Electrochimica Acta 54 (2009) 5307–5319

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

In 1992. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3. . . . . . . . . . and also Hussey and co-workers carried out research deposition. . . . . . . . . . . . . . . . . . . . . . . . . . . . Also the low temperature windows. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Their another virtue is that the 2. . . Osteryoung and ance. 5317 1. . . . . . . . . . . 5316 3. . . literature with such key words as room-temperature molten salt. . . . ILs show good electrical conductivity and have wide electrochemical windows. . . . . . . . . . . . .and water-stable ionic 2. . . . . nitric acid with ethylamine. . . . • high thermal stability. . . . . . . . . . . Group 9 . . . . . . . . . . . . . . . . . . . . . AlCl3 -based ILs have hygro- scopic nature. LiF–CaF2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . a salt may be melted down (‘liquified’) by pro. . . . . . and similar difficulties. . . . . . . . A classical solution of an electrolyte is obtained by dissolution Wilkes and Zaworotko reported the first air. . . . . . . . . . . . . . . . . . . . . . . . . . . .9. . . . . . . . . . . . . . because ionic liquids are usually aprotic [11]. . . . . . . . . . . . . . . . Group 14 . . . . . . . . . . . . . . . Within the last few years ionic ions and their combinations and is free of any solvent molecules. . . . . . . . . . .3. . . . Conclusions . . . . . . . . . . . . . NaCl–KCl. . . . [C2 H5 NH3 ]NO3 . . as solvents. . . low-temperature molten salt. . . . properties of RTILs are the same as those of the high tempera. . . . . . . . . . . . . . Non-aqueous media inert-gas atmosphere. . . . . . . . . . . . . . . . . . . . . . . . . . . 5316 3. . . Electrodeposition from molten salts . . . . . Group 13 . Group 6 . . . . . . . . . . . . . . . .3. . . . . . . .7. . . . ionic liquids can be prepared and safely stored outside the inert viding heat to the system. . . . . . . . . liquid organic salt or ionic liquid. . . . . . .6. . . . . . . . . . . . . . . . . . . . . . . In the 1970s and 1980s. . . . . . . . . . . . . . . General features of molten salts are as follows: they can function especially those containing bis(trifluoromethylsulfonyl)imide [12]. . . . . . they are water insensitive. . . . . . . . . but also other mixtures are used and investigated. . . . . . . . . . . . . Moreover. . . . . . . . . . . . . . . . • low toxicity. 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). . . . . . there are technical issues melting point of 12 ◦ C and is formed by the reaction of concentrated that make their commercialization hard. . . . . . . . . . . . . . . . . . . . . Simka et al. . . . . . . . . . . . . ambient-temperature molten salt. . imidazolium) and satu- of hydrogen molecule during electrolysis. . . . . 5317 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . organic and inorganic materials. . . . . . . . Facing seri. . . . . . . . . . . . . . . . . . good solvents for both as 70 ◦ C. . . . . . . . . . . . to counterbalance the salt lattice energy. . . . . . ammonium salts. .3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10. . . . . . . . . . . . . . . . . . . . . These are the rea. . . . . . . . . . . . . . . . . . . 5317 Appendix A. with ions. . . . Typical application temperatures are 450–1025 ◦ C but can be as low in most cases non-flammable.3. . . . . . . . [EMIM].3. . The synthesis of air. . . . . . . . . . . . . . Group 2 . . Conventional aqueous solu. . . . . . . . . . >700 ◦ C). . . .11. of ILs starts in 1914. .5. . . . . . . . . . . . . . . . . . . . . . • inflammability. . . . . . . . or are based tions cannot be always used as electrolytes due to the liberation on cyclic amines: aromatic (pyridinium. . Anions can be based on cyano groups. . . . . . . . . . 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. . . . . . . . . . . . . . . . . . pyrrolidinium) ones. . . . . . . . . . . . . . The ionic liquids based on AlCl3 can be considered new electrolytes are required. . . . . . . . . . . . . . . . . . Group 1 . . . . . . . . . . . 5315 3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5314 3. . and can be used over a wide tem- Flinak. 5316 3. . . . . and conduct electricity. . . . . List of symbols . . . . . . . . . . . . . . . . . . . . . . . . . liquids (like water). . . . . . . . . . . . . . . . . .3. . . . . . . . . . . . . . . . has attracted interest in their utilization in various fields. . . [C(CN)3 ]− or [N(CN)2 ]− [1]. .3. .2. . . . . . . . . . . . . . . . . Molten salts liquids. . . . . . . . . . . which has a using non-aqueous electrolytes. . . . . . . . . . . Group 11 . . . 5317 3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ILs are usually non-volatile. . . . . . . . . . . . . . . . . . . . can attain Ionic liquids behave very differently to traditional molecular liq- very high temperatures (red heat. . . . . corrosion of cell components. . The room temperature ionic liquids are usually quaternary attracted attention in the last few years. . . . . . Introduction ture ionic liquids. . . . . . . . . . . . . . . . . . . . . . . . less toxic. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3. . . . . . . . . . . . the physicochemical • good solubility. . . . .3. as the first generation of ionic liquids. . . . . . and evaporation. . . . . . . . . . . . . . . so they must be prepared and handled under an 2. . . . . . . . . . . . . . . . . . . . . . . . Group 15 . . . . . such as cell heat bal. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3. . . . . . . . . . . . . . . . when the first report on a room-temperature ous problems concerning the environment and energy scientists molten salt was published by Walden [2]. . . . . . . . . . . . their charged or neutral combinations and solvent molecules. . . . . . 5314 3.12. . The role of non-aqueous electrolytes in such as [Ag(CN)2 ]− . . . . . . . . Such a system consists of solvated ILs based on the 1-ethyl-3-methylimidazolium cation. . . . . . . . . . . . . . . low current efficiency. . . . . . . . . . . . . . . . . . . . . . . . . . 5315 3. . . . . . . . . . . . . . . . . . . . . Group 10 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5317 4. . . . . . . . . . . Group 4 . . to electrodeposit metals. . . . . . . . Group 3 . . . . . . . . . . . Group 5 . .3. . . . . . . . . . . . . . . .and moisture-stable of a salt in a molecular solvent. . . . . . . . . . . . . . . . . . . . . . . . . . . / Electrochimica Acta 54 (2009) 5307–5319 3. . . . . . . . . . . . . . which are regarded as the second generation of ILs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1. . . Generally. . . . . . . . .3. . . . . . . . . . . . . . . . . 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. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . narrow electrochemical rated (piperidinium. . .13. 5316 3. . These On the other hand. . . . . . . .3. . . . 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. . . . . . . . . . . . . . . . . . . . . Group 12 . . . . . . . . . . . . . . . 5316 3. . . 5314 3. . . . . . . . . . . . . . . . low thermal stability. . . . . . . . . . . . . . . have good heat capacity. He reported the physical have found out new possibilities in electrochemical applications properties of ethylammonium nitrate. . . 5314 3. . . . Generally. . . such as tetraalkylammonium. . .4. . . . . . . . . . . . . . . . . . . . . . perature range. . The early history technology has become more and more important. . . . . . . . . . . . . . . . [R4 N]+ . . 5316 3. . . . . . . . . . . . . . .5308 W. . . . . . . . . . . . . . uids when they are used as solvents. . However. . . dendritic co-workers. . . . . . . . . . . . . . . . . . . . . . . . . . .2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . This has delayed progress in their use in many applications. . . . . . Ionic liquids problems associated with hydrogen ions in protic solvents can be eliminated. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . tetrafluoroborate or hexafluorophosphate as anions [10]. . . . . The information about RTILs can be found in the field • non-volatility. . . . . . . . . . . . list of the symbols is placed at the end of article) – consists of ical and chemical properties [11]. . . . . . . . The most common molten systems are LiCl–KCl. . . . . . . . . .8. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . liquids based on more hydrophobic anions have been developed. . . . . . atmosphere. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . To overcome these problems on organic chloride/aluminum chloride ambient-temperature ionic intensive and systematic studies (scientific and technological) of liquids [3–9]. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

