Molecular dynamics simulations of electrochemical interfaces

Abstract

Molecular dynamics (MD) simulations have become a powerful tool for investigating electrical double layers (EDLs), which play a crucial role in various electrochemical devices. In this Review, we provide a comprehensive overview of the techniques used in MD simulations for EDL studies, with a particular focus on methods for describing electrode polarization, and examine the principle behind these methods and their varying applicability. The applications of these approaches in supercapacitors, capacitive deionization, batteries, and electric double-layer transistors are explored, highlighting recent advancements and insights in each field. Finally, we emphasize the challenges and potential directions for future developments in MD simulations of EDLs, such as considering movable electrodes, improving electrode property representation, incorporating chemical reactions, and enhancing computational efficiency to deepen our understanding of complex electrochemical processes and contribute to the progress in the field involving EDLs.

Accurately simulating electrical double layers structure and formation using all-atom scaled-charge force fields

“…9 Hence, imperative reliance on atomistic level simulations emerges as an essential avenue, aiming to furnish a precise microscopic depiction of the EDLs. 11,12 Molecular dynamics (MD) simulations stand as one of the powerful tools to elucidate the structure and formation of the EDLs from a microscopic perspective. [13][14][15] However, the veracity of the simulation is strongly contingent on the choice of force elds.…”

“…9 Hence, imperative reliance on atomistic level simulations emerges as an essential avenue, aiming to furnish a precise microscopic depiction of the EDLs. 11,12…”

Data-Driven Optimization of Carbon Electrodes for Aqueous Supercapacitors

“…Physics-based models have been previously utilized to unravel various mechanisms of enhanced capacitance due to heteroatom doping. ,, For example, ab initio methods has been utilized to predict pseudocapacitances of certain chemically simple doped carbons, such as GO and pyrrolic nitrogen (N-5)-doped carbon nanotubes . In general, the quantum chemistry methods are extremely computationally costly and not practical for systems with more than 1,000 atoms.…”

Molecular Understanding of Charging Dynamics in Supercapacitors with Porous Electrodes and Ionic Liquids

“…36−38 The CPM offers a more accurate depiction by considering the electrical polarizability of the electrode, making it indispensable for precise simulation of charging dynamics, 36,37 as detailed in our recent review. 38 Appropriate electrode models are also key for MD simulations. Typically, subnanometer pores were modeled by slit pores, as they can accurately capture pore size and shape features of the porous electrode and 2D materials.…”

“…The two primary methods are the constant charge method (CCM) and the constant potential method (CPM) . The CCM, while computationally efficient, does not dynamically adapt to the movement of electrolyte atoms, neglecting the equipotential nature of the electrode. − The CPM offers a more accurate depiction by considering the electrical polarizability of the electrode, making it indispensable for precise simulation of charging dynamics, , as detailed in our recent review . Appropriate electrode models are also key for MD simulations.…”