Activation energy - Activation volume master plots for ion transport behavior in polymer electrolytes and supercooled molten salts

被引:26
作者
Ingram, MD [1 ]
Imrie, CT
Stoeva, Z
Pas, SJ
Funke, K
Chandler, HW
机构
[1] Univ Aberdeen, Sch Engn & Phys Sci, Aberdeen AB24 3UE, Scotland
[2] Univ Munster, Sonderforsch Bereich 458, D-48149 Munster, Germany
[3] Univ Munster, Sch Chem, D-48149 Munster, Germany
[4] Univ Munster, Inst Phys Chem, D-48149 Munster, Germany
关键词
D O I
10.1021/jp053400n
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
We demonstrate the use of activation energy versus activation volume "master plots" to explore ion transport in typical fragile glass forming systems exhibiting non-Arrhenius behavior. These systems include solvent free salt complexes in poly(ethylene oxide) (PEO) and low molecular weight poly(propylene oxide) (PPO) and molten 2Ca(NO3)(2)center dot 3KNO(3) (CKN). Plots showing variations in apparent activation energy EA versus apparent activation volume V-A are straight lines with slopes given by M = Delta E-A/Delta V-A. A simple ion transport mechanism is described where the rate determining step involves a dilatation (expressed as VA) around microscopic cavities and a corresponding work of expansion (E-A). The slopes of the master plots M are equated to internal elastic moduli, which vary from 1.1 GPa for liquid PPO to 5.0 GPa for molten CKN on account of differing intermolecular forces in these materials.
引用
收藏
页码:16567 / 16570
页数:4
相关论文
共 34 条