Goodwin Zachary A H, McEldrew Michael, Pedro de Souza J, Bazant Martin Z, Kornyshev Alexei A
Department of Chemistry, Imperial College of London, Molecular Sciences Research Hub, White City Campus, Wood Lane, London W12 0BZ, United Kingdom.
Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02142, USA.
J Chem Phys. 2022 Sep 7;157(9):094106. doi: 10.1063/5.0097055.
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 et al. [J. Phys. Chem. B 125, 2677 (2021)] 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 crowding regime dominated by free ions. This transition from gelation to crowding is conceptually similar to the overscreening to crowding transition.
了解超浓电解质（如离子液体（ILs））的本体和界面性质，因其在超级电容器和电池中的应用前景而备受关注。最近，McEldrew等人[《物理化学杂志B》125, 2677 (2021)] 提出了一种关于本体离子液体中可逆离子缔合的理论，该理论考虑了所有可能的（凯莱树）簇和渗流离子网络（凝胶）的形成。在这里，我们采用并发展这种方法来理解带电界面处双电层中离子液体的缔合。随着电极电荷的增加，该理论预测会从以凝胶态或簇态为主的状态转变为以自由离子为主的拥挤状态。这种从凝胶化到拥挤的转变在概念上类似于从过屏蔽到拥挤的转变。
