Unraveling Spatial Charge Density Distributions at Electrode-Electrolyte Interfaces

Abstract

Charge distributions at electrode-electrolyte interfaces play a crucial role in many electrochemical processes, some of which are electrocatalysis, supercapacitors, batteries etc., However, most experimental techniques, either microscopy or spectroscopy tools that are used to probe these systems, cannot provide any information about the interfacial spatial charge distribution. Techniques based on kelvin-probe force microscopy (KPFM) can provide some information, however they have a very limited depth of resolution and can only work with extremely dilute electrolytes. Recently, we developed a technique known as charge profiling three-dimensional (3D) atomic force microscopy (CP-3D-AFM) which could map out the charge densities at angstrom-depth resolution. The method is based on measuring 3D-AFM maps at different electrode potentials and further using electrostatic calculations to obtain the charge density depth profiles at the respective potentials. We used this method to measure charge distributions in highly ionic electrolyte systems and can explain their differential capacitance profiles. This CP-3D-AFM technique could enable to obtain molecular structural insights for a wide range of electrolyte systems and serve in designing principles for engineering effective electrode-electrolyte interfaces.