orated and then re-condensed.2. the specific the stoichiometric zirconia [21]. Typically it is at the level of 30–50 cP.1. The deposit of lanthanum was contaminated tivity. ing point of this salt is above the room temperature (60 ◦ C). The most prevalent impurity affecting RTILs is water. CdTe. but typically are 4. for ILs are within a broad hol and ZrCl4 . Thus. ionic liquids Electrodeposition of metals and alloys from non-aqueous solu- are almost always aprotic [12]. . A dilution of neat ILs with formamide (DMF) and in the ␥-butyrolactone/tetrahydrofuran solvents (molecular liquids) also brings an increase in the conduc.5 g cm−3 .1. Pd. In this and in the following sections metals are divided in accor- whereas more lipophilic RTILs may be generated by using charge. The experimental results demon- 14 mS cm−1 . it was reported that some ILs may be evap. where their pres- ence is unwanted. but in some cases lutetium showed cracks. electrodeposition of metals and semiconductors.% at 25 ◦ C). Lutetium–cobalt thin films were electrodeposited from anhy- • cost of production. The viscosity of trodeposited potentiostatically on the copper substrate.1–18 mS cm−1 . Deposited the ionic liquids is much higher than that of water (H2 O = 0. there exist some exceptions to the above-mentioned Zn and its alloys. The surface of Lu–Co film The density of the ionic liquids is typically within 1. [PrMeIm][Cl]. The electrochemical a molecular diluent reduces also the viscosity of the mixture [1]. Solutions with low lutetium concentra- much higher viscosities.1. The main drawbacks of ionic liquids tions (such as aromatic.89 cP films were amorphous and deposits having up to 28. solidification point is −140 ◦ C [1]. reaches 540 mS cm−1 . nickel. LuCl3 and CoCl3 . present intentionally or unintentionally. acetone and acetates) are: provides cost-effective and easy to control technique to fabricate thin films and intermetallic compounds. at room temperature. • to produce fine spherical particles of silver. Considering Brønsted acidity/basicity. Pd–Au alloy.77 at. the specific conductivity of neat [EMIM][BF4 ] is by conducting salt cations (Li). such as amorphous [19]. HPLC. with reported. containing LiCl. W. Ta. iron and trochemical experiments on species dissolved within it. The potentials. The assumed non-volatility of ILs in a thermogalvanic cell. at which these bulk • media for detection of gases and development of stable and processes appear. For instance. robust sensors. Electrodeposition from conventional organic solvents constituent ions. had metallic luster and the film was but there are ILs showing the density lower than 1 g cm−3 . It results • solvents for extraction of metals. it is found that the constituent anions are oxidized • as fuel salt in the thorium molten salt nuclear reactor. was uniform. if only carbon. determine the accessible electrochemical win. In electrochemistry the stability window of a solvent is of great b) powder and materials production: importance. These relatively low values are due to high viscosity. In RTILs. Ag.11–18]: solutions. [N(CN)2 ]− . sensing materials for organic vapors in a quartz dow for each liquid [12]. dance with periodic groups. behavior of titanium and Ti4+ compounds was examined in THF Ionic liquids are applied in [1. so as viscosity increases.and biphasic studies (organic synthesis). dimethylsulfone. The high viscosity of ILs causes some difficulties in their lutetium concentration lower than 13 at. InSb. but even the highest conductivity is shape (open macroporous structure). in lithium batteries. Cr. outstanding property of ILs is their high thermal stability.1. Simka et al. as it is observed in the case of e) nanotechnology as: 1-propyl-3-methylimidazolium chloride. self-diffusion because conductivity is inversely proportional to the medium viscosity. • electrolytes for production of nanoscale materials like Al. The stability windows for ILs remain in crystal microbalance device. the broad range from 2 to 6 V. Solvating properties of RTILs vary depending on the nature of the 3. forming agglomerates of a much lower in comparison to the conventional aqueous electrolyte very large surface area. For example. • high viscosity. The next • medium in GC. the conductivity falls. 316 L in a non-aqueous electrolyte based on absolute ethyl alco- Room temperature conductivities. For instance. f) other: Additives. The preparation of lanthanum conductivity of an aqueous KOH (29. From DMSO solution Lu–Ni alloys were also elec- those based on the dicyanoamide anion.5 V [1]. but the Al–Mn alloys. in • high purity. 3. at sufficiently large potentials and organic cations undergo reduc.05 M) presented fine-grained deposits without cracks. Fe. Electrodeposition from the non-aqueous media components. Tetrabutylammonium chloride (TBACl) and LiCl were . Group 4 The self-diffusion coefficients of ILs are of the order of 10−10 to Zirconia films (ZrO2 ) were deposited on the stainless steel SS 10−11 m2 s−1 . like Of course. • electrolytes for: double-layer electrochemical capacitors. Any solvent is suitable for conducting a range of elec. Dilution of the viscous neat ILs with organic medium at room temperature [22]. The melt. electrolysis of aluminum (electrodeposition process) and recovery. in a thermally had been the base of their common reputation of ‘green’ solvents regenerative fuel cell. d) analytical chemistry as: tion at sufficiently low ones. a) electrochemistry as: • high polarity. results of an electrochemical investigation. halide ions or molecular solvents can extremely influence the • as micro-media and a catalysts (in oxidation of methanol). Ge. • low conductivity. but its 2 mol dm−3 solution in acetonitrile shows the strated that uranium could be electrochemically prepared in the conductivity of 47 mS cm−1 .%. 3. such as • mono. it is important to identify and eliminate those 3. even as high as 500–600 cP have been tion (<0. The film consisted of crystallites with a spheroidal range of 0. from the difference between reported melting and solidification • matrixes for UV–MALDI mass spectrometry. applied in and uranium metals at high temperatures was done in dimethyl- alkaline batteries. The alloy phase of Lu–Ni handling. drous dimethylsulfoxide (DMSO) solution. points that may be as high as 200 ◦ C. in features. anions possessing high charge density and organic cations with short alkyl chains stabilize more polar molecules.2–1. Viscosity plays an important role in conductivity and adhered firmly to the substrate after heating at 520 ◦ C [20]. Group 3 • high density. The layer composition was very close to solutions applied in electrochemistry. [1]. / Electrochimica Acta 54 (2009) 5307–5319 5309 • wide electrochemical windows. adhesive.4 wt%) solution. mixture (␥-BL/THF). diffuse anions. electrodeposition of elements that are inaccessible otherwise. these species are more easily oxidized or reduced than the solvent c) nuclear applications: itself.

Propylene carbonate was successfully demonstrated to electrodeposition and dissolution processes in the ionic liquid of be an effective aprotic organic solvent.2:1 AlCl3 /DMSO2 at Gd13. Group 13 and then it was deposited on the cathode. ation of radical alkyls with carbon chain length of four and longer that hampered the generation of electroactive species [32]. The reaction sis in the CoCl2 -(p-CH3 C6 H4 SO3 )3 Gd–urea–DMF solution. leaving a clean and film position technique. stable in the temperature range of 80–150 ◦ C. The electrolyte had a composition of nickel acetate. 3. but dation was Ti4+ . studied again in AlCl3 /DMSO2 electrolyte at 130 ◦ C.1. The solutions contained a 3. Saccharin presence the first time and Tm–Co alloy films were uniform. in the preparation of perpendicular magnetic Gdx (FeCo)y trolytes were investigated. Those baths had at 70 ◦ C. A Pt/Si sub. Co3 Gd alloy phase was firmly on the metal surface. ethylbenzene and xylene–durene electrolytes.1. Obtained deposits were 100–200 nm and the film was amorphous [26].1. Group 12 3. Group 15 electrolytes. As a supporting electrolyte (n-Bu)4 NBF4 was used. ature. The film thickness was Aluminum was electrodeposited from different aromatic sol- determined by the voltage applied during electrolysis [24]. satisfactory. ZnCl2 . toluene.3 (FeCo)86. The size of metal grains obtained [29]. p-xylene and ethylbenzene were investigated. peratures. Generally a rise in temperature had increased the grain size ical method using a sacrificial titanium anode as a cation source in [31]. From toluene a metal-free solvent. ture. cessfully utilized [28].1.2. by the pulse potential mode. Simka et al. The idea 3. The reason for deposition of pure Ti was not the deposit characteristics were dependent on the bath temper- accomplished [23]. sodium acetate and saccharin. The results revealed that an [33]. The electrochemical behavior of Tm3+ ions was investigated in a sodium tungstate. Pyramidal-shaped magnesium deposits of microsize ethylene glycol (EG). Porous Mg depo- bonate bath showed a stoichiometric ratio of ZnTe [30]. mean- adhering to the substrate [27]. titanium and copper alloys as well as steel.4. The film between Al and the electrolyte had led to the formation of a pas- was dense and homogeneous and the content of Gd increased with sivating layer by accumulation of the resulting corrosion products the increasing cathodic potential. The resulting films had to be annealed at high temperature The authors managed to obtain high-quality aluminum coatings to effect crystallization. . The product of pure titanium oxi. The mixed system of a molten salt ing that the corrosion was associated with the reduction of DMSO2 and an organic solvent can be also utilized as an electrolyte.8. solution Al was deposited in the form of individual crystals. vents. Group 10 derivatives. The bath life was also excellent (1 year of operation Gadolinium–cobalt film was electrodeposited from gadolinium with unchanged composition). such electrolyte was used. in aromatic solvents created good electrolytes for Al refinement Copper sheet was used as a substrate. CdSO4 and EDTA were dissolved in free surface. alkylaluminum as well as quaternary ammonium salts dissolved mamide (DMF). completely dissolved electrochemically.3. NuLi and co-workers reported for the first time the magnesium trolyte. adhesive. The underpotential depo. trolyte.7. iodine-dissolved acetone bath. A TiO2 film was obtained by an electrochem. was of about 20 nm [36]. For [34]. containing halide ions as the supporting elec. Na2 S2 O3 . Solvents in non-complexed AlBr3 electrolytes (bro- mide baths) were benzene. adherent Al coatings were obtained over a wide range of tem- strate was utilized for electrodepositing a Gdx (FeCo)y thin film. Finely crystalline films cannot be obtained in magnesium deposition on silver substrate in [BMIM][BF4 ] with methanol or acetonitrile. Nd–Fe could be codeposited by induced codeposition few drawbacks such as high flammability. AlCl3 /DMSO2 electrolytes were very thin film.6. In [35] aluminum deposition processes in DMSO2 -based elec- instance.7 magnetic thin film in the electrolyte was suc. 130 ◦ C. Also. 3. Organoaluminum compounds like toluenesulfonate (salt of rare earth) dissolved in dimethylfor. xylene and their mixtures and 3. The substrates acted as effective barrier against electrolytic corrosion main disadvantage of applying organic solutions was the cre- [25]. com- in the electrolyte decreased the internal stresses in the alloy coating pact and showed a metallic luster. since the acetate nickel-plating electrolyte has some advantages over other known nickel-plating 3. / Electrochimica Acta 54 (2009) 5307–5319 used as