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Title: Instability of Polyvinylidene Fluoride-Based Polymeric Binder in Lithium-Ion Cells: Final Report

Abstract

Thermal instabilities were identified in SONY-type lithium-ion cells and correlated with interactions of cell constituents and reaction products. Three temperature regions of interaction were identified and associated with the state of charge (degree of Li intercalation) of the cell. Anodes were shown to undergo exothermic reactions as low as 100 degree C involving the solid electrolyte interface (SEI) layer and the LiPF(6) salt in the electrolyte (EC-PC:DEC/IM LiPF(6)). These reactions could account for the thermal runaway observed in these cells beginning at 100 degree C. Exothermic reactions were also observed in the 200 degree C to 300 degree C region between the intercalated lithium anodes, the LiPF(6) salt, and the PVDF. These reactions were followed by a high-temperature reaction region, 300 degree C to 400 degree C, also involving the PVDF binder and the intercalated lithium anodes. The solvent was not directly involved in these reactions but served as a moderator and transport medium. Cathode exothermic reactions with the PVDF binder were observed above 200 degree C and increased with the state of charge (decreasing Li content). The stability of the PVDF binder as a function of electrochemical cycling was studied using FTIR. The infrared spectra from the extracts ofmore » both electrodes indicate that PVDF is chemically modified by exposure to the lithium cell electrolyte (as well as electrochemical cycling) in conjunction with NMP extraction. Preconditioning of PVDF to dehydrohalogenation, which may be occurring by reaction with LiPf(6), makes the PVDF susceptible to attack by a range of nucleophiles.« less

Authors:
; ; ;
Publication Date:
Research Org.:
Sandia National Labs., Albuquerque, NM (US); Sandia National Labs., Livermore, CA (US)
Sponsoring Org.:
US Department of Energy (US)
OSTI Identifier:
7020
Report Number(s):
SAND99-1164
TRN: AH200116%%292
DOE Contract Number:  
AC04-94AL85000
Resource Type:
Technical Report
Resource Relation:
Other Information: PBD: 1 May 1999
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; BINDERS; INSTABILITY; SOLID ELECTROLYTES; LITHIUM; METAL-NONMETAL BATTERIES; ORGANIC POLYMERS; LITHIUM FLUORIDES; THERMODYNAMICS; ANODES

Citation Formats

Garcia, M., Nagasubramanian, G., Tallant, D.R., and Roth, E.P. Instability of Polyvinylidene Fluoride-Based Polymeric Binder in Lithium-Ion Cells: Final Report. United States: N. p., 1999. Web. doi:10.2172/7020.
Garcia, M., Nagasubramanian, G., Tallant, D.R., & Roth, E.P. Instability of Polyvinylidene Fluoride-Based Polymeric Binder in Lithium-Ion Cells: Final Report. United States. doi:10.2172/7020.
Garcia, M., Nagasubramanian, G., Tallant, D.R., and Roth, E.P. Sat . "Instability of Polyvinylidene Fluoride-Based Polymeric Binder in Lithium-Ion Cells: Final Report". United States. doi:10.2172/7020. https://www.osti.gov/servlets/purl/7020.
@article{osti_7020,
title = {Instability of Polyvinylidene Fluoride-Based Polymeric Binder in Lithium-Ion Cells: Final Report},
author = {Garcia, M. and Nagasubramanian, G. and Tallant, D.R. and Roth, E.P.},
abstractNote = {Thermal instabilities were identified in SONY-type lithium-ion cells and correlated with interactions of cell constituents and reaction products. Three temperature regions of interaction were identified and associated with the state of charge (degree of Li intercalation) of the cell. Anodes were shown to undergo exothermic reactions as low as 100 degree C involving the solid electrolyte interface (SEI) layer and the LiPF(6) salt in the electrolyte (EC-PC:DEC/IM LiPF(6)). These reactions could account for the thermal runaway observed in these cells beginning at 100 degree C. Exothermic reactions were also observed in the 200 degree C to 300 degree C region between the intercalated lithium anodes, the LiPF(6) salt, and the PVDF. These reactions were followed by a high-temperature reaction region, 300 degree C to 400 degree C, also involving the PVDF binder and the intercalated lithium anodes. The solvent was not directly involved in these reactions but served as a moderator and transport medium. Cathode exothermic reactions with the PVDF binder were observed above 200 degree C and increased with the state of charge (decreasing Li content). The stability of the PVDF binder as a function of electrochemical cycling was studied using FTIR. The infrared spectra from the extracts of both electrodes indicate that PVDF is chemically modified by exposure to the lithium cell electrolyte (as well as electrochemical cycling) in conjunction with NMP extraction. Preconditioning of PVDF to dehydrohalogenation, which may be occurring by reaction with LiPf(6), makes the PVDF susceptible to attack by a range of nucleophiles.},
doi = {10.2172/7020},
journal = {},
number = ,
volume = ,
place = {United States},
year = {1999},
month = {5}
}

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