Enhanced Ionic Conductivity of confined Ionic-Liquid in Angstrom-scale 2D channels

TL;DR

This study demonstrates that ionic conductivity in angstrom-scale channels can be significantly enhanced by nanoconfinement and solvent tuning, revealing key mechanisms of ion transport at the molecular level.

Contribution

It provides a systematic investigation of ion transport under extreme confinement using a well-defined 2D channel system, revealing the effects of channel height and solvent environment.

Findings

Maximum ionic conductivity of 26.7 S/m at 1.02 nm confinement height.

Conductivity increased to ~145 S/m with acetonitrile co-solvent.

Structural rearrangements of ionic layers influence conductivity.

Abstract

Understanding ion-transport under molecular confinement is essential for developing next-generation energy technologies, where ionic motion often occurs within nanoscale or angstrom-scale channels. In this study, we use the model system of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([EMIM]+[TFSI]-) confined within angstrom-scale slit-shaped 2D channels fabricated via van der Waals assembly to exemplify a broader class of confined ionic liquids.This system provides a well-defined platform to unravel generic features of ion transport under extreme confinement. By systematically varying the channel height h, we demonstrate a non-monotonic conductivity dependence on confinement, with a maximum 26.7 S/m at confining height, 1.02 nm, over 30 times of the bulk value for these ionic liquids. The variation of conductivity with confinement arises from structural rearrangements of ionic layers in the slit channel. Enhanced values of conductivity occur under confinements that promote the breakup of ion pairs and larger clusters, thereby increasing the number of free ions. Stronger confinement (h, 0.68 nm) also leads to steric hindrance, lowering conductivity below bulk values. Furthermore, introducing co-solvents with a higher dielectric constant and lower viscosity, such as acetonitrile (ACN), amplifies conductivity to ~145 S/m. Comparative studies using ACN, dimethyl carbonate and diethyl carbonate highlight that both large dielectric constant and low viscosity critically govern ion transport under confinement, as also supported by molecular dynamics simulations. Overall, this work establishes confined [EMIM]+[TFSI]- as a representative system for probing mechanisms of nano- and angstrom-scale ion transport, demonstrating how nanoconfinement and the solvent environment can be systematically tuned to manipulate ionic conductivity at the molecular level.