Frank Endres

Ionic-liquid materials for the electrochemical challenges of the future

Ionic liquids are room-temperature molten salts, composed mostly of organic ions that may undergo almost unlimited structural variations. This review covers the newest aspects of ionic liquids in applications where their ion conductivity is exploited; as electrochemical solvents for metal/semiconductor electrodeposition, and as batteries and fuel cells where conventional media, organic solvents (in batteries) or water (in polymer-electrolyte-membrane fuel cells), fail. Biology and biomimetic processes in ionic liquids are also discussed. In these decidedly different materials, some enzymes show activity that is not exhibited in more traditional systems, creating huge potential for bioinspired catalysis and biofuel cells. Our goal in this review is to survey the recent key developments and issues within ionic-liquid research in these areas. As well as informing materials scientists, we hope to generate interest in the wider community and encourage others to make use of ionic liquids in tackling scientific challenges.

Air and water stable ionic liquids in physical chemistry

Ionic liquids are defined today as liquids which solely consist of cations and anions and which by definition must have a melting point of 100 degrees C or below. Originating from electrochemistry in AlCl(3) based liquids an enormous progress was made during the recent 10 years to synthesize ionic liquids that can be handled under ambient conditions, and today about 300 ionic liquids are already commercially available. Whereas the main interest is still focussed on organic and technical chemistry, various aspects of physical chemistry in ionic liquids are discussed now in literature. In this review article we give a short overview on physicochemical aspects of ionic liquids, such as physical properties of ionic liquids, nanoparticles, nanotubes, batteries, spectroscopy, thermodynamics and catalysis of/in ionic liquids. The focus is set on air and water stable ionic liquids as they will presumably dominate various fields of chemistry in future.

Electrodeposition from Ionic Liquids

PREFACE BASIC CONSIDERATIONS OF DEPOSITION IN IONIC LIQUIDS SYNTHESIS OF IONIC LIQUIDS AlCl3 Based First Generation Ionic Liquids Air and Water Stable Ionic Liquids Deep Eutectic Solvents PHYSICOCHEMICAL PROPERTIES OF IONIC LIQUIDS ELECTRODEPOSITION OF METALS Metal Deposition in AlCl3 Based Ionic Liquids Metal Deposition in Air and Water Stable Ionic Liquids Metal Deposition in Deep Eutectic Solvents Troublesome Aspects ELECTRODEPOSITION OF ALLOYS ELECTRODEPOSITION OF SEMICONDUCTORS ELECTRODEPOSITION OF CONDUCTING POLYMERS ELECTRODEPOSITION OF NANOCRYSTALLINE METALS AND ALLOYS ELECTRODEPOSITION ON THE NANOSCALE PLASMA ELECTROCHEMISTRY TECHNICAL ASPECTS Counter Electrode Reactions / Metal Dissolution Reference Electrodes Upscaling Recycling Impurities SURFACE PRETREATMENT / ELECTROPOLISHING PLATING PROTOCOLS FUTURE DIRECTIONS

The interface ionic liquid(s)/electrode(s): in situ STM and AFM measurements.

The structure of the interfacial layer(s) between the extremely pure air- and water-stable ionic liquid 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl) trifluorophosphate and Au(111) has been investigated using in situ scanning tunneling microscopy (STM) at electrode potentials more positive than the open circuit potential. The in situ STM measurements show that layers/islands form with increasing electrode potential. According to recently published atomic force microscopy (AFM) data the anion is adsorbed even at low anodic overvoltages and adsorption becomes slightly stronger with increasing electrode potential. Furthermore, the number of interfacial layers increases with increasing electrode potential. The present discussion paper shows that these layers are not uniform and have a structure on the nanoscale, supporting earlier results that the interface electrode/ionic liquid is highly complex. It is also shown that the addition of solutes changes this structure considerably. AFM results reveal that in the pure liquid, interfacial layers lead to a repulsive force but the addition of 10 wt% of LiCl leads to an attractive force close to the surface. These preliminary results show that solutes strongly alter the interfacial structure of the ionic liquid/ electrode interface.

Ionic Liquids: Promising Solvents for Electrochemistry

Abstract Ionic liquids are solvents that are solely composed of ions. By definition their melting points are below 100 °C. Typical cations are substituted imidazolium ions, like 1-butyl-3-methylimidazolium, or tetraalkylammonium ions, like e.g. trioctyl-methyl-ammonium. Some important anions are hexafluorophosphate, trifluoromethylsulfonate, bis(trifluoromethylsulfonyl)imide. Many ionic liquids have negligible vapour pressures even at temperatures of 300 °C and more, they can have viscosities similar to water, ionic conductivities of up to 0.1 (Ω cm)−1, and, which makes them interesting for electrochemistry, wide electrochemical windows of more than 6 Volt. In this review article recent results of the author are summarized. It is shown that with the scanning tunneling microscope the processes during phase formation can be probed in situ with high quality. An important result is that semiconductors, shown at the example of germanium, can be made electrochemically on the nanoscale and that the electronic properties (band gap) can be measured in situ with current/voltage tunneling spectroscopy. Ionic liquids will gain a rising interest in electrochemistry as elements and compounds can be made electrochemically which are not accessible by conventional aqueous or organic electrochemistry.

Electrodeposition of 3D ordered macroporous germanium from ionic liquids: a feasible method to make photonic crystals with a high dielectric constant.

