Atomistic Insights into the Layered Microstructure and Time-Dependent Stability of [BMIM][PF₆] Confined within the Meso-Slit of Carbon

Abstract

Clarifying the microstructures and time-dependent stability of ionic liquids (ILs) within the confinement of the meso-slit of carbon is the first step to understand the intrinsic synergy effect between ILs and a promising mesoporous carbon electrode. In this work, we adopted molecular dynamics to systematically investigate the behavior of [BMIM][PF6] in the 2.8 nm-wide meso-slit of carbon. The confined ILs formed a pronounced layered spatial distribution and can be divided into three distinct regions, namely, com-, sub-, and cen-layer, according to valley coordinates in the number density profiles. In the com-layer region, the imidazolium rings of ILs possess two dominant orientations, namely, “parallel” and “tilted standing”. The rotation ability of all the ions is highly restrained. In the sub-layer and cen-layer regions, a part of the [BMIM] imidazolium ring has a preferred “tilted standing” orientation. The [BMIM] cations are still in a rotational restrain state and show a preferred rotation motion along the x–y plane. The hydrogen bond between [BMIM] cations and [PF6] anions play a crucial role in determining the confined multilayered spatial distribution and distinctive orientation properties of ILs.