Accounting for the quantum capacitance of graphite in constant potential molecular dynamics simulations

Molecular 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.

Subjects

carbonaceous electrodes

constant potential molecular dynamics

density of states

supercapacitors

DDC Class

530: Physics

541.37: Electrochemistry

660.6: Biotechnology

Lizenz

https://creativecommons.org/licenses/by-nc/4.0/

Name

Advanced Materials - 2024 - Goloviznina - Accounting for the Quantum Capacitance of Graphite in Constant Potential.pdf

Type

Main Article

Size

1.81 MB

Format

Adobe PDF

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Accounting for the quantum capacitance of graphite in constant potential molecular dynamics simulations