supporting electrolytes. bright and The system consisted of ZnCl2 –DMSO2 melt at 70 ◦ C. toluene. Magnesium sition of Zn (UPD) occurred only in acetonitrile and propylene was found in the deposited film and the deposits were dense.1.2. variation of the com- and the composition of the film varied with Nd(III)/Fe(II) molar position and limited lifetime. It was discovered that aluminum would in acetone bath using Ta and Nb anodes as the metal sources and not have been deposited from benzene solution. be independent of sulfur and cadmium ion concentrations. The solutions of aluminum bromide in solvents like benzene. Nd–Fe films comprised of nanoparticles with the size of was the THF–benzene–AlCl3 –LiAlH4 bath. The increase in system consisting of Tm(NO3 )3 .5. Mg(CF3 SO3 )2 was examined at room temperature. acetonitrile and propylene carbonate baths were used to electrodeposit zinc telluride. The coatings prepared on stainless steel from xylene. Electrodeposition from ionic liquids Methanol. The rare earth surfaces and their alloy films were prepared for ing of coating. LiClO4 and DMSO at room tempera- tungsten(VI) concentration in the electrolyte has resulted in crack. CdS films sition became compact and crystalline and deposited Mg could be were prepared from a non-aqueous solvent using the electrode. The results from Al refining experiments showed that The pulse potential mode for electrodepositing a perpendicular Al alloy could be purified via electrolysis in 0. NaClO4 as a supporting elec. Under the influence of iodide ions TiO2+ was produced as the result of dissolution of the oxide films 3. The films obtained from propylene car. The electroplating of nickel–tungsten alloys from acetate solution was studied. The cathodic and anodic behavior of aluminum had been amorphous Gd–Co film can be obtained by potentiostatic electroly. Group 8 Also. Dense. Another bath used to deposit Al ratio. Group 5 of this electrodeposition was to develop a technological line for Tantalum(V) and niobium(V) oxide films were easily fabricated electroplating workpieces. but its luster has been improved.1. In that region sulfides were found. Group 2 given solvent and also TeCl4 .1. [BMIM][BF4 ] with Mg(CF3 SO3 )2 at room temperature. The quality of the deposits was found to were formed [37–39]. carbonate baths. adherent aluminum coatings were deposited on various alu- The processes of iron(II) and neodymium(III) reduction in the minum alloys. from metal chloride–acetamide–urea–NaBr–KBr melt were investigated AlCl3 –LiAlH4 –diethyl ether baths (the NBS baths).5310 W.

The optimized condition for producing finer particle current efficiency of the alloy were improved by an addition of size and high Ti content in Ti–Al alloys was obtained for the organic solvent. was examined. lic compound. which exhibits sufficient solubility of RuCl3 at room with the H2 PtCl6 -containing ionic liquid droplet-confined GC elec- temperature. trode. containing Pd(II) and Ag(I). propylene carbonate or ethyl alcohol. tial. acidic 40–60 mol% zinc chloride–EMIC ionic liquid. like Pt–Ru [17]. Group 9 The electrochemical behavior of uranium in 1-butyl-3.5 and 3. The IL droplets could form micro- reported for the first time in [50]. melt saturated with CoCl2 at room temperature.5. The electrocrystallization of entrapped during the electrodeposition [40]. The zinc content of Zn–Co 3. to the applied voltages of 1. The experiments were conducted at different temperatures CoCl2 –ZnCl2 –1-butylpyridinium chloride (BPC) system. The morphology and the 1. Adherent. 3. to that of Co and the intermetal- current efficiency of the process [43]. / Electrochimica Acta 54 (2009) 5307–5319 5311 3. only 5 ␮l. as a function of the Co content in the deposit [54].2.2. A porous anodic alumina template was synthesized by the of Ta. Zinc. The electrodepo- 1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide ionic sition of cobalt and zinc–cobalt alloys on nickel. and temperature ranges from 70 to bath. The composition of the Pd–Ag alloys could be var- Mn(II) species were introduced into IL by the anodic dissolution of ied by the deposition potential and concentrations of metal species metallic electrodes. which is electrodeposition process in IL allowed the achievement of an generally the same as the pore diameter of the porous anodic alu- adherent. Zn(II) and 35 to 120 ◦ C. the solution and enabled the electrodeposition to be performed chemical production of Ti–Al alloys was investigated using at a lower temperature (40 ◦ C) [53].2. i. Zn electrodeposits were very stable and exhib. presumably because of kinetic reasons [46]. in the solution. within a temperature range from 1-butylmethylammonium bis(trifluoromethane)imide.8. UO2 was peratures 70–100 ◦ C.e.4. Group 5 were electrodeposited onto a copper cathode from the AlCl3 –BPC The electroplating of tantalum on NiTi alloy in RTIL.0 V. The deposited sur- butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide. The electrodeposition of tantalum was carried current electrodeposition.2. X-ray diffraction deposit micrometer thick tantalum layers at room temperature patterns showed that the Co nanowires fabricated from a mixture fail. containing cobalt(II). 1. of about 500-nm thickness. The optimization of tantalum average diameter of cobalt nanowires was about 45 nm. using 1-octyl. The electrode- were amorphous [47]. containing . 1-butyl-3-methylimidazolium electrodeposition was carried out in the aqueous solution of KPF6 dicyanamide.4 ]TFSA. Platinum nanoparticles were cost-effectively electrodeposited from a droplet 3. AlCl3 –BMIC and [BMIM][PF6 ] ionic liquids [52]. The electrowinning of rhodium resulted in a deposited at the electrode and some electrolyte was also deposition of metallic rhodium [51].3. Group 7 The electrochemistry of manganese in a hydrophobic RTIL. ate co-solvent to the melt decreased the melting temperature of Also Au–Ti surface alloying was observed [42]. obtained from an ambient-temperature molten salt electrolyte. manganese and zinc–manganese position of Pd–Ag alloys was examined in a basic EMIC/BF4 ionic alloys had been electrodeposited from the hydrophobic tri. Metallic Ru films have been deposited. Co5 Zn21 .2. An Co–Zn alloy deposit was TiCl4 –AlCl3 –1-butyl-3-methyl imidazolium chloride electrolytes. was reported in [49]. tungsten. having 1–2 nm thickness. Simka et al. The crystal structure of passive layer on the electrodes. which retards the kinetics of redox the Co–Zn alloy deposit changed from the binary phase of Zn and an reactions and reduces the cathode current density as well as the intermetallic compound. Manganese coatings were pre.6. Mn coatings was examined in a hydrophobic [BMP]Tf2 N [57]. liquid. at 80 ◦ C. face obtained was very smooth and also had a bright metallic color [BMP]Tf2 N. Group 4 alloys was found to vary nonlinearly with the deposition poten- Titanium was electrodeposited from TiCl4 -1-methyl-3. The electrochemical reduction of palladium halide complexes pared by electrodeposition at several substrates. Cobalt–aluminum alloys of different composition (up to 60 at.% Al) 3. The water-immiscible IL droplet (the micro-media) was also solving ruthenium(III) chloride in a 1-butyl-3-methyl imidazolium suitable for the cost-effective electrodeposition of bimetal nanopar- hexafluorophosphate (BMIPF6 ) room temperature ionic liquid at ticles.7. electrochemical anodization of aluminum and was used to grow The coated sample showed a better corrosion resistance than the cobalt nanowires. The electrochemical behavior of rhodium(III) chloride in BMIC methylimidazolium chloride (BMIC) at a glassy carbon electrode was studied at a glassy carbon (GC) working electrode at tem- was studied in the temperature range 70–100 ◦ C. Group 8 of water-immiscible ionic liquid ([BMIM][PF6 ]) that contained The first investigation of ruthenium electrodeposition on metallic precursor-chloroplatinic acid hexahydrate (H2 PtCl6 ). and GC electrodes was examined in 40–60 mol% zinc chloride–EMIC molten salt.5–2.0 V. The bath temperature could be decreased from 130 to 25 ◦ C 100 ◦ C. In [41] the lan. and the cobalt nanowires electrodeposited from a on its surface (Ta2 O5 ) [45]. 3. Group 10 [BMP]Tf2 N. cobalt and its alloys (containing Ni) with Al was investigated in the thanum electrodeposition in ambient atmosphere. homogeneous and protective film of tantalum oxidized mina template. Attempts to solution. can be electrodeposited at 200 ◦ C. An addition of propylene carbon- dimensional clusters of Ti. The electro. and they showed a better squareness. was reported for the first time. for example. The low current efficiency is due to the formation of a TiCl3 by the addition of these organic solvents. The electroreduction of TaF5 on Au(1 1 1) mixture of 1-ethyl-3-methylimidazolium chloride ionic liquid and and on polycrystalline gold substrates was investigated at room ethylene glycol had a smoother surface and better magnetic prop- temperature in the ionic liquid 1-butyl-1-methylpyrrolidinium erties than the cobalt nanowires electrodeposited from an aqueous bis(trifluoromethylsulfonyl)amide. A dense layer of three. and from between 70 and 125 ± 3 ◦ C and at various cell voltages between the bath containing an organic solvent. The electrodeposition of Pt–Zn from a Lewis 90 ◦ C. Group 3 3. The results of tests indicated that the out in the same IL also at 200 ◦ C. of EMIC ionic liquid and ethylene glycol were of a polycrystalline structure [56].2. [Py1. was formed. Also the electrochemical depo. The method demonstrated here required much less amount sition of ruthenium on n-type silicon from an ionic liquid was of IL.2. was investigated. The Au(1 1 1) from an ionic liquid. content of the deposits rose. Zn-Co deposits with a low zinc content were amorphous and butylimidazolium bis(trifluoromethylsulfone)imide at room the crystalline nature of Zn–Co electrodeposits increased as zinc temperature on Au(1 1 1) substrate. The study was performed by dis. media. copper liquid (OMPTf2 N). pact upon increasing the temperature up to 120 ◦ C [58].2. dense and uniform layers [55]. The cobalt nanowires were produced by direct uncoated one [44]. The alloys were nodular and became more com- ited good adhesion [48]. W.

