Reply to comments on the need to reconsider traditional free volume theory for polymer electrolytes

被引:15
作者
Bendler, JT
Fontanella, JJ [1 ]
Shlesinger, MF
Wintersgill, MC
机构
[1] USN Acad, Dept Phys, Annapolis, MD 21402 USA
[2] Off Naval Res, Div Phys Sci, Arlington, VA 22217 USA
关键词
electrical conductivity; complex impedance; lithium electrolytes; high-pressure;
D O I
10.1016/j.electacta.2004.06.033
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
New aspects of the defect diffusion model (DDM) are presented. First, it is shown that if the correlation volume exhibits two dimensional scaling, e.g. grows in two dimensions more rapidly than in a third orthogonal direction, the standard Vogel relation is obtained. Second, it is,pointed out that, independent of the dimensionality, partial derivative ln sigma/partial derivativeP should be proportional to a ln sigma/a ln T where the proportionality constant is -partial derivative ln T-c/partial derivativeP. It is shown that both of these results are consistent with the temperature and pressure variation of the electrical conductivity for 20:1 PPG:LiCF3SO3 below about 1.3 times the glass transition temperature, T-g. Finally, the DDM is compared with the free volume theory (FVT) of Dlubek et al. who have reconsidered "traditional" FVT and presented a formalism where the free volume is not proportional to the macroscopic volume. One aspect of the new FVT, which is difficult to understand is that the compressibility of the occupied volume is larger than the compressibility of the free volume. Published by Elsevier Ltd.
引用
收藏
页码:5249 / 5252
页数:4
相关论文
共 24 条
[1]   Free volume factor in supercooled liquid dynamics [J].
Bartos, J ;
Sausa, O ;
Bandzuch, P ;
Zrubcová, J ;
Kristiak, J .
JOURNAL OF NON-CRYSTALLINE SOLIDS, 2002, 307 :417-425
[2]  
Bendler J. T., 1988, Nuclear Physics B, Proceedings Supplements, V5A, P82, DOI 10.1016/0920-5632(88)90018-7
[3]   GENERALIZED VOGEL LAW FOR GLASS-FORMING LIQUIDS [J].
BENDLER, JT ;
SHLESINGER, MF .
JOURNAL OF STATISTICAL PHYSICS, 1988, 53 (1-2) :531-541
[4]   The need to reconsider traditional free volume theory for polymer electrolytes [J].
Bendler, JT ;
Fontanella, JJ ;
Shlesinger, MF ;
Wintersgill, MC .
ELECTROCHIMICA ACTA, 2003, 48 (14-16) :2267-2272
[5]   Physical basis of fragility [J].
Bendler, JT ;
Fontanella, JJ ;
Shlesinger, MF .
JOURNAL OF CHEMICAL PHYSICS, 2003, 118 (15) :6713-6716
[6]   A new Vogel-like law: Ionic conductivity, dielectric relaxation, and viscosity near the glass transition [J].
Bendler, JT ;
Fontanella, JJ ;
Shlesinger, MF .
PHYSICAL REVIEW LETTERS, 2001, 87 (19) :1-195503
[7]   Effect of high pressure on the electrical conductivity of ion conducting polymers [J].
Bendler, JT ;
Fontanella, JJ ;
Shlesinger, MF ;
Wintersgill, MC .
ELECTROCHIMICA ACTA, 2001, 46 (10-11) :1615-1621
[8]   DEFECT-DIFFUSION MODELS OF RELAXATION [J].
BENDLER, JT ;
SHLESINGER, MF .
JOURNAL OF MOLECULAR LIQUIDS, 1987, 36 :37-46
[9]  
BENDLER JT, UNPUB PHYS REV
[10]   CONTRIBUTIONS OF TORSIONAL BRAID ANALYSIS TO TLL [J].
BOYER, RF .
POLYMER ENGINEERING AND SCIENCE, 1979, 19 (10) :732-748