Suppression of Co-Intercalation Reaction of Propylene Carbonate and Lithium Ion into Graphite Negative Electrode by Addition of Diglyme

Song, Hee-Youb; Fukutsuka, Tomokazu; Miyazaki, Kohei; Abe, Takeshi

doi:10.1149/2.0831607jes

Cited by 14 publications

(9 citation statements)

References 26 publications

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“…49 Recently, Song et al reported that the co-intercalation can be suppressed in a PC-based electrolytes by the addition of small amount of diglyme. 50 In this case, the diglyme-solvated Li + ion preferentially intercalated and decomposed within the graphite and form a surface film (SEI), and the SEI effectively suppresses the co-intercalation of PC-solvated Li + , i.e. the diglyme acts as SEI-forming additive in PC-based electrolytes.…”

Section: 44mentioning

confidence: 99%

A Design Approach to Lithium-Ion Battery Electrolyte Based on Diluted Solvate Ionic Liquids

Ueno

Murai

Moon

et al. 2016

J. Electrochem. Soc.

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An equimolar mixture of lithium bis(trifluoromethylsulfonyl)amide (Li [TFSA]) and triglyme (G3) or tetraglyme (G4) yields the stable molten complexes, [Li(G3)] [TFSA] or [Li(G4)][TFSA], respectively, classified into solvate ionic liquids (SILs). The Li-conducting SIL electrolytes have favorable thermal and electrochemical properties, but their intrinsic high viscosities and low ionic conductivities impede widespread application. In this study, SILs were diluted with organic solvents, such as toluene, hydrofluoroether (HFE) and propylene carbonate (PC), to enhance their ionic conductivity. Subsequently, the performance of a battery consisting of diluted SILs, LiCoO 2 , and graphite electrodes was evaluated. The electrochemical stability and charge/discharge behavior of the LiCoO 2 cathode and graphite anode were greatly influenced by the stability of the complex cations, [Li(G3)] + or [Li(G4)] + , in the diluted SILs. Unfavorable ligand exchange between the glyme and PC occurred in PC-diluted SILs. Oxidative decomposition of the uncoordinated glyme and pitting corrosion of Al current collector deteriorated the battery performance of LiCoO 2 half-cell with PC-diluted SILs. We demonstrate that toluene-and HFE-diluted SILs, which do not contain chemicals such as carbonate solvent and LiPF 6 used in commercialized Li-ion batteries, allow both LiCoO 2 cathode and graphite anode to operate stably. Because of their high specific energy density, Li-based secondary batteries have been the most attractive candidates among a variety of energy storage systems. Research aimed at the development of Li-ion battery technologies has focused mainly on positive and negative electrode material, 1,2 while Li-conducting electrolytes have played a "supporting" role. Indeed, the major components of the electrolyte in commercialized Li-ion batteries, i.e., a mixture of polar ethylene carbonate (EC) and low-viscous linear carbonates such as diethyl carbonate (DEC) with ∼1 mol dm −3 of lithium hexafluorophosphate (LiPF 6 ), 3 have been in use since these batteries were first developed for practical application in 1991.The standard electrolyte (1 mol dm −3 LiPF 6 in EC/DEC) has been selected for the mature Li-ion battery technology, for several reasons, [3][4][5][6][7] and the battery reaction relies on each electrolyte component. The polar EC not only assists the supporting Li-salt to dissociate to a higher degree, but also forms a good solid electrolyte interphase (SEI) on the graphite anode. The SEI is formed via sacrificial initial decomposition and it allows reversible intercalation/deintercalation reactions of Li ions during charge/discharge. Less viscous linear carbonates such as DEC are mixed with the more viscous EC to improve the ionic conductivity of the electrolyte without compromising the high degree of salt dissociation and formation of the SEI. Despite its poor chemical stability, LiPF 6 is used as the supporting salt because of its high degree of dissociation. Moreover, LiPF 6 plays an important role in suppressing the corr...

