Ion Correlations and Partial Ionicities in the Lamellar Phases of Block Copolymeric Ionic Liquids
Ion Correlations and Partial Ionicities in the Lamellar Phases of Block Copolymeric Ionic Liquids
复制标题
嵌段共聚物离子液体层状相中的离子相关性和部分离子度
DOI：
10.1021/acsmacrolett.2c00401
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发表时间：
2022
影响因子：
7.015
通讯作者：
Ganesan, Venkat
中科院分区：
文献类型：
--
作者：
Zhang, Zidan;Sass, Jacob;Krajniak, Jakub;Ganesan, Venkat
最近，人们对动态离子相关性对聚合物电解质材料的电导率和传输性能的影响产生了极大的兴趣。据推测，将离子运动限制在狭窄的通道内可能会减少这种离子相关性并增强最终的离子电导率。出于这些考虑，在本研究中，我们使用多尺度模拟框架来研究嵌段共聚离子液体微相分离片层相中的动态离子相关性，并与均聚物体系的相应结果进行比较。我们通过部分离子度 Δ 探讨了离子相关性的影响，部分离子度 Δ 量化了阴离子相关贡献的真实电导率与理想能斯特-爱因斯坦电导率的比率。与我们最初的假设一致，我们的结果表明，与均聚物相比，嵌段共聚物的层状相中与移动阴离子相关的部分离子性要大得多。对不同电导率贡献的分析表明，这种结果是由于与片层相中的阴离子相关的非理想动态相关性之间的复杂补偿而产生的。总之，我们的结果表明，嵌段共聚物的自组装相可以提供调节聚合物电解质系统中动态离子相关性的途径。
Recently, significant interest has arisen on the impact of dynamical ion correlations on the conductivity and transport properties of polymeric electrolyte materials. It has been hypothesized that confining ion motion to narrow channels may reduce such ion correlations and enhance the resulting ionic conductivity. Motivated by such considerations, in this study we used a multiscale simulation framework to study the dynamical ion correlations in the microphase-separated lamella phase of block copolymeric ionic liquids and compare with the corresponding results for homopolymeric systems. We probed the influence of ion correlations through the partial ionicity, Δ, which quantifies the ratio of true conductivity to the ideal, Nernst–Einstein conductivity for the anion-related contributions. Consistent with our original hypothesis, our results demonstrate that the partial ionicity relating to the mobile anions is much larger in the lamella phases of block copolymers compared to that in homopolymers. Analysis of the distinct conductivity contributions demonstrates that such results arise as a result of an intricate compensation among the nonideal dynamical correlations relating to anions in lamella phases. Together, our results suggest that self-assembled phases of block copolymers may provide an avenue to tune the dynamical ion correlations in polymer electrolyte systems.