Formation mechanism of alkyl dicarbonates in Li-ion cells

Sasaki, Takeshi; Abe, Takeshi; Iriyama, Yasutoshi; Inaba, Masaaki; Ogumi, Zempachi

doi:10.1016/j.jpowsour.2005.02.021

Cited by 106 publications

(140 citation statements)

References 18 publications

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“…This conversion reaction has been attributed to the catalytic effect of the lithium alkoxide (ROLi) species that can be formed by carbonate solvent reduction during the formation of a Li-ion cell. [40][41][42][43] It has been proposed that the use VC, for instance, can dramatically decrease the formation of ROLi species due to the passivating role of VC at the graphite surface and/or that VC can trap the free alkoxide anion (RO − ) in the electrolyte through nucleophilic addition reactions. Therefore, PES more likely forms a less passivating SEI film at the graphite surface that does not prevent the formation of ROLi and/or PES does not efficiently trap the ROLi.…”

Section: Resultsmentioning

confidence: 99%

Understanding the Role of Prop-1-ene-1,3-Sultone and Vinylene Carbonate in LiNi_1/3Mn_1/3Co_1/3O₂/Graphite Pouch Cells: Electrochemical, GC-MS and XPS Analysis

Madec

Petibon

Xia

et al. 2015

J. Electrochem. Soc.

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The role of prop-1-ene-1,3-sultone (PES) used alone or in combination with vinylene carbonate (VC) in LiNi1/3Mn1/3Co1/3O2(NMC)/graphite pouch cells was studied by correlating data from differential capacity (dQ/dV) analysis, gas chromatography/mass spectroscopy (GC−MS), ultrahigh precision coulometry, storage experiments and X-ray photoelectron spectroscopy. VC formed more stable and protective SEI films at both graphite and NMC surfaces due to the formation of a polymer of VC. For PES-containing electrolytes, the preferential reaction of PES led to the formation of SEI films with higher oxygen content at both graphite and NMC surfaces due to the additional oxygen contribution of sulfite species and substantially less LiF compared to control and VC electrolytes. PES also led to thicker SEI films at the NMC surface. When VC was combined with PES, features of the SEI films from both VC and PES were observed. The SEI film features for VC and PES used alone or in combination can explain the improved electrochemical performance as well as the lower production of gas observed with these additives compared to control electrolyte.

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Section: Resultsmentioning

confidence: 99%

Understanding the Role of Prop-1-ene-1,3-Sultone and Vinylene Carbonate in LiNi_1/3Mn_1/3Co_1/3O₂/Graphite Pouch Cells: Electrochemical, GC-MS and XPS Analysis

Madec

Petibon

Xia

et al. 2015

J. Electrochem. Soc.

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“…When Gr/Gr cells are cycled in the electrolyte without SA, three new peaks located at 11.8 minutes, 12.9 minutes and 13.9 minutes arise which are assigned respectively to ethylene glycol bis-(methyl carbonate), ethylene glycol ethylmethyl bis-(carbonate), ethylene glycol bis-(ethyl carbonate). 28 These bis-(alkyl carbonates) are depicted (molar masses and chemical structure) in Table IV. These compounds have been earlier identified as electrolyte degradation byproducts, 29 and form on the graphite electrode according to the reduction mechanism 30,31 reported in Fig. 13.…”