The electrocrystallization of semiconductor ZnSb was was studied. the IL [69]. The based ionic liquids was investigated. trodeposition of zinc on GC and nickel substrates was studied in position and morphology of Pt–Zn electrodeposits could be varied 50–50 mol% zinc chloride–EMIC molten salt. A dense and adhesive Al layer was also with an average diameter of 80 nm and length of 5 ␮m [62].%. The recycling of aluminum metal matrix composite arrays of Zn nanoclusters were obtained and described in [68]. A compact film of Ag also was deposits were also obtained on Al substrate using continuous cur- deposited onto glassy carbon in the presence of nanoparticles [63]. The electrodeposition behavior of obtained by the UPD of Cd on the deposited Te. The electrodeposited on a Mg alloy in the AlCl3 –EMIC ionic liquid at reduction of Ag+ to Ag0 has been studied electrochemically at 25 ◦ C. dense.2. The crystalline 3. Patterned Zn nanoclusters and large-scale Au(1 1 1) [79]. Zinc and tin can be elec. continuous and well adherent.9. applying the ZnCl2 –EMIC ILs by proper control of the temperature and depo. A homogeneous distribution of ZnSb clusters of spherical nanometer size regime. The via electrolysis in the same ionic liquid was examined at 103 ◦ C. electrodeposition of Al in three different water. / Electrochimica Acta 54 (2009) 5307–5319 PtCl2 . Group 13 nature of the nickel deposits was revealed by the powder X-ray The nanocrystalline aluminum was electrodeposited without diffraction spectroscopy results [61]. Nanocrystalline the electrodeposition led to well adherent Al coatings of the good copper was formed in that ionic liquid at room temperature [65].2. using [BMP]Tf2 N saturated with AlCl3 . The electrodeposition of Ni–Zn alloys hol was investigated. Mg alloy [75]. The bulk deposition of Al at room temperature on gold was studied. resistance to mechanical scratching. for instance surfaces in [BMIM][BF4 ]. Dense Al Me2 NH and CO2 in a 1. was investigated at 90 ◦ C.10. Coarse cubic-shaped aluminum particles . The polycrys- per electrodes in the 1-ethyl-3-methylimidazolium dicyanamide talline CdTe was formed through direct electrodeposition without (EMI-DCA) room temperature ionic liquid. Ag+ is known to be chemically surface morphology of Al on W and Al electrodes was studied reduced to form Ag0 nanoparticles by species present in the ‘distil. The authors have found that the in situ electro- amorphous silver gangue [64]. The electrodeposition of baths with higher propylene carbonate concentrations or at higher nickel and nickel–zinc alloys was examined at polycrystalline tung. electrolytic deposition of Zn. The presence of crystalline molten salts ZnCl2 –NiCl2 –EMIC and ZnCl2 –NiCl2 –EMIC–ethyl alco- nickel deposits was indicated. At 100 ◦ C track-etched polycarbonate template from the ionic liquid the quality of the deposit was better with an average size of [BMIM][PF6 ] was studied. Well-adhering bulk zinc sten electrode in a zinc chloride–EMIC molten salt. The quality of the zinc by the deposition potential and Pt(II) concentration [18]. temperatures exhibited larger grain size.11. Results tion of Cd–Te from a Lewis basic EMIC/[BF4 ] was examined in the revealed that UPD is an interesting route for the electrochemical temperature range 80–140 ◦ C. [EMIM]Tf2 N and trihexyl-tetradecyl- morphology and composition can be changed by rational choice of phosphoniumbis(trifluoromethylsulfonyl)imide (P14. The deposits produced from the plating ionic liquid was studied at 120 ◦ C [59]. aggregated the coating. Codepo. Al electrodeposition in AlCl3 –trimethylphenylammonium metals onto Mg and its alloys. In the same electrolyte the electrodeposition and metry and chronoamperometry. dense. The electrodeposits obtained on both lable’ room temperature ionic liquid. SEM images of the nickel subsequent annealing [73]. [78].and air-stable trodeposited individually or as alloys from these liquids.6 Tf2 N).6. A nanoscale electrodeposition of Al on Si(1 1 1):H sub- Also crystalline Zn deposits could be prepared from various acidic strates was investigated at room temperature. ChCl:2 urea mixture was found to be chloride (TMPAC) was performed on W and Al electrodes. Zn can also be nanostructured on Au(1 1 1) features similar to Al deposits on metal substrates. Sn and Zn–Sn alloys from a solution of Pure aluminum was deposited on a copper electrode. Group 11 obtained deposits were uniform. To prepare CdTe nickel was investigated at glassy carbon and polycrystalline cop. deposits indicated that the morphology of the nickel electrode- posits was dependent on the deposition potential. deposits was greatly increased by the addition of propylene car- sition of palladium–indium alloy from a chloride-rich EMIC/[BF4 ] bonate as a co-solvent. The com. The Cd–Te electrodeposits could be preparation of Ni–Zn alloys [60].5312 W. The alloy ionic liquids.6 mol% by changing the bath compo- deposited nickel. The Ni content in the deposits could be was achieved through the underpotential deposition of zinc on the controlled from 12. The 3. The formation of the and the phase types of nickel–zinc alloys were dependent on the amorphous structure in the deposit of the Ni content varying from deposition potential.8:1 ratio). rent deposition [76]. Pt–Zn deposit was amorphous or shape with diameters up to 15 nm was found [70]. The elec- nanocrystalline and the formed film was thick or compact. by Jiang and co-workers.6. DIMCARB (synthesized from electrodes were dense. at form. The electrochemical deposi- on Ni. Smooth. aluminum electrodeposits were obtained on both substrates sealed and more corrosion-resistant Zn layers were formed [66]. A nanocrystalline Al can be electrodeposited in also studied at the electrified ionic liquid/Au(1 1 1) interface. The deposits obtained were uni- ZnCl2 –[C4 mim]+ Cl− (1-butyl-3-methylimidazolium chloride). shining and adherent to The deposition of silver nanowires in a commercial nuclear the substrate. The deposit metal chloride salts in urea and ethylene glycol/choline chloride microstructure ranged from columnar to spherical one [80]. The electrodepo. Group 12 formation of a Fe–Al alloy that resulted in the excellent adhesion Ionic liquids were used as electrolytes for electrodeposition of [77]. Dense the most feasible liquid for successful electrodeposition. temperature and current densities. Simka et al. the zinc content in Ni–Zn was always less than 50 at.3 to 98. of imidazolium liquid crystals containing dicyanoargentate(I) and Pretreatment of substrates played a key role in the adhesion of dicyanoaurate(I) anions. The bulk Al deposition exhibited sition potential [67]. steel was of high quality but it did not exhibit good adherence sition of silver led to the formation of hexagonal platelets in the to the substrate. [BMP]Tf2 N. Dense and electrodeposits on nickel substrate were obtained from these media compact nickel deposits with good adherence could be prepared [71]. Nanowires had a very high aspect ratio crystallites of 34 nm [74]. with very fine crystallites in the 50 ◦ C. The electrodeposition of copper in chemical etching of the substrate by anodic polarization prior to [BMP]Tf2 N was studied at variable temperatures. with crystallites in the nanosize regime. For the Ni–Zn alloys prepared by the UPD of Zn 40 to 70 mol% was confirmed [72]. Al coating made on a conventionally pretreated mild into spheres or multiglobular shapes (100 nm). codeposits an excess amount of Cd(II) was required. The protective Al layer reduced the corrosion rate of the glassy carbon electrodes using the techniques of cyclic voltam.2. The electroplating of mild steel by aluminum Silver and gold nanoparticles were produced during the electrolysis in the first generation ionic liquid EMIC–AlCl3 was investigated. Gold particles were nanodots. shining and adherent. The electrodeposits composition was indicated sition. AlCl3 –[C4 mim]+ Cl− ionic liquid. any additives in the [BMP]Tf2 N saturated with AlCl3 . That was due to dissolution of the pre-formed iron oxide layer and re-deposition of iron or the 3. The deposition of Zn–Ni alloy from the ambient-temperature by controlling the deposition potential.

