Tuning the electronic environment of cations and anions using ionic liquid mixtures

Electrostatic interactions are ubiquitous in ionic liquids and therefore, the electronic environment (i.e. the distribution of electron density) of their constituent ions has a determining influence on their properties and applications. Moreover, the distribution of electron density on atoms is at the core of ionic liquid molecular dynamics simulations. In this work, we demonstrate that changing the composition of ionic liquid mixtures can tune the electronic environment of their constituent ions, both anions and cations. The electronic environment of these ions can be monitored by measuring the characteristic electron binding energies of their constituent atoms by X-ray photoelectron spectroscopy (XPS). The possibility to fine tune, in a controlled way, the electronic environment of specific ions provides an invaluable tool to understand ionic liquid properties and allows the design of ionic liquid mixtures towards specific applications. Here, we demonstrate the power of this tool by tuning the electronic environment of a catalytic centre, and consequently its catalytic activity, by the use of ionic liquid mixtures

Energy applications of ionic liquids

Ionic liquids offer a unique suite of properties that make them important candidates for a number of energy related applications. Cation–anion combinations that exhibit low volatility coupled with high electrochemical and thermal stability, as well as ionic conductivity, create the possibility of designing ideal electrolytes for batteries, super-capacitors, actuators, dye sensitised solar cells and thermoelectrochemical cells. In the field of water splitting to produce hydrogen they have been used to synthesize some of the best performing water oxidation catalysts and some members of the protic ionic liquid family co-catalyse an unusual, very high energy efficiency water oxidation process. As fuel cell electrolytes, the high proton conductivity of some of the protic ionic liquid family offers the potential of fuel cells operating in the optimum temperature region above 100 °C. Beyond electrochemical applications, the low vapour pressure of these liquids, along with their ability to offer tuneable functionality, also makes them ideal as CO2 absorbents for post-combustion CO2 capture. Similarly, the tuneable phase properties of the many members of this large family of salts are also allowing the creation of phase-change thermal energy storage materials having melting points tuned to the application. This perspective article provides an overview of these developing energy related applications of ionic liquids and offers some thoughts on the emerging challenges and opportunities

Ionic cross-linked methacrylic copolymers for carbon fiber reinforced thermoplastic composites

Methacrylic copolymers have high potential as matrix polymers for carbon fiber reinforced thermoplastics (CFRTPs) due to their superior mechanical properties and the versatility of the monomers. However, the methacrylic copolymers have low solvent resistance, compared to epoxy, polyamide, and polypropylene, due to their un-cross-linked amorphous structure. Therefore, an improvement of the solvent resistance by the introduction of metal salts into methacrylic copolymer matrices for CFRTPs was investigated. Infrared spectroscopy, dynamic mechanical analyses and small-angle X-ray scattering clarified that an ionic cross-linked structure was formed. Low-viscosity mixtures of the methacrylic monomers with the metal salts, as a precursor of the matrices for CFRTPs, were easily impregnated into CF fabrics and were then copolymerized within the CF fabrics. Both the flexural strength and shear adhesive strength of the CFRTPs using the in situ polymerized methacrylic ionomer cross-linked with sodium ions were sufficiently high, even after 12 h immersion in methyl ethyl ketone

Branched Alkyl Functionalization of Imidazolium-based Ionic Liquids for Lithium Secondary Batteries

Room temperature ionic liquids (ILs) are the appealing research target as electrolytes for lithium batteries. The cation and anion structure of ILs influences their physical and chemical properties. In this study, an electron-donating branched substituent was introduced into imidazolium cations to promote charge delocalization and to improve the reduction stability of ILs. The ILs with branched substituent group at the third position of imidazolium cation, 1-allyl-3-isobutylimidazolium bis(fluorosulfonyl)amide ([ABisoIm][FSA]) and 1-allyl-3-tert-butylimidazolium bis(fluorosulfonyl)amide ([ABtertIm][FSA]), exhibited lower cathodic potential (−2.54 and −2.79 V vs. Fc/Fc+, respectively). [ABisoIm][FSA] and [ABtertIm][FSA] showed sufficiently high ionic conductivity (4.85 and 3.66 mS/cm at 298 K, respectively), although the viscosity increased with the introduction of bulky branched substituent. Lithium secondary batteries composed of electrolytes using [ABisoIm][FSA] and [ABtertIm][FSA] showed stable charge-discharge behavior