Susan Md Abu Bin Hasan, Kaneko Taketo, Noda Akihiro, Watanabe Masayoshi
Department of Chemistry and Biotechnology, Yokohama National University, and Core Research for Evolutional Science and Technology (CREST), Japan Science and Technology Agency, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan.
J Am Chem Soc. 2005 Apr 6;127(13):4976-83. doi: 10.1021/ja045155b.
To realize polymer electrolytes with high ionic conductivity, we exploited the high ionic conductivity of an ionic liquid. In situ free radical polymerization of compatible vinyl monomers in a room temperature ionic liquid, 1-ethyl-3-methyl imidazolium bis(trifluoromethane sulfonyl)imide (EMITFSI), afforded a novel series of polymer electrolytes. Polymer gels obtained by the polymerization of methyl methacrylate (MMA) in EMITFSI in the presence of a small amount of a cross-linker gave self-standing, flexible, and transparent films. The glass transition temperatures of the gels, which we named "ion gels", decreased with increasing mole fraction of EMITFSI and behaved as a completely compatible binary system of poly(methyl methacrylate) (PMMA) and EMITFSI. The temperature dependence of the ionic conductivity of the ion gels followed the Vogel-Tamman-Fulcher (VTF) equation, and the ionic conductivity at ambient temperature reached a value close to 10(-2) S cm(-1). Similarly to the behavior of the ionic liquid, the cation in the ion gels diffused faster than the anion. The number of carrier ions, calculated from the Nernst-Einstein equation, was found to increase for an ion gel from the corresponding value for the ionic liquid itself. The cation transference number increased with decreasing EMITFSI concentration due to interaction between the PMMA matrix and the TFSI(-) anion, which prohibited the formation of ion clusters or associates, as was the case for the ionic liquid itself.
为了实现具有高离子电导率的聚合物电解质,我们利用了离子液体的高离子电导率。在室温离子液体1-乙基-3-甲基咪唑双(三氟甲烷磺酰)亚胺(EMITFSI)中,使相容的乙烯基单体进行原位自由基聚合,得到了一系列新型聚合物电解质。在少量交联剂存在下,通过甲基丙烯酸甲酯(MMA)在EMITFSI中聚合得到的聚合物凝胶形成了自立、柔韧且透明的薄膜。我们将这些凝胶称为“离子凝胶”,其玻璃化转变温度随着EMITFSI摩尔分数的增加而降低,表现为聚甲基丙烯酸甲酯(PMMA)和EMITFSI的完全相容二元体系。离子凝胶的离子电导率与温度的关系遵循Vogel-Tamman-Fulcher(VTF)方程,在环境温度下离子电导率达到接近10^(-2) S cm^(-1)的值。与离子液体的行为类似,离子凝胶中的阳离子扩散速度比阴离子快。根据能斯特-爱因斯坦方程计算得出,离子凝胶中的载流子离子数相对于离子液体本身的相应值有所增加。由于PMMA基质与TFSI(-)阴离子之间的相互作用,阳离子迁移数随着EMITFSI浓度的降低而增加,这与离子液体本身的情况一样,阻止了离子簇或缔合物的形成。