Raman study of crystalline solvates between glymes CH3(OCH2CH2)nOCH3(n = 1, 2 and 3) and LiClO4

Grondin, Joseph; Talaga, David; Lassègues, J.C.; Henderson, Wesley A.

doi:10.1039/b315475k

Cited by 27 publications

(51 citation statements)

References 22 publications

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“…In addition to this anion band near 740 cm −1 , another anion Raman band positioned near 1240−1255 cm −1 has also been examined in the present study (Supporting Information Figures S4−S6, S8, and S9) to aid in the assignment of the band positions for the uncoordinated TFSI − anion and the anion coordinated to 1 :LiTFSI, (f) AGG-IIb-C 1 (2,6-DMPy) 1/2 :LiTFSI, (g) AGG-IIb-C 2 (EC) 1 :LiTFSI, and (h) AGG-III-C 2 pure LiTFSI (the dark lines indicate that a phase transition has occurredi.e., melting). Note that the additional Raman bands in the spectra for a, c, d, f, and g are due to solvent vibrational bands.…”

Section: Chart 2 Structures and Acronyms Of The Solvents Studiedmentioning

confidence: 97%

“…There are differences, however, in the conformations of the anions. The (EC) 1 :LiTFSI solvate has anions with the C 2 conformation (i.e., AGG-IIb-C 2 , Chart 1), whereas the (AN) 1 :LiTFSI and (2,6-DMPy) 1/2 :LiTFSI solvates have anions with the C 1 conformation (i.e., AGG-IIb-C 1 , Chart 1). (Figure 3) is due to the expansion and contraction of the entire anion.…”

Section: Chart 2 Structures and Acronyms Of The Solvents Studiedmentioning

confidence: 99%

“…The salt was dried at 120°C under high vacuum overnight. The solvents (Chart 2) ethylene glycol dimethyl ether, 1,2-dimethoxyethane or monoglyme (G1, anhydrous, 99.5%), diethylene glycol dimethyl ether, 2-methoxyethyl ether or diglyme (G2, anhydrous, 99.5%), triethylene glycol dimethyl ether or triglyme (G3, 99%), N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA, 99%), N,N,N′,N′-tetramethylethylenediamine (TMEDA, purified by re-distillation, ≥99.5%), ethylene carbonate (EC, 99%), 1,4,7,10-tetraoxacyclododecane or 12-crown-4 (12C4, 98%), phenanthroline (PHEN, ≥99%), neocuproine or 2,9-dimethyl [1,10]phenanthroline (2,9-DMPHEN, ≥99.0%), 2,6-lutidine or 2,6-dimethylpyridine (2,6-DMPy, ≥99.0%), and acetonitrile (AN, anhydrous, 99.9%) were purchased from either Fisher Scientific or SigmaAldrich. These solvents were dried over 3 Å molecular sieves (for the liquids), and the water content of the solvents was verified prior to their use to be negligible (<30 ppm) using a Mettler Toledo DL39 Karl Fischer coulometer.…”

Section: Introductionmentioning

confidence: 99%

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Solvate Structures and Spectroscopic Characterization of LiTFSI Electrolytes

et al. 2014

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A Raman spectroscopic evaluation of numerous crystalline solvates with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI or LiN(SO2CF3)2) has been conducted over a wide temperature range. Four new crystalline solvate structures-(PHEN)3:LiTFSI, (2,9-DMPHEN)2:LiTFSI, (G3)1:LiTFSI and (2,6-DMPy)1/2:LiTFSI with phenanthroline, 2,9-dimethyl[1,10]phenanthroline, triglyme, and 2,6-dimethylpyridine, respectively-have been determined to aid in this study. The spectroscopic data have been correlated with varying modes of TFSI(-)···Li(+) cation coordination within the solvate structures to create an electrolyte characterization tool to facilitate the Raman band deconvolution assignments for the determination of ionic association interactions within electrolytes containing LiTFSI. It is found, however, that significant difficulties may be encountered when identifying the distributions of specific forms of TFSI(-) anion coordination present in liquid electrolyte mixtures due to the wide range of TFSI(-)···Li(+) cation interactions possible and the overlap of the corresponding spectroscopic data signatures.