In the Ga. The deposition of super- rials were discussed in the reference [88]. Deposits obtained at 30 ◦ C had a nodular appearance studied at variable temperatures. The protective action of thin layers of aluminum It was concluded that the addition of LaCl3 into the melts led to electroplated on a carbon steel has been studied. on Au(1 1 1) in an acidic chloroaluminate ionic liquid. and CuCl dissolve readily of Sn(II) to Sn(IV) was not observed [94]. onto platinum and mild steel cathodes from the AlCl3 –BPC molten ranging from 10 to 40 ␮m. Group 14 anions. Al and Al/Pt annealing and subsequent oxidation. in the form of several monolayers. Co-electrodeposition of Al with Pt was electrodeposited in the LaCl3 –saturated AlCl3 –EMIC melt at 25 ◦ C. It was found that the alu. mild steel cathodes. Uniform. AlCl3 –TMPAC. revealed between 600 and 800 ◦ C [91]. Cd and Ni elec- methylimidazolium chloride room temperature ionic liquid. The interfacial reactions of Mo–Si–B with Al–Si butylimidazolium chloride–aluminum chloride. Sn. It was electrochemistry of deposits was investigated [92]. SiO2 and mullite particles) cathodic deposi- liquid the particle size increased with temperature.6. The minum layers deposited from ionic liquids significantly protected deposited surfaces were very smooth and had a bright metallic the substrate from the general corrosion and this action increased color [90]. including Sn. The interfacial region during the Al–Si deposition was the mirror-like Al film containing very fine crystallites of about 20 nm precursor to the formation of compositionally graded mullite by was obtained in P14. Al–Si was deposited conductor alloy precursors (Bi–Sr–Ca–Cu) was studied in a room on Mo–Si–B substrate material by a molten salt (AlCl3 with an temperature molten salt medium based on EMIC–AlCl3 system at . Ni and obtained tin deposit was a smooth and dense facet. adherent. 1-methyl-3- was observed [87]. tion. The formation of metal monolayers (Ga. metallic coatings during processing to achieve high-temperature Different morphologies of Bi crystals were obtained: needle-like corrosion protective mullite coating for advanced turbine mate. Also some codeposition of Al Results showed that the current density certainly caused changes with Co. and the bromide (DMEPAB) solutions in toluene. containing acetylace- type of deposit microstructure was changing rapidly as a function tonate of a corresponding metal. Also galvano. Ni) has with the ternary Alx Iny Sb100−x−y alloys [85]. crack-free aluminum of the process temperature. to minimize the effects Pt. The 1-ethyl-3-methylimidazolium dicyanamide (EMI. Zn or Mn from AlBr3 –dimethylethylphenylammonium in the morphology and microstructure of the deposit. wire electrodes in the Lewis acidic aluminum chloride-1-ethyl-3. and Cu was successfully demonstrated in [93]. The fact that good Sb electrodeposits can be obtained from [65].6 Tf2 N at room temperature [81]. Coatings of different thickness. obtained within a deposition temperature range between 30 and 1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide was 120 ◦ C. Aluminum deposition process on tungsten electrodes was this RTIL suggests that such liquids may be useful for the deposi- conducted in a room temperature molten salt. bath saturated with nickel(II) chloride at room temperature. In this ionic organic electrolyte. Binary aluminium–chromium alloys were deposited with the thickness of the coating. The coatings the increase in deposition overpotential affecting the orientation were obtained via electroreduction. Group 15 can be obtained from the DCA-based ILs. 1-n- aluminum can be electrodeposited almost exclusively from the butyl-1-methylpyrrolidinium bis(trifluoromethyl-sulfonyl)imide highly water-sensitive Lewis acidic chloroaluminate ILs and the (BMPTFSI) at 25 ◦ C. Cr-rich and Al-rich solid solutions and intermetallic com- chloride) ionic liquid at variable temperatures (581–601 ◦ C). Ultrathin Ge N-butyl-N-methyl pyrrolidinium dicyanamide (BMP-DCA) ILs were films with varying thickness were obtained at relatively low used. The chromium content of the electrodeposit static electrodeposition was used to electrodeposit aluminum varied from 0 to 94 at. ZnCl2 . Zn. liquid. The electrodeposition of bismuth underpotential deposition of Al. The oxidation Cu. 1-butyl-3-methylimidazolium dicyanamide (BMI-DCA). It is found that SnCl2 . structures and ultrathin Bi films [96]. The electrochemical reaction of Sn(II)/Sn of importance because according to the previous literature data was investigated in a room temperature ionic liquid.% Cr. with nanometer or atomic resolution. This research suggested that alloys could be deposited from the room temperature ionic liquids the metallic precursor should be deposited by organic electrolysis of AlCl3 and benzyltrimethyl ammonium chloride (BTMAC) on rather than by molten salt electrolysis. The excellent high temperature oxidation resistance of a Effects of variations in current density and temperature on surface series of Al–Cr alloys on the mild steel. While Ni and Zn could not be electrodeposited from most Lewis basic or neutral ILs reported in literature. The electrodeposition of indium and copper in 1-butyl. The nanocrystalline In with grain whereas those obtained at 80 and 120 ◦ C consisted of fine polygonal size between 100 and 200 nm was formed at room temperature crystals. The deposit microstructure consisted of on mild steel in AlCl3 /[bmim]Cl (1-butyl-3-methylimidazolium both. 1-methyl-3-butylimidazolium chloride/aluminum chloride ing the electrodeposition process indicated that at higher applied mixture was used.6. containing 20–50 at. W. Dense deposits were [86]. and AlInSb alloys was examined at the copper rotating on metal and semiconductor substrates at room temperature. An aluminium–lanthanum alloy was deposits were obtained. in the EMI-DCA IL. / Electrochimica Acta 54 (2009) 5307–5319 5313 in the micrometer range were obtained in [EMIM]Tf2 N. especially at higher current densities. Mn. The trodeposition experiments a Lewis acidic room temperature ionic behavior of the partial current densities for In and Sb observed dur. and was investigated in AlCl3 –BMIC and [BMIM][PF6 ]. of aluminium–nickel intermetallic compounds was carried out tachloroaluminate ([BMIM]Al2 Cl7 ).2. The ability of electrodepositing Al from the BMP-DCA IL is temperatures [52]. Already the present results show from 2:1 AlCl3 –N-(n-butyl)pyridinium chloride room temperature the possibility of utilizing ionic liquids as electrochemical media molten salt.13. were obtained. The electrodeposition was carried out on platinum and for coating processes of industrial relevance [83]. also studied [82]. was examined. was investigated. the ionic liquids (ILs) composed of 1-methyl-3-alkylimidazolium or N-methyl-N-alkylpyrrolidinium cations with dicyanamide 3. The electrodeposition of germanium on Au(1 1 1) and Si(1 1 1):H DCA). In this work. The tion of InSb semiconductors [95]. AlSb. The application indicated that all of the electrodeposits exhibited mainly the of ionic liquid electrolytes succeeded in the electrodeposition of (2 0 0) crystallographic orientation [84]. Ni. they 3. from and improving the surface morphology [89].12. Cr. the AlCl3 was current densities a phase rich in In and Sb was deposited in parallel replaced by ZnCl2 . Zn. Here only the of temperature. The electrodeposition been contrasted with the occurrence of surface alloying (Cd–Au) of Al. Simka et al. The electrodeposition an ionic liquid constituted by 1-butyl-3-methyl-imidazolium hep. The morphology of the for electrodeposition of various metals. was morphology and crystal orientations were systematically studied. The electrodeposition of Sn on a Cu substrate water-stable TFSA-based ILs. pounds. NiCl2 . Al and Fe electrodes.%. The electrodeposition of light and transition metals as well as compound semiconductors AlIn. EMI-DCA was examined was possible in BMPTFSI containing Sn(II). Moreover. the ability to The electrodeposition of antimony was performed on GC and electrodeposit reactive metals such as Al and Mn is of significance nickel electrodes in a basic EMIC/[BF4 ] RTIL. at room temperature. In the case of ZnSb deposition.2. A very thin.

