Physicochemical and Electrochemical Properties of Glyme-LiN(SO2F)2 Complex for Safe Lithium-ion Secondary Battery Electrolyte

Seki, Shiro; Takei, Katsuhito; Miyashiro, Hajime; Watanabe, Masayoshi

doi:10.1149/1.3582822

Cited by 66 publications

(66 citation statements)

References 33 publications

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“…A JEOL ECX-400 NMR spectrometer with a 9.4 T narrow-bore superconducting magnet and a pulsed-field gradient probe was used for the measurements. 1 H, 7 Li, and 19 F NMR spectra were recorded for the solvents, Li + , and [TFSA] − , respectively. The self-diffusion coefficients were measured via the use of a modified Hahn spin echo-based PGSE sequence incorporating a pulsed-field gradient (PFG) in each τ period.…”

Section: Methodsmentioning

confidence: 99%

Chelate Effects in Glyme/Lithium Bis(trifluoromethanesulfonyl)amide Solvate Ionic Liquids. I. Stability of Solvate Cations and Correlation with Electrolyte Properties

et al. 2014

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To develop a basic understanding of a new class of ionic liquids (ILs), "solvate" ILs, the transport properties of binary mixtures of lithium bis(trifluoromethanesulfonyl)amide (Li[TFSA]) and oligoethers (tetraglyme (G4), triglyme (G3), diglyme (G2), and monoglyme (G1)) or tetrahydrofuran (THF) were studied. The self-diffusion coefficient ratio of the solvents and Li(+) ions (Dsol/DLi) was a good metric for evaluating the stability of the complex cations consisting of Li(+) and the solvent(s). When the molar ratio of Li(+) ions and solvent oxygen atoms ([O]/[Li(+)]) was adjusted to 4 or 5, Dsol/DLi always exceeded unity for THF and G1-based mixtures even at the high concentrations, indicating the presence of uncoordinating or highly exchangeable solvents. In contrast, long-lived complex cations were evidenced by a Dsol/DLi ∼ 1 for the longer G3 and G4. The binary mixtures studied were categorized into two different classes of liquids: concentrated solutions and solvate ILs, based on Dsol/DLi. Mixtures with G2 exhibited intermediate behavior and are likely the borderline dividing the two categories. The effect of chelation on the formation of solvate ILs also strongly correlated with electrolyte properties; the solvate ILs showed improved thermal and electrochemical stability. The ionicity (Λimp/ΛNMR) of [Li(glyme or THF)x][TFSA] exhibited a maximum at an [O]/[Li(+)] ratio of 4 or 5.

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Section: Methodsmentioning

confidence: 99%

Chelate Effects in Glyme/Lithium Bis(trifluoromethanesulfonyl)amide Solvate Ionic Liquids. I. Stability of Solvate Cations and Correlation with Electrolyte Properties

et al. 2014

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“…The local relaxation and segmental motion of PEO host are needed for efficient lithium ion transport in the polymer electrolyte, and ionic mobility occurs predominantly in the amorphous phase of PEO. 79,85,90,94,99,122 The perfluoroalkyl sulfonic-type conducting salts like lithium trifluoromethanesulfonate (LiTf), 38,79,99,102,103,109,110,116,[123][124][125][126][127][128][129] lithium bis(trifluoromethanesulfonimidate) (LiTFSI), 103,110,123,[130][131][132][133][134][135] lithium bis(trifluoromethanesulfonimide) (LiBETI), 103,[136][137][138][139][140][141][142] and lithium bis(fluorosulfonyl)amide (LiFSI) 143,144 have high solubility, high ionic conductivity, and high electrochemical stability. These lithium salts with large anions have attracted much attention.…”

Section: Salt-in-polymermentioning

confidence: 99%

Poly(ethylene oxide)-based electrolytes for lithium-ion batteries

2015

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This article reviews the PEO-based electrolytes for lithium-ion batteries.Poly(ethylene oxide) (PEO) based materials are widely considered as promising candidates of polymer hosts in solid-state electrolytes for high energy density secondary lithium batteries. They have several specific advantages such as high safety, easy fabrication, low cost, high energy density, good electrochemical stability, and excellent compatibility with lithium salt. However, the typical linear PEO does not reach the production requirement because its insufficient ionic conductivity due to the high crystallinity of the ethylene oxide (EO) chains, which can restrain the ionic transition due to the stiff structure especially at low temperature. The scientists have explored different approaches to reduce the crystallinity hence to improve the ionic conductivity of PEO-based electrolytes, including: blending, modifying and making PEO derivatives etc. This review is focused on surveying the recent developments and issues about PEO-based electrolytes for lithium-ion batteries.

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“…They also observed a stable charge–discharge cycling behavior of [LiCoO 2 |[Li(G4)][CTFSI]|Li metal] cell during 50 cycles, implying the applicability of the [Li(G4)][CTFSI] complex in a 4 V class lithium secondary battery. The Watanabe group 177 investigated the physicochemical and electrochemical properties of 1:1 complexing mixture of triglyme and Li[N(SO 2 F) 2 ] (lithium bis(fluorosulfonyl)amide) as the safe lithium-ion secondary battery electrolyte. This new electrolyte has a relatively high thermal stability, and enabled a stable charge/discharge of Li + ions with both LiFePO 4 positive electrode and graphite negative electrode leading to high coulombic efficiency and long cycles.…”

Section: Electrochemical Applicationsmentioning

confidence: 99%

Glymes as versatile solvents for chemical reactions and processes: from the laboratory to industry

2014

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Glymes, also known as glycol diethers, are saturated non-cyclic polyethers containing no other functional groups. Most glymes are usually less volatile and less toxic than common laboratory organic solvents; in this context, they are more environmentally benign solvents. However, it is also important to point out that some glymes could cause long-term reproductive and developmental damages despite their low acute toxicities. Glymes have both hydrophilic and hydrophobic characters that common organic solvents are lack of. In addition, they are usually thermally and chemically stable, and can even form complexes with ions. Therefore, glymes are found in a broad range of laboratory applications including organic synthesis, electrochemistry, biocatalysis, materials, and Chemical Vapor Deposition (CVD), etc. In addition, glyme are used in numerous industrial applications, such as cleaning products, inks, adhesives and coatings, batteries and electronics, absorption refrigeration and heat pumps, as well as pharmaceutical formulations, etc. However, there is a lack of comprehensive and critical review on this attractive subject. This review aims to accomplish this task by providing an in-depth understanding of glymes’ physicochemical properties, toxicity and major applications.

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Physicochemical and Electrochemical Properties of Glyme-LiN(SO2F)2 Complex for Safe Lithium-ion Secondary Battery Electrolyte

Cited by 66 publications

References 33 publications

Chelate Effects in Glyme/Lithium Bis(trifluoromethanesulfonyl)amide Solvate Ionic Liquids. I. Stability of Solvate Cations and Correlation with Electrolyte Properties

Chelate Effects in Glyme/Lithium Bis(trifluoromethanesulfonyl)amide Solvate Ionic Liquids. I. Stability of Solvate Cations and Correlation with Electrolyte Properties

Poly(ethylene oxide)-based electrolytes for lithium-ion batteries

Glymes as versatile solvents for chemical reactions and processes: from the laboratory to industry

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