Mixtures of ionic liquids

Niedermeyer, Heiko; Hallett, Jason P.; Villar‐García, Ignacio J.; Hunt, Patricia A.; Welton, Tom

doi:10.1039/c2cs35177c

Cited by 562 publications

(519 citation statements)

References 200 publications

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“…This implies, together with the electrolyte incompressibility assumption (1), that the maximal average concentration (achieved whens = 0), equals the harmonic average of p max and n max…”

Section: Model Equations For a Ternary Compositionmentioning

confidence: 99%

“…Concentrated electrolytes are being examined for a broad range of applications, [1][2][3][4] and specifically for energy related devices, examples of which include dye sensitized solar cells, fuel cells, batteries and super-capacitors. [5][6][7] The optimized design of these devices requires the mechanistic spatiotemporal understanding of ionic arrangement and charge transport in electrolytes.…”

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confidence: 99%

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From Solvent-Free to Dilute Electrolytes: Essential Components for a Continuum Theory

Gavish

Elad

Yochelis

2017

J. Phys. Chem. Lett.

108

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The increasing number of experimental observations on highly concentrated electrolytes and ionic liquids show qualitative features that are distinct from dilute or moderately concentrated electrolytes, such as self-assembly, multiple-time relaxation, and under-screening, which all impact the emergence of fluid/solid interfaces, and transport in these systems. Since these phenomena are not captured by existing mean field models of electrolytes, there is a paramount need for a continuum framework for highly concentrated electrolytes and ionic liquids. In this work, we present a self-consistent spatiotemporal framework for a ternary composition that comprises ions and solvent employing free energy that consists of short and long range interactions, together with a dissipation mechanism via Onsagers' relations. We show that the model can describe multiple bulk and interfacial morphologies at steady-state. Thus, the dynamic processes in the emergence of distinct morphologies become equally as important as 1

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“…This implies, together with the electrolyte incompressibility assumption (1), that the maximal average concentration (achieved whens = 0), equals the harmonic average of p max and n max…”

Section: Model Equations For a Ternary Compositionmentioning

confidence: 99%

mentioning

confidence: 99%

From Solvent-Free to Dilute Electrolytes: Essential Components for a Continuum Theory

Gavish

Elad

Yochelis

2017

J. Phys. Chem. Lett.

108

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“…On average, 50 % of the pure DES nature remains at 10 w (77 mol % water). Whilst weakening of the “DES–DES” interactions (namely the choline–urea, choline–chloride, choline–choline, urea–chloride, urea–urea, and chloride–chloride hydrogen bonds, which may be strong or weak, and nonionic, ionic, or doubly ionic)19 by water is anticipated,20 this deviates significantly from Raoult's ideal entropic dissolution 21. This is corroborated by the DES/water N coord values (namely choline–water, urea–water, and chloride–water interactions), most of which increase as a function of hydration (Figure 2, bottom).…”

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confidence: 99%

The Effect of Water upon Deep Eutectic Solvent Nanostructure: An Unusual Transition from Ionic Mixture to Aqueous Solution

2017

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The nanostructure of a series of choline chloride/urea/water deep eutectic solvent mixtures was characterized across a wide hydration range by neutron total scattering and empirical potential structure refinement (EPSR). As the structure is significantly altered, even at low hydration levels, reporting the DES water content is important. However, the DES nanostructure is retained to a remarkably high level of water (ca. 42 wt % H2O) because of solvophobic sequestration of water into nanostructured domains around cholinium cations. At 51 wt %/83 mol % H2O, this segregation becomes unfavorable, and the DES structure is disrupted; instead, water–water and DES–water interactions dominate. At and above this hydration level, the DES–water mixture is best described as an aqueous solution of DES components.

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“…Recently, the class of protic ionic liquids (PILs), obtained by proton transfer between a Brønsted acid and a Brønsted base, became of particular interest as possible replacements for aqueous solutions in batteries and fuel cells [5]. Naturally, the wide range of actual and potential applications for RTILs has inspired an impressive range of research activity [3, 4,5,6]. Nevertheless, many fundamental issues concerning the structure and especially the dynamics of these fascinating fluids are still not well understood.…”

Section: Introductionmentioning

confidence: 99%

Dynamics of RTILs: A comparative dielectric and OKE study

Sonnleitner

Turton

Waselikowski

et al. 2014

Journal of Molecular Liquids

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The dynamics of room-temperature ionic liquids (RTILs) were studied by investigating their dielectric relaxation (DR) and timeresolved optical Kerr-effect (OKE) spectra in the frequency range of ∼10 MHz to ∼20 THz. For the studied RTILs the OKE and DR spectra are dominated by a relaxation in the GHz region and extend to a relatively sharp band at around 10 THz. Whilst the first feature is mainly associated with the structural relaxation of the fluid through ion rotation (α relaxation), the second indicates the short-time limit of intermolecular dynamics. The rather featureless intermediate region is mainly associated with intermolecular vibrations that are strongly coupled to hindered rotations. In contrast to other RTILs, imidazolium salts show an additional sub-α relaxation which dominates the OKE signal and is indicative of the breathing motion of rather long-lived cages.Mixed with polar solvents RTILs were found to retain their ionic liquid-like character up to relatively high levels of dilution, but with the overall dynamics considerably speeded up. Below RTIL mole fractions of ∼0.2-0.4 these systems behave like conventional electrolyte solutions with more or less pronounced ion pairing.

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Mixtures of ionic liquids

Cited by 562 publications

References 200 publications

From Solvent-Free to Dilute Electrolytes: Essential Components for a Continuum Theory

From Solvent-Free to Dilute Electrolytes: Essential Components for a Continuum Theory

The Effect of Water upon Deep Eutectic Solvent Nanostructure: An Unusual Transition from Ionic Mixture to Aqueous Solution

Dynamics of RTILs: A comparative dielectric and OKE study

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