An innovative experimental approach aiming to understand and quantify the actual fire hazards of ionic liquids

Diallo, Alpha-Oumar; Morgan, Alexander B.; Len, Christophe; Marlair, Guy

doi:10.1039/c2ee23926d

Cited by 57 publications

(53 citation statements)

References 35 publications

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“…In Figure 6, the electropherogram of the determined m/z ratios from the mixture of the LIB electrolyte, PS and DEP (9) is illustrated. Beside DEP (9), the decomposition products (2)(3)(4)(5)(6)(7) were the same as in the previous sample. Additionally, the m/z ratio of 126.9966 (10) was In Figure 6, the electropherogram of the determined m/z ratios from the mixture of the LIB electrolyte, PS and DEP (9) is illustrated.…”

Section: Application For the Investigation Of Decomposition Products mentioning

confidence: 70%

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Capillary Electrophoresis as Analysis Technique for Battery Electrolytes: (i) Monitoring Stability of Anions in Ionic Liquids and (ii) Determination of Organophosphate-Based Decomposition Products in LiPF6-Based Lithium Ion Battery Electrolytes

Pyschik¹,

Winter²,

Nowak³

2017

Separations

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Abstract:In this work, a method for capillary electrophoresis (CE) hyphenated to a high-resolution mass spectrometer was presented for monitoring the stability of anions in ionic liquids (ILs) and in commonly used lithium ion battery (LIB) electrolytes. The investigated ILs were 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR 13 TFSI) and 1-methyl-1-propylpyrrolidinium bis(fluorosulfonyl)imide (PYR 13 FSI). The method development was conducted by adjusting the following parameters: buffer compositions, buffer concentrations, and the pH value. Also the temperature and the voltage applied on the capillary were optimized. The ILs were aged at room temperature and at 60 • C for 16 months each. At both temperatures, no anionic decomposition products of the FSI − and TFSI − anions were detected. Accordingly, the FSI − and TFSI − anions were thermally stable at these conditions. This method was also applied for the investigation of LIB electrolyte samples, which were aged at 60 • C for one month. The LP30 (50/50 wt. % dimethyl carbonate/ethylene carbonate and 1 M lithium hexafluorophosphate) electrolyte was mixed with the additive 1,3-propane sultone (PS) and with one of the following organophosphates (OP): dimethyl phosphate (DMP), diethyl phosphate (DEP), and triethyl phosphate (TEP), to investigate the influence of these compounds on the formation of OPs.

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Section: Application For the Investigation Of Decomposition Products mentioning

confidence: 70%

“…For the use of IL-based electrolytes for LIBs, high thermal stability as well as flame retardant performance and negligible vapor pressure are considered beneficial [7]. According to the literature, the most commonly used anion is bis(trifluoromethanesulfonyl)imide (TFSI).…”

Section: Introductionmentioning

confidence: 99%

Capillary Electrophoresis as Analysis Technique for Battery Electrolytes: (i) Monitoring Stability of Anions in Ionic Liquids and (ii) Determination of Organophosphate-Based Decomposition Products in LiPF6-Based Lithium Ion Battery Electrolytes

Pyschik¹,

Winter²,

Nowak³

2017

Separations

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“…In particular, one of these new anions, bis(fl uorosulfonyl)amide, denoted as [(FSO 2 ) 2 N] − , dramatically reverses the poor impression of ILs as a lithium battery electrolyte [ 6 -9 ]. Recent research on the thermal stability of ILs, which have been seriously investigated since the appearance of new ILs composed of [(FSO 2 ) 2 indeed harder to ignite; however, once ignited by an external source of energy, signifi cantly high heat release occurs when the ILs burn under forced conditions [ 10 ]. Furthermore, not all ILs exhibited an expected safety feature as a nonfl ammable electrolyte under severe conditions such as the charged state [ 11 , 12 ].…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in Ionic Liquids for Lithium Secondary Batteries

Matsumoto

2014

Modern Aspects of Electrochemistry

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“…1 To provide safer cells, ionic liquids (IL) are widely studied as they possess negligible vapor pressure and reduced flammability. 2 However, though information concerning the thermal stability of IL during combustion is beginning to emerge, 3,4 few data exist concerning their stability in case of short-circuit, overcharge or overdischarge. The aim of this work is to compare cycling and overcharge behavior at 25 and 60…”

