Ion and solvent diffusion and ion conduction of PC-DEC and PC-DME binary solvent electrolytes of LiN(SO2CF3)2

被引:61
作者
Hayamizu, K [1 ]
Aihara, Y
机构
[1] Natl Inst Adv Ind Sci & Technol, AIST Ctr 5, Tsukuba, Ibaraki 3058565, Japan
[2] Yuasa Corp, Odawara, Kanagawa 2500001, Japan
关键词
binary solvent system; self-diffusion coefficient; PGSE NMR; ionic conductivity; lithium battery;
D O I
10.1016/j.electacta.2004.03.007
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
Two binary mixed solvent systems typically used for lithium batteries were studied by measuring the self-diffusion coefficients of the solvent, lithium ion and anion, independently by using the multi-nuclear pulsed field-gradient spin-echo (PGSE) H-1, Li-7 and F-19 NMR method. One system was propylene carbonate (PC) and diethyl carbonate (DEC) system and the other binary system was PC and 1,2-dimethoxyethane (DME), and the lithium salt used was LiN(SO2CF3)2 (LiTFSI). The relative ratio of the PC was changed from zero (pure DME and DEC) to 100% (pure PC) in the DME-PC and the DEC-PC systems, respectively. The self-diffusion coefficients of the solvents were measured with and without the lithium salt, and the two solvents had almost the same diffusion coefficient in the DEC-PC system, while DME diffused faster than PC in the DME-PC system. In the electrolytes the solvents diffused the fastest, followed by the anion with the lithium ion diffusing the slowest. The degree of ion dissociation was estimated for each electrolyte by comparing the ionic conductivities estimated from the ion diffusion and those measured directly by the electrochemical method. (C) 2004 Elsevier Ltd. All rights reserved.
引用
收藏
页码:3397 / 3402
页数:6
相关论文
共 17 条
[1]   Ion transport properties of six lithium salts dissolved in γ-butyrolactone studied by self-diffusion and ionic conductivity measurements [J].
Aihara, Y ;
Bando, T ;
Nakagawa, H ;
Yoshida, H ;
Hayamizu, K ;
Akiba, E ;
Price, WS .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2004, 151 (01) :A119-A122
[2]   Ionic conduction and self-diffusion near infinitesimal concentration in lithium salt-organic solvent electrolytes [J].
Aihara, Y ;
Sugimoto, K ;
Price, WS ;
Hayamizu, K .
JOURNAL OF CHEMICAL PHYSICS, 2000, 113 (05) :1981-1991
[4]   Conductivity and viscosity of PC-DEC and PC-EC solutions of LiPF6 [J].
Ding, MS ;
Jow, TR .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2003, 150 (05) :A620-A628
[5]   Electrolytic characteristics of ethylene carbonate-diglyme-based electrolytes for lithium batteries [J].
Geoffroy, I ;
Willmann, P ;
Mesfar, K ;
Carré, B ;
Lemordant, D .
ELECTROCHIMICA ACTA, 2000, 45 (13) :2019-2027
[6]   EMPIRICAL PARAMETERS FOR DONOR AND ACCEPTOR PROPERTIES OF SOLVENTS [J].
GUTMANN, V .
ELECTROCHIMICA ACTA, 1976, 21 (09) :661-670
[7]   A new type of sample tube for reducing convection effects in PGSE-NMR measurements of self-diffusion coefficients of liquid samples [J].
Hayamizu, K ;
Price, WS .
JOURNAL OF MAGNETIC RESONANCE, 2004, 167 (02) :328-333
[8]   Pulse-gradient spin-echo 1H, 7Li, and 19F NMR diffusion and ionic conductivity measurements of 14 organic electrolytes containing LiN(SO2CF3)2 [J].
Hayamizu, K ;
Aihara, Y ;
Arai, S ;
Martinez, CG .
JOURNAL OF PHYSICAL CHEMISTRY B, 1999, 103 (03) :519-524
[9]  
Hayamizu K., UNPUB
[10]   Solvation of lithium ions in mixed organic electrolyte solutions by electrospray ionization mass spectroscopy [J].
Matsuda, Y ;
Fukushima, T ;
Hashimoto, H ;
Arakawa, R .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2002, 149 (08) :A1045-A1048