Ionic transport in polymer electrolytes: The essential role of associated ionic species

被引:31
作者
Frech, R [1 ]
York, S
Allcock, H
Kellam, C
机构
[1] Univ Oklahoma, Dept Chem & Biochem, Norman, OK 73019 USA
[2] Penn State Univ, Dept Chem, University Pk, PA 16802 USA
关键词
D O I
10.1021/ma040067x
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Polymer electrolytes based on poly(bis(methoxyethoxyethoxy)phosphazene) (MEEP) exhibit some of the highest room temperature ionic conductivities reported in a single-phase system. The mechanism of ionic transport in polymer electrolytes, particularly the nature of the charge-carrying species, has been poorly understood at the molecular level. Vibrational spectroscopy is used to determine the nature and relative amounts of ionic species present in MEEP-LiCF3SO3 as a function of salt concentration. The composition corresponding to the conductivity maximum is completely dominated by neutral cation-anion contact ion pairs and the triple anion species, {Li(CF3SO3)(2)}(-). Furthermore, the conductivity changes only slightly at higher salt concentrations where triple cations dominate. These data require a dissociation-reassociation mechanism of ion transport in which dynamic equilibrium is established between the various ionically associated species by exchange of individual Li+ and CF3SO3- ions. The individual ions migrate between associated ionic species through the liquidlike domains defined by the entangled ethylene oxide side chains.
引用
收藏
页码:8699 / 8702
页数:4
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