Electron and ion transport in semi-dilute conjugated polyelectrolytes: view from a coarse-grained tight binding model
Electron and ion transport in semi-dilute conjugated polyelectrolytes: view from a coarse-grained tight binding model
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半稀释共轭聚电解质中的电子和离子传输：从粗粒度紧密结合模型来看
DOI：
10.1039/d2me00285j
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发表时间：
2023
影响因子：
3.6
通讯作者：
Jackson, Nicholas E.
中科院分区：
文献类型：
--
作者：
Friday, David M.;Jackson, Nicholas E.
共轭聚电解质（cpe）是一类新兴的有机混合离子电子导体，在生物界面电子学和能量收集和存储设备中有着广泛的应用。在这里，我们采用量子力学的粗粒度模型与半经典速率理论相结合，以产生半稀CPE形态及其相应的离子和电子输运性质的第一个视图。我们观察到，CPE主干的溶剂质量差，驱动了静电排斥纤维的形成，能够在半稀浓度下形成渗透网络。发现纤维的厚度和纤维内的连通性对电子输运有很大的影响。计算的结构因子表明，相对于良好的溶剂预测，纤维的形成改变了链间PE峰的位置和缩放，并导致链间间距分布更窄。我们还观察到静电相互作用在决定CPE形态中起着重要作用，但对局部位点的能量学只有很小的影响。这项工作在预测CPE形态和离子-电子输运性质方面迈出了重要的一步，并为形态如何影响共轭材料中的电子和离子输运提供了见解。
Conjugated polyelectrolytes (CPEs) are a rising class of organic mixed ionic-electronic conductors, with applications in bio-interfacing electronics and energy harvesting and storage devices. Here, we employ a quantum mechanically informed coarse-grained model coupled with semiclassical rate theory to generate a first view of semidilute CPE morphologies and their corresponding ionic and electronic transport properties. We observe that the poor solvent quality of CPE backbones drives the formation of electrostatically repulsive fibers capable of forming percolating networks at semi-dilute concentrations. The thickness of the fibers and the degree of intrafiber connectivity are found to strongly influence electronic transport. Calculated structure factors reveal that fiber formation alters the position and scaling of the inter-chain PE peak relative to good solvent predictions and induces a narrower distribution of interchain spacings. We also observe that electrostatic interactions play a significant role in determining CPE morphology, but have only a small impact on the local site energetics. This work presents a significant step forward in the ability to predict CPE morphology and ion-electron transport properties, and provides insights into how morphology influences electronic and ionic transport in conjugated materials.