Electrodeposition of Metals in Air- and Water-stable Ionic Liquids

Electrodeposition of Metals in Air- and Water-stable Ionic Liquids 

Chloroaluminate ionic liquids are regarded as the first generation of ionic liquids. However, their hygroscopic nature has delayed progress in many applications since they must be prepared and handled under an inert gas atmosphere. Thus, the synthesis of air- and water-stable ionic liquids, which are considered as the second and third generations of ionic liquids, has attracted further interest in the use of ionic liquids in various fields. Unlike the chloroaluminate ionic liquids, these ionic liquids can be prepared and safely stored outside an inert atmosphere. Generally, they are water insensitive. However, water-containing [BMIM]PF can 

Zinc and its alloys are good materials for corrosion-resistant coatings and they are widely used in the automobile industry. The electrodeposition of zinc or its alloys is normally performed in aqueous electrolyte solutions. However, zinc and its alloys can be obtained in improved quality from ionic liquids. It was shown that Lewis acidic ZnCl2-[EMIM]Cl (l-ethyl-3-methylimidazolium chloride) liquids in which 

The electrodeposition of chromium in a mixture of choline chloride and chromium(III) chloride hexahydrate has been reported recently [39]. A dark green, viscous liquid is obtained by mixing choline chloride with chromium(III) chloride hexahydrate and the physical properties of this deep eutectic solvent are characteristic of an ionic liquid. The eutectic composition is found to be 1 2 choline chloride/chromium chloride. From this ionic liquid chromium can be electrode-posited efficiently to yield a crack-free deposit [39]. Addition of LiCl to the choline chloride-CrCl3-6H20 liquid was found to allow the deposition of nanocrystalline black chromium films [40], The use of this ionic liquid might offer an environmentally friendly process for electrodeposition of chromium instead of the current chromic acid-based baths. However, some efforts are still necessary to get shining 

Palladium is employed in a number of industrial applications and fundamental studies because of its high catalytic activity for many chemical reactions, e.g. its ability to absorb hydrogen [41], On the other hand, due to hydrogen absorption, only brittle Pd deposits can be obtained in aqueous solutions. The advantage of performing electrodeposition of Pd in ionic liquids is that hydrogen evolution does not occur. Sun et al. demonstrated that Pd and some of its alloys, namely Pd-Ag [42], Pd-Au [43] and Pd-In [44], can be obtained from the basic l-ethyl-3-methylimidazolium chloride/tetrafluoroborate ionic liquid. Compact alloy deposits were obtained and the Pd content in the deposits increased with the increase in Pd mole fraction in the plating bath. 

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In the 1990s John Wilkes and coworkers introduced air- and water-stable ionic liquids (see Chapter 2.2) which have attractive electrochemical windows (up to 3 V vs. NHE) and extremely low vapor pressures. Furthermore, they are free from any aluminum species per se. Nevertheless, it took a while until the first electrodeposition experiments were published. The main reason might have been that purity was a concern in the beginning, making reproducible results a challenge. Water and halide were prominent impurities interfering with the dissolved metal salts and/or the deposits. Today about 300 different ionic liquids with different qualities are commercially available from several companies. Section 4.2 summarizes the state-of-the-art of electrodeposition in air- and water-stable ionic liquids. These liquids are for example well suited to the electrodeposition of reactive elements such as Ge, Si, Ta, Nb, Li and others. 

The electrodeposition of Zn-Mn was investigated at 80 °C in the hydrophobic tri-1-butylmethylammonium bis((trifluoromethyl)sulfonyl)amide ([TBMA]+Tf2N ) [46] ionic liquid containing Zn(II) and Mn(II) species that were introduced into the ionic liquid by anodic dissolution of the respective metal electrodes. Cyclic voltam-mograms indicated that the reduction of Zn(II) occurs at a potential less negative than that of the Mn(II). Due to some kinetic limitations, which is a common phenomenon in air- and water-stable ionic liquids, incomplete oxidation of Mn electrodeposits was observed in this system. The current efficiency of Mn electrodeposition in this ionic liquid approaches 100%, which is a great improvement compared to the results obtained in aqueous solution (20-70%). Electrodeposition of Zn-Mn alloy coatings has never been carried out in chloroaluminate ionic liquid because of the unavoidable codeposition of Mn and Al. 

