Study of Li-S batteries by S K-edge RIXS spectroscopyMatjaž Kavčič
, Matjaž Žitnik
, Klemen Bučar
, Marko Petrič
, Iztok Arčon
, Robert Dominko
, Alen Vižintin
, 2016, published scientific conference contribution abstract
Abstract: Li-S batteries are considered as one of the most promising candidates for future batteries in applications where high energy density is required . Despite that the general principle of operation is known for a long time , the lack of detailed understanding of relevant operation mechanisms has so far prevented their extensive use. A Li-S battery is composed of a lithium metal anode and a sulfur based cathode, separated by a porous separator wetted with electrolyte. During the battery cycle the reduction and oxidation of S to Li2S and back proceeds through a complicated equilibrium mixture of compounds that are typically dissolved in the electrolyte in the form of long and short chain polysulfides. In order to improve our understanding of polysulfide formation and its interactions within electrode, which are essential to achieve the long term cycling stability, development and application of new analytical tools is required.
In this work sulfur K-edge resonant X-ray emission (RXES) measurements were performed on the Li-S battery in operando mode. The experiment was performed at the ID26 beamline at ESRF using the Johansson type tender x-ray emission spectrometer . Full K-L RIXS maps were recorded on a set of chemically prepared Li2Sx sample standards characterized by different Li:S stoichiometric ratio, followed by the operando measurements on Li-S battery. Using the spectra recorded on Li2Sx standards two excitation energies were chosen and RXES spectra from the back of the battery cathode were sequentially acquired during one discharge cycle (C20). The relative amounts of each sulfur compound in the cathode during the discharge cycle were determined from the linear combination fit using measured reference standard spectra. Because of resonant excitation conditions the sensitivity for the polysulfide detection was significantly enhanced. Our work sets up S K-edge RIXS spectroscopy as an important analytical tool to study the mechanism of Li-polysulfide formation in the cathode and their interaction with the host matrix and electrolyte.
Keywords: RIXS, RXES, Li-S battery, operando, Sulphur K-edge XANES, Lithium polysulphides, Li2S
Published in RUNG: 28.06.2016; Views: 5159; Downloads: 0
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