Solvate Ionic Liquids and Their Application to Lithium Batteries: Glyme-Lithium Bis(fluorosulfonyl)amide Equimolar Complexes

2012 ◽  
Vol 1473 ◽  
Author(s):  
Kazuki Yoshida ◽  
Mizuho Tsuchiya ◽  
Naoki Tachikawa ◽  
Kaoru Dokko ◽  
Masayoshi Watanabe
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Lithium Batteries ◽  
Diffusion Coefficients ◽  
Room Temperature ◽  
Spin Echo ◽  
The Self ◽  
Resonance Spectroscopy ◽  
Lithium Secondary Battery ◽  
Self Diffusion ◽  
Secondary Battery

ABSTRACTThe physicochemical properties of glyme-Li[FSA] (FSA: bis(fluorosulfonyl)amide) equimolar complexes were investigated. The self-diffusion coefficients of glymes and Li+ as determined by pulsed-field gradient spin-echo nuclear magnetic resonance spectroscopy in equimolar complexes were almost identical, suggesting that all of the glyme molecules coordinated with Li+. Electrochemical characterization revealed that the oxidative stability of glyme molecules was enhanced by complexing with Li+. Using [Li(glyme)1][FSA] electrolytes and a LiFePO4cathode, a lithium secondary battery could be stably operated for more than 100 cycles at room temperature.

Diffusionskonstanten einiger organischer Flüssigkeiten

1970 ◽  
Vol 25 (5) ◽  
pp. 777-780 ◽  
Author(s):  
Gottfried J. Krüger ◽  
Rene Weiss
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Acetic Acid ◽  
Magnetic Resonance ◽  
Diffusion Coefficients ◽  
Spin Echo ◽  
The Self ◽  
Self Diffusion ◽  
Resonance Spin ◽  
Nuclear Magnetic

The self diffusion coefficients of acetone, ethanol, diethoxymethane, diethylether, diglycole-dimethylether, 1,2-dimethoxyethane, acetic acid, methyliodide, tetrahydrofuran, toluene, trimethylphosphite, and 1,3,5-trifluorobenzene have been measured in dependence on temperature using nuclear magnetic resonance spin echo techniques.

Seif Diffusion of Liquid 6Li and 7Li as Measured by Nuclear Magnetic Resonance

1971 ◽  
Vol 26 (1) ◽  
pp. 94-98 ◽  
Author(s):  
G. J. Krüger ◽  
W. Müller-Warmuth ◽  
A. Klemm
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Diffusion Coefficients ◽  
Spin Echo ◽  
Absolute Measurement ◽  
The Self ◽  
Square Root ◽  
Mass Ratio ◽  
Experimental Procedure ◽  
Self Diffusion

Abstract The self-diffusion coefficients of liquid 6Li and 7Li have been measured using NMR spin echo techniques with pulsed gradients. In the experimental procedure, and in the sample preparation, particular attention has been paid to a relative, rather than to an absolute measurement. At 190 °C, the ratio of the self-diffusion coefficients is found to be D6 (x6 = 1) / D7 (x7 = 1) = 1.09 ± 0.06, in agree­ment with the square root of the mass ratio (m7-m6)1/2 = 1.08. In an atomic mixture of 80% 6Li and 20% 7Li, D6 (x6 = 0.8)/D7 (x6 = 0.8) = 1.0 3 ± 0.08 has been obtained

scholarly journals An NMR Spin-Echo Study of Diffusion in a Room-Temperature Molten Salt

2004 ◽  
Vol 59 (1-2) ◽  
pp. 59-63 ◽  
Author(s):  
Günter Palmer ◽  
Joachim Richter ◽  
Manfred D. Zeidler
Keyword(s):  
High Pressure ◽  
Molten Salt ◽  
Diffusion Coefficients ◽  
Pressure Range ◽  
Room Temperature ◽  
Spin Echo ◽  
Ambient Pressure ◽  
The Self ◽  
Pressure Probe ◽  
Self Diffusion

Pressure-dependent measurements of self-diffusion in the room-temperature molten salt (RTMS) N,N-butylmethylimidazoliumhexafluorophosphate were carried out at 298 and 308 K. The pressure range lied between ambient pressure and 300 MPa. In addition, methanolic solutions of this RTMS were investigated at ambient pressure. The self-diffusion coefficients of both components are reported as functions of concentration and temperature in the range 293 - 313 K. A modified version of a recently published high-pressure probe is described.

