A detailed investigation of the thermal reactions of LiPF6 solution in organic carbonates using ARC and DSC

J. S. Gnanaraj; E. Zinigrad; L. Asraf; H. E. Gottlieb; M. Sprecher; M. Schmidt; W. Geissler; D. Aurbach

doi:10.1149/1.1617301

A detailed investigation of the thermal reactions of LiPF₆ solution in organic carbonates using ARC and DSC

J. S. Gnanaraj, E. Zinigrad, L. Asraf, H. E. Gottlieb, M. Sprecher, M. Schmidt, W. Geissler, D. Aurbach^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

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Abstract

The thermal stability of 1 M LiPF₆ solutions in mixtures of ethylene carbonate, diethyl carbonate, and dimethyl carbonate in the temperature range of 40 to 350°C was studied by accelerating rate calorimeters (ARC) and differential scanning calorimeters (DSC). Nuclear magnetic resonance (NMR) was used to analyze the condensed reaction products at different reaction stages. Studies by DSC and pressure measurements during ARC experiments with LiPF₆ solutions detected a gas-releasing endothermic reaction starting at ∼170°C, involving diethyl carbonate which occurs before a number of exothermic reactions, which follow as the temperature increases. Fluoride ions are released and react with the alkyl carbonate molecules both as bases and as nucleophiles. The bulk analysis by NMR shows that HO-CH₂-CH₂-OH, FCH₂CH₂-OH, F-CH₂CH₂-F, and polymer are major products. Gas analysis by NMR and Fourier transform infrared spectroscopy shows PF₅, CO₂, CH₂F, CH₃CH₂F, and H₂O as major gaseous products of the thermal reaction of these solutions.

Original language	American English
Pages (from-to)	A1533-A1537
Journal	Journal of the Electrochemical Society
Volume	150
Issue number	11
DOIs	https://doi.org/10.1149/1.1617301
State	Published - Nov 2003
Externally published	Yes

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@article{49093d2867a9403d862af2ab1b7445a7,

title = "A detailed investigation of the thermal reactions of LiPF6 solution in organic carbonates using ARC and DSC",

abstract = "The thermal stability of 1 M LiPF6 solutions in mixtures of ethylene carbonate, diethyl carbonate, and dimethyl carbonate in the temperature range of 40 to 350°C was studied by accelerating rate calorimeters (ARC) and differential scanning calorimeters (DSC). Nuclear magnetic resonance (NMR) was used to analyze the condensed reaction products at different reaction stages. Studies by DSC and pressure measurements during ARC experiments with LiPF6 solutions detected a gas-releasing endothermic reaction starting at ∼170°C, involving diethyl carbonate which occurs before a number of exothermic reactions, which follow as the temperature increases. Fluoride ions are released and react with the alkyl carbonate molecules both as bases and as nucleophiles. The bulk analysis by NMR shows that HO-CH2-CH2-OH, FCH2CH2-OH, F-CH2CH2-F, and polymer are major products. Gas analysis by NMR and Fourier transform infrared spectroscopy shows PF5, CO2, CH2F, CH3CH2F, and H2O as major gaseous products of the thermal reaction of these solutions.",

author = "Gnanaraj, {J. S.} and E. Zinigrad and L. Asraf and Gottlieb, {H. E.} and M. Sprecher and M. Schmidt and W. Geissler and D. Aurbach",

year = "2003",

month = nov,

doi = "10.1149/1.1617301",

language = "American English",

volume = "150",

pages = "A1533--A1537",

journal = "Journal of the Electrochemical Society",

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T1 - A detailed investigation of the thermal reactions of LiPF6 solution in organic carbonates using ARC and DSC

AU - Gnanaraj, J. S.

AU - Zinigrad, E.

AU - Asraf, L.

AU - Gottlieb, H. E.

AU - Sprecher, M.

AU - Schmidt, M.

AU - Geissler, W.

AU - Aurbach, D.

PY - 2003/11

Y1 - 2003/11

N2 - The thermal stability of 1 M LiPF6 solutions in mixtures of ethylene carbonate, diethyl carbonate, and dimethyl carbonate in the temperature range of 40 to 350°C was studied by accelerating rate calorimeters (ARC) and differential scanning calorimeters (DSC). Nuclear magnetic resonance (NMR) was used to analyze the condensed reaction products at different reaction stages. Studies by DSC and pressure measurements during ARC experiments with LiPF6 solutions detected a gas-releasing endothermic reaction starting at ∼170°C, involving diethyl carbonate which occurs before a number of exothermic reactions, which follow as the temperature increases. Fluoride ions are released and react with the alkyl carbonate molecules both as bases and as nucleophiles. The bulk analysis by NMR shows that HO-CH2-CH2-OH, FCH2CH2-OH, F-CH2CH2-F, and polymer are major products. Gas analysis by NMR and Fourier transform infrared spectroscopy shows PF5, CO2, CH2F, CH3CH2F, and H2O as major gaseous products of the thermal reaction of these solutions.

AB - The thermal stability of 1 M LiPF6 solutions in mixtures of ethylene carbonate, diethyl carbonate, and dimethyl carbonate in the temperature range of 40 to 350°C was studied by accelerating rate calorimeters (ARC) and differential scanning calorimeters (DSC). Nuclear magnetic resonance (NMR) was used to analyze the condensed reaction products at different reaction stages. Studies by DSC and pressure measurements during ARC experiments with LiPF6 solutions detected a gas-releasing endothermic reaction starting at ∼170°C, involving diethyl carbonate which occurs before a number of exothermic reactions, which follow as the temperature increases. Fluoride ions are released and react with the alkyl carbonate molecules both as bases and as nucleophiles. The bulk analysis by NMR shows that HO-CH2-CH2-OH, FCH2CH2-OH, F-CH2CH2-F, and polymer are major products. Gas analysis by NMR and Fourier transform infrared spectroscopy shows PF5, CO2, CH2F, CH3CH2F, and H2O as major gaseous products of the thermal reaction of these solutions.

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U2 - 10.1149/1.1617301

DO - 10.1149/1.1617301

M3 - Article

AN - SCOPUS:0242582187

SN - 0013-4651

VL - 150

SP - A1533-A1537

JO - Journal of the Electrochemical Society

JF - Journal of the Electrochemical Society

IS - 11

ER -

A detailed investigation of the thermal reactions of LiPF₆ solution in organic carbonates using ARC and DSC

Abstract

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