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Section: 44mentioning

confidence: 99%

A Design Approach to Lithium-Ion Battery Electrolyte Based on Diluted Solvate Ionic Liquids

Ueno

Murai

Moon

et al. 2016

J. Electrochem. Soc.

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“…So far, there are a variety of studies to develop the electrolyte solutions and additives and various strategies for the fabrication of the superior SEI were proposed. [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] Also, the SEI is dependent on the electrode structure. For example, the SEI achieved on the basal and edge planes of a graphite show different physical and electrochemical properties such as density, hardness, and conductivity.…”

Section: Introductionmentioning

confidence: 99%

Solvated Lithium Ion Intercalation Behavior of Graphitized Carbon Nanospheres

et al. 2020

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To prolong durability of lithium-ion batteries, stability of solid electrolyte interphase (SEI) formed at a graphite negative electrode should be improved, but the correlation of the SEI stability with the graphite structure is still unclear. This study focused on co-intercalation of dimethoxyethane (DME) into SEI-covered graphitized carbon nanosphere (GCNS) to investigate SEI degradation behavior. In situ Raman spectroscopy revealed that both ethylene carbonate (EC)-derived and propylene carbonate (PC)-derived SEIs partly passivated the DME cointercalation, but the PC-derived SEI degraded more rapidly than the EC-derived one. Additionally, the SEI at GCNS heat-treated at 2900°C had less stability than that at GCNS heat-treated at 2600°C, which is attributable to the graphite layer stacking and surface morphology.

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“…In this case, the solvation structure of the lithium ion drastically changes because of the decrease in the solvation number as compared with that in low-concentration electrolyte solutions. Since solvation structure is a critical factor influencing SEI formation on graphite negative electrodes, various strategies for controlling the solvation structure have been proposed (e.g., increasing the salt concentration and the addition of a Lewis acid or base) [8][9][10][11][12][13][14]. Among these, increasing the salt concentration is a simple method for forming an effective SEI at graphite negative electrodes.…”

Section: Introductionmentioning

confidence: 99%

Improving Electrochemical Performance at Graphite Negative Electrodes in Concentrated Electrolyte Solutions by Addition of 1,2-Dichloroethane

Song

Jung²,

Jeong

2019

Applied Sciences

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In concentrated propylene carbonate (PC)-based electrolyte solutions, reversible lithium intercalation and de-intercalation occur at graphite negative electrodes because of the low solvation number. However, concentrated electrolyte solutions have low ionic conductivity due to their high viscosity, which leads to poor electrochemical performance in lithium-ion batteries. Therefore, we investigated the effect of the addition of 1,2-dichloroethane (DCE), a co-solvent with low electron-donating ability, on the electrochemical properties of graphite in a concentrated PC-based electrolyte solution. An effective solid electrolyte interphase (SEI) was formed, and lithium intercalation into graphite occurred in the concentrated PC-based electrolyte solutions containing various amounts of DCE, while the reversible capacity improved. Raman spectroscopy results confirmed that the solvation structure of the lithium ions, which allows for effective SEI formation, was maintained despite the decrease in the total molality of LiPF6 by the addition of DCE. These results suggest that the addition of a co-solvent with low electron-donating ability is an effective strategy for improving the electrochemical performance in concentrated electrolyte solutions.

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Suppression of Co-Intercalation Reaction of Propylene Carbonate and Lithium Ion into Graphite Negative Electrode by Addition of Diglyme

Cited by 14 publications

References 26 publications

A Design Approach to Lithium-Ion Battery Electrolyte Based on Diluted Solvate Ionic Liquids

A Design Approach to Lithium-Ion Battery Electrolyte Based on Diluted Solvate Ionic Liquids

Solvated Lithium Ion Intercalation Behavior of Graphitized Carbon Nanospheres

Improving Electrochemical Performance at Graphite Negative Electrodes in Concentrated Electrolyte Solutions by Addition of 1,2-Dichloroethane

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