Magnesium–sulfur batteries are considered as attractive energy-storage devices due to the abundance of electrochemically active materials and high theoretical energy density. Here we report the ...mechanism of a Mg–S battery operation, which was studied in the presence of simple and commercially available salts dissolved in a mixture of glymes. The electrolyte offers high sulfur conversion into MgS in the first discharge with low polarization. The electrochemical conversion of sulfur with magnesium proceeds through two well-defined plateaus, which correspond to the equilibrium between sulfur and polysulfides (high-voltage plateau) and polysulfides and MgS (low-voltage plateau). As shown by XANES, RIXS (resonant inelastic X-ray scattering), and NMR studies, the end discharge phase involves MgS with Mg atoms in a tetrahedral environment resembling the wurtzite structure, while chemically synthesized MgS crystallizes in the rock-salt structure with octahedral coordination of magnesium.
In this work, we characterise the performance of a Sharp optical aerosol sensor model GP2Y1010AU0F. The sensor was exposed to different environments: to a clean room, to a controlled atmosphere with ...known aerosol size distribution and to the ambient atmosphere on a busy city street. During the exposure, the output waveforms of the sensor pulses were digitised, saved and a following offline analysis enabled us to study the behaviour of the sensor pulse-by-pulse. A linear response of the sensor on number concentration of the monosized dispersed PSL particles was shown together with an almost linear dependence on particle diameters in the 0.4 to 4 micrometer range. The gathered data about the sensor were used to predict its response to an ambient atmosphere, which was observed simultaneously with a calibrated optical particle counter.
X-ray Raman spectroscopy (XRS) is an emerging spectroscopic technique that utilizes inelastic scattering of hard X-rays 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.
Human hair absorbs numerous biomolecules from the body during its growth. This can act as a fingerprint to determine substance intake of an individual, which can be useful in forensic studies. The ...cocaine concentration profile along the growth axis of hair indicates the time evolution of the metabolic incorporation of cocaine usage. It could be either assessed by chemical extraction and further analysis of hair bundels, or by direct single hair fibre analysis with mass spectroscopy imaging (MSI). Within this work, we analyzed the cocaine distribution in individual hair samples using MeV-SIMS. Unlike conventional surface analysis methods, we demonstrate high yields of nonfragmented molecular ions from the surface of biological materials, resulting in high chemical sensitivity and non-destructive characterisation. Hair samples were prepared by longitudinally cutting along the axis of growth, leaving half-cylindrical shape to access the interior structure of the hair by the probing ion beam, and attached to the silicon wafer. A focused 5.8 MeV 35Cl6+ beam was scanned across the intact, chemically pristine hair structure. A non-fragmented protonated M+ H+ cocaine molecular peak at m/z = 304 was detected and localized along the cross-section of the hair. Its intensity exhibits strong fluctuations along the direction of the hair's growth, with pronounced peaks as narrow as 50 micrometres, corresponding to a metabolic incorporation time of approx. three hours.
An experimental and theoretical study of phosphorus electronic structure based on high energy resolution X-ray emission spectroscopy was performed. The Kα and Kβ emission spectra of several ...phosphorus compounds were recorded using monochromatic synchrotron radiation and megaelectronvolt (MeV) proton beam for target excitation. Measured spectra are compared to the results of ab initio quantum chemical calculations based on density functional theory (DFT). Clear correlation between energy position of the Kα emission line and the phosphorus formal oxidation state as well as DFT-calculated number of valence electrons is obtained; measured energy shifts are reproduced by the calculations. Chemical sensitivity is increased further by looking at the Kβ emission spectra probing directly the structure of occupied molecular orbitals. Energies and relative intensities of main components are given together with the calculated average atomic character of the corresponding molecular orbitals involved in transitions.
The electronic structure of phosphorus, sulfur, and chlorine in compounds with T d and C 3v local symmetries was studied with high-resolution Kβ X-ray emission spectroscopy (XES) in the tender X-ray ...range. Measured spectra are compared to the results of ab initio quantum chemical calculations based on density functional theory (DFT). The spectral structure is reproduced by the model spectra of isolated XO4 n– and XO3 n– (X = P, S, or Cl) anions incorporating only the first coordination sphere around the central atom. The main spectral components can be explained by the molecular orbital theory. Finally, the potential of XES spectroscopy combined with DFT calculations to study the electronic structure of third-row elements in a slightly larger molecule is investigated.
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 π∗/σ∗ 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.
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•Higher carbonization temperatures yield Hard Carbons with increased graphitic order.•Na ion insertion during desodiation causes decrease of graphitic order.•Pore filling is observed only in hard carbons at high preparation temperatures.
In this paper we report an X-ray emission study of bulk aqueous sulfuric acid. Throughout the range of molarities from 1 M to 18 M the sulfur Kβ emission spectra from H2SO4 (aq) depend on the molar ...fractions and related deprotonation of H2SO4. We compare the experimental results with results from emission spectrum calculations based on atomic structures of single molecules and structures from ab initio molecular dynamics simulations. We show that the S Kβ emission spectrum is a sensitive probe of the protonation state of the acid molecules. Using non-negative matrix factorization we are able to extract the fractions of different protonation states in the spectra, and the results are in good agreement with the simulation for the higher part of the concentration range.
Particle induced X-ray emission (PIXE) at microprobe of Jožef Stefan Institute is used to measure two-dimensional quantitative elemental maps of biological tissue. To improve chemical and biological ...understanding of the processes in vivo, supplementary information about chemical bonding and/or molecular distributions could be obtained by heavy-ion induced molecular desorption and a corresponding mass spectroscopy with Time-Of-Flight (TOF) mass spectrometer. As the method combines the use of heavy focused ions in MeV energy range and TOF Secondary Ion Mass Spectrometry, it is denoted as MeV SIMS.
At Jožef Stefan Institute, we constructed a linear TOF spectrometer and mount it to our multipurpose nuclear microprobe. A beam of 8MeV 35Cl7+ could be focused to a diameter of better than 3μm×3μm and pulsed by electrostatic deflection at the high-energy side of accelerator. TOF mass spectrometer incorporates an 1m long drift tube and a double stack microchannel plate (MCP) as a stop detector positioned at the end of the drift path. Secondary ions are focused at MCP using electrostatic cylindrical einzel lens.
Time of flight spectra are currently acquired with a single-hit time-to-digital converter. Pulsed ion beam produces a shower of secondary ions that are ejected from positively biased target and accelerated towards MCP. We start our time measurement simultaneously with the start of the beam pulse. Signal of the first ion hitting MCP is used to stop the time measurement. Standard pulses proportional to the time of flight are produced with time to analog converter (TAC) and fed into analog-to-digital converter to obtain a time histogram. To enable efficient detection of desorbed fragments with higher molecular masses, which are of particular interest, we recently implemented a state-of art Field Programmable Gate Array (FPGA)-based multi-hit TOF acquisition. To test the system we used focused 8MeV 35Cl7+ ion beam with pulse length of 180ns. Mass resolution of measured SIMS spectra, dominantly determined by the duration of the beam pulse, is in good agreement with resolution estimated from pulse length. With improved high-voltage switching ability that will enable beam pulses with duration of 50ns, a mass resolution of better than 500 is anticipated.
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