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Temperature-Dependent Electrochemical Stability Window of Bis(trifluoromethanesulfonyl)imide and Bis(fluorosulfonyl)imide Anion Based Ionic Liquids.

ABSTRACT: The electrochemical stability of 22 commercially available hydrophobic ionic liquids was measured at different temperatures (288.15, 298.15, 313.15, 333.15 and 358.15 K), to systematically investigate ionic liquids towards electrolytes for supercapacitors in harsh weather conditions. Bis(trifluoromethanesulfonyl)imide and bis(fluorosulfonyl)imide anions in combination with 1-Butyl-1-methylpyrrolidinium, 1-Ethyl-3-methylimidazolium, N-Ethyl-N, N-dimethyl-N(2methoxyethyl)ammonium, 1-Methyl-1-(2-methoxyethyl)pyrrolidinium, N-Pentyl-N-methylpyrrolidinium, N, N-Diethyl-N-methyl-N-propylammonium, N, N-Dimethyl-N-ethyl-N-benzyl ammonium, N, N-Dimethyl-N-Ethyl-N-phenylethylammonium, N-Butyl-N-methylpiperidinium, 1-Methyl-1-propylpiperidinium, N-Tributyl-N-methylammonium, N-Trimethyl-N-butylammonium, N-Trimethyl-N-butylammonium, N-Trimethyl-N-propylammonium, N-Propyl-N-methylpyrrolidinium cations were selected for the study. Linear regression with a numerical model was used in combination with voltammetry experiments to deduce the temperature sensitivity of both anodic and cathodic potential limits (defining the electrochemical stability window), in addition to extrapolating results to 283.15 and 363.15 K. We evaluated the influence of the cations, anions, and the presence of functional groups on the observed electrochemical stability window which ranged from 4.1 to 6.1 V.

SUBMITTER: Lethesh KC

PROVIDER: S-EPMC9247390 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:1H and 19F spin-lattice relaxation experiments have been performed for butyltriethylammonium bis(trifluoromethanesulfonyl)imide in the temperature range from 258 to 298 K and the frequency range from 10 kHz to 10 MHz. The results have thoroughly been analysed in terms of a relaxation model taking into account relaxation pathways associated with 1H-1H, 19F-19F and 1H-19F dipole-dipole interactions, rendering relative translational diffusion coefficients for the pairs of ions: cation-cation, anion-anion and cation-anion, as well as the rotational correlation time of the cation. The relevance of the 1H-19F relaxation contribution to the 1H and 19F relaxation has been demonstrated. A comparison of the diffusion coefficients has revealed correlation effects in the relative cation-anion translational movement. It has also turned out that the translational movement of the anions is faster than of cations, especially at high temperatures. Moreover, the relative cation-cation diffusion coefficients have been compared with self-diffusion coefficients obtained by means of NMR (Nuclear Magnetic Resonance) gradient diffusometry. The comparison indicates correlation effects in the relative cation-cation translational dynamics-the effects become more pronounced with decreasing temperature.

| S-EPMC8431572 | biostudies-literature

In Situ Generated Platinum Catalyst for Methanol Oxidation via Electrochemical Oxidation of Bis(trifluoromethylsulfonyl)imide Anion in Ionic Liquids at Anaerobic Condition.

Project description:The bis(trifluoromethylsulfonyl)imide anion is widely used as an ionic liquid anion due to its electrochemical stability and wide electrochemical potential window at aerobic conditions. Here we report an innovative strategy by directly oxidizing bis(trifluoromethylsulfonyl)imide anion to form a radical electrocatalyst on platinum electrode at anaerobic condition. The in situ generated radical catalyst was shown to catalytically and selectively promote the electrooxidation of methanol to form methoxyl radical, in which the formation potential was drastically decreased with the existence of bis(trifluoromethylsulfonyl)imide radical. The electrochemically generated radical catalyst not only facilitates the oxidation of methanol but also provides good selectivity. The unique double layer structure of the 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([Bmpy][NTf2]) likely excludes the diffusion of larger molar mass molecules onto the electrode surface and enables the highly selective methanol oxidation at this IL-electrode interface. Cyclic voltammetry (CV) experiments were used to systematically characterize the details of the electrochemical processes with and without methanol in several other ILs, and a mechanism of the chemical and redox processes was proposed. This study provides a promising new approach for utilizing the unique properties of ionic liquids not only as solvents and electrolytes but also as the medium for in situ generation of electrocatalysts to promote methanol redox reactions for practical applications.

| S-EPMC5640268 | biostudies-literature

Electrochemical performance and interfacial properties of Li-metal in lithium bis(fluorosulfonyl)imide based electrolytes.

