Related papers: Concentration Fluctuations and Capacitive Response…
We revisit the statistical mechanics of charge fluctuations in capacitors. In constant-potential classical molecular simulations, the atomic charge of electrode atoms are treated as additional degrees of freedom which evolve in time so as…
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…
Understanding the loss of non-equilibrium capacitance in the electric double layer capacitor (EDLC) during continuous charging compared to equilibrium capacitance is crucial for the design of high-rate energy storage devices. Due to three…
The fluctuations of the charge on an electrode contain information on the microscopic correlations within the adjacent fluid and their effect on the electronic properties of the interface. We investigate these fluctuations using molecular…
Effect of an oscillatory decay of the charge density in concentrated ionic solutions and ionic liquids on the double-layer capacitance is studied in a framework of a mesoscopic theory. Only Coulomb and steric forces between the ions that…
Nanoporous carbon-based supercapacitors store electricity through adsorption of ions from the electrolyte at the surface of the electrodes. Room temperature ionic liquids, which show the largest ion concentrations among organic liquid…
A parallel plate capacitor containing an electrolytic solution is the simplest model of a supercapacitor, or electric double layer capacitor. Using both analytical and numerical techniques, we solve the Poisson-Nernst-Planck equations for…
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…
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…
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…
Correlated anion and cation motion can significantly reduce the overall ion conductivity in electrolytes versus the ideal conductivity calculated based on the diffusion constants alone. Using coarse-grained molecular dynamics simulations,…
We examine electrolyte systems confined between two parallel, grounded metal plates using a field-theoretic approach truncated at one-loop order. For symmetric electrolytes, the density distribution of the ions is non-uniform, with a…
Correlation functions in concentrated ionic systems are studied within the mesoscopic theory at the level of the Gaussian approximation. The previously neglected fluctuation contribution to the inverse charge-charge correlation function is…
We numerically investigate the statistical properties of electrochemical capacitance in disordered two-dimensional mesoscopic capacitors. Based on the tight-binding Hamiltonian, the Green's function formalism is adopted to study the average…
We use molecular dynamics simulations of the primitive model of electrolytes to study the ionic structure in aqueous monovalent electrolyte solutions confined by charged planar interfaces over a wide range of electrolyte concentration,…
Surfaces are able to control physical-chemical processes in multi-component solution systems and, as such, find application in a wide range of technological devices. Understanding the structure, dynamics and thermodynamics of non-ideal…
We use molecular dynamics simulations to explore the impact of a non-ionic solvent on the structural and capacitive properties of supercapacitors based on an ionic liquid electrolyte and carbon electrodes. The study is focused on two pure…
We use fluctuating hydrodynamics to analyze the dynamical properties in the non-equilibrium steady state of a diffusive system coupled with reservoirs. We derive the two-time correlations of the density and of the current in the…
Electrostatic correlations between ions dissolved in water are known to impact their transport properties in numerous ways, from conductivity to ion selectivity. The effects of these correlations on the solvent itself remain, however, much…
We present an exact field-theoretic formulation for a fluctuating, generally asymmetric, salt density in the presence of a charged plate. The non-linear Poisson-Boltzmann equation is obtained as the saddle-point of our field theory action.…