Imbrogno Jennifer, Maruyama Kazuya, Rivers Frederick, Baltzegar Jacob R, Zhang Zidan, Meyer Paul W, Ganesan Venkat, Aoshima Sadahito, Lynd Nathaniel A
Department of Macromolecular Science, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan.
ACS Macro Lett. 2021 Aug 17;10(8):1002-1007. doi: 10.1021/acsmacrolett.1c00305. Epub 2021 Jul 19.
We report a partial elucidation of the relationship between polymer polarity and ionic conductivity in polymer electrolyte mixtures comprising a homologous series of nine poly(vinyl ether)s (PVEs) and lithium bis(trifluoromethylsulfonyl)imide. Recent simulation studies have suggested that low dielectric polymer hosts with glass transition temperatures far below ambient conditions are expected to have ionic conductivity limited by salt solubility and dissociation. In contrast, high dielectric hosts are expected to have the potential for high ion solubility but slow segmental dynamics due to strong polymer-polymer and polymer-ion interactions. We report results for PVEs in the low polarity regime with dielectric constants of about 1.3 to 9.0. Ionic conductivity measured for the PVE and salt mixtures ranged from about 10 to 10 S/cm. In agreement with the predictions from computer simulations, the ionic conductivity increased with dielectric constant and plateaued as the dielectric approached 9.0, comparable to the dielectric constant of the widely used poly(ethylene oxide).
我们报告了在包含九个同系物系列的聚（乙烯基醚）（PVE）和双（三氟甲基磺酰）亚胺锂的聚合物电解质混合物中，聚合物极性与离子电导率之间关系的部分阐释。最近的模拟研究表明，玻璃化转变温度远低于环境条件的低介电聚合物主体，其离子电导率预计受盐溶解度和解离的限制。相比之下，高介电主体预计具有高离子溶解度的潜力，但由于强烈的聚合物 - 聚合物和聚合物 - 离子相互作用，其链段动力学较慢。我们报告了介电常数约为1.3至9.0的低极性区域中PVE的结果。PVE与盐混合物的离子电导率测量值范围约为10至10 S/cm。与计算机模拟的预测一致，离子电导率随介电常数增加，并在介电常数接近9.0时趋于平稳，这与广泛使用的聚环氧乙烷的介电常数相当。
