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Title: Studies on the thermal breakdown of common Li-ion battery electrolyte components

Abstract

While much attention is paid to the impact of the active materials on the catastrophic failure of lithium ion batteries, much of the severity of a battery failure is also governed by the electrolytes used, which are typically flammable themselves and can decompose during battery failure. The use of LiPF 6 salt can be problematic as well, not only catalyzing electrolyte decomposition, but also providing a mechanism for HF production. This work evaluates the safety performance of the common components ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) in the context of the gasses produced during thermal decomposition, looking at both the quantity and composition of the vapor produced. EC and DEC were found to be the largest contributors to gas production, both producing upwards of 1.5 moles of gas/mole of electrolyte. DMC was found to be relatively stable, producing very little gas regardless of the presence of LiPF 6. EMC was stable on its own, but the addition of LiPF 6 catalyzed decomposition of the solvent. As a result, while gas analysis did not show evidence of significant quantities of any acutely toxic materials, the gasses themselves all contained enough flammable components tomore » potentially ignite in air.« less

Authors:
 [1];  [1];  [1];  [1]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1235360
Report Number(s):
SAND-2015-6333J
Journal ID: ISSN 0013-4651; 606215
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 162; Journal Issue: 10; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; electrolyte; gas generation; lithium ion battery; safety; thermal breakdown; thermal runaway

Citation Formats

Lamb, Joshua, Orendorff, Christopher J., Roth, Emanuel Peter, and Langendorf, Jill Louise. Studies on the thermal breakdown of common Li-ion battery electrolyte components. United States: N. p., 2015. Web. doi:10.1149/2.0651510jes.
Lamb, Joshua, Orendorff, Christopher J., Roth, Emanuel Peter, & Langendorf, Jill Louise. Studies on the thermal breakdown of common Li-ion battery electrolyte components. United States. doi:10.1149/2.0651510jes.
Lamb, Joshua, Orendorff, Christopher J., Roth, Emanuel Peter, and Langendorf, Jill Louise. Thu . "Studies on the thermal breakdown of common Li-ion battery electrolyte components". United States. doi:10.1149/2.0651510jes. https://www.osti.gov/servlets/purl/1235360.
@article{osti_1235360,
title = {Studies on the thermal breakdown of common Li-ion battery electrolyte components},
author = {Lamb, Joshua and Orendorff, Christopher J. and Roth, Emanuel Peter and Langendorf, Jill Louise},
abstractNote = {While much attention is paid to the impact of the active materials on the catastrophic failure of lithium ion batteries, much of the severity of a battery failure is also governed by the electrolytes used, which are typically flammable themselves and can decompose during battery failure. The use of LiPF6 salt can be problematic as well, not only catalyzing electrolyte decomposition, but also providing a mechanism for HF production. This work evaluates the safety performance of the common components ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) in the context of the gasses produced during thermal decomposition, looking at both the quantity and composition of the vapor produced. EC and DEC were found to be the largest contributors to gas production, both producing upwards of 1.5 moles of gas/mole of electrolyte. DMC was found to be relatively stable, producing very little gas regardless of the presence of LiPF6. EMC was stable on its own, but the addition of LiPF6 catalyzed decomposition of the solvent. As a result, while gas analysis did not show evidence of significant quantities of any acutely toxic materials, the gasses themselves all contained enough flammable components to potentially ignite in air.},
doi = {10.1149/2.0651510jes},
journal = {Journal of the Electrochemical Society},
number = 10,
volume = 162,
place = {United States},
year = {2015},
month = {8}
}

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Cited by: 7 works
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Works referenced in this record:

Thermal stability of LiPF6–EC:EMC electrolyte for lithium ion batteries
journal, July 2001


A Detailed Investigation of the Thermal Reactions of LiPF[sub 6] Solution in Organic Carbonates Using ARC and DSC
journal, January 2003

  • Gnanaraj, J. S.; Zinigrad, E.; Asraf, L.
  • Journal of The Electrochemical Society, Vol. 150, Issue 11
  • DOI: 10.1149/1.1617301

Thermal Stability of Electrolytes with Mixtures of LiPF[sub 6] and LiBF[sub 4] Used in Lithium-Ion Cells
journal, January 2004

  • Hong, Eui-Sun; Okada, Shigeto; Sonoda, Takaki
  • Journal of The Electrochemical Society, Vol. 151, Issue 11
  • DOI: 10.1149/1.1802136

Decomposition reaction of LiPF6-based electrolytes for lithium ion cells
journal, June 2006


Decomposition kinetics of anhydrous and moisture exposed LiPF6 salts by thermogravimetry
journal, May 2013


How does lithium salt anion affect oxidation decomposition reaction of ethylene carbonate: A density functional theory study
journal, December 2013


Ab Initio Calculations of Thermal Decomposition Mechanism of LiPF 6 -Based Electrolytes for Lithium-Ion Batteries
journal, December 2012

  • Okamoto, Yasuharu
  • Journal of The Electrochemical Society, Vol. 160, Issue 2
  • DOI: 10.1149/2.020303jes

Impact of delithiated Li0FePO4 on the decomposition of LiPF6-based electrolyte studied by accelerating rate calorimetry
journal, August 2013


Chemical Reactivity of PF[sub 5] and LiPF[sub 6] in Ethylene Carbonate/Dimethyl Carbonate Solutions
journal, January 2001

  • Sloop, S. E.; Pugh, J. K.; Wang, S.
  • Electrochemical and Solid-State Letters, Vol. 4, Issue 4
  • DOI: 10.1149/1.1353158

Decomposition of LiPF[sub 6] and Stability of PF[sub 5] in Li-Ion Battery Electrolytes
journal, January 2003

