Ionic liquids in conducting nanoslits: how important is the range of the screened electrostatic interactions?

J Phys Condens Matter. 2022 May 2;34(26). doi: 10.1088/1361-648X/ac6307.

Abstract

Analytical models for capacitive energy storage in nanopores attract growing interest as they can provide in-depth analytical insights into charging mechanisms. So far, such approaches have been limited to models with nearest-neighbor interactions. This assumption is seemingly justified due to a strong screening of inter-ionic interactions in narrow conducting pores. However, how important is the extent of these interactions? Does it affect the energy storage and phase behavior of confined ionic liquids? Herein, we address these questions using a two-dimensional lattice model with next-nearest and further neighbor interactions developed to describe ionic liquids in conducting slit confinements. With simulations and analytical calculations, we find that next-nearest interactions enhance capacitance and stored energy densities and may considerably affect the phase behavior. In particular, in some range of voltages, we reveal the emergence of large-scale mesophases that have not been reported before but may play an important role in energy storage.

Keywords: Bethe-lattice; nanostructured electrodes; re-entrant phase transitions; supercapacitors; superionic state.