Mean-Field Theory of Electrical Double Layer In Ionic Liquids with Account of Short-Range Correlations

被引：127

作者：

Goodwin, Zachary A. H. ^{[1
]}

Feng, Guang ^{[2
]}

Kornyshev, Alexei A. ^{[1
]}

机构：

[1] Imperial Coll London, Dept Chem, Imperial Coll Rd, London SW7 2AZ, England

[2] Huazhong Univ Sci & Technol, State Key Lab Coal Combust, Sch Energy & Power Engn, Wuhan 430074, Peoples R China

来源：

ELECTROCHIMICA ACTA | 2017年 / 225卷

基金：

英国工程与自然科学研究理事会;

关键词：

Ionic liquids; Double layer; short-range correlations; ion pairing; DIFFERENTIAL CAPACITANCE; GRAPHITE-ELECTRODES; HYDRATION FORCES; MOLTEN-SALT; ELECTROCHEMICAL INTERFACES; SOLVATION FORCES; MODEL; SURFACE; ELECTROLYTES; CARBON;

D O I：

10.1016/j.electacta.2016.12.092

中图分类号：

O646 [电化学、电解、磁化学];

学科分类号：

081704 ;

摘要：

We develop the theory of the electrical double layer in ionic liquids as proposed earlier by Kornyshev (2007). In the free energy function we keep the so called short-range correlation terms which were omitted there. With some simplifying assumptions, we arrive at a modified expression for differential capacitance, which makes differential capacitance curves less sharply depending on electrode potential and having smaller values at extrema than in the previous theory. This brings the results closer to typical experimental observations, and makes it appealing to use this formalism for treatment of experimental data. Implications on Debye length and the extent of ion paring in ionic liquids are then briefly discussed. (C) 2016 Elsevier Ltd. All right reserved.

引用

页码：190 / 197

页数：8

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