  • Tasaki, Ken; Kanda, Katsuya; Nakamura, Shinichiro
  • Journal of The Electrochemical Society, Vol. 150, Issue 12
  • DOI: 10.1149/1.1622406

Initial stages of thermal decomposition of LiPF6-based lithium ion battery electrolytes by detailed Raman and NMR spectroscopy
journal, January 2013

  • Wilken, Susanne; Treskow, Marcel; Scheers, Johan
  • RSC Advances, Vol. 3, Issue 37
  • DOI: 10.1039/c3ra42611d

Thermal stability of LiPF6-based electrolyte and effect of contact with various delithiated cathodes of Li-ion batteries
journal, June 2009


Thermal stability of LiPF6 salt and Li-ion battery electrolytes containing LiPF6
journal, October 2006


On the thermal stability of LiPF6
journal, November 2005

  • Zinigrad, Ella; Larush-Asraf, Liraz; Gnanaraj, Josef S.
  • Thermochimica Acta, Vol. 438, Issue 1-2
  • DOI: 10.1016/j.tca.2005.09.006

Thermal Decomposition of LiPF[sub 6]-Based Electrolytes for Lithium-Ion Batteries
journal, January 2005

  • Campion, Christopher L.; Li, Wentao; Lucht, Brett L.
  • Journal of The Electrochemical Society, Vol. 152, Issue 12
  • DOI: 10.1149/1.2083267

In-depth safety-focused analysis of solvents used in electrolytes for large scale lithium ion batteries
journal, January 2013

  • Eshetu, Gebrekidan Gebresilassie; Grugeon, Sylvie; Laruelle, Stéphane
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 23
  • DOI: 10.1039/c3cp51315g

The use of accelerating rate calorimetry (ARC) for the study of the thermal reactions of Li-ion battery electrolyte solutions
journal, June 2003


Thermal stability of alkyl carbonate mixed-solvent electrolytes for lithium ion cells
journal, February 2002


Suppression of Toxic Compounds Produced in the Decomposition of Lithium-Ion Battery Electrolytes
journal, January 2004

  • Campion, Christopher L.; Li, Wentao; Euler, William B.
  • Electrochemical and Solid-State Letters, Vol. 7, Issue 7
  • DOI: 10.1149/1.1738551

Investigation on gas generation of Li4Ti5O12/LiNi1/3Co1/3Mn1/3O2 cells at elevated temperature
journal, September 2013


Polymerization of propylene carbonate
journal, January 1977

  • Soga, Kazuo; Tazuke, Yutaka; Hosoda, Satoru
  • Journal of Polymer Science: Polymer Chemistry Edition, Vol. 15, Issue 1
  • DOI: 10.1002/pol.1977.170150120

The influence of lithium salt on the interfacial reactions controlling the thermal stability of graphite anodes
journal, May 2002


Understanding Solid Electrolyte Interface Film Formation on Graphite Electrodes
journal, January 2001

  • Zhang, Shengshui; Ding, Michael S.; Xu, Kang
  • Electrochemical and Solid-State Letters, Vol. 4, Issue 12
  • DOI: 10.1149/1.1414946

The role of Li-ion battery electrolyte reactivity in performance decline and self-discharge
journal, June 2003


Density Functional Theory Study of the Role of Anions on the Oxidative Decomposition Reaction of Propylene Carbonate
journal, December 2011

  • Xing, Lidan; Borodin, Oleg; Smith, Grant D.
  • The Journal of Physical Chemistry A, Vol. 115, Issue 47
  • DOI: 10.1021/jp206153n

The mechanism of HF formation in LiPF6 based organic carbonate electrolytes
journal, January 2012


Characteristics of lithium-ion batteries during fire tests
journal, December 2014


HF Formation in LiPF6-Based Organic Carbonate Electrolytes
journal, January 2013

  • Lux, S. F.; Chevalier, J.; Lucas, I. T.
  • ECS Electrochemistry Letters, Vol. 2, Issue 12
  • DOI: 10.1149/2.005312eel

    Works referencing / citing this record:

    Experimental Quantification of Vent Mechanism Flow Parameters in 18650 Format Lithium Ion Batteries
    journal, April 2019

    • Austin Mier, Frank; Hargather, Michael J.; Ferreira, Summer R.
    • Journal of Fluids Engineering, Vol. 141, Issue 6
    • DOI: 10.1115/1.4042962

    Perspective—From Calorimetry Measurements to Furthering Mechanistic Understanding and Control of Thermal Abuse in Lithium-Ion Cells
    journal, January 2019

    • Shurtz, Randy C.; Preger, Yuliya; Torres-Castro, Loraine
    • Journal of The Electrochemical Society, Vol. 166, Issue 12
    • DOI: 10.1149/2.0341912jes

    Chromatographic Techniques in the Research Area of Lithium Ion Batteries: Current State-of-the-Art
    journal, May 2019


    Experimental Quantification of Vent Mechanism Flow Parameters in 18650 Format Lithium Ion Batteries
    journal, April 2019

    • Austin Mier, Frank; Hargather, Michael J.; Ferreira, Summer R.
    • Journal of Fluids Engineering, Vol. 141, Issue 6
    • DOI: 10.1115/1.4042962

    Perspective—From Calorimetry Measurements to Furthering Mechanistic Understanding and Control of Thermal Abuse in Lithium-Ion Cells
    journal, January 2019

    • Shurtz, Randy C.; Preger, Yuliya; Torres-Castro, Loraine
    • Journal of The Electrochemical Society, Vol. 166, Issue 12
    • DOI: 10.1149/2.0341912jes

    Chromatographic Techniques in the Research Area of Lithium Ion Batteries: Current State-of-the-Art
    journal, May 2019