Mechanically Robust Poly(ionic liquid) Block Copolymers as Self-Assembling Gating Materials for Single-Walled Carbon-Nanotube-Based Thin-Film Transistors.

The proliferation of high-performance thin-film electronics depends on the development of highly conductive solid-state polymeric materials. We report on the synthesis and properties investigation of well-defined cationic and anionic poly(ionic liquid) AB-C type block copolymers, where the AB block was formed by random copolymerization of highly conductive anionic or cationic monomers with poly(ethylene glycol) methyl ether methacrylate, while the C block was obtained by post-polymerization of 2-phenylethyl methacrylate. The resulting ionic block copolymers were found to self-assemble into a lamellar morphology, exhibiting high ionic conductivity (up to 3.6 × 10-6 S cm-1 at 25 °C) and sufficient electrochemical stability (up to 3.4 V vs Ag+/Ag at 25 °C) as well as enhanced viscoelastic (mechanical) performance (storage modulus up to 3.8 × 105 Pa). The polymers were then tested as separators in two all-solid-state electrochemical devices: parallel plate metal-insulator-metal (MIM) capacitors and thin-film transistors (TFTs). The laboratory-scale truly solid-state MIM capacitors showed the start of electrical double-layer (EDL) formation at ∼103 Hz and high areal capacitance (up to 17.2 µF cm-2). For solid-state TFTs, low hysteresis was observed at 10 Hz due to the completion of EDL formation and the devices were found to have low threshold voltages of -0.3 and 1.1 V for p-type and n-type operations, respectively.

Tunning CO2 Separation Performance of Ionic Liquids through Asymmetric Anions.

This work aims to explore the gas permeation performance of two newly-designed ionic liquids, [C2mim][CF3BF3] and [C2mim][CF3SO2C(CN)2], in supported ionic liquid membranes (SILM) configuration, as another effort to provide an overall insight on the gas permeation performance of functionalized-ionic liquids with the [C2mim]+ cation. [C2mim][CF3BF3] and [C2mim][CF3SO2C(CN)2] single gas separation performance towards CO2, N2, and CH4 at T = 293 K and T = 308 K were measured using the time-lag method. Assessing the CO2 permeation results, [C2mim][CF3BF3] showed an undermined value of 710 Barrer at 293.15 K and 1 bar of feed pressure when compared to [C2mim][BF4], whereas for the [C2mim][CF3SO2C(CN)2] IL an unexpected CO2 permeability of 1095 Barrer was attained at the same experimental conditions, overcoming the results for the remaining ILs used for comparison. The prepared membranes exhibited diverse permselectivities, varying from 16.9 to 22.2 for CO2/CH4 and 37.0 to 44.4 for CO2/N2 gas pairs. The thermophysical properties of the [C2mim][CF3BF3] and [C2mim][CF3SO2C(CN)2] ILs were also determined in the range of T = 293.15 K up to T = 353.15 K at atmospheric pressure and compared with those for other ILs with the same cation and anion's with similar chemical moieties.

Tuning the miscibility of water in imide-based ionic liquids.

Liquid-liquid phase behavior measurements were performed for binary mixtures of water and ionic liquids (ILs) containing the same 1-ethyl-3-methylimidazolium ([C2mim]+) cation and different imide-based anions, having symmetric (bis(fluorosulfonyl)imide ([FSI]-)) or asymmetric structures (2,2,2-trifluoromethylsulfonyl-N-cyanoamide ([TFSAM]-) and 2,2,2-trifluoro-N-(trifluoromethylsulfonyl)acetamide ([TSAC]-)). An inversion of phase behavior was observed: while below ∼298 K, the miscibility of water in the studied ILs increases according to the order [C2mim][TSAC] < [C2mim][FSI] < [C2mim][NTf2], for temperatures above ∼303 K, the reverse trend is observed [C2mim][NTf2] < [C2mim][FSI] < [C2mim][TSAC]. In turn, above ∼306 K the [C2mim][TFSAM] is completely miscible with H2O in all ranges of concentrations. The obtained results also revealed an unusual water solubility variation of 11% in [C2mim][FSI], and 20% in [C2mim][TSAC], when the system temperature was changed by less than 1 K, around 298 K and 301 K, respectively. Molecular Dynamics (MD) simulations were used to understand the IL-water interactions and rationalize the experimental observations. These results suggested that the miscibility trends are mainly related to the ability of the water molecules to form water-anion and water-water aggregates in solution.

