Understanding how electrochemical materials evolve during operation remains a central challenge in energy conversion and storage technologies. While conventional electrochemical measurements provide macroscopic performance metrics, the nanoscale structural processes governing degradation often remain hidden. Electrochemical liquid-phase electron microscopy (EC-LP-EM) offers direct access to dynamic solid–liquid interfaces, yet quantitative interpretation is frequently hindered by radiolysis, complex electrochemical environments, and uncertainties regarding the relationship between nanoscale observations and bulk behavior.

In this contribution, I will present a quantitative workflow that bridges operando nanoscale imaging with complementary electrochemical and analytical techniques to establish causal links between structural evolution and macroscopic electrochemical responses. Using silver electrodeposition and dissolution on platinum as a model system, EC-LP-EM is combined with automated image analysis, radiolysis assessment, conventional electrochemistry, and on-line scanning flow cell inductively coupled plasma mass spectrometry (SFC-ICP-MS). This correlative approach enables the direct quantification of nanoscale structural transformations and their translation into measurable electrochemical observables.

The experiments reveal a surprising phenomenon: freshly electrodeposited silver dissolves spontaneously under open-circuit conditions immediately after deposition. Real-time nanoscale observations show that dissolution initiates preferentially at the electrode–electrolyte interface and coincides with equilibration of the open-circuit potential. Correlative electrochemical analysis demonstrates that this behavior originates from thermodynamic and kinetic equilibration processes involving silver oxidation, oxygen reduction, and platinum surface chemistry rather than from externally applied electrochemical stimuli. Beyond elucidating this specific mechanism, the study establishes a general framework for correlating dynamic nanoscale processes with bulk electrochemical behavior. The results demonstrate that substantial structural transformations can occur even under nominally inactive open-circuit conditions and highlight the dynamic nature of electrochemical interfaces. More broadly, the presented methodology provides a blueprint for investigating degradation phenomena in electrocatalysts, batteries, corrosion science, and other energy materials, thereby advancing the development of predictive structure–performance relationships across electrochemical technologies.[1]