论文标题

离子液体电气双层中的凝胶化,聚类和拥挤

Gelation, Clustering and Crowding in the Electrical Double Layer of Ionic Liquids

论文作者

Goodwin, Zachary A. H., McEldrew, Michael, de Souza, J. Pedro, Bazant, Martin Z., Kornyshev, Alexei A.

论文摘要

了解超浓缩电解质(例如离子液体(ILS))的散装和界面特性最近引起了对它们在超级电容器和电池中有希望的应用的极大关注。最近,McEldrew \ textit {et al。}开发了一种用于散装ILS的可逆离子关联的理论,该理论解释了所有可能的Cayley树簇的形成和一个渗透离子网络(GEL)。在这里,我们采用并开发这种方法来了解电气界面上电气双层中IL的关联。随着电极电荷的越来越多,该理论预测了从凝胶状或聚集状态支配的政权转变为以自由,拥挤的离子为主的制度。从凝胶化到拥挤的这种过渡在概念上类似于过度拼凑到拥挤的过渡。

Understanding the bulk and interfacial properties of super-concentrated electrolytes, such as ionic liquids (ILs), has attracted significant attention lately for their promising applications in supercapacitors and batteries. Recently, McEldrew \textit{et al.} developed a theory for reversible ion associations in bulk ILs, which accounted for the formation of all possible Cayley tree clusters and a percolating ionic network (gel). Here we adopt and develop this approach to understand the associations of ILs in the electrical double layer at electrified interfaces. With increasing charge of the electrode, the theory predicts a transition from a regime dominated by a gelled or clustered state to a regime dominated by free, crowded ions. This transition from gelation to crowding is conceptually similar to the overscreening to crowding transition.

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