Ionic Polyureas-A Novel Subclass of Poly(Ionic Liquid)s for CO2 Capture.

The growing concern for climate change and global warming has given rise to investigations in various research fields, including one particular area dedicated to the creation of solid sorbents for efficient CO2 capture. In this work, a new family of poly(ionic liquid)s (PILs) comprising cationic polyureas (PURs) with tetrafluoroborate (BF4) anions has been synthesized. Condensation of various diisocyanates with novel ionic diamines and subsequent ion metathesis reaction resulted in high molar mass ionic PURs (Mw = 12 ÷ 173 × 103 g/mol) with high thermal stability (up to 260 °C), glass transition temperatures in the range of 153-286 °C and remarkable CO2 capture (10.5-24.8 mg/g at 0 °C and 1 bar). The CO2 sorption was found to be dependent on the nature of the cation and structure of the diisocyanate. The highest sorption was demonstrated by tetrafluoroborate PUR based on 4,4'-methylene-bis(cyclohexyl isocyanate) diisocyanate and aromatic diamine bearing quinuclidinium cation (24.8 mg/g at 0 °C and 1 bar). It is hoped that the present study will inspire novel design strategies for improving the sorption properties of PILs and the creation of novel effective CO2 sorbents.

Li Coordination of a Novel Asymmetric Anion in Ionic Liquid-in-Li Salt Electrolytes.

We analyze the influence of the asymmetry of the anion on coordination and transport processes in a Li salt/ionic liquid system. The relatively new asymmetric 2,2,2-trifluoromethylsulfonyl-N-cyanamide (TFSAM) anion was investigated in Pyr14TFSAM(1-x)LiTFSAMx over a broad concentration range (up to x = 0.7 Li salt) and was compared to the well-known bis(trifluoromethanesulfonyl)amide (TFSA) anion. In contrast to the TFSA-based system, the system with TFSAM has no phase transition over the whole concentration range. Raman spectroscopy and NMR chemical shifts elucidate the Li coordination in detail. Up to x = 0.3, the asymmetric anion coordinates to Li+ only via the cyano group. With increasing Li salt fraction, the contribution of Li-oxygen coordination increases. This coordination effects influence the transport properties of the system, as examined via pulsed-field-gradient NMR (PFG-NMR). Although the overall diffusivity of both systems is decreasing because of viscosity effects, the relative diffusivity of the Li cation is increasing with x. This suggests a change in the transport mechanism depending on the Li salt fraction. Interestingly, the contribution of structural diffusion at high Li salt concentrations (x ≥ 0.6) seems to be higher in the TFSAM system, influenced by the nonsymmetric coordination, while in the TFSA system, the vehicular transport seems to be still predominant at x ≥ 0.6.

Neat ionic liquids versus ionic liquid mixtures: a combination of experimental data and molecular simulation.

Simple mixtures of ionic liquids (IL-IL mixtures) can become a promising approach for the substitution of task-specific ILs. Such a concept was explored in this article by comparison of the thermophysical properties of neat 1-ethyl-3-methylimidazolium 2,2,2-trifluoromethylsulfonyl-N-cyanoamide, [C2mim][TFSAM], and equimolar mixtures of two structurally similar ILs having more common ions. Molecular dynamics (MD) simulations were additionally used to further highlight structural aspects of these systems at a molecular level.

Ionic liquids with anions based on fluorosulfonyl derivatives: from asymmetrical substitutions to a consistent force field model.