Self-Diffusion in Molten Lithium Nitrate

1992 ◽  
Vol 47 (10) ◽  
pp. 1047-1050 ◽  
Author(s):  
C. Herdlicka ◽  
J. Richter ◽  
M. D. Zeidler
Keyword(s):  
Diffusion Coefficient ◽  
Diffusion Coefficients ◽  
Spin Echo ◽  
The Self ◽  
Lithium Nitrate ◽  
Equimolar Ratio ◽  
Self Diffusion ◽  
Field Gradients ◽  
Molten Lithium ◽  
Self Diffusion Coefficient

AbstractSelf-diffusion coefficients of 7Li+ ions have been measured in molten LiNO3 with several compositions of 6Li+ and 7Li+ over a temperature range from 537 to 615 K. The NMR spin-echo method with pulsed field gradients was applied. It was found that the self-diffusion coefficient depends on the isotopic composition and shows a maximum at equimolar ratio. At temperatures above 600 K this behaviour disappears.

scholarly journals Liquid Structures and Transport Properties of Lithium Bis(fluorosulfonyl)amide/Glyme Solvate Ionic Liquids for Lithium Batteries

2019 ◽  
Vol 72 (2) ◽  
pp. 70 ◽  
Author(s):  
Shoshi Terada ◽  
Kohei Ikeda ◽  
Kazuhide Ueno ◽  
Kaoru Dokko ◽  
Masayoshi Watanabe
Keyword(s):  
Ionic Liquids ◽  
Transport Properties ◽  
Lithium Batteries ◽  
Diffusion Coefficients ◽  
The Self ◽  
Metal Anode ◽  
Self Diffusion ◽  
Molar Ratios ◽  
Li Metal Anode ◽  
A Current

The liquid structures and transport properties of electrolytes composed of lithium bis(fluorosulfonyl)amide (Li[FSA]) and glyme (triglyme (G3) or tetraglyme (G4)) were investigated. Raman spectroscopy indicated that the 1:1 mixtures of Li[FSA] and glyme (G3 or G4) are solvate ionic liquids (SILs) comprising a cationic [Li(glyme)]+ complex and the [FSA]− anion. In Li[FSA]-excess liquids with Li[FSA]/glyme molar ratios greater than 1, anionic Lix[FSA]y(y–x)– complexes were formed in addition to the cationic [Li(glyme)]+ complex. Pulsed field gradient NMR measurements revealed that the self-diffusion coefficients of Li+ (DLi) and glyme (Dglyme) are identical in the Li[FSA]/glyme=1 liquid, suggesting that Li+ and glyme diffuse together and that a long-lived cationic [Li(glyme)]+ complex is formed in the SIL. The ratio of the self-diffusion coefficients of [FSA]− and Li+, DFSA/DLi, was essentially constant at ~1.1–1.3 in the Li[FSA]/glyme<1 liquid. However, DFSA/DLi increased rapidly as the amount of Li[FSA] increased in the Li[FSA]/glyme>1 liquid, indicating that the ion transport mechanism in the electrolyte changed at the composition of Li[FSA]/glyme=1. The oxidative stability of the electrolytes was enhanced as the Li[FSA] concentration increased. Furthermore, Al corrosion was suppressed in the electrolytes for which Li[FSA]/glyme>1. A battery consisting of a Li metal anode, a LiNi1/3Mn1/3Co1/3O2 cathode, and Li[FSA]/G3=2 electrolyte exhibited a discharge capacity of 105mAhg−1 at a current density of 1.3mAcm−2, regardless of its low ionic conductivity of 0.2mScm−1.

scholarly journals Diffusion Coefficients at Infinite Dilution of Carbon Dioxide and Methane in Water, Ethanol, Cyclohexane, Toluene, Methanol, and Acetone: A PFG-NMR and MD Simulation Study

2021 ◽  
Author(s):  
Daniel Bellaire ◽  
Oliver Großmann ◽  
Kerstin Münnemann ◽  
Hans Hasse
Keyword(s):  
Carbon Dioxide ◽  
Diffusion Coefficient ◽  
Diffusion Coefficients ◽  
Infinite Dilution ◽  
The Self ◽  
Resonance Spectroscopy ◽  
Self Diffusion ◽  
P Diffusion ◽  
Dynamics Simulations ◽  
Pfg Nmr

Diffusion coefficients at infinite dilution are important basic data for all processes involving mass transfer. They can be obtained from studying samplesin equilibrium using nuclear magnetic resonance spectroscopy with pulsed field gradients (PFG-NMR), a technique which is widely used in chemistry but isonly rarely applied in engineering studies. This advantageous technique was employed here to measure the self-diffusion coefficients of diluted solutions ofcarbon dioxide and methane in the pure solvents water, ethanol, cyclohexane, toluene, methanol, and acetone at 298.15 K. For the systems (carbon dioxide +water) and (carbon dioxide + ethanol), measurements were also carried out at 308.15 K, 318.15 K and 333.15 K. Except for (methane + water) and (methane +toluene), no literature data for the methane-containing systems were previously available. At the studied solute concentrations, there is practically no differencebetween the self-diffusion coefficient and the mutual diffusion coefficient. The experimental results are compared to experimental literature data as well as toresults from semi-empirical methods for the prediction of diffusion coefficients at infinite dilution. Furthermore, molecular dynamics simulations were carried outfor all systems to determine the diffusion coefficient at infinite dilution based on force fields that were taken from the literature, and the results are compared tothe experimental data and those from the classical prediction methods.

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