In this chapter some results on the electrodeposition of alloys from ionic liquids are summarized. Many fundamental studies have been performed in chloroaluminate first generation ionic liquids but the number of studies employing air- and water-stable ionic liquids rather than the chloroaluminates is increasing. Currently, new ionic liquids with better electrochemical properties are being developed. For example, Abbott et al. [47] have prepared a series of ionic liquids by mixing commercially available low-cost choline chloride and MCI2 (M = Zn, Sn) or urea and demonstrated that these ILs are good media for electrodeposition for pure metals (see Chapter 4.3). It can be expected that in the near future, the electrodeposition of alloys from ILs may become available for industrial applications. Furthermore, due to their variety, their wide electrochemical and thermal windows air- and water-stable ionic liquids have unprecedented prospects for electrodeposition. 

In this chapter we present a few selected results on the nanoscale electrodeposition of some important metals and semiconductors, namely, Al, Ta and Si, in air- and water-stable ionic liquids. Here we focus on the investigation of the electrode/electrolyte interface during electrodeposition with the in situ scanning tunneling microscope and we would like to draw attention to the fascinating... 

Zein El Abedin S, Endres F (2006) Electrodeposition of metals and semiconductors in air- and water-stable ionic liquids. Chem Phys Chem 7 58 Endres F (2002) Ionic liquids solvents for the electrodeposition of metals and semiconductors. Chem Phys Chem 3 144... 

In this section we will show that air- and water-stable ionic liquids can be used for the electrodeposition of highly reactive elements which cannot be obtained from aqueous solutions, such as aluminum, magnesium and lithium, and also refractory metals such as tantalum and titanium. Although these liquids are no longer air-and water-stable when AICI3, TaFs, TiCU and others are dissolved, quite interesting results can be obtained in these liquids. 

In this chapter we have briefly discussed the high potential of air- and water-stable ionic liquids as electrolytes for metal deposition. Their extraordinary physical properties, superior to those of water or organic solvents, and their stability, open the door to the electrodeposition of many metals. Some advantages of air- and water-stable ionic liquids in electrodeposition are that they are quite easy to purify and handle and in most cases they do not decompose under environmental conditions. They can have pretty wide electrochemical windows of up to 6 V, and hence they... 

Over the past two decades, ionic liquids (ILs) have attracted considerable interest as media for a wide range of applications. For electrochemical applications they exhibit several advantages over the conventional molecular solvents and high temperature molten salts they show good electrical conductivity, wide electrochemical windows of up to 6 V, low vapor pressure, non-flammability in most cases, and thermal windows of 300-400 °C (see Chapter 4). Moreover, ionic liquids are, in most cases, aprotic so that the complications associated with hydrogen evolution that occur in aqueous baths are eliminated. Thus ILs are suitable for the electrodeposition of metals and alloys, especially those that are difficult to prepare in an aqueous bath. Several reviews on the electrodeposition of metals and alloys in ILs have already been published [1-4], A selection of published examples of the electrodeposition of alloys from ionic liquids is listed in Table 5.1 [5-40]. Ionic liquids can be classified into water/air sensitive and water/air stable ones (see Chapter 3). Historically, the water-sensitive chloroaluminate first generation ILs are the most intensively studied. However, in future the focus will rather be on air- and water-stable ionic liquids due to their variety and the less strict conditions under which... 

For the electrodeposition of metals or alloys from air- and water-stable ionic liquids, it is necessary first to dissolve the corresponding metal ions in the ionic liquid. Such a dissolution process is made possible by introducing excess amounts of halide ions (such as Cl ) to form soluble metal-halide complex anions. Alternatively, the metal is dectrochemically oxidized in the ionic liquid to form the soluble salt such as Sn(Tf2N) in the trimethyl-n-hexylammonium [bis(trifluoromethyl)sulfonyl]amide ([TMHAj TfiN ) ionic liquid. 

Tantalum Tantalum has unique properties that make it useful for many applications, from electronics to mechanical and chemical systems. Many efforts have been made to develop an electroplating process for the electrodeposition of Ta. High-temperature molten salts were found to be efficient baths for the dectrodepo-sition of refractory metals. To the best of our knowledge, imtil now no successful attempts have been made for Ta electrodeposition at room temperature or even at low temperature in ionic liquids. We present here the first results of tantalum dec-trodeposition in the air and water stable ionic liquid 1-butyl-l-methyl-pyrrolidinium bis(tri-fiuoromethylsulfonyl)amide ([BMP][Tf2N]). 

Additive free electrodeposition of nanocrystalline aluminium in a water and air stable ionic liquid. Electrochem. Commun., 7,1111-1116 Zhong, C. Sasaki, T. Jimbo-Kobayashi, A. Fujiwara, E. Kobayashi, A. Tada, M. Iwasawa, Y. (2007). Syntheses, structures, and properties of a series of metal ion-containing dialkylimidazolium ionic liquids. Bull. Chem. Soc. fpn., 80, 2365-2374... 

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