Elucidating the Interfacial Structure at the Ionic Liquid-Solid Interface Using Atomic Force Microscopy and Molecular Dynamics

Thursday, October 15, 2015: 17:00
101-A (Phoenix Convention Center)
J. Black (Oak Ridge National Laboratory), G. Feng (Huazhong University of Science and Technology), Y. Zhang (Vanderbilt University), M. B. Okatan, P. Zhang, S. Dai (Oak Ridge National Laboratory), S. V. Kalinin, P. T. Cummings (Vanderbilt University), and N. Balke (Oak Ridge National Laboratory)
The structure and properties of ionic liquids (ILs) at the solid-liquid interface will govern their performance in all applications including energy storage and catalysis. Although it is well known that the interfacial structure of ionic liquids is very different to that of classical dilute electrolytes, a comprehensive understanding of the ion structure within the electrical double layer for this class of electrolytes is still lacking.  Therefore it is necessary to have experimental methods to elucidate the interfacial ion structure which can be related to electrochemical performance. Atomic force microscopy (AFM) force spectroscopy is capable of probing the layered ion structure formed at the interface, and offers advantages over other techniques (e.g. x-ray and neutron reflectivity, surface force apparatus) due to its high spatial resolution allowing for the ion structure to be examined in a spatially resolved manner. Although there are several studies demonstrating the impressive ability of AFM to probe the interfacial ion structure in ionic liquids, several questions remain regarding the measured AFM response. (e.g. what is the role of the AFM probe?, Do we measure cations or anions? Can we tune ion selectivity?)

In this work we examine the AFM force profiles of various ionic liquids at different substrates to examine how the substrate and ionic liquid properties affect the interfacial ion structure. We also use a series of different AFM probes of different geometry and chemistry to determine the effect on the measured force profiles. Our experimental results are compared directly with molecular dynamics simulations, and through a combination of experimental and theoretical approaches we are able to develop a better understanding of the measured force response and factors determining the interfacial structure at the ion-liquid solid interface.