Probing corrosion using a simple and versatile in situ multimodal corrosion measurement system.

In this work, we have developed a unique in situ multimodal corrosion system that is capable of acquiring electrochemical data, sample imaging/visualization and hydrogen collection, simultaneously. Each of these modalities yield valuable information pertaining to the ongoing corrosion process. Combining them can yield holistic information on the role of microstructure, processing history, presence of coatings, etc., on the sequence of steps occurring during the corrosion process, and how they correlate with the acquired electrochemical data. Four materials systems, namely AA6061-T6 aluminum alloy, AZ91 magnesium alloy, galvanized DP590 steel, and pure Zn, were investigated under open circuit potential and under potentiodynamic polarization. The multimodal corrosion system was utilized to observe processes such as surface passivation and dissolution, pit and filiform corrosion initiation and propagation, and was correlated with location and magnitude of hydrogen evolution. This approach is shown to yield a truly multimodal understanding of the ongoing corrosion processes.

Investigating electrochemical corrosion at Mg alloy-steel joint interface using scanning electrochemical cell impedance microscopy (SECCIM).

Developing strategies to prevent corrosion at the interface of dissimilar metal alloys is challenging because of the presence of heterogenous distribution of galvanic couples and microstructural features that significantly change the corrosion rate. Devising strategies to mitigate this interfacial corrosion requires quantitative and correlative understanding of its surface electrochemical reaction. In this work, scanning electrochemical cell impedance microscopy (SECCIM) was employed to study location-specific corrosion in the interfacial region of dissimilar alloys, such as AZ31 (magnesium alloy) and DP590 (steel) welded using the Friction-stir Assisted Scribe Technique (FAST) processes. Herein, SECCM and SECCIM were used to perform correlative mapping of the local electrochemical impedance spectroscopic and potentiodynamic polarization to measure the effect of electronic and microstructural changes in the welded interfacial region on corrosion kinetics. Microstructural characterization including scanning electron microscopy and electron backscatter diffraction was performed to correlate changes in microstructural features and chemistry with the corresponding electronic properties that affect corrosion behavior. The variations in corrosion potential, corrosion current density, and electrochemical impedance spectroscopy behavior across the interface provide deeper insights on the interfacial region-which is chemically and microstructurally distinct from both bare AZ31 and DP590 that can help prevent corrosion in dissimilar metal structures.

Scanning Electrochemical Microscopy for Chemical Imaging and Understanding Redox Activities of Battery Materials.

Improving the charge storage capacity and lifetime and charging/discharging efficiency of battery systems is essential for large-scale applications such as long-term grid storage and long-range automobiles. While there have been substantial improvements over the past decades, further fundamental research would help provide insights into improving the cost effectiveness of such systems. For example, it is critical to understand the redox activities of cathode and anode electrode materials and stability and the formation mechanism and roles of the solid-electrolyte interface (SEI) that forms at the electrode surface upon an external potential bias. The SEI plays a critical role in preventing electrolyte decay while still allowing charges to flow through the system while serving as a charge transfer barrier. While surface analytical techniques such as X-ray photoelectron (XPS), X-ray diffraction (XRD), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and atomic force microscopy (AFM) provide invaluable information on anode chemical composition, crystalline structure, and morphology, they are often performed ex situ, which can induce changes to the SEI layer after it is removed from the electrolyte. While there have been efforts to combine these techniques using pseudo-in situ approaches via vacuum-compatible devices and inert atmosphere chambers connected to glove boxes, there is still a need for true in situ techniques to obtain results with improved accuracy and precision. Scanning electrochemical microscopy (SECM) is an in situ scanning probe technique that can be combined with optical spectroscopy techniques such as Raman and photoluminescence spectroscopy methods to gain insights into the electronic changes of a material as a function of applied bias. This Review will highlight the potential of SECM and recent reports on combining spectroscopic measurements with SECM to gain insights into the SEI layer formation and redox activities of other battery electrode materials. These insights provide invaluable information for improving the performance of charge storage devices.

Studying Corrosion Using Miniaturized Particle Attached Working Electrodes and the Nafion Membrane.

We developed a new approach to attach particles onto a conductive layer as a working electrode (WE) in a microfluidic electrochemical cell with three electrodes. Nafion, an efficient proton transfer molecule, is used to form a thin protection layer to secure particle electrodes. Spin coating is used to develop a thin and even layer of Nafion membrane. The effects of Nafion (5 wt% 20 wt%) and spinning rates were evaluated using multiple sets of replicates. The electrochemical performance of various devices was demonstrated. Additionally, the electrochemical performance of the devices is used to select and optimize fabrication conditions. The results show that a higher spinning rate and a lower Nafion concentration (5 wt%) induce a better performance, using cerium oxide (CeO2) particles as a testing model. The WE surfaces were characterized using atomic force microscopy (AFM), scanning electron microscopy-focused ion beam (SEM-FIB), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and X-ray photoelectron spectroscopy (XPS). The comparison between the pristine and corroded WE surfaces shows that Nafion is redistributed after potential is applied. Our results verify that Nafion membrane offers a reliable means to secure particles onto electrodes. Furthermore, the electrochemical performance is reliable and reproducible. Thus, this approach provides a new way to study more complex and challenging particles, such as uranium oxide, in the future.

Investigating the Redox Properties of Two-Dimensional MoS2 Using Photoluminescence Spectroelectrochemistry and Scanning Electrochemical Cell Microscopy.

Control over photophysical and chemical properties of two-dimensional (2D) transition metal dichalcogenides (TMDs) is the key to advance their applications in next-generation optoelectronics. Although chemical doping and surface modification with plasmonic metals have been reported to tune the photophysical and catalytic properties of 2D TMDs, there have been few reports of tuning optical properties using dynamic electrochemical control of electrode potential. Herein, we report (1) the photoluminescence (PL) enhancement and red-shift in the PL spectrum of 2D MoS2, synthesized by chemical vapor deposition and subsequent transfer onto an indium tin oxide electrode, upon electrochemical anodization and (2) spatial heterogeneities in its photoelectrochemical (PEC) activities. Spectroelectrochemistry shows that positive electrochemical bias causes an initial ten-fold increase in the PL intensity followed by a quick decrease in the enhancement. The PL enhancement and spectrum red-shift are associated with the decrease in nonradiative decay rates of excitons formed upon electrochemical anodization of 2D MoS2. Additionally, scanning electrochemical cell microscopy (SECCM) study shows that the 2D MoS2 crystal is spatially sensitive to PEC oxidation at positive potentials. SECCM also shows a photocurrent increase caused by spatially heterogeneous edge-type defect sites of the crystal.