U-graphite intercalation compound (GIC) helped the self-scraping ductor alloy precursors [97].3. Group 2 a LiF–NdF3 –Nd2 O3 melt was possible. A much thicker SmNi2 film with different phases were prepared via galvanostatic electrolysis (20 ␮m) was obtained by cathodic galvanostatic electrolysis [121]. formation of the alloy PuCd6 was observed as well as other inter- chemical insertion of sodium into graphite was examined in a metallic compounds. Al. refractory metals.75 wt. americium was the most difficult to separate [108]. The electrodeposition of Nd in 3.g. of U–Zr electrodeposit was dendritic with aggregates of fine grains Lithium intercalation into graphite had occurred before deposition [113]. The behavior The Mg-Li alloy films with ␣-Mg and ␤-Li phases were obtained of plutonium and proper conditions for plutonium recovery at by potentiostatic electrolysis at −2. were investigated on a W electrode in a molten eutectic LiCl–KCl For the extraction of Eu from a molten salt the use of a reactive in the temperature range 420–550 ◦ C. tin) in an in [125]. lanthanides.1.5314 W. Also some experiments were carried out on lithium metallic compound PuCd6 [115]. Much thicker alloy film was formed of the superconductive boride. [100] it was mentioned that liquid calcium–lithium successfully collected up to 7. Electrorefining experiments of the alloy and Al was found to be the best for depositing alkaline of uranium were successfully carried out in the LiCl–KCl eutectic earth metal alloys. The cathodically deposited calcium can be used to reduce most of was prepared by the electrochemical reduction of thermally com- the other metals. It for temperatures ranging from 380 to 550 ◦ C. [104] the formed on Cu substrate by potentiostatic electrolysis [119]. fused at 600 ◦ C. The electrochemistry of the formation of an alloy. The method is applicable to the industrial fabrication of in the LiCl–KCl eutectic at temperatures ranging from 400 to 550 ◦ C. The surface of lithium chloride and tin(II) chloride was examined at 625 ◦ C. Electrochemical proper- at the inert and active electrodes in the molten LiCl–KCl eutectic.55 V. while samples from electrode in a molten lithium chloride and a molten mixture deposits containing Zr showed polycrystalline features. The had a diameter of 0. The electrodeposi- MgCl2 –MgF2 mixtures was studied at 780 ◦ C. Also uranium deposits were prepared by the electrolysis in a fused chloride melt (NaCl–KCl) 3. lead.35 and −2. Cu and Ag were used as substrates for deposition of thorium was only examined [110]. An adhesive DyFe2 film was 3. A very thin film of Mg(II) occurred to solid magnesium. PuCd2 and PuCd4 [116]. The electrochemical formation reported in [105].1 ␮m and was 1 ␮m long [101]. The electrochemical behavior of praseodymium was investigated position of uranium and plutonium in the LiCl–KCl eutectic salt on in two molten chlorides.% without the disturbance by alloy deposits were formed in the LiCl–KCl–CaCl2 eutectic melt at solid phase formation at the surface. onto graphite substrates was by Li codeposition method [120]. actinides. The electrochemical reduction of studied in a LiCl–KCl–SmCl3 system at 450 ◦ C. The Zn on a molybdenum electrode in LiCl–KCl–MgCl2 –ZnCl2 melts at formation of SmNi2 phase was confirmed and the thickness of 1216 ◦ C to form Mg–Li–Zn alloys was investigated. par- ticularly in LiF–CaF2 at 810 ◦ C [117]. The electrochemical molten sodium fluoride at 1025 ◦ C in [102]. e. The electrode.3. A fiber-like lithium was deposited which tigated at 450. An electroplating technique SmCo2 alloy was obtained. tion of samarium and cobalt on copper substrate was investigated cess on a magnesium electrode showed that probably a very thin in a molten LiCl–KCl–SmCl3 –CoCl2 system at 450 ◦ C. A [106]. 500 and 550 ◦ C CaCl2 –NaCl melt. The nucleation pro. potassium chloride. trodeposition some terbium–iron intermetallic compound. TbFe2 .3. The electrochemical codeposition of Mg. magnesium boride films on large-scaled surfaces of various shapes. Electrodeposition from molten salts at 670–710 ◦ C [112]. MgB2 . the eutectic LiCl–KCl and the equimolar W and Mo working electrodes was studied at 450. The alloy film was thin and not adhesive. silver. Also is easy to scale up because of the simple and low-priced instal. The electrodeposition of magnesium ions was examined in a molten electrochemical formation of Sm–Co alloy films at Co cathode was CaCl2 –NaCl system at 550 ◦ C. Features of neptunium dissolved in the LiCl–KCl eutectic of metallic lithium started [98].3. Depending on the electrode The electrodeposition of magnesium from molten MgCl2 and substrate the co-reduction of Li+ occurred [118]. In Ref. the electrochemistry of Gd(III) was studied at W and Al electrodes lations. At the aluminum elec- in [109]. films was done in a molten LiCl–KCl–DyCl3 system at 500 ◦ C.3. at different temperatures. Plutonium was [99]. Ti. Here the electrochemistry electrode made of aluminum led to Al4 Eu alloy formation [129]. The electrochemical formation of dysprosium–iron alloy situ hybrid process [107]. On Al electrode a stable Gd–Al alloy was formed [123]. respectively the liquid cadmium cathode (LCC) were examined. In Ref. The electrochemical behavior of DyCl3 was LiCl–KCl eutectic-liquid metal systems has been examined. SmCo3 was oxide layer was formed at these conditions [103]. . without surface analysis [114]. The behavior of Li+ was studied were investigated on tungsten electrodes. Pt. rare pounded powders of Tb4 O7 and Fe2 O3 in a molten CaCl2 at 900 ◦ C earths and other precious metals (titanium. mechanism of uranium dendrite [111]. sodium chloride ture range 700–750 ◦ C. Films of MgB2 with a thickness of tens of micrometer were possibility of gadolinium boride synthesis in the chloride–fluoride fabricated on graphite substrates by means of electrolysis in a mix. ties were only studied. The electroplating of MgB2 nanotubes were synthesized on a molybdenum cathode [122]. Group 3 obtained at the activated Fe electrode after cathodic electrodeposi- A pyrochemical separation of actinides from the rare earths in tion of Dy metal [126]. For the first time gadolinium hexaboride and magnesium borate. Erbium formed some was essential to use a porous ceramic diaphragm around the anode alloys with solid Al electrodes [124]. Plutonium formed the inter- 450–600 ◦ C. As an example of terbium elec- to separate the anolyte and catholyte in order to deposit calcium. behavior of neodymium was studied in several molten media. The electrode reactions of U and Pu were complicated by trode a stable Pr–Al alloy was formed [128]. melt (NaCl–KCl–NaF–GdF3 –KBF4 ) was examined in the tempera- ture of magnesium chloride. The behav- Metallic calcium can be produced electrolytically by dissociating ior of erbium(III) was investigated in the molten LiCl–KCl eutectic calcium oxide in a molten calcium chloride electrolyte at 900 ◦ C. It was examined in LiCl–KCl at different temperatures. Also the electrode reaction of deposition from 2MeTHF–ethylene carbonate (EC)–LiAsF6 on a Pu3+/ Pu couple at the surface of a liquid Cd electrode was inves- stainless steel substrate. Group 1 deposits were built of chains of uranium crystals with a rhomboidal The electrochemical reduction behavior of lithium at a graphite shape and complex internal porosity structure.2. Simka et al. The compositions of the electrodeposits were molten salt at 500 ◦ C with a graphite cathode. The formation of in close agreement with the mole ratios of Bi–Sr–Ca–Cu supercon. The properties of thorium chloride ions europium on GC was studied in the temperature range 400–550 ◦ C. The electro. Pure U 3. / Electrochimica Acta 54 (2009) 5307–5319 120 ◦ C. Mg–Li–Zn alloys the film was estimated to be 100 nm. The SEM–EDX anal- shown that actinide metals were recovered on the cathodes and ysis of the deposits confirmed the formation of DyAl3 alloy [127]. Uranium and uranium–zirconium electrode- posits were produced in the molten LiCl–KCl eutectic. 500 and 550 ◦ C in the LiCl–KCl eutectic melt. Li and of Sm–Ni alloys was performed in LiCl–KCl–SmCl3 at 450 ◦ C.