Project description:Successful usage of lithium metal as the negative electrode or anode in rechargeable batteries can be an important step to increase the energy density of lithium batteries. Performance of lithium metal in a relatively promising electrolyte solution composed of lithium bis(fluorosulfonyl)imide (LiN(SO2F)2; LiFSI) salt dissolved in 1,2-dimethoxyethane (DME) is here studied. The influence of the concentration of the electrolyte salt -1 M or 4?M LiFSI- is investigated by varying important electrochemical parameters such as applied current density and plating capacity. X-ray photoelectron spectroscopy analysis as a surface sensitive technique is here used to analyze that how the composition of the solid electrolyte interphase varies with the salt concentration and with the number of cycles.

| S-EPMC5698312 | biostudies-literature

Effect of Bulky Anion around the Dication on the Electronic Structure and Normal Frequencies in 1,3-Bis(3-methylimidazolium-1-yl)propane Bis(trifluoromethanesulfonyl)imide Ionic Liquid.

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| S-EPMC8444328 | biostudies-literature

Measurements of Activity Coefficients at Infinite Dilution for Organic Solutes in the Ionic Liquids N-Ethyl- and N-Octyl-N-methylmorpholinium Bis(trifluoromethanesulfonyl)imide. A Useful Tool for Solvent Selection.

Project description:In recent years, many papers describing ionic liquids (IL) as promising solvents in separation techniques have been published. The conscious choice of appropriate ionic liquid as absorption media in effective extraction of selected types of analytes requires deeper understanding of the analyte-IL interactions. Therefore, intensive research is conducted to determine the values of activity coefficient at infinite dilution, which allows us to characterize the nature of these interactions. Based on the inverse gas chromatography retention data, activity coefficients at infinite dilution ? 13 ? of 48 different organic compounds in the ionic liquids N-ethyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide [C2C1Mor][TFSI] and N-octyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide [C8C1Mor][TFSI] were determined. The measurements covered a broad range of volatile organic compounds, including n-alkanes, n-alkenes, n-alkynes, alcohols, aldehydes, ketones, aromatic compounds and common polar solvents, representing different types of interactions. Activity coefficients at infinite dilution were measured in the temperature range from 313.15 to 363.15 K. The excess partial molar enthalpies and entropies at infinite dilution were determined. Selectivity at infinite dilution was also calculated for exemplary separation processes in the hexane/benzene system. The obtained results were analyzed and compared with literature data for ionic liquids containing the same anion [TFSI]¯ and different cations. The study results indicate that some potential applications of the investigated ionic liquids in separation problems exist.

| S-EPMC7037026 | biostudies-literature

Experimental dataset on electrolyte mixtures containing fluoroethylene carbonate and lithium bis(trifluoromethanesulfonyl)imide.

Project description:These data and analyses support the research article "Low-flammable electrolytes with fluoroethylene carbonate based solvent mixtures and lithium bis(trifluoromethanesulfonyl)-imide (LiTFSI) for lithium-ion batteries" [1]. The data and analyses presented here include fitted data for density measurements, temperature dependence of density and specific volume of the mixtures, detailed viscosity measurements and conductivity data, current density plots with respect to anodic aluminum dissolution, half-cell C-rate capability of mixtures with the additives used in research article as well as the SEM images and EDX data of the full-cell with the electrolyte selected and controlled.

| S-EPMC6373205 | biostudies-literature

Isothermal and Nonisothermal Crystallization Kinetics of Poly(ε-caprolactone) Blended with a Novel Ionic Liquid, 1-Ethyl-3-propylimidazolium Bis(trifluoromethanesulfonyl)imide.

Project description:Recently, ionic liquids (ILs) and biodegradable polymers have become crucial functional materials in green sustainable science and technology. In this study, we investigated the influence of a novel IL, 1-ethyl-3-propylimidazolium bis(trifluoromethanesulfonyl)imide ([EPrI][TFSI]), on the crystallization kinetics of a widely studied biodegradable polymer, poly(ε-caprolactone) (PCL). To obtain a comprehensive understanding, both the isothermal and nonisothermal crystallization kinetics of the PCL blends were studied. Incorporating [EPrI][TFSI] reduced the isothermal and nonisothermal crystallization rates of PCL. Regarding isothermal crystallization, the small k and 1/t0.5 values of the blend, estimated using the Avrami equation, indicated that [EPrI][TFSI] decreased the rate of isothermal crystallization of PCL. The Mo model adequately described the nonisothermal crystallization kinetics of the blends. Increasing the [EPrI][TFSI] content caused the rate-related parameter F(T) to increase. This indicated that the crystallization rate of PCL decreased when [EPrI][TFSI] was incorporated. The spherulite appearance temperature of the blending sample was found to be lower than that of neat PCL under a constant cooling rate. The analysis of the effective activation energy proposed that the nonisothermal crystallization of PCL would not be favorited when the [EPrI][TFSI] was incorporated into the blends. The addition of [EPrI][TFSI] would not change the crystal structures of PCL according to the results of wide angle X-ray diffraction. Fourier transform infrared spectroscopy suggested that interactions occurred between [EPrI][TFSI] and PCL. The crystallization kinetics of PCL were inhibited when [EPrI][TFSI] was incorporated.

| S-EPMC6415448 | biostudies-literature

Electrical and Electrochemical Behavior of Carbon Paste Electrodes Modified with Ionic Liquids Based in <i>N</i>-Octylpyridinium Bis(Trifluoromethylsulfonyl)Imide. A Theoretical and Experimental Study.

