Real-Space Charge Density Profiling of Electrode–Electrolyte Interfaces with Angstrom Depth Resolution

The accumulation and depletion of charges at electrode-electrolyte interfaces is crucial for all types of electrochemical processes. However, the spatial profile of such interfacial charges remains largely elusive. Here we develop charge profiling three-dimensional (3D) atomic force microscopy (CP-3D-AFM) to experimentally quantify the real-space charge distribution of the electrode surface and electric double layers (EDLs) with angstrom depth resolution. We first measure the 3D force maps at different electrode potentials using our recently developed electrochemical 3D-AFM. Through statistical analysis, peak deconvolution, and electrostatic calculations, we derive the depth profile of the local charge density. We perform such charge profiling for two types of emergent electrolytes, ionic liquids, and highly concentrated aqueous solutions, observe pronounced sub-nanometer charge variations, and find the integrated charge densities to agree with those derived from macroscopic electrochemical measurements.