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Section: Chart 2 Structures and Acronyms Of The Solvents Studiedmentioning

confidence: 97%

Section: Chart 2 Structures and Acronyms Of The Solvents Studiedmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Solvate Structures and Spectroscopic Characterization of LiTFSI Electrolytes

et al. 2014

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“…[24][25][26][27] Meanwhile, highly concentrated Li salt-glyme mixtures emerged as a new family of ionic liquids. At an early stage from the late 1990's to 2000's, they were studied as an amorphous analogue of Li + -conducting solid polymer electrolytes based on poly(ethylene oxide) (PEO), [28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43] whose phase behavior and solvate structures were scrutinized by Henderson et al [33][34][35][36][37][38][39][40][41][42] From 2010 onward, Watanabe and his co-workers successively reported various physicochemical features analogous to ionic liquids in specific Li salt-glyme equimolar complexes, and established a new class of ionic liquids named "solvate ionic liquids" with clear classification criteria. 60 This review summarizes research activities on highly concentrated electrolytes for Li-based batteries.…”

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confidence: 99%

Review—Superconcentrated Electrolytes for Lithium Batteries

Yamada

2015

J. Electrochem. Soc.

687

667

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Ever-increasing demand for better batteries has set extraordinarily high standards for electrolyte materials, which are far beyond the realm of a conventional nonaqueous electrolyte design. Superconcentrated (or highly concentrated) solutions are emerging as a new class of liquid electrolytes with various unusual functionalities beneficial for advanced lithium (Li) battery applications. This article reviews unique features, as well as basic physicochemical properties, of highly concentrated electrolytes from the viewpoint of their peculiar solution structure, and discusses their future contributions to advanced battery technologies. © The Author(s) An electrolyte is an indispensable component in rechargeable batteries. In general, it serves as a carrier ion-conductive and electroninsulating medium facilitating ion transport between a pair of electrodes, simultaneously withstanding the strong reducing and oxidizing forces of negative and positive electrodes, respectively. From this perspective, an ion-transport property and reductive/oxidative stability are the major two metrics in a battery electrolyte design. For lithium (Li)-ion batteries, the reductive/oxidative stability is of particular importance, because they employ extremely strong reducer and oxidizer as negative and positive electrodes, respectively, to deliver the highest voltage (currently ca. 3.8 V) among various battery chemistries. To address this severe situation, an electrochemically stable nonaqueous electrolyte, rather than a highly conductive aqueous electrolyte, has been used with some compromise on ionic transport properties.The composition of nonaqueous electrolytes makes critical impacts on the performance of Li-ion batteries.1-3 This fact is seemingly paradoxical to the "rocking chair" concept of Li-ion batteries, in which electrolyte components principally do not participate in the battery faradaic reactions. This paradox arises, at least partly, from the inherent thermodynamic instability of the electrode/electrolyte interfaces; in most cases, the interfaces are stabilized in a kinetic way (by electrode passivation) based on electrolyte decomposition products, 4 and thus the nature of the interfaces strongly depends on electrolyte composition. In other words, the design of electrolytes often corresponds to the control of the interfaces where faradaic charge-transfer reactions occur, thus making significant effects on the battery performance.A nonaqueous electrolyte design seems to have infinite variations of aprotic solvents (and additives), Li salts, and their mixing ratios (i.e., electrolyte concentrations). Indeed, however, there are many restrictions in the choice of aprotic solvents and Li salts in terms of the kinetic stability of the interfaces they form. First, only specific organic carbonates (e.g., ethylene carbonate (EC)) are compatible with graphite negative electrodes. 5,6 This peculiarity results from solvent's passivation ability. Because almost all aprotic solvents are unstable at such a low potential as ∼0 V vs. Li +...

