Conductivity and viscosity of PC-DEC and PC-EC solutions of LiBF4

被引:51
作者
Ding, MS [1 ]
机构
[1] USA, Res Lab, Adelphi, MD 20783 USA
关键词
D O I
10.1149/1.1630593
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
The conductivity kappa of propylene carbonate-diethyl carbonate (PC-DEC) and PC-EC (ethylene carbonate) solutions of LiBF4 was experimentally determined at temperatures theta from 60 to -80degreesC and at salt molalities m from 0.2 to 2.1 mol kg(-1) and solvent compositions w from 0 to 0.7 weight fraction of DEC for the former solution and from 0.3 to 2.7 of m and 0 to 0.6 of w of EC for the latter. Viscosity eta of these solutions was also studied by measuring their glass transition temperatures T-g in the same ranges of m and w. The T-g was found to rise with m, and fall with w of DEC but rise with w of EC, indicating a concurrent change in the eta of the solutions. The kappa of the PC-DEC solution of LiBF4 peaked in both m and w thus forming a dome in its 3D presentation in the mw coordinates, while the kappa of the PC-EC solution peaked only in m, resulting in an archshaped surface. As theta lowered, these kappa surfaces fell in height and shifted in the direction of low eta. These observations correlated well with the changes of dielectric constant epsilon and viscosity eta of the solutions with the same set of variables. A more detailed study of the effects of DEC and EC on the kappa of PC solution of LiFB4 demonstrated that ion association in these solutions was very weakly dependent on theta, in agreement with an earlier finding. The kappa-T data of the PC-DEC solution was fitted with a Vogel-Fulcher-Tammann equation for an evaluation of its vanishing mobility temperature T-0 and apparent activation energy, E-a, both were shown to form simple surfaces in the mw coordinates slanting up in the direction of high eta. Furthermore, when compared to the T-g surface of the same solution, the T-0 surface was oriented similarly but lower in value by a few dozen degrees. (C) 2003 The Electrochemical Society.
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页码:A40 / A47
页数:8
相关论文
共 32 条
[1]   TEST OF THE ENTROPY BASIS OF THE VOGEL-TAMMANN-FULCHER EQUATION - DIELECTRIC-RELAXATION OF POLYALCOHOLS NEAR TG [J].
ANGELL, CA ;
SMITH, DL .
JOURNAL OF PHYSICAL CHEMISTRY, 1982, 86 (19) :3845-3852
[2]  
[Anonymous], 2002, HDB BATTERIES
[3]   Density, relative permittivity, and viscosity of propylene carbonate plus dimethoxyethane mixtures from 25 °C to 125 °C [J].
Barthel, J ;
Neueder, R ;
Roch, H .
JOURNAL OF CHEMICAL AND ENGINEERING DATA, 2000, 45 (06) :1007-1011
[4]   TEMPERATURE-DEPENDENCE OF THE PROPERTIES OF ELECTROLYTE-SOLUTIONS .3. CONDUCTANCE OF VARIOUS SALTS AT HIGH-CONCENTRATIONS IN PROPYLENE CARBONATE AT TEMPERATURES FROM -45-DEGREES-C TO +25-DEGREES-C [J].
BARTHEL, J ;
GORES, HJ ;
SCHMEER, G .
BERICHTE DER BUNSEN-GESELLSCHAFT-PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 1979, 83 (09) :911-920
[5]   A new class of electrochemically and thermally stable lithium salts for lithium battery electrolytes .2. Conductivity of lithium organoborates in dimethoxyethane and propylene carbonate [J].
Barthel, J ;
Buestrich, R ;
Carl, E ;
Gores, HJ .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1996, 143 (11) :3565-3571
[6]   Density, viscosity, and specific conductivity of trifluoromethanesulfonic acid monohydrate from 309.15 K to 408.15 K [J].
Barthel, J ;
Meier, R ;
Conway, BE .
JOURNAL OF CHEMICAL AND ENGINEERING DATA, 1999, 44 (01) :155-156
[7]  
Barthel J., 2000, CHEM DATA SERIES, VXII
[8]  
Barthel J., 1996, CHEM DATA SERIES, V12
[9]  
BLOMGREN GE, 1983, LITHIUM BATTERIES
[10]   SPECIFIC CONDUCTANCE OF CONCENTRATED SOLUTIONS OF MAGNESIUM SALTS IN WATER-ETHANOL SYSTEM [J].
CASTEEL, JF ;
AMIS, ES .
JOURNAL OF CHEMICAL AND ENGINEERING DATA, 1972, 17 (01) :55-&