Two-dimensional ion chromatography for the separation of ionic organophosphates generated in thermally decomposed lithium hexafluorophosphate-based lithium ion battery electrolytes

Kraft, Vadim; Grützke, Martin; Weber, Waldemar; Menzel, J.; Wiemers‐Meyer, Simon; Winter, Martin; Nowak, Sascha

doi:10.1016/j.chroma.2015.07.054

Cited by 63 publications

(49 citation statements)

References 30 publications

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“…Accordingly, DMP reacted completely to other decomposition products from the electrolyte mixture. The following OPs were determined in the aged sample: (2) [37,41,[43][44][45][46]. In the electropherogram ( Figure 5), some of the reported m/z ratios were detected.…”

Section: Application For the Investigation Of Decomposition Products mentioning

confidence: 99%

“…In the electropherogram ( Figure 5), some of the reported m/z ratios were detected. The advantage of the applied CE method is the baseline separation of the OPs without using a non-commercially available two-dimensional setup [46]. The two-dimensional IC technique with heart-cutting mode was developed to separate the ionic OPs from each other.…”

Section: Application For the Investigation Of Decomposition Products mentioning

confidence: 99%

“…On the first dimension, the OPs were pre-separated from the hexafluorophosphate anion, then the analytes were retarded on a preconcentration column and separated isocratically on the second dimension. Different stationary phases and eluents were used on the second dimension as compared to the first dimension [46]. The fluorinated decomposition product (8) with the m/z ratio of 266.9833 was formed by reaction of two OPs.…”

Section: Application For the Investigation Of Decomposition Products mentioning

confidence: 99%

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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: 99%

Section: Application For the Investigation Of Decomposition Products mentioning

confidence: 99%

Section: Application For the Investigation Of Decomposition Products mentioning

confidence: 99%

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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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“…[7][8][9][10][11][12][13][14][15][16][17][18][19][20] These instruments are costly, and these methods require the preparation and measurement of many calibration solutions. Often the columns or detectors used in chromatography experiments cannot be exposed to the high temperature decomposition products of LiPF 6 , so these experiments often focus on the organic portions of the electrolyte, after the water-soluble portions of the electrolyte have been removed.…”

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confidence: 99%

A New Method for Determining the Concentration of Electrolyte Components in Lithium-Ion Cells, Using Fourier Transform Infrared Spectroscopy and Machine Learning

Ellis

Buteau

Hames

et al. 2018

J. Electrochem. Soc.

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A new method is introduced for determining unknown concentrations of major components in typical lithium-ion battery electrolytes. The method is quick, cheap, and accurate. Machine learning techniques are used to match features of the Fourier transform infrared (FTIR) spectrum of an unknown electrolyte to the same features of a database of FTIR spectra with known compositions. With this method, LiPF 6 concentrations can be determined with similar accuracy and precision as an inductively coupled plasma optical emission spectrometry (ICP-OES) method. The ratios of organic carbonate solvent species can be determined with more rapidity than gas chromatography (GC). This FTIR method is faster and less expensive than GC and ICP-OES, and has the added benefit of being able to determine LiPF 6 concentration and solvent fractions simultaneously. Application of this tool can facilitate electrolyte analysis of aged lithium-ion cells, and will help elucidate mechanisms for cell degradation. A dominant cause of lithium-ion cell failure, especially in high voltage cells, is degradation of the electrolyte, particularly at the surface of the charged electrodes.1 Most studies on the topic of cell degradation and electrolyte decomposition have focused on the formation of films of electrolyte decomposition products which build up on the surfaces of the electrodes.2-6 These films contain chemical moieties derived from both the electrolyte solvents and the electrolyte salt, LiPF 6 . Although mechanisms for the consumption of solvents and LiPF 6 in lithium-ion cells have been determined, there have been few systematic studies which quantify the changes in the bulk electrolyte as a function of cell aging.Quantitative analyses of electrolyte solutions typically employ nuclear magnetic resonance (NMR) spectroscopy, gas chromatography (GC), high performance liquid chromatography (HPLC), and inductively coupled plasma optical emission spectrometry (ICP-OES). [7][8][9][10][11][12][13][14][15][16][17][18][19][20] These instruments are costly, and these methods require the preparation and measurement of many calibration solutions. Often the columns or detectors used in chromatography experiments cannot be exposed to the high temperature decomposition products of LiPF 6 , so these experiments often focus on the organic portions of the electrolyte, after the water-soluble portions of the electrolyte have been removed. 20A method of determining the concentration of LiPF 6 and weight fractions of solvents in unknown electrolyte solutions, using attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy is presented here. Until now, FTIR has only been used for qualitative electrolyte analysis, and for the determination of solvation structures. Quantitative analysis was achieved using a machine learning (ML) algorithm to match features in the FTIR spectra of unknown electrolyte solutions to those interpolated from a spectral database of known electrolyte solutions. This method is very fast. Once the spectral database and mac...

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“…As a matter of fact, the aging processes in lithium-ion cells were investigated in many papers. [12][13][14] Nevertheless, there exist rather few combined researches in the area of the processes of the thermal runaway and the aging. [15][16][17] Besides, as it was highlighted in the paper, 17 in main, the combined researches focused on influence of aging parameters on cells operation safety without a clarification of mechanisms and underlying causes.…”

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Mechanism of Thermal Runaway in Lithium-Ion Cells

Galushkin

Yazvinskaya

Галушкин

2018

J. Electrochem. Soc.

117

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In this investigation, it was shown that a probability of thermal runaway in commercial lithium-ion cells of the type 18650 grows with number increase of charge/discharge cycles and increase of cells state of charge (SOC). Notably, experiments in an accelerating rate calorimeter (ARC) showed that with the number growth of cells charge/discharge cycles, it is observed a considerable decline of an initiation temperature of exothermic reactions of thermal runaway and increase of released energy. Additional ARC-experiments with the following analysis of the gas released showed that in a course of cells cycling in anode graphite, hydrogen is accumulated. It was proven in experiments that a recombination of released-from-graphite-anode atomic hydrogen is exactly that powerful exothermic reaction, which increases the released energy in the beginning of the thermal runaway and decreases the temperature of its initiation. Thus, the reason for the initiation of thermal runaway in lithium-ion cells is a powerful exothermic reaction of recombination of atomic hydrogen accumulated in anode graphite in a during of cells cycling. The possible mechanism of initiation thermal runaway has been proposed corresponding to all the experimental results obtained. At present, lithium-ion batteries are ones of the most promising electrochemical systems of energy storing. They are dominant energy sources in hand-hold devices: smartphones, notebooks, tablets, etc.

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Two-dimensional ion chromatography for the separation of ionic organophosphates generated in thermally decomposed lithium hexafluorophosphate-based lithium ion battery electrolytes

Cited by 63 publications

References 30 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

A New Method for Determining the Concentration of Electrolyte Components in Lithium-Ion Cells, Using Fourier Transform Infrared Spectroscopy and Machine Learning

Mechanism of Thermal Runaway in Lithium-Ion Cells

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