The relative electrochemical properties of second phases compared to the surrounding matrix gives rise to localization of corrosion on magnesium (Mg) alloys. Localized corrosion and its subsequent propagation in Mg alloys is largely driven by so-called ‘microgalvanic coupling’ of microstructural constituents within the alloy microstructure. In the present work, atomic force microscopy (AFM) imaging coupled with scanning Kelvin probe force microscopy (SKPFM) were used to generate surface Volta potential maps of a range of Mg alloys. In this manner, the relative Volta potential difference(s) between the respective alloy matrix phase and the microconstituent phase(s) of each sample were determined. Correlations between relative Volta potentials and phase composition were then inferred based on comparison of AFM optical and topographical images with corresponding scanning electron microscopy (SEM) images and energy dispersive x-ray spectroscopy (EDS) maps of the same or similar features. Sample preparation technique, testing conditions, and proper calibration of the SKPFM were all seen to influence the Volta potentials acquired. Because the relative Volta potential difference is known to serve as an index for local corrosion—particularly under thin electrolyte layers and in chloride solutions—a review of published SKPFM data was conducted to provide a critical assessment of the surface Volta potential differences between different microconstituent phases in a variety of Mg alloys to aid in understanding and in the future improvement of the atmospheric corrosion of Mg alloys

Abstract:The nature of microgalvanic couple driven corrosion of brazed joints was investigated. 316L stainless steel samples were joined using Cu-Ag-Ti and Cu-Ag-In-Ti braze alloys. Phase and elemental composition across each braze and parent metal interface was characterized and scanning Kelvin probe force microscopy (SKPFM) was used to map the Volta potential differences. Co-localization of SKPFM with Energy Dispersive Spectroscopy (EDS) measurements enabled spatially resolved correlation of potential differences with composition and subsequent galvanic corrosion behavior. Following exposure to the aggressive solution, corrosion damage morphology was characterized to determine the mode of attack and likely initiation areas. When exposed to 0.6 M NaCl, corrosion occurred at the braze-316L interface preceded by preferential dissolution of the Cu-rich phase within the braze alloy. Braze corrosion was driven by galvanic couples between the braze alloys and stainless steel as well as between different phases within the braze microstructure. Microgalvanic corrosion between phases of the braze alloys was investigated via SKPFM to determine how corrosion of the brazed joints developed.

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Operando synchrotron X-ray diffraction (XRD) studies have not previously been used to directly study Li metal in standard batteries due to the extremely weak scattering from Li atoms. In this work, it is demonstrated the stripping and plating of Li metal can be effectively quantified during battery cycling in appropriately designed synchrotron XRD experiments that utilize an anode-free battery configuration in which a Li-containing cathode material of LiNi0.6Mn0.2Co0.2O2 (NMC622) is paired with a bare anode current collector consisting of either Cu metal (Cu/NMC) or Mo metal (Mo/NMC). In this configuration, it is possible to probe local variations in the deposition and stripping of Li metal with sufficient spatial sensitivity to map the inhomogeneity in pouch cells and to follow Li deposition and stripping with sufficient time resolution to track state of charge dependent variations in the rate of Li usage at a single point. For the Cu/NMC and Mo/NMC batteries, it was observed that the initial plating of Li occurred in a very homogeneous manner but severe macroscopic inhomogeneity arose on a mm-scale during the subsequent stripping of Li, contrasting with the conventional wisdom that the greatest challenges in Li metal batteries are associated with Li deposition.

Thanks to its high specific capacity and low electrochemical potential, lithium metal is an ideal anode for next-generation high-energy batteries. However, the unstable heterogeneous surface of lithium gives rise to safety and efficiency concerns that prevent it from being utilized in practical applications. In this work, the formation of a closed-host bi-layer solid electrolyte interphase (SEI) improves the stability of lithium metal anode. This is successfully realized by forming an interconnected porous LiFrich artificial SEI in contact with Li metal, and a dense, stable in-situ formed upper layer SEI. The porous layer increases the number of Li/LiF interfaces, which reduces local volume fluctuations and improves Li + diffusion along these interfaces. Additionally, the tortuous porous structure guides uniform Li + flux distribution and mechanically suppresses dendrite propagation. The dense upper layer of the SEI accomplishes a closed-host design, preventing continuous consumption of active materials. The duality of a dense top layer with porous bottom layer led to extended cycle life and improved rate performance, evidenced with symmetric cell testing, as well as full cell testing paired with sulfur and LiFePO 4 (LFP) cathodes. This work is a good example of a rational design of the SEI, based on comprehensive consideration of various critical factors to improve Li-metal anode stability, and highlights a new pathway to improve cycling and rate performances of Li metal batteries.