Thermal stability of alkyl carbonate mixed-solvent electrolytes for lithium ion cells

Tetsuya Kawamura, Arihisa Kimura, Minato Egashira, Shigeto Okada, Jun Ichi Yamaki

Research output: Contribution to journalArticle

185 Citations (Scopus)

Abstract

The thermal stability of some mixed-solvent electrolytes used in lithium cells was measured by differential scanning calorimetry (DSC) using airtight containers. The electrolytes used were ethylene carbonate (EC) + diethylcarbonate(DEC), EC + dimethylcarbonate(DMC), propylene carbonate (PC) + DEC, and PC + DMC in which was dissolved 1 M LiPF6 or 1 M LiClO4. The influence of water addition and lithium metal addition on the thermal behavior of these electrolytes was also investigated. The exothermic peak of LiPF6 electrolytes containing DEC was found at 255 °C, and the peak temperature of the electrolytes containing DEC was 15-20 °C lower than that of LiPF6 electrolytes containing DMC. This effect was also observed in the electrolytes including LiClO4. DMC was found to be more reactive than DEC. The thermal behavior of various kinds of LiPF6 electrolytes with lithium metal was measured by DSC. The exothermic reaction of 1 M LiPF6/EC + DEC, 1 M LiPF6/EC + DMC, and 1 M LiPF6/PC + DMC with lithium metal began at the melting point of lithium metal because of the break down of the solid electrolyte interface (SEI). The temperature was approximately 180 °C, whereas the self-heating of 1 M LiPF6/PC + DEC occurred before the melting point of lithium metal. The temperature at which the self-exothermal reaction began was 140 °C. Therefore, the lithium metal in this electrolyte was found to be thermally unstable. When water was added to the above electrolytes with lithium metal, the exothermic reaction began at less than 130 °C, probably due to a collapse of SEI in response to the HF that was a product of the reaction between LiPF6 and the added water.

Original languageEnglish
Pages (from-to)260-264
Number of pages5
JournalJournal of Power Sources
Volume104
Issue number2
DOIs
Publication statusPublished - Feb 15 2002

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Carbonates
Lithium
Electrolytes
carbonates
Thermodynamic stability
thermal stability
lithium
electrolytes
Ions
Metals
cells
ions
propylene
Propylene
metals
Ethylene
ethylene
Exothermic reactions
exothermic reactions
Solid electrolytes

All Science Journal Classification (ASJC) codes

  • Renewable Energy, Sustainability and the Environment
  • Energy Engineering and Power Technology
  • Physical and Theoretical Chemistry
  • Electrical and Electronic Engineering

Cite this

Thermal stability of alkyl carbonate mixed-solvent electrolytes for lithium ion cells. / Kawamura, Tetsuya; Kimura, Arihisa; Egashira, Minato; Okada, Shigeto; Yamaki, Jun Ichi.

In: Journal of Power Sources, Vol. 104, No. 2, 15.02.2002, p. 260-264.

Research output: Contribution to journalArticle

Kawamura, Tetsuya ; Kimura, Arihisa ; Egashira, Minato ; Okada, Shigeto ; Yamaki, Jun Ichi. / Thermal stability of alkyl carbonate mixed-solvent electrolytes for lithium ion cells. In: Journal of Power Sources. 2002 ; Vol. 104, No. 2. pp. 260-264.
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abstract = "The thermal stability of some mixed-solvent electrolytes used in lithium cells was measured by differential scanning calorimetry (DSC) using airtight containers. The electrolytes used were ethylene carbonate (EC) + diethylcarbonate(DEC), EC + dimethylcarbonate(DMC), propylene carbonate (PC) + DEC, and PC + DMC in which was dissolved 1 M LiPF6 or 1 M LiClO4. The influence of water addition and lithium metal addition on the thermal behavior of these electrolytes was also investigated. The exothermic peak of LiPF6 electrolytes containing DEC was found at 255 °C, and the peak temperature of the electrolytes containing DEC was 15-20 °C lower than that of LiPF6 electrolytes containing DMC. This effect was also observed in the electrolytes including LiClO4. DMC was found to be more reactive than DEC. The thermal behavior of various kinds of LiPF6 electrolytes with lithium metal was measured by DSC. The exothermic reaction of 1 M LiPF6/EC + DEC, 1 M LiPF6/EC + DMC, and 1 M LiPF6/PC + DMC with lithium metal began at the melting point of lithium metal because of the break down of the solid electrolyte interface (SEI). The temperature was approximately 180 °C, whereas the self-heating of 1 M LiPF6/PC + DEC occurred before the melting point of lithium metal. The temperature at which the self-exothermal reaction began was 140 °C. Therefore, the lithium metal in this electrolyte was found to be thermally unstable. When water was added to the above electrolytes with lithium metal, the exothermic reaction began at less than 130 °C, probably due to a collapse of SEI in response to the HF that was a product of the reaction between LiPF6 and the added water.",
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