Degradation mechanism of alkyl carbonate solvents used in lithium-ion cells during initial charging

Yoshida, Harumi; Fukunaga, Tetsuo; Hazama, T.; Terasaki, Masanao; Mizutani, Mamoru; Yamachi, Masanori

doi:10.1016/s0378-7753(97)02635-9

Cited by 258 publications

(246 citation statements)

References 6 publications

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“…Other workers have also shown reduction reactions leading to R-OLi products on the anode carbon such as [20,23] …”

Section: Anode Reaction Mechanismsmentioning

confidence: 97%

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Advanced technology development program for lithium-ion batteries : thermal abuse performance of 18650 Li-ion cells.

Crafts¹,

Doughty²,

McBreen

et al. 2004

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Li-ion cells are being developed for high-power applications in hybrid electric vehicles currently being designed for the FreedomCAR (Freedom Cooperative Automotive Research) program. These cells offer superior performance in terms of power and energy density over current cell chemistries. Cells using this chemistry are the basis of battery systems for both gasoline and fuel cell based hybrids. However, the safety of these cells needs to be understood and improved for eventual widespread commercial application in hybrid electric vehicles. The thermal behavior of commercial and prototype cells has been measured under varying conditions of cell composition, age and state-of-charge (SOC). The thermal runaway behavior of full cells has been measured along with the thermal properties of the cell components. We have also measured gas generation and gas composition over the temperature range corresponding to the thermal runaway regime. These studies have allowed characterization of cell thermal abuse tolerance and an understanding of the mechanisms that result in cell thermal runaway. 4This page intentionally left blank. 5 Executive SummaryThe use of high-power Li-ion cells in hybrid electric vehicles is determined not only by the electrical performance of the cells but by the inherent safety and stability of the cells under normal and abusive conditions. The thermal response of the cells is determined by the intrinsic thermal reactivity of the cell components and the thermal interactions in the full cell configuration. The purpose of this program has been to identify the thermal response of these constituent cell materials and their contribution to the overall cell thermal performance. We have investigated commercial cell chemistries (Sony) as well as custom cells (Gen1 and Gen2) designed to achieve high levels of performance as well as safety. Calorimetric techniques such as Accelerating Rate Calorimetry (ARC) and Differential Scanning Rate Calorimetry (DSC) were used as a sensitive measure of the thermophysical properties. The program objectives, approach and accomplishments are summarized below. Objectives• Develop abuse methods which can establish cause and effect relationships between variations in abuse tolerance, thermal instabilities, or reduced lifetimes to changes in cell design or materials • Identify mechanisms and chemical constituents leading to reduced thermal tolerance, reduced thermal stability, or reduced operational lifetime in Li-ion cells.• Identify chemical mechanisms resulting in gas generation that leads to cell venting.• Determine factors affecting flammability of cell vent products under abusive conditions. • Characterize the thermal response and gas generation products of cells under various overcharge conditions. • Develop a knowledge base of cell thermal properties leading to improved cell designs. Approach• Test full size cells by the method of Accelerating Rate Calorimetry (ARC) to determine cell properties leading to cell thermal runaway. • Measure gas generation in full cells a...

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“…Other workers have also shown reduction reactions leading to R-OLi products on the anode carbon such as [20,23] …”

Section: Anode Reaction Mechanismsmentioning

confidence: 97%

“…The EMC, unsymmetrical chain alkyl carbonate solvent has been shown to be inherently unstable and forms an equilibrium balance with the symmetrical linear alkyl carbonates through an alkyl exchange reaction (sometimes call a "transesterification" reaction) as shown below [20].…”

Section: Electrolyte Decomposition -Liquid Chromatography/mass Spectrmentioning

confidence: 99%

Advanced technology development program for lithium-ion batteries : thermal abuse performance of 18650 Li-ion cells.

