Nesterova Irina, Evstigneev Nikolay M, Ryabkov Oleg I, Gerke Kirill M, Khlyupin Aleksey
Moscow Institute of Physics and Technology, Institutskiy Pereulok 9, Dolgoprudny, 141700, Moscow, Russia.
Federal Research Center "Computer Science and Control", Institute for System Analysis, Russian Academy of Science, Vavilova str., 40, Moscow, 119333, Russia.
J Colloid Interface Sci. 2025 Jan;677(Pt B):396-405. doi: 10.1016/j.jcis.2024.08.040. Epub 2024 Aug 12.
The interfacial nature of the electric double layer (EDL) assumes that electrode surface morphology significantly impacts the EDL properties. Since molecular-scale roughness modifies the structure of EDL, it is expected to disturb the overscreening effect and alter differential capacitance (DC). In this paper, we present a model that describes EDL near atomically rough electrodes with account for short-range electrostatic correlations. We provide numerical and analytical solutions for the analysis of conditions for the overscreening breakdown and DC shift estimation. Our findings reveal that electrode surface structure leads to DC decrease and can both break or enhance overscreening depending on the relation of surface roughness to electrostatic correlation length and ion size asymmetry.
双电层（EDL）的界面性质表明，电极表面形态会显著影响EDL的性质。由于分子尺度的粗糙度会改变EDL的结构，因此预计它会干扰过屏蔽效应并改变微分电容（DC）。在本文中，我们提出了一个模型，该模型描述了考虑短程静电相关性的原子级粗糙电极附近的EDL。我们提供了数值和解析解，用于分析过屏蔽击穿的条件和DC偏移估计。我们的研究结果表明，电极表面结构会导致DC降低，并且根据表面粗糙度与静电相关长度以及离子尺寸不对称性的关系，既可以破坏也可以增强过屏蔽。
