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The capacitance of the double layer formed at a metal/ionic-conductor interface can be remarkably large, so that the apparent width of the double layer is as small as 0.3 \AA. Mean-field theories fail to explain such large capacitance. We…

Soft Condensed Matter · Physics 2010-03-30 Brian Skinner , M. S. Loth , B. I. Shklovskii

Mean-field theories claim that the capacitance of the double-layer formed at a metal/ionic conductor interface cannot be larger than that of the Helmholtz capacitor, whose width is equal to the radius of an ion. However, in some experiments…

Soft Condensed Matter · Physics 2015-03-17 M. S. Loth , Brian Skinner , B. I. Shklovskii

We investigate the liquid-vapor interface of the restricted primitive model for an ionic fluid using a density functional approach. The applied theory includes the electrostatic contribution to the free energy functional arising from the…

Soft Condensed Matter · Physics 2011-06-17 A. Patrykiejew , S. Sokolowski , O. Pizio

The purpose of this study is to provide data for the primitive model of the electrical double layer, where ions are modeled as charged hard spheres, the solvent as an implicit dielectric background (with dielectric constant $\epsilon=…

Soft Condensed Matter · Physics 2017-12-01 Mónika Valiskó , Tamás Kristóf , Dirk Gillespie , Dezső Boda

In this work we theoretically study the differential capacitance of an aqueous electrolyte in contact with a planar electrode, using classical Density Functional Theory, and show how this measurable quantity can be used as a probe to better…

Soft Condensed Matter · Physics 2021-09-16 Peter Cats , René van Roij

We formulate a general mean-field theory of a flat electric double layer in ionic liquids and electrolyte solutions with ions possessing static polarizability and a permanent dipole moment on a charged electrode. We establish a new…

Statistical Mechanics · Physics 2021-08-17 Yu. A. Budkov , S. V. Zavarzin , A. L. Kolesnikov

Using molecular dynamics simulations with recently developed importance sampling methods, we show that the differential capacitance of a model ionic liquid based double-layer capacitor exhibits an anomalous dependence on the applied…

We study the interaction between two neutral plane-parallel dielectric bodies in the presence of a highly asymmetric ionic fluid, containing multivalent as well as monovalent (salt) ions. Image charge interactions, due to dielectric…

Soft Condensed Matter · Physics 2015-06-11 Matej Kanduc , Ali Naji , Jan Forsman , Rudolf Podgornik

Ionic liquids are widely used as electrolytes in electrochemical devices. In this context, many experimental and theoretical approaches have been recently developed for characterizing their interface with electrodes. In this perspective…

Materials Science · Physics 2017-09-13 Céline Merlet , Benjamin Rotenberg , Paul Madden , Mathieu Salanne

When an ionic liquid adsorbs onto a porous electrode, its ionic arrangement is deeply modified due to a screening of the Coulombic interactions by the metallic surface and by the confinement imposed upon it by the electrode's morphology. In…

Progress in electrochemical applications of ionic liquids builds on an understanding of electrical double-layer. This computational study focuses on structure-determined quantities -- maximum packing density, potentials and capacitances --…

We investigate the liquid-vapor interface of the restricted primitive model (RPM) for an ionic fluid using a density-functional approximation based on correlation functions of the homogeneous fluid as obtained from the mean-spherical…

Condensed Matter · Physics 2009-10-30 B. Groh , R. Evans , S. Dietrich

We study the electric double layer by combining the effects of ion finite size and dielectric decrement. At high surface potential, both mechanisms can cause saturation of the counter-ion concentration near a charged surface. The modified…

Soft Condensed Matter · Physics 2015-03-31 Yasuya Nakayama , David Andelman

The electrical double layer (EDL) at aqueous solution-metal oxide interfaces critically affects many fundamental processes in electrochemistry, geology and biology, yet understanding its microscopic structure is challenging for both theory…

Recent advances in experimental and computational techniques have allowed for an accurate description of the adsorption of ionic liquids on metallic electrodes. It is now well established that they adopt a multi-layered structure, and that…

Materials Science · Physics 2016-03-15 Benjamin Rotenberg , Mathieu Salanne

The Bragg-Williams free energy is used to incorporate nearest-neighbor interactions into the lattice gas model of a solvent-free ionic liquid near a planar electrode. We calculate the differential capacitance from solutions of the…

Chemical Physics · Physics 2018-12-04 Rachel Downing , Bjorn K. Berntson , Guilherme V. Bossa , Sylvio May

We study ionic liquids interacting with electrified interfaces. The ionic fluid is modeled as a Coulomb lattice gas. We compare the ionic density profiles calculated using a popular modified Poisson-Boltzmann equation with the explicit…

Soft Condensed Matter · Physics 2017-12-21 Matheus Girotto , Thiago Colla , Alexandre P. dos Santos , Yan Levin

Electric double layer supercapacitors are a fast-rising class of high-power energy storage devices based on porous electrodes immersed in a concentrated electrolyte or ionic liquid. As of yet there is no microscopic theory to describe their…

Materials Science · Physics 2015-03-17 Brian Skinner , Tianran Chen , M. S. Loth , B. I. Shklovskii

Understanding the electrodes' surface morphology influence on the ions' distribution is essential for designing the supercapacitors with enhanced energy density characteristics. We develop a model for the structure of electrolytes near the…

Statistical Mechanics · Physics 2021-06-30 Timur Aslyamov , Konstantin Sinkov , Iskander Akhatov

Ions in ionic liquids and concentrated electrolytes reside in a crowded, strongly-interacting environment, leading to the formation of discrete layers of charges at interfaces. Here, we propose a continuum theory that captures the…

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