Study of Electrolyte Components in Li Ion Cells Using Liquid-Liquid Extraction and Gas Chromatography Coupled with Mass Spectrometry

Petibon, R.; Rotermund, Lina M.; Nelson, K. J.; Gozdz, A. S.; Xia, Jian; Dahn, J. R.

doi:10.1149/2.117406jes

Cited by 71 publications

(110 citation statements)

References 26 publications

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“…10,17 In freshly formed cells the presence of these products indicates the existence of Li-alkoxides, likely formed from the reduction of EMC at an un-passivated anode. 8,10,17 Li-alkoxide formation and subsequent reaction with linear carbonate are shown in Equation 1 and Equation 2, respectively. The presence of transesterification products later in life was hypothesized to originate from the passivation of dissolved transition metals upon deposition at the negative electrode.…”

Section: Resultsmentioning

confidence: 99%

“…Some of the extract is removed and filtered with a syringe filter containing a PTFE membrane with a 0.45 μm pore size into a second PTFE vial containing additional CH 2 Cl 2 and deionized-water for LiPF 6 and HF extraction. 17 The new solution is then shaken for another 5 minutes, centrifuged for 20 minutes at 2200 RPM (800 g) to separate the organic and inorganic layers. The bottom, organic layer is then removed for gas chromatography-mass spectrometry (GC-MS) analysis.…”

Section: Methodsmentioning

confidence: 99%

“…17 A minimum 5-point calibration curve with an r 2 value of > 0.998 was generated from standards prepared on analysis day with known concentrations. Each sample and standard were injected twice to ensure reproducibility.…”

Section: Methodsmentioning

confidence: 99%

“…16 Here, analysis methods are presented that can track some of these changes to Li-ion cells to ultimately measure the impact of these reactions throughout cell lifetime. First, a simple, modified extraction method compared to that presented by Petibon et al 17 is introduced to obtain pure electrolyte from pouch cells. This allows the electrolyte to undergo multiple analyses to determine its organic and inorganic components.…”

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confidence: 99%

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Quantifying Changes to the Electrolyte and Negative Electrode in Aged NMC532/Graphite Lithium-Ion Cells

Thompson

Stone

Eldesoky

et al. 2018

J. Electrochem. Soc.

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103

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A set of LiNi 0.5 Mn 0.3 Co 0.2 O 2 /graphite lithium-ion cells underwent 750 charge-discharge cycles during about 8 months at 55 • C to upper cutoff potentials of 4.0, 4.1, 4.2, 4.3, and 4.4 V. The electrolyte in these cells was extracted using a centrifuge method and studied using gas chromatography/mass spectrometry to determine the changes to the solvents and by inductively coupled plasma-mass spectrometry to determine the changes to the salt content in the electrolyte. The negative electrodes from the cells were harvested and studied by micro-X-ray fluorescence to quantify the amount of transition metals which migrated from the positive electrode to the negative electrode during the testing. Emphasis is given to a detailed description of the quantitative methods used in the hope that others will adopt them in similar studies of different types of aged lithium-ion cells. The cells studied here initially had 1.1 molal LiPF 6 ethylene carbonate (EC): ethyl methyl carbonate (EMC) (3:7 by weight) electrolyte. The aged cells showed increasing amounts of dimethyl carbonate and diethyl carbonate created by transesterification as the upper cutoff potential increased. Only extremely small amounts of Mn, less than 0.1% of the total Mn in the positive electrode, were found on the negative electrode after this aggressive testing. Lithium-ion batteries are currently used in a wide range of applications: cell phones, power tools, vehicles and even grid energy storage.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

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Quantifying Changes to the Electrolyte and Negative Electrode in Aged NMC532/Graphite Lithium-Ion Cells

Thompson

Stone

Eldesoky

et al. 2018

J. Electrochem. Soc.

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103

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“…18 In this work, different concentrations of the enablers VC, MEC, FEC and DiFEC were used in EMC-based electrolyte added to NMC442/graphite pouch cells. EC was not chosen as an enabler in these studies because it did not perform competitively at high potentials (4.4 V) compared to VC or FEC.…”

