Anomalously large capacitance of an ionic liquid described by the restricted primitive model

TL;DR

This study uses Monte Carlo simulations to reveal that ionic liquids at metal surfaces can exhibit capacitances much larger than expected, due to ion-image interactions forming correlated dipoles that influence the electrostatic double-layer.

Contribution

It introduces a model considering discrete ion-image interactions beyond mean-field theory, explaining anomalously large capacitance and voltage-dependent behavior in ionic liquid interfaces.

Findings

Capacitance can be up to three times smaller than ion radius at low temperatures.

Formation of correlated ion-image dipoles causes a bell-shaped capacitance-voltage curve.

Finite electrode screening shifts the capacitance behavior to a camel-shaped curve.

Abstract

We use Monte Carlo simulations to examine the simplest model of an ionic liquid, called the restricted primitive model, at a metal surface. We find that at moderately low temperatures the capacitance of the metal/ionic liquid interface is so large that the effective thickness of the electrostatic double-layer is up to 3 times smaller than the ion radius. To interpret these results we suggest an approach which is based on the interaction between discrete ions and their image charges in the metal surface and which therefore goes beyond the mean-field approximation. When a voltage is applied across the interface, the strong image attraction causes counterions to condense onto the metal surface to form compact ion-image dipoles. These dipoles repel each other to form a correlated liquid. When the surface density of these dipoles is low, the insertion of an additional dipole does not require much energy. This leads to a large capacitance $C$ that decreases monotonically with voltage $V$, producing a "bell-shaped" curve $C(V)$. We also consider what happens when the electrode is made from a semi-metal rather than a perfect metal. In this case, the finite screening radius of the electrode shifts the reflection plane for image charges to the interior of the electrode and we arrive at a "camel-shaped" $C(V)$. These predictions seem to be in qualitative agreement with experiment.