Nanoscale capillary freezing of ionic liquids confined between metallic interfaces and the role of electronic screening

Abstract

Room temperature Ionic liquids (RTIL) received considerable attention as a new class of materials with fundamental importance for energy storage \cite{Armand2009, Uesugi2013} and active lubrication \cite{Palacio2010, Dold2015, Smith2013a}. Their unique properties result from the competition of strong electrostatic interactions with properly designed molecular structure to avoid crystalization at room temperature. They are however unsual liquids, which challenge fundamentally the classical frameworks of electrolytes. In particular their behavior at electrified interfaces remains elusive with very rich and exotic responses relevant to their electrochemical activity \cite{Kornyshev2014,Merlet2012,Perkin2013,Atkin2009,Rotenberg2015,Endres2012,Bovio2009a,Bovio2009,Yokota2010}. In this work, we use quartz tuning fork based AFM nanorheological measurements to explore the properties of RTIL in nanometric confinement. We unveil a dramatic change of the RTIL towards a solid-like phase below a threshold thickness, pointing to a capillary freezing in confinement. This threshold thickness is found to be intimately related to the metallic nature of the confining materials, with more metallic surfaces facilitating capillary freezing. This behavior is interpreted theoretically in terms of the shift of the freezing transition, taking into account the influence of the electronic screening on RTIL wetting of the confining surfaces, as described by the simple Thomas-Fermi approach. Our findings provides fresh views on the properties of confined RTIL with important implications for their statics and dynamics inside nanoporous metallic structures. This also suggests applications to tune nanoscale lubrication with the phase-changing RTIL, by varying the nature as well as the patterning of the subtrate, and the application of active polarisation.