Crafts¹,

Doughty²,

McBreen

et al. 2004

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“…Diethyl 2,5-dioxahexane dicarboxylate (DEDOHC) and a polymerized form of ethylene carbonate (which we will refer to as poly-EC) have been suggested as products of electrochemical reduction of EC-based electrolytes in LIBs. Yoshida et al 5 first reported the formation of DEDOHC (referred to as a transesterification byproduct) in LIBs with 1 M LiPF 6 /EC+DEC (1:1 v/v) electrolyte. Other groups have detected DEDOHC formation by gas chromatography-mass spectroscopy (GC-MS), [6][7][8] and storage tests imply that this product is catalyzed by lithium alkoxide.…”

Section: Introductionmentioning

confidence: 99%

Identification of Diethyl 2,5-Dioxahexane Dicarboxylate and Polyethylene Carbonate as Decomposition Products of Ethylene Carbonate Based Electrolytes by Fourier Transform Infrared Spectroscopy

et al. 2014

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The formation of passive films on electrode by electrolyte decomposition plays a crucial role in maintaining the reversibility of Li ion batteries (LIBs); however the understanding of the electrolyte decomposition process is still lacking. In this study, we investigated the decomposition of an electrolyte based on ethylene carbonate (EC) solvent, and identified the decomposition products on Sn and Ni surface by matching the IR spectra to that of synthesized reference compounds. The reference compounds diethyl 2,5-dioxahexane dicarboxylate (DEDOHC) and polyethylene carbonate (poly-EC) were synthesized and the chemical structures were characterized by nuclear magnetic resonance (NMR) andFourier transform infrared (FTIR) spectroscopy. Peak assignments were made based on quantum chemical (Hartree-Fock) calculations. By introducing the synthesized product compounds into the electrolyte, we studied the effect of Li-ion solvation on the IR spectra and were able to match the spectra of the decomposition products on Sn and Ni electrode surfaces to those of DEDOHC and poly-EC for the first time. This study clearly demonstrated the importance to include solvation effects in the IR spectra of reference compounds in identification of electrolyte decomposition products in LIBs.2

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“…The composition of the SEI layer on the Mag-10 anodes was studied ex situ with FTIR microscopy in the reflectance mode ( The observation of fragments of ethylene oxides, carbonate ethers as well as their numerous short and long chain combinations, denotes products of ester exchange reactions, 26,34,35,36,37 and ring-opening polymerisation of EC. 26,38,39 The latter is catalysed by acids or bases and is thermodynamically driven by the extrusion of CO 2 from the resulting polycarbonates.…”

mentioning

confidence: 99%

An Investigation of the Effect of Graphite Degradation on Irreversible Capacity in Lithium-ion Cells

Hardwick

Marcinek

Beer

et al. 2008

J. Electrochem. Soc.

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The effect of surface structural damage on graphitic anodes, commonly observed in tested Li-ion cells, was investigated. Similar surface structural disorder was artificially induced in Mag-10 synthetic graphite anodes using argon-ion sputtering. Raman microscopy, scanning electron microscopy (SEM) and Brunauer Emmett Teller (BET) measurements confirmed that Ar-ion sputtered Mag-10 electrodes display similar degree of surface degradation as the anodes from tested Li-ion cells. Artificially modified Mag-10 anodes showed double the irreversible charge capacity during the first formation cycle, compared to fresh un-altered anodes. Impedance spectroscopy and Fourier transform infrared (FTIR) spectroscopy on surface modified graphite anodes indicated the formation of a thicker and slightly more resistive SEI layer. Gas for the surface modified electrode with no evidence of elevated M w species for the unmodified electrode. The structural disorder induced in the graphite during long-term cycling maybe responsible for the slow and continuous SEI layer reformation, and consequently, the loss of reversible capacity due to the shift of lithium inventory in cycled Li-ion cells.3

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Degradation mechanism of alkyl carbonate solvents used in lithium-ion cells during initial charging

Cited by 258 publications

References 6 publications

Advanced technology development program for lithium-ion batteries : thermal abuse performance of 18650 Li-ion cells.

Advanced technology development program for lithium-ion batteries : thermal abuse performance of 18650 Li-ion cells.

Identification of Diethyl 2,5-Dioxahexane Dicarboxylate and Polyethylene Carbonate as Decomposition Products of Ethylene Carbonate Based Electrolytes by Fourier Transform Infrared Spectroscopy

An Investigation of the Effect of Graphite Degradation on Irreversible Capacity in Lithium-ion Cells

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