11. ZAČETNE FAZE RASTI ORGANSKIH POLPREVODNIKOV NA SiO2Alen Oršulić, 2018, magistrsko delo Opis: Pričujoče delo obravnava začetne faze rasti organskega polprevodnika N, N´-1H, 1H- perfluorobutil diciano perilen karboksamid (PDIF-CN2) na površini silicijevega dioksida (SiO2). PDIF-CN2 je bil na površino SiO2 nanešen z rotacijskim nanašalcem pod različnimi pogoji. Glede na pogoje nanosa se je spreminjala morfologija narejenih vzorcev. Morfologije so bile analizirane z mikroskopom na atomsko silo. S slik mikroskopa na atomsko silo smo z višinsko porazdelitvijo in funkcijo spektralne gostote moči pridobili podatke o prekritosti vzorcev z otoki molekul PDIF-CN2, višini otokov na površini vzorca, povprečni hrapavosti vzorca, korelacijski dolžini med otoki ter spektralni dolžini in indeksu. Z višinsko porazdelitvijo je bilo ugotovljeno, da znaša povprečna višina otokov na površini vzorcev približno 1,1 nm in da se prekritost vzorcev z molekulami povečuje s povečevanjem koncentracije raztopine in zmanjševanjem kotne hitrosti pri nanosu z rotacijskim nanašalcem. Analiza funkcije spektralne gostote moči površin je pokazala, da je pri večini vzorcev korelacijska dolžina čez celotno preiskano območje, da se povprečna hrapavost povečuje s povečevanjem koncentracije raztopine in kotne hitrosti ter da pospešek pri rotacijskem nanašanju skupaj s kotno hitrostjo vpliva na obliko fraktalov na površini vzorcev. Ključne besede: PDIF-CN2, mikroskop na atomsko silo, rotacijsko nanašanje, Gwyddion, avtokorelacijska funkcija, funkcija spektralne gostote moči. Objavljeno v RUNG: 24.09.2018; Ogledov: 4907; Prenosov: 166 Celotno besedilo (2,26 MB) |
12. Sulfur based batteries studied by in-operando S K-edge RIXS and XAS spectroscopyMatjaž Kavčič, Ana Robba, Janez Bitenc, Alen Vižintin, Iztok Arčon, Matjaž Žitnik, Klemen Bučar, Robert Dominko, 2018, objavljeni povzetek znanstvenega prispevka na konferenci Opis: 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). Ključne besede: Mg-Sulphur batteries, XANES, RIXS Objavljeno v RUNG: 13.09.2018; Ogledov: 4506; Prenosov: 0 Gradivo ima več datotek! Več... |
13. Fluorinated ether based electrolyte for high-energy lithium-sulfur batteries : Li [sup] + solvation role behind reduced polysulfide solubilitySara Drvarič Talian, Steffen Jeschke, Alen Vižintin, Klemen Pirnat, Iztok Arčon, Giuliana Aquilanti, Patrik Johansson, Robert Dominko, 2018, objavljeni povzetek znanstvenega prispevka na konferenci Ključne besede: Li-žveplive baterije, XANES, polisulfidi Objavljeno v RUNG: 12.09.2018; Ogledov: 3228; Prenosov: 0 Gradivo ima več datotek! Več... |
14. Polysulfides formation in different electrolytes from the perspective of X-ray absorption spectroscopyRobert Dominko, Alen Vižintin, Giuliana Aquilanti, Lorenzo Stievano, Maria Joseph Helen, Anji Reddy Munnangi, Maximilian Fichtner, Iztok Arčon, 2018, izvirni znanstveni članek Opis: Li-S batteries are promising energy storage technology for the future, however there two major problems remained which need to be
solved before successful commercialization. Capacity fading due to polysulfide shuttle and corrosion of lithium metal are directly
connected with the type and quantity of electrolyte used in the cells. Several recent works show dependence of the electrochemical
behavior of Li-S batteries on type of the electrolyte. In this work we compare and discuss a discharge mechanism of sulfur conversion
in three different electrolytes based on measurements with sulfur K-edge XAS. The sulfur conversion mechanism in the ether based
electrolytes, the most studied type of solvents in the Li-S batteries, which are enabling high solubility of polysulfides are compared
with the fluorinated ether based electrolytes with a reduced polysulfide solubility and in carbonate based electrolytes with the sulfur
confined into a ultramicroporous carbon. In all three cases the sulfur reduction proceeds through polysulfide intermediate phases
with a difference on the type polysulfides detected at different steps of discharge. Ključne besede: Li-S batteries, operando sulphur K-edge XANES, EXAFS, Li-polysulphides Objavljeno v RUNG: 01.06.2018; Ogledov: 3616; Prenosov: 0 Gradivo ima več datotek! Več... |
15. A Mechanistic Study of Magnesium Sulfur BatteriesAna Robba, Alen Vižintin, Jan Bitenc, Gregor Mali, Iztok Arčon, Matjaž Kavčič, Matjaž Žitnik, Klemen Bučar, Giuliana Aquilanti, Charlotte Martineau-Corcos, Anna Randon-Vitanova, Robert Dominko, 2017, izvirni znanstveni članek Opis: 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 and
NMR studies, the end discharge phase involves MgS with Mg atoms in a tetrahedral
environment resembling the wurtzite structure, while chemically synthesized MgS crystalizes
in the rock-salt structure with octahedral coordination of magnesium. Ključne besede: magnesium, sulfur, rechargeable batteries, XAS, NMR Objavljeno v RUNG: 19.10.2017; Ogledov: 4438; Prenosov: 0 Gradivo ima več datotek! Več... |
16. 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: 5172; Prenosov: 0 Gradivo ima več datotek! Več... |
17. 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: 5700; Prenosov: 0 Gradivo ima več datotek! Več... |
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