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Restructuring of the electrical double layer in ionic liquids upon charging

机译:充电后离子液体中的双电层的重组

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摘要

We have investigated the electrical double layer (EDL) structure at an interface between ionic liquid (IL) and charged surface using molecular dynamics simulations. We show that for three different models of ILs the EDL restructuring, driven by surface charging, can be rationalized by the use of two parameters - renormalized surface charge (κ) and charge excess in the interfacial layers (λ). Analysis of the relationship between the λ and κ parameters provides new insights into mechanisms of over-screening and charge-driven structural transitions in the EDL in ionic liquids. We show that the restructuring of the EDL upon charging in all three studied systems has two characteristic regimes: (1) transition from the bulk-like (κIon=0) to the multilayer structure (κIon≈0.5) through the formation of an ionic bilayer of counter- and co-ions; and (2) transition from the multilayer (κIon≈0.5) to the crowded (κIon>1) structure through the formation of a monolayer of counter-ions at κIon=1.
机译:我们已经使用分子动力学模拟研究了离子液体(IL)和带电表面之间的界面处的双电层(EDL)结构。我们显示,对于三种不同的离子液体模型,可以通过使用两个参数-重新归一化的表面电荷(κ)和界面层中的电荷过量(λ)使由表面电荷驱动的EDL重组合理化。 λ和κ参数之间关系的分析为离子液体中EDL中的过筛和电荷驱动的结构转变机理提供了新见解。我们显示,在所有三个研究的系统中,带电时的EDL重组具有两个特征性机制:(1)通过形成离子双层,从块状(κIon= 0)过渡到多层结构(κIon≈0.5)抗衡离子和共离子; (2)通过在κIon= 1处形成单层抗衡离子,从多层(κIon≈0.5)过渡到拥挤(κIon> 1)结构。

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