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Abstract Due to its outstanding safety and high energy density, all‐solid‐state lithium‐sulfur batteries (ASLSBs) are considered as a potential future energy storage technology. The electrochemical reaction pathway in ASLSBs with inorganic solid‐state electrolytes is different from Li‐S batteries with liquid electrolytes, but the mechanism remains unclear. By combining operando Raman spectroscopy and ex situ X‐ray absorption spectroscopy, we investigated the reaction mechanism of sulfur (S₈) in ASLSBs. Our results revealed that no Li₂S_8,Li₂S_6,and Li₂S₄were formed, yet Li₂S₂was detected. Furthermore, first‐principles structural calculations were employed to disclose the formation energy of solid state Li₂S_n(1≤n≤8), in which Li₂S₂was a metastable phase, consistent with experimental observations. Meanwhile, partial S₈and Li₂S₂remained at the full lithiation stage, suggesting incomplete reaction due to sluggish reaction kinetics in ASLSBs. 

It is undeniable that novel 2D devices and heterostructures will have a lasting impact on the advancement of future technologies. However, the inherent instability of many exfoliated van der Waals (vdW) materials is a well-known hurdle yet to be overcome. Thus, the sustained interest in exfoliated vdW materials underscores the importance of understanding the mechanisms of sample degradation to establish proactive protective measures. Here, the impact of prolonged synchrotron-based X-ray beam exposure on exfoliated flakes of two contemporary vdW materials, ${\mathrm{N}\mathrm{i}\mathrm{P}\mathrm{S}}_3$and $\alpha$- ${\mathrm{R}\mathrm{u}\mathrm{C}\mathrm{l}}_3$, is explored using resonant inelastic X-ray scattering (RIXS) and total fluorescence yield X-ray absorption spectroscopy (XAS). In ${\mathrm{N}\mathrm{i}\mathrm{P}\mathrm{S}}_3$, the resulting RIXS and XAS spectra show a suppression, then vanishing, of NiS₆multiplet excitations coupled with an upward shift of the peak energy of the XAS as a function of X-ray dose. In $\alpha$- ${\mathrm{R}\mathrm{u}\mathrm{C}\mathrm{l}}_3$, the signs of beam damage from the RIXS spectra are less evident. However, the post-experiment characterization of both materials using Raman spectroscopy exhibits signals of an amorphous and disordered system compared to pristine flakes; in addition, energy-dispersive X-ray spectroscopy of ${\mathrm{N}\mathrm{i}\mathrm{P}\mathrm{S}}_3$shows evidence of ligand vacancies. As synchrotron radiation is fast becoming a required probe to study 2D vdW materials, these findings lay the groundwork for the development of future protective measures for synchrotron-based prolonged X-ray beam exposure, as well as for X-ray free electron laser. 

α-RuCl3, a narrow-band Mott insulator with a large work function, offers intriguing potential as a quantum material or as a charge acceptor for electrical contacts in van der Waals devices. In this work, we perform a systematic study of the optical reflection contrast of α-RuCl3 nanoflakes on oxidized silicon wafers and estimate the accuracy of this imaging technique to assess the crystal thickness. Via spectroscopic micro-ellipsometry measurements, we characterize the wavelength-dependent complex refractive index of α-RuCl3 nanoflakes of varying thickness in the visible and near-infrared. Building on these results, we simulate the optical contrast of α-RuCl3 nanoflakes with thicknesses below 100 nm on SiO2/Si substrates under different illumination conditions. We compare the simulated optical contrast with experimental values extracted from optical microscopy images and obtain good agreement. Finally, we show that optical contrast imaging allows us to retrieve the thickness of the RuCl3 nanoflakes exfoliated on an oxidized silicon substrate with a mean deviation of −0.2 nm for thicknesses below 100 nm with a standard deviation of only 1 nm. Our results demonstrate that optical contrast can be used as a non-invasive, fast, and reliable technique to estimate the α-RuCl3 thickness.