Project description:In this work, we studied carbon paste electrodes (CPEs) with two kinds of binders: mineral oil or ionic liquids (IL) derived from N-substituted octyl pyridinium bis(trifluoromethylsulfonyl)imide with the substituents H-, CH3-, CN- and CF3-. The work aims to study this series of IL and determine a possible effect of the substituent of the cation in the behavior of the IL as a binder of graphite for obtaining IL-CPEs. The electrochemical response and the electrical behavior were measured by cyclic voltammetry and electrochemical impedance spectroscopy, respectively. Surprisingly, the substituent does not affect the cyclic voltammetry response because in all the cases, high resistance and high capacitive currents were obtained. The best response in terms of conductivity is obtained by CPE. In the case of impedance measurements, the substituent does not cause differences, and in all the cases, the IL-CPEs show nearly the same responses. CPE shows lower capacitance and higher resistance for diffusion compared to the IL-CPEs due to his lower porosity. The high resistance showed by the IL-CPEs by cyclic voltammetry can be attributed to poorly intermolecular forces among graphite, water, electrolyte, and ILs as demonstrated by theoretical calculations.

| S-EPMC6767309 | biostudies-literature

Characterization of Room-Temperature Ionic Liquids to Study the Electrochemical Activity of Nitro Compounds.

Project description:Over the past few years, room-temperature ionic liquid (RTIL) has evolved as an important solvent-cum-electrolyte because of its high thermal stability and excellent electrochemical activity. Due to these unique properties, RTILs have been used as a solvent/electrolyte/mediator in many applications. There are many RTILs, which possess good conductivity as well as an optimal electrochemical window, thus enabling their application as a transducer for electrochemical sensors. Nitroaromatics are a class of organic compounds with significant industrial applications; however, due to their excess use, detection is a major concern. The electrochemical performance of a glassy carbon electrode modified with three different RTILs, [EMIM][BF4], [BMIM][BF4] and [EMIM][TF2N], has been evaluated for the sensing of two different nitroaromatic analytes: 2,6-dinitrotoluene (2,6 DNT) and ethylnitrobenzene (ENB). Three RTILs have been chosen such that they have either a common anion or cation amongst them. The sensory response has been measured using square wave voltammetry (SQWV). We found the transducing ability of [EMIM][BF4] to be superior compared to the other two RTILs. A low limit of detection (LOD) of 1 ppm has been achieved with a 95% confidence interval for both the analytes. The efficacy of varying the cationic and anionic species of RTIL to obtain a perfect combination has been thoroughly investigated in this work, which shows a novel selection process of RTILs for specific applications. Moreover, the results obtained from testing with a glassy carbon electrode (GCE) have been replicated using a miniaturized sensor platform that can be deployed easily for on-site sensing applications.

| S-EPMC7070553 | biostudies-literature

Anion-Ordering Phase Transitions in Biferrocenium and Ferrocenium Salts with the Bis(trifluoromethanesulfonyl)amide Anion.

Project description:The bis(trifluoromethanesulfonyl)amide anion (Tf2N), which is a common component of ionic liquids, often exhibits disorder in the solid state. In this study, the phase transitions and crystal structures of the Tf2N salts of 1,1‴-dineopentyl-1',1″-biferrocene (=npBifc), 1',1″-biferrocene (=Bifc), ferrocene, and cobaltocene (1-4, respectively) were compared. All the salts exhibited phase transitions at low temperatures, which are accompanied by anion ordering, though the ordering was not complete in 2 and 3. X-ray crystallographic investigation revealed that the cations and anions in 1 and 2 adopted alternating arrangements and segregated columnar arrangements, respectively. The cation in 1 exhibited a symmetrical, average-valence structure in the room-temperature phase owing to rapid valence tautomerization, whereas the cation exhibited an unsymmetrical structure in the low-temperature phase. The cation in 2 exhibited an unsymmetrical, trapped-valence structure in both phases. The cation valence states in these salts were accounted for by the electrostatic interactions between the cations and anions. The crystal structures and phase behavior of the ferrocenium salt 3 were very different from those of 4.

| S-EPMC8375087 | biostudies-literature

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