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Abstract: This study explores the structural changes of hard carbon (HC) negative electrodes in sodium-ion batteries induced by insertion of Na ions during sodiation. X-ray Raman spectroscopy (XRS) was used to record both C and Na K-edge absorption spectra from bulk HC anodes carbonized at different temperatures and at several points during sodiation and desodiation. Comparing the [pi]*/[sigma]* regions in the C K-edge spectra sp2/sp3 hybridization ratio of material was determined. Higher carbonization temperatures led to increased order in graphitic structure and shorter bond lengths. Sodiation caused a decrease in graphitic layer order due to inserted Na ions. Complementary operando solid state 23Na nuclear magnetic resonance (ssNMR) studies confirmed the structural changes, while showing pore filling mechanism, which is not observed in ex situ measurements, primarily at higher carbonization temperatures. XRS analysis of Na K-edge spectra revealed systematic variations in the solid electrolyte interface (SEI) composition during cycling. Changes in XRS spectra were attributed to both SEI composition alterations, accompanied by the insertion/adsorption of Na ions at defect sites within the carbon structure.
Keywords: hard carbon, RIXS, carbon XANES, EXAFS, NMR, Na battery
Published in RUNG: 10.09.2024; Views: 2352; Downloads: 9
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Abstract: X-ray Raman spectroscopy (XRS) is an emerging spectroscopic technique that utilizes inelastic scattering of hard Xrays to study X-ray absorption edges of low Z elements in bulk material. It was used to identify and quantify the amount of carbonyl bonds in a cathode sample, in order to track the redox reaction inside metal−organic batteries during the charge/ discharge cycle. XRS was used to record the oxygen K-edge absorption spectra of organic polymer cathodes from different multivalent metal−organic batteries. The amount of carbonyl bond in each sample was determined by modeling the oxygen K-edge XRS spectra with the linear combination of two reference compounds that mimicked the fully charged and the fully discharged phases of the battery. To interpret experimental XRS spectra, theoretical calculations of oxygen K-edge absorption spectra based on density functional theory were performed. Overall, a good agreement between the amount of carbonyl bond present during different stages of battery cycle, calculated from linear combination of standards, and the amount obtained from electrochemical characterization based on measured capacity was achieved. The electrochemical mechanism in all studied batteries was confirmed to be a reduction of double carbonyl bond and the intermediate anion was identified with the help of theoretical calculations. X-ray Raman spectroscopy of the oxygen K-edge was shown to be a viable characterization technique for accurate tracking of the redox reaction inside metal−organic batteries.
Keywords: X-ray Raman spectroscopy, meta-organic batteries, oxygen K-edge XANES, electrochemical processes
Published in RUNG: 24.03.2022; Views: 3109; Downloads: 22
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Keywords: Li-sulphur batteries, Sulphur XANES, magnesium
Published in RUNG: 15.10.2020; Views: 3888; Downloads: 0

Abstract: We report the synthesis and detailed structural and chemical characterization including electrochemical properties of a lithium vanadium oxy/fluoro-phosphate material. To the best of our knowledge, we have for the first time synthesized a LiVPO4O-type phase with a mixed O/F ligand. In the synthesis procedure, the LiVPO4O precursor compound was fluorinated via LiF incorporation, with preservation of the LiVPO4O framework structure. The operating potential of the synthesized material is increased compared to that of the LiVPO4O precursor (4.12 V vs 3.95 V versus metallic lithium, respectively). The related increase in operating potential was assigned to the effect of the intermixing O/F ligand, which is attained via the successful fluorine incorporation into the LiVPO4O structure. A characterization of the investigated materials was performed using microscale-covering XRD, XANES, and NMR techniques as well as nanoscale spatially resolved imaging and analytical STEM techniques. The obtained oxy/fluoro-phosphate phase is isostructural to LiVPO4O; however, the presence of the mixed O/F ligand promoted a higher symmetry of vanadium octahedra. These variations of the vanadium local environment along with the observed inhomogeneous distribution of the incorporated fluorine gave rise to the minor local deviations in vanadium valence. Our results clearly emphasize the connection among the fluorine ligand incorporation, its local distribution, and the electrochemical properties of the material.
Keywords: LiVPO4O, XRD, SEM, V XANES, Tavorite-Type, electrochemical properties
Published in RUNG: 17.02.2020; Views: 4451; Downloads: 0
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Abstract: Sulfur based batteries are considered as very attractive energy storage devices. Sulfur is one of the most abundant elements in the earth, it is electrochemically active material which can accept up to two electrons per atom. In combination with alkali metals, sulfur forms electrochemical couples with much higher theoretical energy density compared to Li-ion batteries commonly available today. At the moment, the electrochemical couple with Li is most extensively studied. While the main principle of operation is known the relevant operation mechanism(s) is not completely clear. Even more promising is the electrochemical couple with Mg providing almost twofold higher volumetric energy density due to its ability to provide two electrons during oxidation. However, Mg-S batteries are still in the very early stage of research and development and the complex mechanism of sulfur conversion has been less extensively studied. In order to improve the understanding of sulfur electrochemical conversion and its interactions within electrode, we need to apply new experimental approaches capable to provide precise information about local environment of S in the cathode during battery operation. In our work, resonant inelastic X-ray scattering (RIXS) and XAS measurements at the sulfur K-edge performed in operando mode were used to study the lithium-polysulfide formation during the discharge process. Measurements were performed at ID26 beamline of the ESRF synchrotron using tender X-ray emission spectrometer [1]. Resonant excitation condition enhanced the sensitivity for the lithium−polysulfide detection. On the other hand, the sulfate signal from the electrolyte was heavily suppressed and the self-absorption effects minimized due to fixed excitation energy. This experimental methodology was used to provide quantitative analysis of sulfur compounds in the cathode of a Li−S battery cell during the discharge process [2]. The high-voltage plateau in the discharge curve was characterized by a rapid conversion of solid sulfur into liquid phase Li polysulfides reaching its maximum at the end of this plateau. At this point the starting point for the precipitation of the Li2S from the liquid polysulfide phase was observed. The same approach has been used also for the Mg-S battery revealing similar mechanism as in case of Li-S battery [3]. The electrochemical conversion of sulfur with magnesium proceeds through two well-defined plateaus, which correspond to the equilibrium between sulfur and Mg polysulfides (high-voltage plateau) and polysulfides and MgS (low-voltage plateau).
Keywords: Mg-Sulphur batteries, XANES, RIXS
Published in RUNG: 13.09.2018; Views: 7039; Downloads: 0
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