Experimental evaluation of thermolysis-driven gas emissions from LiPF6-carbonate electrolyte used in lithium-ion batteries

doi:10.1016/j.jechem.2020.01.030

能源化学(英文版) ›› 2020, Vol. 49 ›› Issue (10): 124-135.DOI: 10.1016/j.jechem.2020.01.030

Experimental evaluation of thermolysis-driven gas emissions from LiPF₆-carbonate electrolyte used in lithium-ion batteries

Zhenghai Liao^a,b, Shen Zhang^c, Yikun Zhao^a,b, Zongjia Qiu^a, Kang Li^a, Dong Han^a,b, Guoqiang Zhang^a,b, Thomas G.Habetler^c

a Institute of Electrical Engineering,Chinese Academy of Sciences,Beijing 100190,China;
b University of Chinese Academy of Sciences,Beijing 100039,China;
c School of Electrical and Computer Engineering,Georgia Institute of Technology,Atlanta,GA 30332,United States

收稿日期:2019-12-19 修回日期:2020-01-15 出版日期:2020-10-15 发布日期:2020-12-18
通讯作者: Guoqiang Zhang
基金资助:
This work was supported by the National Natural Science Foundation of China(51877203),and the Science and Technology Foundation of State Grid Corporation of China(521205190014).

Experimental evaluation of thermolysis-driven gas emissions from LiPF₆-carbonate electrolyte used in lithium-ion batteries

Zhenghai Liao^a,b, Shen Zhang^c, Yikun Zhao^a,b, Zongjia Qiu^a, Kang Li^a, Dong Han^a,b, Guoqiang Zhang^a,b, Thomas G.Habetler^c

a Institute of Electrical Engineering,Chinese Academy of Sciences,Beijing 100190,China;
b University of Chinese Academy of Sciences,Beijing 100039,China;
c School of Electrical and Computer Engineering,Georgia Institute of Technology,Atlanta,GA 30332,United States

Received:2019-12-19 Revised:2020-01-15 Online:2020-10-15 Published:2020-12-18
Contact: Guoqiang Zhang
Supported by:
This work was supported by the National Natural Science Foundation of China(51877203),and the Science and Technology Foundation of State Grid Corporation of China(521205190014).

摘要/Abstract

摘要： This paper performs an experimental evaluation of thermolysis-driven gases generated by the thermal decomposition of 1 M LiPF₆+EC/DMC=1/1 v/v electrolytes at various decomposition temperatures,pyrolysis durations,and oxygen concentrations.Carried out in a home-built autoclave filled with pure helium,the experiment reveals that as the decomposition temperature increases,more types and larger quantities of gases will be released.Specifically,the experimental results demonstrate trends of logistic growth in the volume concentration of CO₂,C₂H₆O,C₂H₄,CO,and C₂H₄O₂ with the increase of decomposition temperature.With a prolonged pyrolysis duration,while volume concentrations of certain gases,such as CO₂,C₂H₆O,C₂H₅F,and CO would increase,the concentration of C₂H₄O₂ actually decreases.Moreover,concentrations of both C₂H₄ and C₂H₅F will first decrease and reach their minimum values at 1% v/v oxygen concentration,and then they would quickly climb back at higher oxygen concentrations,while the concentrations of C₂H₆ and C₂H₃F would decrease monotonically.It is envisioned that the detailed experimental results and findings on the gas generation pattern of 1 M LiPF₆+EC/DMC=1/1 v/v electrolytes can facilitate the development of an early warning mechanism of thermal runaway based on gas sensing technology,which can be effectively applied to monitor the potential thermal failures of lithium-ion batteries with the same type of electrolyte and thus promote the thermal safety of battery packs in safety-critical applications.

关键词: LiPF₆-carbonate electrolyte, Thermal decomposition, Gas analysis, Lithium-ion battery, Thermal safety

Abstract: This paper performs an experimental evaluation of thermolysis-driven gases generated by the thermal decomposition of 1 M LiPF₆+EC/DMC=1/1 v/v electrolytes at various decomposition temperatures,pyrolysis durations,and oxygen concentrations.Carried out in a home-built autoclave filled with pure helium,the experiment reveals that as the decomposition temperature increases,more types and larger quantities of gases will be released.Specifically,the experimental results demonstrate trends of logistic growth in the volume concentration of CO₂,C₂H₆O,C₂H₄,CO,and C₂H₄O₂ with the increase of decomposition temperature.With a prolonged pyrolysis duration,while volume concentrations of certain gases,such as CO₂,C₂H₆O,C₂H₅F,and CO would increase,the concentration of C₂H₄O₂ actually decreases.Moreover,concentrations of both C₂H₄ and C₂H₅F will first decrease and reach their minimum values at 1% v/v oxygen concentration,and then they would quickly climb back at higher oxygen concentrations,while the concentrations of C₂H₆ and C₂H₃F would decrease monotonically.It is envisioned that the detailed experimental results and findings on the gas generation pattern of 1 M LiPF₆+EC/DMC=1/1 v/v electrolytes can facilitate the development of an early warning mechanism of thermal runaway based on gas sensing technology,which can be effectively applied to monitor the potential thermal failures of lithium-ion batteries with the same type of electrolyte and thus promote the thermal safety of battery packs in safety-critical applications.

Key words: LiPF₆-carbonate electrolyte, Thermal decomposition, Gas analysis, Lithium-ion battery, Thermal safety

Zhenghai Liao, Shen Zhang, Yikun Zhao, Zongjia Qiu, Kang Li, Dong Han, Guoqiang Zhang, Thomas G.Habetler. Experimental evaluation of thermolysis-driven gas emissions from LiPF₆-carbonate electrolyte used in lithium-ion batteries[J]. 能源化学(英文版), 2020, 49(10): 124-135.

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Experimental evaluation of thermolysis-driven gas emissions from LiPF₆-carbonate electrolyte used in lithium-ion batteries

Experimental evaluation of thermolysis-driven gas emissions from LiPF₆-carbonate electrolyte used in lithium-ion batteries

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