Live imaging of silver nanostructures electrochemically dissolving at open circuit potential

The stability of electrode and electrocatalyst materials is of paramount importance for sustainable and persistent technological solutions for energy conversion systems. In fact, dissolution of electrodes at open-circuit potential occurs both during electrochemical testing operando and using a scanning flow cell inductively coupled plasma mass spectrometry (SFC-ICP-MS) setup. Even though these phenomena occur often, their mechanisms remain concealed. This is because structural changes take place at the nanoscale which are difficult to directly observe. Herein, we introduce a workflow comprising automated image analysis, beam effect assessment, and correlative electrochemical testing, to obtain quantitative and representative data from electrochemical liquid phase electron microscopy (EC-LP-EM). In a demonstrator experiment, we reveal the mechanism of bimetallic corrosion for silver electrodeposited on a platinum electrode substrate upon system equilibration. This process is governed by electrochemical reactions occurring at the electrode-electrolyte interface under zero net current conditions as an example of structural changes on the nanoscale during operation. Our experimental findings, furthermore, act as a blueprint for correlating nanoscale live imaging information with macroscopic electrochemical responses for investigating degradation mechanisms of electrocatalysts and materials beyond. These insights aid to design efficient electrochemical conversion systems urgently needed in renewable energy technology.