PVD physical vapour deposition
metallic alloys that cannot be deposited by the traditional electroly- Ro molar ratio of oxygentantalum
sis of aqueous solutions. It is due to the potential of their liberation, RTIL room temperature ionic liquid(s)
much lower than the potential of hydrogen liberation, when the SEMEDX scanning electron microscopyenergy dispersive X-ray
hydrogen overpotential is relatively low. In many cases the deposits detection
have better physical and chemical properties than the coatings pro- TBACl tetrabutylammonium chloride
duced from aqueous solutions. Tf2 N bis(triuoromethylsulfonyl)imide
The subject of the electrodeposition from non-aqueous solutions THF tetrahydrofuran
is very interesting, which shows the increasing number of papers TMPAC trimethylphenylammonium chloride
published in the last years. The development of technologies of UPD under potential deposition
obtaining the solid and dense metallic coatings from non-aqueous
solutions may facilitate achieving new materials of specic prop-
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