Accounting for the Quantum Capacitance of Graphite in Constant Potential Molecular Dynamics Simulations.

• DOI: 10.48550/arxiv.2404.07848
• Publication Date: 2024-08-03
• Authors: Kateryna Goloviznina; Johann Fleischhaker; Tobias Binninger; Benjamin Rotenberg; Heigo Ers; Vladislav Ivanistsev; Robert Meissner; Alessandra Serva; Mathieu Salanne
• Keywords: [PHYS]Physics [physics]; Condensed Matter - Materials Science; supercapacitors; Materials Science (cond-mat.mtrl-sci); FOS: Physical sciences; 02 engineering and technology; carbonaceous electrodes; constant potential molecular dynamics carbonaceous electrodes density of states supercapacitors; [PHYS] Physics [physics]; constant potential molecular dynamics; density of states; [CHIM] Chemical Sciences; [CHIM]Chemical Sciences; 0210 nano-technology

AbstractMolecular dynamics (MD) simulations at a constant electric potential are an essential tool to study electrochemical processes, providing microscopic information on the structural, thermodynamic, and dynamical properties. Despite the numerous advances in the simulation of electrodes, they fail to accurately represent the electronic structure of materials such as graphite. In this work, a simple parameterization method that allows to tune the metallicity of the electrode based on a quantum chemistry calculation of the density of states (DOS) is introduced. As a first illustration, the interface between graphite electrodes and two different liquid electrolytes, an aqueous solution of NaCl and a pure ionic liquid, at different applied potentials are studied. It is shown that the simulations reproduce qualitatively the experimentally‐measured capacitance; in particular, they yield a minimum of capacitance at the point of zero charge (PZC), which is due to the quantum capacitance (QC) contribution. An analysis of the structure of the adsorbed liquids allows to understand why the ionic liquid displays a lower capacitance despite its large ionic concentration. In addition to its relevance for the important class of carbonaceous electrodes, this method can be applied to any electrode materials (e.g. 2D materials, conducting polymers, etc), thus enabling molecular simulation studies of complex electrochemical devices in the future.