ELECTRODE: An electrochemistry package for atomistic simulations

Abstract

The constant potential method (CPM) is a commonly used tool to address challenges at the solid-liquid interface at conducting electrodes in molecular dynamics (MD) and can be used, for example, to model the behavior of ionic liquids or water in salt electrolytes in supercapacitors and batteries. CPM achieves this by updating charges of individual electrode atoms according to the applied electric potential and the (time-dependent) local electrolyte structure. Here we present a feature-rich CPM implementation for the Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS), which includes, in addition, a related atom-wise constrained charge method and a thermo-potentiostat. Moreover, features such as a finite-field approach, multiple corrections for non-periodic boundary conditions of the particle-particle particle-mesh solver (P 3 M), and a Thomas-Fermi model for using non-ideal metals as electrodes are included. We demonstrate the capabilities of this implementation for a simple electrical double layer capacitor (EDL), for which we have studied the effects on charging time using the different approaches. To confirm the one-dimensional correction, we estimated the vacuum capacitance of a double-cylindrical capacitor and compared it to the analytical result. In summary, the ELECTRODE package enables efficient electrochemical simulations using state-of-the-art methods that open up the possibility of simulating heterogeneous electrodes or electrodes consisting of isolated carbon nanotubes to investigate the influence of curvature on capacitance in more detail.