Refine
Has Fulltext
- no (3)
Year of publication
- 2021 (3) (remove)
Document Type
- Article (3) (remove)
Language
- English (3)
Is part of the Bibliography
- yes (3) (remove)
Keywords
- catalysis (1)
- dichalcogenides (1)
- hydrogen evolution reaction (1)
- phase transitions (1)
- photoelectron spectroscopy (1)
Institute
The layered dichalcogenide MoS2 is relevant for electrochemical Li adsorption/intercalation, in the course of which the material undergoes a concomitant structural phase transition from semiconducting 2H-MoS2 to metallic 1T-LixMoS2. With the core hole clock approach at the S L1 X-ray absorption edge we quantify the ultrafast directional charge transfer of excited S3p electrons in-plane () and out-of-plane (perpendicular to) for 2H-MoS2 as tau 2H,=0.38 +/- 0.08 fs and tau 2H,perpendicular to =0.33 +/- 0.06 fs and for 1T-LixMoS2 as tau 1T,=0.32 +/- 0.12 fs and tau 1T,perpendicular to =0.09 +/- 0.07 fs. The isotropic charge delocalization of S3p electrons in the semiconducting 2H phase within the S-Mo-S sheets is assigned to the specific symmetry of the Mo-S bonding arrangement. Formation of 1T-LixMoS2 by lithiation accelerates the in-plane charge transfer by a factor of similar to 1.2 due to electron injection to the Mo-S covalent bonds and concomitant structural repositioning of S atoms within the S-Mo-S sheets. For excitation into out-of-plane orbitals, an accelerated charge transfer by a factor of similar to 3.7 upon lithiation occurs due to S-Li coupling.
Visible light is shown to create a transient metallic S-Mo-S surface layer on bulk semiconducting p-doped indirect-bandgap 2H-MoS2. Optically created electron-hole pairs separate in the surface band bending region of the p-doped semiconducting crystal causing a transient accumulation of electrons in the surface region. This triggers a reversible 2H-semiconductor to 1T-metal phase-transition of the surface layer. Electron-phonon coupling of the indirect-bandgap p-doped 2H-MoS2 enables this efficient pathway even at a low density of excited electrons with a distinct optical excitation threshold and saturation behavior. This mechanism needs to be taken into consideration when describing the surface properties of illuminated p-doped 2H-MoS2. In particular, light-induced increased charge mobility and surface activation can cause and enhance the photocatalytic and photoassisted electrochemical hydrogen evolution reaction of water on 2H-MoS2. Generally, it opens up for a way to control not only the surface of p-doped 2H-MoS2 but also related dichalcogenides and layered systems. The findings are based on the sensitivity of time-resolved electron spectroscopy for chemical analysis with photon-energy-tuneable synchrotron radiation.
Development of functional and stable solid polymer electrolytes (SPEs) for battery applications is an important step towards both safer batteries and for the realization of lithium-based or anode-less batteries. The interface between the lithium and the solid polymer electrolyte is one of the bottlenecks, where severe degradation is expected. Here, the stability of three different SPEs - poly(ethylene oxide) (PEO), poly(epsilon-caprolactone) (PCL) and poly(trimethylene carbonate) (PTMC) - together with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt, is investigated after they have been exposed to lithium metal under UHV conditions. Degradation compounds, e.g. Li-O-R, LiF and LixSyOz, are identified for all SPEs using soft X-ray photoelectron spectroscopy. A competing degradation between polymer and salt is identified in the outermost surface region (<7 nm), and is dependent on the polymer host. PTMC:LiTFSI shows the most severe decomposition of both polymer and salt followed by PCL:LiTFSI and PEO:LiTFSI. In addition, the movement of lithium species through the decomposed interface shows large variation depending on the polymer electrolyte system.