5. A very thin YbNi2 film was formed by potentiostatic electrol. the niobium–stainless steel interface no alloys were detected but The electroplating was carried out at 800 ◦ C for 60 min. 94–6 mol%). After addition and Zr(IV) became larger with the increase of temperature. respectively) as the electroactive components. having few atomic layers of thickness.91 mass% of the erogeneous nucleus and 450 ◦ C. The content Ni cathode was carried out in a molten system. was studied. at of zirconium was about 9. The electrodeposition of tantalum in the same molten flu- The intermediate product was ZrCl2 . Also ceramics can be coated with other metals when using appropriate baths [140]. TiB2 coatings over a molybdenum were prepared from alkali chloride melts on Ni and AISI316 stain- substrate were examined by comparing the electrochemical tech. ers could be prepared at 750 ◦ C. A pure titanium layer could not have been obtained by this deposition. LiCl–KCl–YbCl3 . was carried out using The electrodeposition of metallic niobium on a surface of car- continuous current plating (CCP) and pulse current plating (PCP) bon electrode in fused electrolytes (NaCl–KCl. TiB2 . ing of ␥-Al8 Cr5 deposit reduced the oxide thickness to 1/40 of that on Ti–Al alloy without the deposit [133]. A niobium carbide temperature of the process was 600 ◦ C and all the results were coating. containing K2 TiF6 and KBF4 (in as NbNi3 was formed at the interface of the nickel substrate. ceramic substrates of complicated structures. Hf and Al were deposited by the trode were immersed into a molten salt (NaCl–TiCl2 ) at 900 and molten-salt electrolysis. Niobium–titanium alloys can be prepared by ing niobium electrodeposition. Ni. Zr–Al alloy method [130].3. The alloy cov- molten salt containing CrCl2 at 150 ◦ C. On this alloy after the oxidation at 900 ◦ C for 24 h. cov. tantalum deposition was observed. and the ratio between Zr(II) orides as in the ref. Group 4 formation of a coating layer consisting of Ni–aluminide containing In Ref.4.8 mass% [139]. The presence of suboxides like Nb6 O dery deposit [136]. K2 TaF7 . [144] was conducted at 800 ◦ C. Electrochemical studies on zirconium chloride in 700 ◦ C [143]. microstructure such as a better adhesion and reduction of the num. the zirconium concentration of the whole Mg–Zr alloy was about ysis. Zr and the formation of lutetium–aluminum alloys were investigated metal and alloy film were formed in the LiCl–KCl melt contain- in the eutectic LiCl–KCl in the temperature range 946–1096 ◦ C. in which pure titanium and iron elec. The plat. [132] an attempt was described to propose an electroplat. At the center region troplating the aluminium–chromium alloys in a AlCl3 –NaCl–KCl of this coating. [137] was focused on the preparation of in the metallic phase was caused by a high negative overpotential titanium diboride coatings by electroplating in fluoride–chloride during the pulse current period. [144]. On Ti–Al specimen. the gram size of the TiB2 coatings prepared by the quality Nb deposits when the temperature is equal or exceeds PIC was smaller. The metallic coating could not prevent the for- containing K2 TiF6 and KBF4 in a mass relation of one to four. / Electrochimica Acta 54 (2009) 5307–5319 5315 The electrochemical formation of ytterbium–nickel alloy films at −1. were obtained from the molten carbonate. The electrodeposition of lutetium on inert electrodes and carbon film on ceramic substrates had been introduced. showing on carbon substrates and the quality of them could be improved by fewer cracks and better adhesion to the substrate when compared monitoring other parameters [142]. (equimolar) mixtures. The nucleation of tantalum in molten alkaline fluoride the molten LiCl–KCl eutectic were carried out in the presence and media was investigated in the 670–750 ◦ C temperature range. ated. uniform AlCr2 layer was formed during the showed a high cyclic-oxidation resistance. The tantalum nuclei were presence of an insoluble species in the melt [138]. As a result homogenous adherent layers of 50-␮m thickness were obtained. whereas a carbon film was formed in a Al3 Lu and mixtures of Al3 Lu and Al2 Lu. A working electrode consisted of a metal part and LiCl–KCl melt containing Lu(III) by potentiostatic electrolysis using a ceramic substrate. subsequently treated with the Ni-deposition. At the molar ratio 1:5. Ni was deposited by the elec- galvanic contact deposition. Generally all chloride electrolytes can be used to produce high- pared with CCP. less steel substrates by the constant current and by pulse current niques of CCP and periodically interrupted current (PIC) at 700 ◦ C methods. Both layers acted as a superior protection barrier This scale mainly consisted of ␣-Al2 O3 . bright coatings the nature. Ref. The influence of electrolysis conditions on ing K2 TiF6 and KBF4 (1:5 molar ratio). The of both K2 TaF7 and Na2 O. Com.%Cr–8 at. A thin layer of Nb–Ni alloy such electrolytes (KF–KCl. the electrochemistry of by the diffusion of tantalum ions.3 V (versus Ag/AgCl) by potentiostatic electrolysis. The electrode. and Al. the high-quality TiB2 coatings were prepared by CCP and PIC. The absence of Zr metal. This study showed the feasibility of niobium electrodeposition position with PCP produced coatings with better quality. The melts used were the LiCl–KCl (eutectic) and NaCl–KCl for 30 min. cles [141]. Hf on a Ni–10 at. For the sample first treated with the Hf- 930 ◦ C. was rapidly gener- obtained on graphite electrodes as the substrates.%Al alloy substrate was attempted by the ing method for producing a thin titanium layer on iron surface by electrodeposition of Hf. Also.3. The 3. followed method. The examination of the 3. a coating consisting of Ni2 Al3 of about 40-␮m the oxidation resistance of Ti–Al alloy was investigated by elec. a Hf-concentration layer was formed. produced by PIC showed improvements in the morphology and No metallic niobium was obtained at temperatures below 500 ◦ C. The metallic. Group 5 electrodeposition of titanium diboride. Pure Nb lay- 600 ◦ C. The LiCl–KCl melt was an inconvenient electrolyte for perform- ber of pores [135]. such as silver and copper. For electroforming zirconium metal. and contained HfO2 parti- against the high temperature oxidation of Ti–Al alloy. W. dense Al2 O3 . Under high temperature conditions the improvement of by the Al-deposition. known as Flinak) metal deposition. The mation of the first layer of preliminary carbide. The Mg–Zr alloy was prepared at the liquid magnesium electrode at electrodeposition had been run on copper cathodes and showed . ered with the Ni2 Al3 coating containing the Hf-concentrated layer ered with ␥-Al8 Cr5 . To investigate hemispherical and their growth was three-dimensional and limited the electrodeposition mechanism of Zr(IV). ing Zr(II) at 410–550 ◦ C. some niobium deposits to those obtained by CCP [134]. The obtained alloys showed poor appearance of a pow. trolysis in an aqueous solution. The sol. morphology and purity of the deposits was studied. Simka et al. thickness was uniformly formed on the alloy. An AlCr2 layer was covered by a thin oxidation test an adhesive scale having a spiked shape was formed. in the temperature range 1046–1121 ◦ C. The formation of niobium carbide occurred before the vent used was a fluoride mixture (LiF–NaF–KF. but a much thicker alloy film was formed by the Li codeposition 0. 50:50 mol%) at 720 ◦ C to produce a uniform and of very low porosity coating. At temperatures between 550 and codeposition (galvanostatic electrolysis) in NaCl–KCl–NaF melts at 650 ◦ C the deposits were dendritic and non-adherent. It was aim of this work was to prepare tantalum coatings for anode materi- noticed that it was one of the very few molten salt systems showing als. The increase of the current density a LiCl–KCl–K2 ZrF6 melt at molybdenum and tungsten electrodes and temperature enhanced the nucleation rate and nuclei density was studied at the temperature ranging between 1046 and 1246 ◦ C. An eutectic LiF–NaF melt (60/40 mol%) crossovers of the forward and reverse sweeps at different potential was used and tantalum ions were introduced to the system as regions in convolutive potential sweep voltammetry indicative of potassium heptafluorotantalate. The solvent used was an eutectic Flinak mixture contain. The conclusion was that it was possible to coat an Al electrode [131].

