Gas generation mechanism due to electrolyte decomposition in commercial lithium-ion cell

Kumai, Kazuma; Miyashiro, Hajime; Kobayashi, Yo; Takei, Katsuhito; Ishikawa, Rikio

doi:10.1016/s0378-7753(98)00234-1

Cited by 261 publications

(160 citation statements)

References 5 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: 98%

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: 98%

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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“…Figure 2b shows the percentage of EMC that underwent trans-esterification producing dimethyl carbonate (DMC) and diethyl carbonate (DEC). 23,24 The presence of lithium alkoxides caused by the reduction of linear alkyl carbonates causes these trans-esterification reactions. Therefore, when trans-esterification of EMC occurs it is a signal that EMC was reduced at the graphite negative electrode during formation.…”

Section: Uhpcmentioning

confidence: 99%

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

Glazier

Petibon

et al. 2016

J. Electrochem. Soc.

130

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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“…13 Actually, significant evolution of gaseous products such as CO 2 , CO, O 2 , H 2 , CH 4 , C 2 H 4 , C 2 H 6 , C 3 H 6 and C 3 H 8 from the decomposition of carbonate solvents and lithium during battery operation has been detected by various characterization techniques. [14][15][16][17][18][19][20][21] In addition, utilizing isotope analysis, Onuk et al have unambiguously identified the origin of gases evolving in LIBs. 22 Furthermore, by adopting in situ transmission electron microscopy (TEM) 23 and neutron radiography (NR), 9,11 the generation of gaseous bubbles channels formed by the gas have recently been visualized.…”

Section: Introductionmentioning

confidence: 99%

Three-Dimensional Visualization of Gas Evolution and Channel Formation inside a Lithium-Ion Battery

Sun

Markötter

Manke

et al. 2016

ACS Appl. Mater. Interfaces

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Gas generation within lithium ion batteries (LIBs) gives rise to safety concerns that question their applicability. By employing synchrotron X-ray imaging, the gas and channel evolution occurring in an operating LIB have been directly visualized in their inherent 3D state as a function of discharge and charge. Using the spatial 3D distribution of gas bubbles and channels, the active particles that dictate the performance of a functional LIB were identified and visualized in 3D. Delithiation and lithiation are interpreted as the process of activating particles continuously in a step-bystep way. The present work not only demonstrates the generation and evolution of gas within LIB in 3D, but also reveals the distribution of active particles for the first time. These fundamentally findings presented here shed light on a range of processes that could not previously be characterized in 3D and can provide practical guidance for the

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Gas generation mechanism due to electrolyte decomposition in commercial lithium-ion cell

Cited by 261 publications

References 5 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.

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

Three-Dimensional Visualization of Gas Evolution and Channel Formation inside a Lithium-Ion Battery

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