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confidence: 99%

Characterization of LTO//NMC Batteries Containing Ionic Liquid or Carbonate Electrolytes after Cycling and Overcharge

Chancelier

Benayad

Gutel

et al. 2015

J. Electrochem. Soc.

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Electrochemical stabilities under cycling and overcharge of Li 4 Ti 5 O 12 (LTO) // LiNi 1/3 Mn 1/3 Co 1/3 O 2 (NMC) batteries with two ionic liquid-based electrolytes and a commercial electrolyte were investigated at 25 and 60 • C. The electrolytes were constituted of ethylene carbonate / dimethyl carbonate mixtures with LiPF 6 , and of imidazolium and pyrrolidinium-based ionic liquids containing the bis(trifluoromethanesulfonyl)imide anion (NTf 2 ) associated to LiNTf 2 salt. The experiments were performed in coin and pouch cells in order to follow the evolution of the stability of both solid, liquid and gas phases. The decomposition products and stability of the electrolytes was assessed by gas chromatography coupled with infrared spectroscopy. The characterization of the electrode surfaces by SEM, XRD and XPS techniques was reported, after cycling and overcharge. The XPS analysis of both electrodes indicated that their surfaces were covered by an IL film in the case of NMC, and by several NTf 2 anion decomposition products in the case of LTO. This work highlights the difference between thermal and electrochemical stability, especially for imidazolium-based electrolytes. Commercial lithium-ion batteries could lead to safety issues related to the use of flammable carbonates as electrolyte solvents.1 To provide safer cells, ionic liquids (IL) are widely studied as they possess negligible vapor pressure and reduced flammability.2 However, though information concerning the thermal stability of IL during combustion is beginning to emerge, 3,4 few data exist concerning their stability in case of short-circuit, overcharge or overdischarge. The aim of this work is to compare cycling and overcharge behavior at 25 and 60• C of two IL-based electrolytes and a commercial electrolyte, in a system using Li 4 Figure 1. For each electrolyte, cycling and overcharge experiments were run in LTO // NMC coin or pouch cells. The evolved gases and the battery components (electrolyte and electrodes) were analyzed after cycling and overcharge at 60• C. Results and DiscussionIn a first set of experiments, the cycling performances of LTO // NMC coin cells (∼ 2 mAh) and pouch cells (∼ 10 mAh) with the three electrolytes were investigated at 25• C and 60 • C. In the case of pouch cells, the battery evolutions were monitored by measuring the volume increase, and analyzing evolved gases. In a second set of experiments, the batteries were submitted to a charge at C/10-rate up to 4.5 V (NMC potential reached 6 V vs Li + /Li) followed by a floating of 20 h at this voltage at 60• C. Meanwhile the currents required to maintain the cell voltage and the cell volumes were measured. The emitted gases were identified by gas chromatography coupled with infrared spectroscopy (GC-IR). The post mortem analyses of the electrode surfaces were carried out by scanning electron microscopy (SEM), Xray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques. * Electrochemical Society Student Member.z E-mail: lea.chancelier@univ-lyon1.frCycling ...

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An innovative experimental approach aiming to understand and quantify the actual fire hazards of ionic liquids

Cited by 57 publications

References 35 publications

Capillary Electrophoresis as Analysis Technique for Battery Electrolytes: (i) Monitoring Stability of Anions in Ionic Liquids and (ii) Determination of Organophosphate-Based Decomposition Products in LiPF6-Based Lithium Ion Battery Electrolytes

Capillary Electrophoresis as Analysis Technique for Battery Electrolytes: (i) Monitoring Stability of Anions in Ionic Liquids and (ii) Determination of Organophosphate-Based Decomposition Products in LiPF6-Based Lithium Ion Battery Electrolytes

Recent Advances in Ionic Liquids for Lithium Secondary Batteries

Characterization of LTO//NMC Batteries Containing Ionic Liquid or Carbonate Electrolytes after Cycling and Overcharge

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