Section: Xps Analysis Of Lithiated Graphite Interfaces-symmetricmentioning

confidence: 92%

Reactivity of Succinic Anhydride at Lithium and Graphite Electrodes

Charton

Santos-Peña

Biller

et al. 2017

J. Electrochem. Soc.

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Succinic anhydride (SA) is an useful electrolyte additive for high voltage cathodes but has also a negative impact on graphite (Gr) or Li anodes. For this reason, the Li/electrolyte and Gr/electrolyte interfaces were investigated at 20 • C and 45 • C using half or symmetrical cells. When SA is added at 1% by weight to the electrolyte (alkylcarbonate mixture + LiPF 6 ), an increase in the Li/Li cell impedance at 20 • C occurs owing to the formation of a resistive solid electrolyte interphase (SEI), composed of an inorganic inner layer and an organic outer layer, whereas at 45 • C or in absence of SA, the interphase is more inorganic in nature. The reversible capacity of graphite, cycled in Gr/Li half-cells in the presence of SA, is very low at 20 • C but almost ten times larger at 45 • C. Cycling symmetrical Gr/Gr cells at 45 • C indicates that Gr capacity is lower in the presence of SA in connection with the presence of an organic and polymer rich SEI. GC-MS analysis of the electrolyte after cycling shows that ethylene glycol bis-(alkylcarbonate) derivatives disappear when SA is present, owing to the ability of SA to react with lithium alkoxides to yield oligopolyester. Lithium ion batteries (LIBs) are a reliable way to store electric energy, with high gravimetric and volumetric energy density, which allows their application in nomad systems including electric and/or hybrid vehicles. However, electric vehicles range is unsuitable for most of the consumers and, therefore, energy density should be improved. In the past twenty years, many researches have been performed on electrode materials and electrolytes with the aim to enhance battery performance. Use of 5V class positive electrodes (cathodes) is a convenient way to increase LIBs energy density. It explains the development of promising "high voltage" materials like Li 3 V 2 (PO 4 ) 3 , 1 Li 2 CoPO 4 F 2 or the LiNi 0.5 Mn 1.5 O 4 (LNMO) 3 spinel. Nevertheless, the use of new cathodes operating at high voltage leads to the degradation of the battery electrolyte, usually based on a mixture of cyclic and linear alkylcarbonates containing LiPF 6 as salt and functional additives. Unfortunately, standard electrolytes are oxidized on 5 V cathodes and this significantly limits the battery cycling life. From the first cycles, electrolyte components degrade forming by-products, which in turn, can interact with electrodes surface. As an example, a passive layer is formed on graphite (Gr)/electrolyte interface at the first charge. This layer, known as the Solid Electrolyte Interphase (SEI), has a strong impact on the LIBs performances. Electrolyte formulation influences the chemical nature and structure of the SEI. With the aim to improve SEI quality and stability, SEI-forming additives like vinylene carbonate (VC) are generally added to the electrolyte in low amount (less than 5% by weight). These additives are designed to generate a protective passive layer on the active material surface preventing continuous electrolyte decomposition reactions.Whereas additives can be ...

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“…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. 8,9 Poly-EC has also been identified to be a product of EC electrolyte degradation, initiated by a Lewis acid such as PF 5 9-11 .…”

Section: Introductionmentioning

confidence: 99%

“…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. 8,9 Poly-EC has also been identified to be a product of EC electrolyte degradation, initiated by a Lewis acid such as PF 5 9-11 . The proposed reduction pathways of DEDOHC and poly-EC are shown in equations (1) and (2).…”

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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Formation mechanism of alkyl dicarbonates in Li-ion cells

Cited by 106 publications

References 18 publications

Understanding the Role of Prop-1-ene-1,3-Sultone and Vinylene Carbonate in LiNi_1/3Mn_1/3Co_1/3O₂/Graphite Pouch Cells: Electrochemical, GC-MS and XPS Analysis

Understanding the Role of Prop-1-ene-1,3-Sultone and Vinylene Carbonate in LiNi_1/3Mn_1/3Co_1/3O₂/Graphite Pouch Cells: Electrochemical, GC-MS and XPS Analysis

Reactivity of Succinic Anhydride at Lithium and Graphite Electrodes

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

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Formation mechanism of alkyl dicarbonates in Li-ion cells

Cited by 106 publications

References 18 publications

Understanding the Role of Prop-1-ene-1,3-Sultone and Vinylene Carbonate in LiNi1/3Mn1/3Co1/3O2/Graphite Pouch Cells: Electrochemical, GC-MS and XPS Analysis

Understanding the Role of Prop-1-ene-1,3-Sultone and Vinylene Carbonate in LiNi1/3Mn1/3Co1/3O2/Graphite Pouch Cells: Electrochemical, GC-MS and XPS Analysis

Reactivity of Succinic Anhydride at Lithium and Graphite Electrodes

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

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Understanding the Role of Prop-1-ene-1,3-Sultone and Vinylene Carbonate in LiNi_1/3Mn_1/3Co_1/3O₂/Graphite Pouch Cells: Electrochemical, GC-MS and XPS Analysis

Understanding the Role of Prop-1-ene-1,3-Sultone and Vinylene Carbonate in LiNi_1/3Mn_1/3Co_1/3O₂/Graphite Pouch Cells: Electrochemical, GC-MS and XPS Analysis