Toward Electrochemical Studies on the Nanometer and Atomic Scales: Progress, Challenges, and Opportunities

Abstract

Electrochemical reactions and ionic transport underpin the operation of a broad range of devices and applications, from energy storage and conversion to information technologies, as well as biochemical processes, artificial muscles, and soft actuators. Understanding the mechanisms governing function of these applications requires probing local electrochemical phenomena on the relevant time and length scales. Here, we discuss the challenges and opportunities for extending electrochemical characterization probes to the nanometer and ultimately atomic scales, including challenges in down-scaling classical methods, the emergence of novel probes enabled by nanotechnology and based on emergent physics and chemistry of nanoscale systems, and the integration of local data into macroscopic models. Scanning probe microscopy (SPM) methods based on strain detection, potential detection, and hysteretic current measurements are discussed. We further compare SPM to electron beam probes and discuss the applicability of electron beam methods to probe local electrochemical behavior on the mesoscopic and atomic levels. Similar to a SPM tip, the electron beam can be used both for observing behavior and as an active electrode to induce reactions. We briefly discuss new challenges and opportunities for conducting fundamental scientific studies, matter patterning, and atomic manipulation arising in this context.

Characterizing Batteries by In Situ Electrochemical Atomic Force Microscopy: A Critical Review

“…To date, reviews detailing AFM [ 21,22 ] and SPM [ 23–25 ] approaches in battery research have not fully considered the degree to which the limitations of the systems being studied impact our ability to translate the findings onto our understanding of real batteries. [ 26 ]…”

Full-Self-Powered Humidity Sensor Based on Electrochemical Aluminum–Water Reaction

“…In this report, we investigate in detail the principle of operation of the aluminum IDC sensor, especially looking for evidence of an aluminum–water electrochemical interaction. The full understanding of the underlying process required micro- and nanotesting of the sensor’s surface using the following methods: micro-Fourier transform infrared spectroscopy (µ-FTIR), atomic force microscopy (AFM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), electrochemical impedance spectroscopy (EIS), and X-ray diffraction (XRD) [ 21 ]. We also considered possible concurrent processes such as the hydrovoltaic effect [ 22 , 23 ] and radiofrequency harvesting [ 12 ].…”

Characterization of Vegard strain related to exceptionally fast Cu-chemical diffusion in Cu$$_2$$Mo$$_6$$S$$_8$$ by an advanced electrochemical strain microscopy method

“…grain boundaries or interface regimes showing improved transport properties 2 – 9 . Gaining nanoscale insight into the correlation between structure and electrochemical transport properties is thus not only a problem of fundamental interest 10 – 12 , but it is also considered essential for further improvement of high-performance energy storage devices 13 . Consequently, the conventional approaches to measure macroscopic transport parameters need to be complemented by analyses at the nanoscale.…”

“…However, not only Vegard strains contribute to the measured ESM signals, but also electrostatic interactions between tip and sample 13 , 36 , 37 . In several cases, the electrostatically induced ESM signals were considered to be even the dominant signals 38 , 39 , and were, for instance, recently exploited for the analysis of local chemical distributions in solid state electrolytes 40 .…”