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“…Thus, it is considered that the electrode surface is covered dominantly with BMP + and that [Li(TFSA) 2 ] can not access to the electrode surface. Since the donor numbers of glyme are larger than that of TFSA as listed in Table 1, Li + is expected to be coordinated by the glymes to give a positively charged species [6][7][8][9][10][11][12][13], which can approach to the electrode surface. Thus, Li + -glyme complexes are considered to be adsorbed on the electrode surface together with BMP + .…”

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confidence: 99%

The Influence of Additives on Lithium Dope/Undope Reactions for a Tin Film Electrode in a Room-Temperature Ionic Liquid Electrolyte

Miyashita¹,

Katayama²,

Miura³

et al. 2010

ECS Trans.

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Lithium dope-undope reactions of a tin thin film electrode were investigated in a room-temperature ionic liquid, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (BMPTFSA) containing 1 M LiTFSA with and without glyme as an additive. Lithium dope-undope was possible in 1 M LiTFSA/BMPTFSA with glymes. The resistance of the electrode-electrolyte interface with glyme was smaller than that without glyme, indicating the solvation environment of Li + affects the interfacial resistance in the ionic liquid electrolyte. IntroductionVarious organic solvent-based solutions have been widely used as rechargeable lithium battery electrolytes. However, these electrolytes may cause combustion and/or explosion in case of accidents due to their flammability and volatility. Since roomtemperature ionic liquids are regarded as nonflammable and nonvolatile, ionic liquid electrolytes are expected to improve safety of rechargeable lithium battery. Among many kinds of ionic liquids, 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)amide (BMPTFSA) containing LiTFSA has been investigated as a promising electrolyte because of acceptable cathodic stability and conductivity [1][2][3][4][5].Poly(ethylene glycol)dialkyl ethers are generally known as glyme , and have the chemical structure of CH 3 O (CH 2 CH 2 O) n CH 3 . Glymes have more than two oxygen atoms per molecule. These oxygen atoms exhibit the nucleophilic ability, resulting in high solvation with regard to lithium cations. The coordination and solvation states of lithium ions in glyme have been discussed [6][7][8][9][10][11][12][13] and the electrode reaction of lithium has been studied in the mixtures of ionic liquids and glymes [14][15][16][17]. ECS Transactions, 25 (36) 169-176 (2010) 10.1149/1.3393853 © The Electrochemical Society 169 ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 132.236.-224.35 Downloaded on 2015-06-26 to IPLithium is able to form alloy with tin at room temperature. The equilibrium phase diagram of Li-Sn system has been investigated [18] and the coulometric titration curve of Li-Sn have been measured [19,20]. The theoretical specific capacity of Li-Sn alloy (Li 4.4 Sn, 994 mAhg [21]) is higher than that of lithiated graphites (LiC 6 , 372 mAhg ). Thus, tin has been found considerable interest for use as anode materials in rechargeable lithium batteries and many reports on tin anodes have appeared in the literature [21][22][23][24][25][26][27][28][29].A tin anode reaction has been studied in a chloroaluminate ionic liquid (1-methyl-3-ethylimidazolium chloride (MEICl):AlCl 3 :LiCl =1:1.2:0.2) [30]. However, the tin anode reaction has not been studied extensively in non-chloroaluminate ionic liquids. In this study, the influence of addition of glymes on lithium dope / undope reactions for a tin film electrode was investigated in BMPTFSA containing LiTFSA. ExperimentalBMPTFSA was purchased from Kanto Kagaku. A tin film electrode was prepared by electroplating (Me...

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Raman study of crystalline solvates between glymes CH₃(OCH₂CH₂)_nOCH₃(n = 1, 2 and 3) and LiClO₄

Cited by 27 publications

References 22 publications

Solvate Structures and Spectroscopic Characterization of LiTFSI Electrolytes

Solvate Structures and Spectroscopic Characterization of LiTFSI Electrolytes

Review—Superconcentrated Electrolytes for Lithium Batteries

The Influence of Additives on Lithium Dope/Undope Reactions for a Tin Film Electrode in a Room-Temperature Ionic Liquid Electrolyte

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