Herein, seven anions including four imide-based, namely bis[(trifluoromethyl)sulfonyl]imide (TFSI), bis(fluorosulfonyl)imide (FSI), bis[(pentafluoroethyl)sulfonyl]imide (BETI), 2,2,2-trifluoromethylsulfonyl-N-cyanoamide (TFSAM) and 2,2,2-trifluoro-N-(trifluoromethylsulfonyl) acetamide (TSAC), and two sulfonate anions, trifluoromethanesulfonate (triflate, TF) and nonafluorobutanesulfonate (NF), are considered and compared. The volumetric mass density and dynamic viscosity of five ionic liquids containing these anions combined with the commonly used 1-ethyl-3-methylimidazolium cation (C2C1im), [C2C1im][FSI], [C2C1im][BETI], [C2C1im][TFSAM], [C2C1im][TSAC] and [C2C1im][NF] are measured in the temperature range of 293.15 ≤ T/K ≤ 353.15 and at atmospheric pressure. The results show that [C2mim][FSI] and [C2mim][TFSAM] exhibit the lowest densities and viscosities among all the studied ionic liquids. The experimental volumetric data is used to validate a more consistent re-parameterization of the CL&P force field for use in MD simulations of ionic liquids containing the ubiquitous bis[(trifluoromethyl)sulfonyl]imide and trifluoromethanesulfonate anions and to extend the application of the model to other molten salts with similar ions.

Exploring the effect of fluorinated anions on the CO2/N2 separation of supported ionic liquid membranes.

The CO2 and N2 permeation properties of ionic liquids (ILs) based on the 1-ethyl-3-methylimidazolium cation ([C2mim]+) and different fluorinated anions, namely 2,2,2-trifluoromethylsulfonyl-N-cyanoamide ([TFSAM]-), bis(fluorosulfonyl) imide ([FSI]-), nonafluorobutanesulfonate ([C4F9SO3]-), tris(pentafluoroethyl)trifluorophosphate ([FAP]-), and bis(pentafluoroethylsulfonyl)imide ([BETI]-) anions, were measured using supported ionic liquid membranes (SILMs). The results show that pure ILs containing [TFSAM]- and [FSI]- anions present the highest CO2 permeabilities, 753 and 843 Barrer, as well as the greatest CO2/N2 permselectivities of 43.9 and 46.1, respectively, with CO2/N2 separation performances on top of or above the Robeson 2008 upper bound. The re-design of the [TFSAM]- anion by structural unfolding was investigated through the use of IL mixtures. The gas transport and CO2/N2 separation properties through a pure [C2mim][TFSAM] SILM are compared to those of two different binary IL mixtures containing fluorinated and cyano-functionalized groups in the anions. Although the use of IL mixtures is a promising strategy to tailor gas permeation through SILMs, the pure [C2mim][TFSAM] SILM displays higher CO2 permeability, diffusivity and solubility than the selected IL mixtures. Nevertheless, both the prepared mixtures present CO2 separation performances that are on top of or above the Robeson plot.

A New Volume-Based Approach for Predicting Thermophysical Behavior of Ionic Liquids and Ionic Liquid Crystals.

Volume-based prediction of melting points and other properties of ionic liquids (ILs) relies on empirical relations with volumes of ions in these low-melting organic salts. Here we report an accurate way to ionic volumes by Bader's partitioning of electron densities from X-ray diffraction obtained via a simple database approach. For a series of 1-tetradecyl-3-methylimidazolium salts, the volumes of different anions are found to correlate linearly with melting points; larger anions giving lower-melting ILs. The volume-based concept is transferred to ionic liquid crystals (ILs that adopt liquid crystalline mesophases, ILCs) for predicting the domain of their existence from the knowledge of their constituents. For 1-alkyl-3-methylimidazolium ILCs, linear correlations of ionic volumes with the occurrence of LC mesophase and its stability are revealed, thus paving the way to rational design of ILCs by combining suitably sized ions.

A first truly all-solid state organic electrochromic device based on polymeric ionic liquids.

Using polymeric ionic liquids and PEDOT as ion conducting separators and electrodes, respectively, an all-polymer-based organic electrochromic device (ECD) has been constructed. The advantages of such an ECD are: fast switching time (3 s), high coloration efficiency (390 cm(2) C(-1) at 620 nm), optical contrast up to ΔT = 22% and the possibility of working under vacuum.