Thermal stability of electrolytes with LixCoO2 cathode or lithiated carbon anode

Jun Ichi Yamaki, Yasunori Baba, Noriko Katayama, Hideyasu Takatsuji, Minato Egashira, Shigeto Okada

Research output: Contribution to journalConference article

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Abstract

The thermal stability of electrolytes with LixCoO2 cathode or lithiated carbon anode was reviewed including our recent results. From our experiments, it was found that LixCoO2, delithiated by a chemical method using H2SO4 showed two exothermic peaks, one beginning at 190 °C and the other beginning at 290 °C. From high-temperature XRD, it was found that the first peak, from 190 °C, was the phase transition from a monoclinic (R-3m) to a spinel structure (Fd3 m). The spinel structure LixCoO2 showed a very small cycling capacity. Probably, cation mixing was induced by the heat treatment. The DSC measurements of Li0.49CoO2 with 1M LiPF6/EC+DMC showed two exothermic peaks. The peak starting at 190°C probably resulted from the decomposition of solvent due to an active cathode surface, and the peak starting at 230°C was electrolyte oxidation caused by released oxygen from Li0.49CoO2. From DSC profiles of chemically delithiated Li0.49CoO2 and 1M PC electrolytes with various Li salts, it was found that the inhibition effect of the surface reaction starting at 190 °C was large when LiBF4, LiPF6, and LiClO4 were used. The thermal stability of electrochemically lithiated graphite with 1M LiPF6/EC+DMC and PVdF-binder has been investigated. DSC revealed a mild heat generation starting from 130°C with a small peak at 140 °C. The mild heat generation continued until a sharp exothermic peak appeared at 280 °C. The lithiated graphite with the electrolyte without PVdF-binder did not show the small peak at 140 °C. The peak at 140 °C seems to be caused by the reaction (the solid electrolyte interphase (SEI) formation) of the electrolyte and lithiated graphite, which surface is covered by poly(vinylidene fluoride) (PVdF)-binder without formation of SEI at a lower temperature.

Original languageEnglish
Pages (from-to)789-793
Number of pages5
JournalJournal of Power Sources
Volume119-121
DOIs
Publication statusPublished - Jun 1 2003
EventSelected Papers Presented at the 11th IMLB - Monterey, CA, United States
Duration: Jun 22 2002Jun 28 2002

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Electrolytes
Anodes
Cathodes
anodes
Thermodynamic stability
thermal stability
Carbon
cathodes
electrolytes
Graphite
carbon
Binders
Solid electrolytes
Heat generation
vinylidene
fluorides
graphite
heat generation
solid electrolytes
Surface reactions

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 electrolytes with LixCoO2 cathode or lithiated carbon anode. / Yamaki, Jun Ichi; Baba, Yasunori; Katayama, Noriko; Takatsuji, Hideyasu; Egashira, Minato; Okada, Shigeto.

In: Journal of Power Sources, Vol. 119-121, 01.06.2003, p. 789-793.

Research output: Contribution to journalConference article

Yamaki, Jun Ichi ; Baba, Yasunori ; Katayama, Noriko ; Takatsuji, Hideyasu ; Egashira, Minato ; Okada, Shigeto. / Thermal stability of electrolytes with LixCoO2 cathode or lithiated carbon anode. In: Journal of Power Sources. 2003 ; Vol. 119-121. pp. 789-793.
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abstract = "The thermal stability of electrolytes with LixCoO2 cathode or lithiated carbon anode was reviewed including our recent results. From our experiments, it was found that LixCoO2, delithiated by a chemical method using H2SO4 showed two exothermic peaks, one beginning at 190 °C and the other beginning at 290 °C. From high-temperature XRD, it was found that the first peak, from 190 °C, was the phase transition from a monoclinic (R-3m) to a spinel structure (Fd3 m). The spinel structure LixCoO2 showed a very small cycling capacity. Probably, cation mixing was induced by the heat treatment. The DSC measurements of Li0.49CoO2 with 1M LiPF6/EC+DMC showed two exothermic peaks. The peak starting at 190°C probably resulted from the decomposition of solvent due to an active cathode surface, and the peak starting at 230°C was electrolyte oxidation caused by released oxygen from Li0.49CoO2. From DSC profiles of chemically delithiated Li0.49CoO2 and 1M PC electrolytes with various Li salts, it was found that the inhibition effect of the surface reaction starting at 190 °C was large when LiBF4, LiPF6, and LiClO4 were used. The thermal stability of electrochemically lithiated graphite with 1M LiPF6/EC+DMC and PVdF-binder has been investigated. DSC revealed a mild heat generation starting from 130°C with a small peak at 140 °C. The mild heat generation continued until a sharp exothermic peak appeared at 280 °C. The lithiated graphite with the electrolyte without PVdF-binder did not show the small peak at 140 °C. The peak at 140 °C seems to be caused by the reaction (the solid electrolyte interphase (SEI) formation) of the electrolyte and lithiated graphite, which surface is covered by poly(vinylidene fluoride) (PVdF)-binder without formation of SEI at a lower temperature.",
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AU - Egashira, Minato

AU - Okada, Shigeto

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