A promising method for the production of germanium photonic crystals consists of electrodeposition of Ge from GeCl(4)-containing ionic liquids inside templates of polystyrene colloidal crystals and subsequent removal of the template. This room-temperature method gives rise to the fabrication of a three-dimensional highly ordered macroporous germanium nanostructure (see picture; scale: 2 microm) as a prototype of a photonic crystal.

Ionic liquids as green electrolytes for the electrodeposition of nanomaterials

Ionic liquids, especially air and water stable ones, experience much attention, since they have attractive physical properties. We exemplify in this paper the potential of ionic liquids in the electrodeposition of nanocrystalline metals without additives. The results show that nanocrystalline copper and aluminium can be electrodeposited in the air and water stable ionic liquids 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate ([BMP]TFO) and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([BMP]Tf2N), respectively, on conventional solid electrodes with sufficient electronic conductivity. Generally, the obtained Al or Cu deposits are shiny, dense and adherent with very fine crystallites with average sizes of about 30 and 40 nm, respectively. The [BMP]+ cation might act as a grain refiner, leading to nanosized deposits. The results of first attempts to use plasmas as mechanically contact-free electrodes for the cathodic deposition of nanoscaled metals (glow discharge electrodeposition) are also presented. The relevance of our results for the development of a green process to make nanomaterials as catalysts for fuel processing is briefly discussed.

Electrodeposition of Ge, Si and SixGe1−x from an air- and water-stable ionic liquid

The electrodeposition of Ge, Si and, for the first time, of Si(x)Ge(1-x) from the air- and water-stable ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([Py(1,4)]Tf(2)N) containing GeCl(4) and/or SiCl(4) as precursors is investigated by cyclic voltammetry and high-resolution scanning electron microscopy. GeCl(2) in [Py(1,4)]Tf(2)N is electrochemically prepared in a two-compartment cell to be used as Ge precursor instead of GeCl(4) in order to avoid the chemical attack of Ge(iv) on deposited Ge. Silicon, germanium and Si(x)Ge(1-x) can be deposited reproducibly and easily in this ionic liquid. Interestingly, the Si(x)Ge(1-x) deposit showed a strong colour change (from red to blue) at room temperature during electrodeposition, which is likely to be due to a quantum size effect. The observed colours are indicative of band gaps between at least 1.5 and 3.2 eV. The potential of ionic liquids in Si(x)Ge(1-x) electrodeposition is demonstrated.

Electroreduction of tantalum fluoride in a room temperature ionic liquid at variable temperatures

The present paper deals with the electroreduction of TaF5 in the room temperature ionic liquid 1-buty-1-methyl-pyrrolidinium bis(tri-fluoromethylsulfonyl)imide ([BMP]Tf2N) at different temperatures for the sake of electrodeposition of tantalum. The study was carried out using cyclic voltammetry and chronoamperometry measurements complemented by SEM-EDAX and XRD investigations. In situ scanning tunneling microscopy and I-U tunneling spectroscopy were also utilized for characterization of the electrodeposits. The results show that, in addition to the formation of insoluble compounds, Ta can be electrodeposited in the ionic liquid ([BMP]Tf2N) containing 0.5 M TaF5 at 200 degrees C on polycrystalline Pt and Au(111) electrodes. By addition of LiF to the electrolyte, the quality and the adherence of the electrodeposit were found to be improved. An in situ I-U tunneling spectrum with about 300 nm thickness of the electrodeposit shows metallic behaviour indicating the formation of elemental tantalum. Moreover, the XRD patterns of the electrodeposit, obtained potentiostatically at -1.8 V (vs. Pt) in ([BMP]Tf2N) containing 0.25 M TaF5 and 0.25 M LiF on Pt electrode at 200 degrees C, show the characteristic patterns of crystalline tantalum.

Probing Lithium and Alumina Impurities in Air- and Water Stable Ionic Liquids by Cyclic Voltammetry and In Situ Scanning Tunneling Microscopy

In this paper we report on some results on the electrochemical breakdown of ionic liquids at the cathodic limit of the electrochemical window and on the probing of inorganic impurities in ionic liquids (originating from the synthesis) at the interface electrode/electrolyte by in situ scanning tunneling microscopy on Au(111). It will be shown that the restructuring/reconstruction of Au(111) in ultrapure 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([Py1,4]Tf2N) leads to a transition from a wormlike surface structure to a surface with well defined terraces. Close to the cathodic decomposition of the liquid the quality of the STM pictures gets worse and at the onset of massive ionic liquid breakdown a film forms on the gold surface finally shielding completely the gold terraces. When the [Py1,4]Tf2N liquid, made by a metathesis reaction from [Py1,4]Cl and LiTf2N, is not thoroughly washed after the synthesis, the in situ STM pictures show in a wide potential range the same surface structures as with the ultrapure liquid, but in the cathodic regime the deposition of lithium in only a few monolayers is observed. In the respective cyclic voltammograms on Au(111) there is clear evidence for lithium deposition. We show furthermore that a spectroscopically ultrapure 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ionic liquid ([EMIm]Tf2N) can show unexpected behaviour at the electrode/electrolyte interface when after synthesis it is subject to an Al2O3 treatment with the aim to remove organic impurities. Al2O3 seems to be dissolved in the ionic liquid in low concentrations and deposited at the electrode surface. At lower electrode potentials the alumina seems to be reduced to metallic aluminium. Our results show that even ultrapure ionic liquids can contain inorganic impurities which are very difficult to probe with conventional analytical methods. Better synthesis routes will be necessary to make ultrapure ionic liquids for fundamental physicochemical studies.