Thermal aging of electrolytes used in lithium-ion batteries – An investigation of the impact of protic impurities and different housing materials

Handel, Patricia; Fauler, Gisela; Kapper, Katja; Schmuck, Martin; Stangl, Christoph; Fischer, Roland; Uhlig, F.; Koller, Stefan

doi:10.1016/j.jpowsour.2014.05.080

Cited by 89 publications

(75 citation statements)

References 20 publications

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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.…”

mentioning

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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mentioning

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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“…Graphite is commonly adopted as the anode material for lithium-ion batteries with organic electrolytes, such as LiPF6, with co-solvents like ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC)) [7]. When the anode operates at a potential that exceeds the electrochemically stable window of the electrolyte components, some major reactions in a LiPF6 salt system with EC and DMC are supposed to take place with the consumption of lithium ions [8][9][10][11][12].…”

Section: Evolution Of the Passivated Surface Layer At The Anode/electmentioning

confidence: 99%

“…[6]. Furthermore, the ROCO2Li can undergo a reduction reaction with traces of H2O and CO2 in the electrolyte to form LiCO3 [13][14][15][16][17][18][19], which further reacts with EC to form transesterification products [6,[9][10][11][12][13]. Additionally, anion contaminates, such as F-from LiPF6, readily react with lithium ions to form insoluble reaction products LiF, which are non-uniform, electrically insulating, and unstable on the surface of the graphite particles.…”

Section: Evolution Of the Passivated Surface Layer At The Anode/electmentioning

confidence: 99%

“…When the side reactions continue during prolonged cycling, the produced deposits accumulate in the SEI and consequently lead to stable growth of the SEI, which, in turn, leads to the loss of active lithium and further decomposition of the electrolyte [20,21]. Subsequently, a restructuring of the damaged SEI or a re-precipitation of the dissolved SEI products might occur as the SEI membrane begins to dissolve or to decompose [12,22].…”

Section: Evolution Of the Passivated Surface Layer At The Anode/electmentioning

confidence: 99%

“…Because manganese ions do not change their oxidation state to Mn3+ during storage within the NMC and the spinel phase, manganese dissolution caused by HF is more likely. Dissolved transition metals are transported through the electrolyte to the surface of the anode, resulting in the deposition of cation contaminates, such as Mn, Co and Fe, which are incorporated into the SEI layer [1,2,7,12].…”

Section: Evolution Of the Passivated Surface Layer At The Anode/electmentioning

confidence: 99%

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Aging Mechanisms of Anode Materials in Lithium-ion Batteries for Electric Vehicles

Tang¹

2017

dtetr

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1Electrode material aging leads to a decrease in capacity and/or a rise in resistance of the whole cell and thus can dramatically affect the performance of lithium-ion batteries. In this paper, we give an interpretation of capacity/power fading of anode-oriented aging mechanisms under cycling and various storage conditions for carbon-based anodes. For the anode, the main aging mechanisms are the loss of recyclable lithium ions caused by the formation and increasing growth of a Solid Electrolyte Interphase (SEI) and the mechanical fatigue caused by the diffusion-induced stress on the carbon anode particles. Additionally, anode aging largely depends on the electrochemical behaviour under cycling and storage conditions and results from both structural/morphological changes and side reactions aggravated by decomposition products and protic impurities in the electrolyte. Please keep this in mind when designing your figures and tables etc.

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Face to Face at the Cathode Electrolyte Interphase: From Interface Features to Interphase Formation and Dynamics

Kuhn

Edström

Winter

et al. 2022

Adv Materials Inter

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Development of high‐performing lithium‐based batteries inevitably calls for a profound understanding and elucidation of the reactivity at the electrode–liquid electrolyte interface and its impact on the overall performance and safety. The formation, composition, properties, and mechanisms of the cathode electrolyte interphase (CEI) formation and function are still to a large extent unknown for most lithium‐based battery materials, whereas the same is well considered for the solid electrolyte interphase on negative electrodes in the literature. In particular, in high voltage regions >4.3 V, the oxidative stability limit of most liquid electrolytes is reached and new mechanisms, involving surface reactivity of the active material beside electrolyte decomposition, contribute to the interfacial reactivity and nature of the CEI. Focusing on lithium‐based cell chemistries, this review aims to highlight the impact of the still less understood electrolyte decomposition chemistry, dictated by the nature of its components, as well as the in‐depth research on the physicochemical and electrochemical properties of CEI formation and evolution at positive electrode material surface and sub‐surfaces.

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Thermal aging of electrolytes used in lithium-ion batteries – An investigation of the impact of protic impurities and different housing materials

Cited by 89 publications

References 20 publications

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

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

Aging Mechanisms of Anode Materials in Lithium-ion Batteries for Electric Vehicles

Face to Face at the Cathode Electrolyte Interphase: From Interface Features to Interphase Formation and Dynamics

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