11. The mechanism of Li2S activation in lithium-sulfur batteries: Can we avoid the polysulfide formation?Alen Vižintin, Laurent Chabanne, Elena Tchernychova, Iztok Arčon, Lorenzo Stievano, Giuliana Aquilanti, Markus Antonietti, Tim-Patric Fellinger, Robert Dominko, 2017, izvirni znanstveni članek Opis: Electrochemical reactions in the LieS batteries are considered as a multistep reaction process with at least
2e3 equilibrium states. Here we report a possibility of having a conversion of Li2S into sulfur without
detectible formation of polysulfides. That was confirmed by using a novel material system consisting of
carbon coated Li2S particles prepared by carbothermal reduction of Li2SO4. Two independent in operando
measurements showed direct oxidation of Li2S into sulfur for this system, with almost negligible formation
of polysulfides at potentials above 2.5 V vs. Li/Liþ. Our results link the diversity of first charge profiles in the
literature to the Li2S oxidation mechanism and show the importance of ionic wiring within the material.
Furthermore, we demonstrate that the Li2S oxidation mechanism depends on the relative amount of
soluble sulfur in the electrolyte. By controlling the type and the amount of electrolyte within the encapsulating
carbon shell, it is thereby possible to control the reaction mechanism of Li2S activation. Ključne besede: Lithium-sulfur batteries
Li2S active material
XAS
UV/Vis spectroscopy
Li2S activation Objavljeno v RUNG: 03.03.2017; Ogledov: 5184; Prenosov: 0 Gradivo ima več datotek! Več... |
12. Operando characterization of batteries using x-ray absorption spectroscopy: advances at the beamline XAFS at synchrotron ElettraGiuliana Aquilanti, marco Giorgetti, Robert Dominko, Lorenzo Stievano, Iztok Arčon, Nicola Novello, Luca Ivanc Olivieri, 2017, izvirni znanstveni članek Opis: X-ray absorption spectroscopy is a synchrotron radiation based technique that is able to
provide information on both local structure and electronic properties in a chemically selective
manner. It can be used to characterize the dynamic processes that govern the electrochemical
energy storage in batteries, and to shed light on the redox chemistry and changes in structure
during galvanostatic cycling to design cathode materials with improved properties. Operando
XAS studies have been performed at beamline XAFS at Elettra on different systems. For
Li-ion batteries, a multiedge approach revealed the role of the different cathode components
during the charge and discharge of the battery. In addition, Li-S batteries for automotive
applications were studied. Operando sulfur K-edge XANES and EXAFS analysis was used to
characterize the redox chemistry of sulfur, and to relate the electrochemical mechanism to its
local structure. Ključne besede: operando studies, x-ray absorption spectroscopy, Li-ion batteries, Li-S batteries Objavljeno v RUNG: 03.03.2017; Ogledov: 6190; Prenosov: 0 Gradivo ima več datotek! Več... |
13. 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, objavljeni povzetek znanstvenega prispevka na konferenci Opis: Li-S batteries are considered as one of the most promising candidates for future batteries in applications where high energy density is required [1]. Despite that the general principle of operation is known for a long time [2], 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 [3]. 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. Ključne besede: RIXS, RXES, Li-S battery, operando, Sulphur K-edge XANES, Lithium polysulphides, Li2S Objavljeno v RUNG: 28.06.2016; Ogledov: 5715; Prenosov: 0 Gradivo ima več datotek! Več... |
14. |