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confidence: 99%

A Guide to Ethylene Carbonate-Free Electrolyte Making for Li-Ion Cells

Glazier

Petibon

et al. 2016

J. Electrochem. Soc.

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120

119

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Li [Ni 0.42 Mn 0.42 Co 0.16 ]O 2 (NMC442)/graphite pouch cells demonstrate superb performance at high voltage when ethylene carbonate (EC)-free electrolytes, using a solvent mixture that is >95% ethyl methyl carbonate (EMC) and between 2 and 5% of an "enabler", are used. The "enablers", required to passivate graphite during formation, can be vinylene carbonate (VC), methylene-ethylene carbonate (MEC), fluoroethylene carbonate (FEC) or difluoro ethylene carbonate (DiFEC), among others. In order to optimize the amount of "enabler" added to EMC, gas chromatography coupled with mass spectrometry (GC-MS) was used to track the consumption of "enabler" during the formation step. Storage tests, electrochemical impedance spectroscopy (EIS), ultrahigh precision coulometry (UHPC), long-term cycling, differential voltage analysis and isothermal microcalorimetry were used to determine the optimum amount of enabler to add to the cells. It was found that the graphite negative electrode cannot be fully passivated when the amount of "enabler" is too low resulting in gas production and capacity fade. Using excess "enabler" can cause large impedance and gas production in most cases. The choice of "enabler" also impacts cell performance. A solvent blend of 5% FEC with 95% EMC (by weight) provides the best combination of properties in NMC442/graphite cells operated to 4.4 V. It is our opinion that the experiments and their interpretation presented here represent a primer for the design of EC-free electrolytes. Lithium-ion batteries (LIB) are now widely used in electrified vehicles and energy storage systems.1 These applications require longer calendar and cycle lifetime as well as higher energy density. In order to increase the energy density of LIB, researchers focus on developing electrode materials with high specific capacity that may involve charging to increased upper cutoff potentials.2,3

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Electrolyte Degradation During Aging Process of Lithium‐Ion Batteries: Mechanisms, Characterization, and Quantitative Analysis

Liao,

Zhang,

Peng

et al. 2024

Advanced Energy Materials

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Given that the non‐aqueous electrolyte in Li‐ion battery plays a specific role as an ion‐transport medium and interfacial modifier for both cathode and anode, understanding and evaluating the evolution and degradation of electrolytes throughout the life cycle is a fundamental concern within the lithium‐ion battery (LIB) community. This article provides a comprehensive overview of the electrolyte decomposition processes, mechanisms, effects of electrolyte degradation on the battery performance, characterization techniques, and modeling analysis. First, it thoroughly discusses the processes and mechanisms involved in electrolyte degradation from two primary perspectives: 1) the formation of the electrode‐electrolyte interphase and 2) the decomposition of the bulk electrolyte. Subsequently, it systematically outlines the effects of electrolyte degradation on the battery performance. The article further introduces cutting‐edge characterization and detection techniques used to assess electrolyte degradation, with a specific emphasis on quantitative methods for analyzing residual electrolytes in practical cells. Moreover, it summarizes advanced physical models of electrolyte decomposition. Finally, the paper concludes by offering insights into future trends and potential challenges in battery degradation research, it offers valuable references and guidance for further exploration of electrolyte degradation in LIBs.

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Study of Electrolyte Components in Li Ion Cells Using Liquid-Liquid Extraction and Gas Chromatography Coupled with Mass Spectrometry

Cited by 71 publications

References 26 publications

Quantifying Changes to the Electrolyte and Negative Electrode in Aged NMC532/Graphite Lithium-Ion Cells

Quantifying Changes to the Electrolyte and Negative Electrode in Aged NMC532/Graphite Lithium-Ion Cells

A Guide to Ethylene Carbonate-Free Electrolyte Making for Li-Ion Cells

Electrolyte Degradation During Aging Process of Lithium‐Ion Batteries: Mechanisms, Characterization, and Quantitative Analysis

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