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^–10 to 10^–3 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).

中文翻译：

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聚（乙烯醚）锂电解质中离子电导率、玻璃化转变温度和介电常数的关系

我们报告部分阐明了聚合物电解质混合物中聚合物极性和离子电导率之间的关系，该混合物包含九种聚（乙烯基醚）（PVE）和双（三氟甲基磺酰）亚胺锂的同源系列。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的离子电导率预计会受到盐溶解度和解离的限制。相比之下，由于聚合物-聚合物和聚合物-离子的强相互作用，高介电主体有望具有高离子溶解度但节段动力学缓慢的潜力。我们报告了介电常数约为 1.3 至 9.0 的低极性 PVE 的结果。测得的 PVE 和盐混合物的离子电导率范围约为 10 ^–10至 10 ^–3 S/cm。与计算机模拟的预测一致，离子电导率随着介电常数的增加而增加，并随着介电常数接近 9.0 而趋于稳定，与广泛使用的聚（环氧乙烷）的介电常数相当。