Interactions of ligands with lithium picrate in dioxane

Tsvetanov, Christo B.; Petrova, Emilia; Dimov, D. K.; Panayotov, Ivan M.; Smid, Johannes

doi:10.1007/bf00650375

Cited by 14 publications

(10 citation statements)

References 26 publications

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“…35 This dimeric form may partially form in the liquid state and would be responsible for the lower ionic conductivity ( 36 Using fluorenyl lithium as another lithium salt probe, the K values of the glymes in 1,4-dioxane solutions were reported to be 0.055, 3.1, 130, and 240 M −1 for G1, G2, G3, and G4, respectively. 37,38 The K likely depends on various factors such as the lithium salt probe used, the solvent, and the Li salt concentration.…”

Section: Resultsmentioning

confidence: 98%

Chelate Effects in Glyme/Lithium Bis(trifluoromethanesulfonyl)amide Solvate Ionic Liquids. I. Stability of Solvate Cations and Correlation with Electrolyte Properties

et al. 2014

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To develop a basic understanding of a new class of ionic liquids (ILs), "solvate" ILs, the transport properties of binary mixtures of lithium bis(trifluoromethanesulfonyl)amide (Li[TFSA]) and oligoethers (tetraglyme (G4), triglyme (G3), diglyme (G2), and monoglyme (G1)) or tetrahydrofuran (THF) were studied. The self-diffusion coefficient ratio of the solvents and Li(+) ions (Dsol/DLi) was a good metric for evaluating the stability of the complex cations consisting of Li(+) and the solvent(s). When the molar ratio of Li(+) ions and solvent oxygen atoms ([O]/[Li(+)]) was adjusted to 4 or 5, Dsol/DLi always exceeded unity for THF and G1-based mixtures even at the high concentrations, indicating the presence of uncoordinating or highly exchangeable solvents. In contrast, long-lived complex cations were evidenced by a Dsol/DLi ∼ 1 for the longer G3 and G4. The binary mixtures studied were categorized into two different classes of liquids: concentrated solutions and solvate ILs, based on Dsol/DLi. Mixtures with G2 exhibited intermediate behavior and are likely the borderline dividing the two categories. The effect of chelation on the formation of solvate ILs also strongly correlated with electrolyte properties; the solvate ILs showed improved thermal and electrochemical stability. The ionicity (Λimp/ΛNMR) of [Li(glyme or THF)x][TFSA] exhibited a maximum at an [O]/[Li(+)] ratio of 4 or 5.

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Section: Resultsmentioning

confidence: 98%

Chelate Effects in Glyme/Lithium Bis(trifluoromethanesulfonyl)amide Solvate Ionic Liquids. I. Stability of Solvate Cations and Correlation with Electrolyte Properties

et al. 2014

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“…In light of the high ionic conductivity and high lithium transference number, PBA is a better choice for the The different ionic transport process and the stability of [Li(G4) 1 ] + discussed above were ascribed to the distinct polymerion interactions [44]. G4 and PEO have the same ethylene oxide unit as the solvation site, and it was reported that PEO has a slightly higher complex formation constant with Li + ions (K complex ) than G4 [45]. Therefore, the competition between G4 and PEO to interact with Li + ions makes [Li(G4) 1 ] + unstable.…”

Section: Ionic Transport Propertiesmentioning

confidence: 96%

Li+ Ion Transport in Polymer Electrolytes Based on a Glyme-Li Salt Solvate Ionic Liquid

Kido

Ueno

Iwata

et al. 2015

Electrochimica Acta

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Keywords: solvate ionic liquid polymer electrolyte polymer-in-salt ionicity glyme A B S T R A C T Polymer electrolytes (PEs) have served as the focus of intensive research as new ion-conducting materials, especially for lithium battery applications. A new strategy to develop fast lithium-conducting PEs is reported here. The thermal, ionic transport, and electrochemical properties of polymer solutions in a glyme-Li salt solvate ionic liquid, [Li(G4) 1 ][TFSA], composed of an equimolar mixture of lithium bis (trifluoromethanesulfonyl) amide (Li[TFSA]) and tetraglyme (G4), were characterized. Poly(ethylene oxide) (PEO), poly(methyl methacrylate) (PMMA), and poly(butyl acrylate) (PBA) were combined with [Li(G4) 1 ][TFSA] in order to explore the effects of polymer structure on the properties. The self-diffusion coefficient ratio of the glyme and Li + ions (D G /D Li ) was investigated to evaluate the stability of the complex (solvate) cations. The D G /D Li values suggested that the [Li(G4) 1 ] + complex cations underwent a ligand exchange reaction between G4 and PEO in the PEO-based solution, whereas the cations remained stable (D G /D Li = 1) in the PMMA-and PBA-based solutions. The robustness of the [Li(G4) 1 ] + complex cations in the PMMA-and PBA-based solutions was reflected in high weight-loss temperature, greater Li transference number, and high oxidative stability.Owing to the lower glass transition temperature and low affinity towards Li + ions, the PBA-based solutions yielded superior lithium transport properties (ionic conductivity of 10 À4 $10 À3 Scm À1 and Li transference number as high as 0.5) among the investigated polymer solutions.

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“…However, the K complex values for the dilute systems involving lithium pictate and some ligand molecules in dioxane have been studied by Tsvetanov and co-workers. 65 The K complex values between Li + ions and the ligand molecules in dioxane were reported to be 1.8, 2.1, 8.5, 17.0, and 24.5 for PC, G1, G2, G3, and G4, respectively. The K complex value becomes larger with increasing number of the coordinating sites in a single ligand molecule.…”

Section: Chelate Effectmentioning

confidence: 99%

Criteria for solvate ionic liquids

Mandai

Yoshida

Ueno

et al. 2014

Phys. Chem. Chem. Phys.

259

361

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Certain concentrated mixtures of salts and solvents are not simply "solutions" anymore, but they may be described as "ionic liquids". In this perspective paper, we describe possible criteria for the new family of ionic liquids: "solvate" ionic liquids. This subclass of ionic liquids was originally proposed by Angell et al. in their recent review; however, their criteria remain to be debated. Concentrated mixtures of lithium salts and organic solvents are useful models for these solvate ionic liquids, and the effects of the salt concentration, types of solvents, and counter anions of the lithium salts on their structure and properties have been explored to enable contrast with traditional solutions, and to help determine whether a given mixture belongs to the solvate ionic liquid or not.

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Interactions of ligands with lithium picrate in dioxane

Cited by 14 publications

References 26 publications

Chelate Effects in Glyme/Lithium Bis(trifluoromethanesulfonyl)amide Solvate Ionic Liquids. I. Stability of Solvate Cations and Correlation with Electrolyte Properties

Chelate Effects in Glyme/Lithium Bis(trifluoromethanesulfonyl)amide Solvate Ionic Liquids. I. Stability of Solvate Cations and Correlation with Electrolyte Properties

Li+ Ion Transport in Polymer Electrolytes Based on a Glyme-Li Salt Solvate Ionic Liquid

Criteria for solvate ionic liquids

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