The low-valency tantalum com. electrodeposited on glass sheets covered with SnO2 . WCl4 was added as a source of tungsten ion.8. This melt was suitable for the electrowin- ble and dense U–Al deposits were obtained with high faradic yields ning of Nb–Al alloys [162].9. Group 9 was larger than 45%. acidic melt with KI addition as a surfactant. Group 10 resulting in a loose and layered product on its surface during elec- The electrochemical reduction of lanthanum ion and forma. alloy in AlCl3 –NaCl–KCl–MnCl2 molten salts at 170 ◦ C. 3. In LiF–NaF–KF eutectic melt the formation of Au2 Na alloy phase vent for potassium and cesium oxyfluorotantalates. The behavior of copper ions in pound. Mul. phase was introduced into the structure [161]. it may be overcome by pre-deposition of a thin was confirmed for both samples electrolyzed at 0. non- so the solubility was increased by the addition of KF. Group 6 3. The addition of KF to the melt gave a dense. tride and the inner layer containing metallic Al and AlN. WO3 hardly dissolved in this medium. The tetragonal MoSi2 phase was addi. Sta. Group 13 W film without incorporated melts and impurities. a dense and uniform Pd3 La alloy salts. This process was expected to become a new process 250 ◦ C. The coating of The electrochemical deposition of aluminum from a basic and microparts with an adhesive and smooth W film was successfully an acidic molten AlCl3 –NaCl–KCl mixture on a graphite electrode demonstrated [147].6:0. The electro- at 550 ◦ C was investigated using various substrates like Mo. Al morphologies were evident. having 1–5 ␮m of electrodeposited in the ZnCl2 –NaCl–KCl melt containing MoCl3 at diameter. The the electrocrystallization of Al was studied in the AlCl3 –NaCl–KCl behavior of chromium ions in the equimolar CaCl2 –NaCl mixture molten salt onto a polished graphite electrode at 140 ◦ C. The nucleation of metallic Cu on tungsten electrode had containing melts were also found [146]. A smooth porous and very stable metallic form of Al was deposited in the and fine film of metallic tungsten was obtained on a nickel sub. The formation of Pd3 La alloy films coating. was present in almost all obtained cathodic deposits. molybdenum metal film was particles of wurtzite structure were produced. The analyses of the deposits indicated the formation was the fcc aluminum solution. values the coatings were powdery and contained Na3 TaO4 . However.7. Yellow. At higher Ro be electrodeposited in this melt [154]. content was between 25 and 45%. Group 11 The behavior of molten salt systems. spongy and non-compact probe pin was successfully coated with a smooth and adhesive [158]. dominated the deposition process [156]. Lanthanum metal cannot content (Ro < 0. The structure of a deposit demonstrated. from ZnCl2 –NaCl–KCl melt at 250 ◦ C were reported. where CsCl was used as a sol. Also a similar investigation was reported in [159]. Niobium–aluminum chemical techniques in the molten LiCl–KCl eutectic. A mixture of amorphous and intermetallic Al8 Mn5 was obtained when the manganese content 3. compact. depending smaller than 17%. The electrochemical behavior thicker metal film under the same electrolysis conditions.45 V for 2 h and zinc layer on the substrate before the electrodeposition in molten 0. UAl3 and UAl4 ). trans- mung) microparts to give higher strength and heat resistance for the parent and adherent thin films were obtained. adhesive and of the AlN powder formation [160].2:0. when the manganese content was of different intermetallic phases (UAl2 . Also. The surface of Ni contact the deposit morphology was dull grey. Instantaneous and literature. chemical works in that melt [155]. showed. but a silver-bright. NaTaO3 together with traces of Ta metal from the deposition of TaO [145]. In the work only electrochemical properties of Cr were LiCl–KCl–Li3 N systems at 450 ◦ C.3. of niobium in an AlCl3 –NaCl molten salt electrolyte was investi- sented process was regarded as a new method for molybdenum gated by linear sweep voltammetry at 190 ◦ C. The working electrode was an Au The molten systems were CsCl–K3 TaOF6 and CsCl–Cs3 TaOF6 . 3.10. As the Nb content had increased an amorphous has been studied in the temperature range of 400–550 ◦ C by electro. was investigated at 500 ◦ C. surface to form an AlN film. CoGd3 film was The Al–Mn alloy coatings were electrodeposited on the AZ31B Mg formed on Co substrate by cathodic electrolysis [153]. The formation of the U–Al alloy were fcc aluminum. The oxidation of nitride ions pro- studied [149]. For the latter case. The amorphous phase Al–Mn alloy coating with compact . Molybdenum silicide was coated in the molten salt ceeded to form adsorbed nitrogen atoms which reacted with the (NaCl–KCl–NaF–Na2 SiF6 –SiO2 ) and Si powder for obtaining the oxi. hitherto rarely mentioned in the filed ZnCl2 –2NaCl mixture was examined at 450 ◦ C. Al–Mn amorphous plating layers were and the possibility to load the whole bulk of a thin Al plate was electrodeposited in AlCl3 –NaCl–MnCl2 . The pre. Also AlN tionally formed at 700 ◦ C [150].3. The obtained nitride film had a thick- dation resistance of molybdenum in air.3. Low Nb deposits coating at low temperatures [151]. wire. / Electrochimica Acta 54 (2009) 5307–5319 that pure and coherent Ta coatings were obtained at a lower oxide film of 30 ␮m in thickness was obtained. The (Au2 Na + Au) electrode showed excellent stability and tiphase deposits crystallized and the number of phases inherent in can be used as a good reference electrode for further electro- one deposit could be as more as six. was examined. Simka et al.3. The three-dimensional nucleation and crystal growth of copper was conditions for the electrodeposition of pure Ta metal from oxygen. trodeposition of Al–Mn alloy on Mg alloy from molten salts was tion of palladium–lanthanum alloy film were studied in the obviously an obstacle for adhesion of the deposited Al–Mn alloy LiF–NaF–KF–LaF3 melt at 500 ◦ C. The electrodeposition of metallic tungsten at 140 ◦ C was examined. and amorphous phase when the manganese on the experimental conditions [152].11.25 V for 1 h. niobium electrodes. The corrosion resistance of Al–Mn amorphous The electrochemical formation of Gd–Co alloys was investi.5316 W. aiming to improve the corrosion resistance. The severe corrosion of Mg alloy 3. The obtained nitride layer consisted of formed as a single phase with homogeneous thickness of tens of two regions: the outer layer containing AlN and aluminum oxyni- micrometer above 800 ◦ C.6. Group 12 An attempt was made to apply the electroplating of refrac. The characteristics of tungsten film electrodeposited of well crystallized ZnSe and of 1-mm grain size [157].3. Galvanostatic alloys were formed in the LiCl–KCl eutectic melt at tungsten and electrolyses were carried out both on solid Al rods and plates. containing up to 90% microparts. gated in a molten LiCl–KCl–GdCl3 system at 450 ◦ C. The electrolysis gave a smooth 3.3. In the basic solution strate by the potentiostatic electrolysis. It was shown that depending on the cur- was studied also in the similar ZnCl2 –NaCl–KCl (0. plating layer was about four times that of aluminum layers [163].2 mole rent density and AlCl3 concentration (acidic or basic melt) different fraction) melt at 250 ◦ C. CsTa2+z 5−x O5+y F1−y . The electrodeposition of the semiconductor ZnSe was per- tory metals in molten salts to the LIGA process or to the surface formed in a molten CaCl2 –NaCl mixture at 550 ◦ C.5 where Ro is the molar ratio of O–Ta). ZnSe was coating of conventional LIGA (Lithographic Galvanoforming Abfor. A hexagonal MoSi2 was ness of sub-micron order. W chemical formation of aluminum nitride was examined in molten and GC. where tungsten film by using this method at low temperature [148].

6. Acad. Miller. 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 . while no intercalation of tin into CVD chemical vapour deposition the graphite bulk took place. Chem. The application of the above-mentioned solu.3. such as lack ˛ [1] M. because of the difficulties to overcome. Galiński. Chem. Stable deposit layers of pure Bi were not obtained ITO indium tin oxide under the constant potential control. A mixture of intermetallic compounds of Cr2 Al. Inorg. The electrochemical deposition of alu. V. bis(trifluoromethylsulfonyl)imide PCP pulse current plating 4. R.L. / Electrochimica Acta 54 (2009) 5307–5319 5317 tumor-like morphology exhibited much higher corrosion resistance electrodeposition of metals is definitely more economic than the than the solid solution Al–Mn alloy coating with loose faceted mor. Chem. mainly of ionic [2] P. Koch. Osteryoung. 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. Lewandowski. of knowledge on the effect of non-aqueous solutions. A. R. BiCl3 . Good adherence of liquid tin. coatings. Osteryoung. 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. L.A. RTIL room temperature ionic liquid(s) much lower than the potential of hydrogen liberation. while in the presence of PbCl2 smoother EMIC 1-ethyl-3-methylimidazolium chloride and non-porous aluminum was formed [167]. ionic liquids and molten P14. TeCl4 at 150 ◦ C IL ionic liquid(s) was investigated. Ro molar ratio of oxygen–tantalum sis of aqueous solutions. also improve the corrosion resistance by reducing the corrosion current density and enhancing the breakdown potential [164]. Am.A. 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.12. 101 (1979) 323. The increase of the Mn content in the alloy coating can CVD. W. Stepniak.R. Walden. to the electrode materials was observed [166].  conductivity (mS cm−1 ) A surface area (cm2 ) 3. PVD. Soc. Ni3 Al. DMSO2 dimethyl sulfone minum and lead from the basic molten AlCl3 –NaCl–KCl mixture DMSO dimethyl sulfoxide on an aluminum electrode at 180 ◦ C was studied by voltammetry. formed in the reduction bis(trifluoromethylsulfonyl)imide process. 17 (1978) 2728. However. Group 14 ␥-BL ␥-butyrolactone The electrochemistry of tin(II) was studied at tungsten and [BF4 ] tetrafluoroborate anion GC electrodes in acidic and basic molten salts (ZnCl2 + 2NaCl. and H2 O viscosity of water (cP) Al3 Ni was formed [165]. Soc. A stable Bi–Sb alloy deposit of metallic Sb and NBS National Bureau of Standards Bi–Sb solid solution was obtained. The Appendix A. [4] J. when the SEM–EDX scanning electron microscopy–energy dispersive X-ray hydrogen overpotential is relatively low. (1914) 1800. Conclusions [PF6 ] hexafluorophosphate anion PIC periodically interrupted current The electrodeposition of metals from non-aqueous solutions. Bull. 97 (1975) 3264. Group 15 GC glassy carbon The electrochemistry of antimony and bismuth in the GIC graphite intercalation compound AlCl3 –NaCl–KCl molten salt containing SbCl3 . . Tf2 N bis(trifluoromethylsulfonyl)imide The subject of the electrodeposition from non-aqueous solutions THF tetrahydrofuran is very interesting. Gilbert. formation of coatings with methods such as plasma spray. in relation to the classical electrolysis of aqueous solu. It is due to the potential of their liberation. or phology. In many cases the deposits detection have better physical and chemical properties than the coatings pro. the OMPTf2 N 1-octyl-1-methyl-pyrrolidinium alloy had good crystallinity [168]. In basic solutions the deposit morphology was dull grey.6 Tf2 N trihexyl-tetradecyl-phosphonium salts. Also a stable Bi-Te alloy deposit [N(CN)2 ] dicyanoamide anion was obtained with the molten salt containing BiCl3 and TeCl4 . 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 specific prop- References erties.6. Osteryoung. TBACl tetrabutylammonium chloride duced from aqueous solutions. tions. EG ethylene glycol spongy and non-compact. B. The elec. Electrochim. 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