Glyme-Lithium Salt Equimolar Molten Mixtures: Concentrated Solutions or Solvate Ionic Liquids?

被引:361
作者
Ueno, Kazuhide [1 ]
Yoshida, Kazuki [1 ]
Tsuchiya, Mizuho [1 ]
Tachikawa, Naoki [1 ]
Dokko, Kaoru [1 ]
Watanabe, Masayoshi [1 ]
机构
[1] Yokohama Natl Univ, Dept Chem & Biotechnol, Hodogaya Ku, Yokohama, Kanagawa 2408501, Japan
基金
日本科学技术振兴机构;
关键词
PHYSICOCHEMICAL PROPERTIES; POLYMER ELECTROLYTES; TRANSPORT-PROPERTIES; LOW-VISCOSITY; COMPLEXES; CONDUCTIVITY; DIFFUSION; BIS(TRIFLUOROMETHANESULFONYL)IMIDE; BIS(TRIFLUOROMETHYLSULFONE)IMIDE; CONFORMATION;
D O I
10.1021/jp307378j
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
To demonstrate a new family of ionic liquids (ILs), i.e., "solvate" ionic liquids, the properties (thermal, transport, and electrochemical properties, Lewis basicity, and ionicity) of equimolar molten mixtures of glymes (triglyme (G3) and tetraglyme (G4)) and nine different lithium salts (LiX) were investigated. By exploring the anion-dependent properties and comparing them with the reported data on common aprotic ILs, two different classes of liquid regimes, i.e., ordinary concentrated solutions and "solvate" ILs, were found in the glyme-Li salt equimolar mixtures ([Li(glyme)]X) depending on the anionic structures. The class a given [Li(glyme)]X belonged to was governed by competitive interactions between the glymes and Li cations and between the counteranions (X) and Li cations. [Li(glyme)]X with weakly Lewis basic anions can form long-lived [Li(glyme)](+) complex cations. Thus, they behaved as typical ionic liquids. The lithium "solvate" ILs based on [Li(glyme)]X have many desirable properties for lithium-conducting electrolytes, including high ionicity, a high lithium transference number, high Li cation concentration, and high oxidative stability, in addition to the common properties of ionic liquids. The concept of "solvate" ionic liquids can be utilized in an unlimited number of combinations of other metal salts and ligands, and will thus open a new field of research on ionic liquids.
引用
收藏
页码:11323 / 11331
页数:9
相关论文
共 60 条
  • [1] Ionic Liquids: Past, present and future
    Angell, C. Austen
    Ansari, Younes
    Zhao, Zuofeng
    [J]. FARADAY DISCUSSIONS, 2012, 154 : 9 - 27
  • [2] Armand M, 2009, NAT MATER, V8, P621, DOI [10.1038/NMAT2448, 10.1038/nmat2448]
  • [3] Stable solvates in solution of lithium bis(trifluoromethylsulfone)imide in glymes and other aprotic solvents: Phase diagrams, crystallography and Raman spectroscopy
    Brouillette, D
    Irish, DE
    Taylor, NJ
    Perron, G
    Odziemkowski, M
    Desnoyers, JE
    [J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2002, 4 (24) : 6063 - 6071
  • [4] Apparent molar volume, heat capacity, and conductance of lithium bis(trifluoromethylsulfone)imide in glymes and other aprotic solvents
    Brouillette, D
    Perron, G
    Desnoyers, JE
    [J]. JOURNAL OF SOLUTION CHEMISTRY, 1998, 27 (02) : 151 - 182
  • [5] High Capacity, Safety, and Enhanced Cyclability of Lithium Metal Battery Using a V2O5 Nanomaterial Cathode and Room Temperature Ionic Liquid Electrolyte
    Chou, Shu-Lei
    Wang, Jia-Zhao
    Sun, Jia-Zeng
    Wexler, David
    Forsyth, Maria
    Liu, Hua-Kun
    MacFarlane, Douglas R.
    Dou, Shi-Xue
    [J]. CHEMISTRY OF MATERIALS, 2008, 20 (22) : 7044 - 7051
  • [6] CONFORMATIONAL-CHANGES IN DIETHYLENE GLYCOL DIMETHYL ETHER AND POLY(ETHYLENE OXIDE) INDUCED BY LITHIUM ION COMPLEXATION
    FRECH, R
    HUANG, WW
    [J]. MACROMOLECULES, 1995, 28 (04) : 1246 - 1251
  • [7] Anion conformation of low-viscosity room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(fluorosulfonyl) imide
    Fujii, Kenta
    Seki, Shiro
    Fukuda, Shuhei
    Kanzaki, Ryo
    Takamuku, Toshiyuki
    Ulmebayashi, Yasuhiro
    Ishiguro, Shin-ichi
    [J]. JOURNAL OF PHYSICAL CHEMISTRY B, 2007, 111 (44) : 12829 - 12833
  • [8] Ionic liquids as electrolytes
    Galinski, Maciej
    Lewandowski, Andrzej
    Stepniak, Izabela
    [J]. ELECTROCHIMICA ACTA, 2006, 51 (26) : 5567 - 5580
  • [9] Room temperature molten salts as lithium battery electrolyte
    Garcia, B
    Lavallée, S
    Perron, G
    Michot, C
    Armand, M
    [J]. ELECTROCHIMICA ACTA, 2004, 49 (26) : 4583 - 4588
  • [10] Raman study of tetraglyme-LiClO4 solvate structures
    Grondin, J
    Lassègues, JC
    Chami, M
    Servant, L
    Talaga, D
    Henderson, WA
    [J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2004, 6 (17) : 4260 - 4267