• Journal of Electrochemical Science and Technology
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• v.14 no.4
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• pp.361-368
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• 2023

In lithium-sulfur (Li-S) batteries, encapsulation of sulfur in activated carbon (AC) materials is a promising strategy for preventing the dissolution of lithium polysulfide into electrolytes and enhancing cycle life, because instead of solid-liquid-solid reactions, quasi-solid-state (QSS) reactions occur in the AC micropores. While a high weight fraction of sulfur in S/AC composites is essential for achieving a high energy density of Li-S cells, the deterioration mechanisms under such conditions are still unclear. In this study, we report the deterioration mechanisms during charge-discharge cycling when the discharge products overflow from the AC. Analysis using scanning electron microscopy and energy-dispersive X-ray spectrometry confirms that the sulfur in the S/AC composites migrates outside the AC as cycling progresses, and it is barely present in the AC after 20 cycles, which corresponds to the capacity decay of the cell. Impedance analysis clearly shows that the electrical resistance of the S/AC composite and the charge-transfer resistance of QSS reactions significantly increase as a result of sulfur migration. On the other hand, the charge-discharge cycling performance under limited-capacity conditions, where the discharge products are encapsulated inside the AC, is extremely stable. These results reveal the degradation mechanism of a Li-S cell with micro-porous carbon and provide crucial insights into the design of a S/AC composite cathode and its operating conditions needed to achieve stable cycling performance.

• Korean Chemical Engineering Research
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• v.58 no.2
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• pp.235-247
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• 2020

Simulation study and validation on 50 L/hr pilot-scale Bunsen process was carried out in order to investigate thermodynamics parameters, suitable reactor type, separator configuration, and the optimal conditions of reactors and separation. Sulfur-Iodine is thermochemical process using iodine and sulfur compounds for producing hydrogen from decomposition of water as net reaction. Understanding in phase separation and reaction of Bunsen Process is crucial since Bunsen Process acts as an intermediate process among three reactions. Electrolyte Non-Random Two-Liquid model is implemented in simulation as thermodynamic model. The simulation results are validated with the thermodynamic parameters and the 50 L/hr pilot-scale experimental data. The SO₂ conversions of PFR and CSTR were compared as varying the temperature and reactor volume in order to investigate suitable type of reactor. Impurities in H₂SO₄ phase and HI_X phase were investigated for 3-phase separator (vapor-liquid-liquid) and two 2-phase separators (vapor-liquid & liquid-liquid) in order to select separation configuration with better performance. The process optimization on reactor and phase separator is carried out to find the operating conditions and feed conditions that can reach the maximum SO₂ conversion and the minimum H₂SO₄ impurities in HI_X phase. For reactor optimization, the maximum 98% SO₂ conversion was obtained with fixed iodine and water inlet flow rate when the diameter and length of PFR reactor are 0.20 m and 7.6m. Inlet water and iodine flow rate is reduced by 17% and 22% to reach the maximum 10% SO₂ conversion with fixed temperature and PFR size (diameter: 3/8", length:3 m). When temperature (121℃) and PFR size (diameter: 0.2, length:7.6 m) are applied to the feed composition optimization, inlet water and iodine flow rate is reduced by 17% and 22% to reach the maximum 10% SO₂ conversion.

• Korean Chemical Engineering Research
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• v.61 no.3
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• pp.426-438
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• 2023

Lithium-sulfur batteries, recently attracting attention as next-generation batteries, have high energy density but are limited in application due to sulfur's insulating properties, shuttle phenomenon, and volume expansion. This study used an economical and simple vacuum filtration method to prepare a freestanding electrode without a binder and collector. Carbon nanotubes (CNTs) are used to improve the electrical conductivity of sulfur, where CNT also acts as both collector and conductor. In addition, metal oxides (MO_x, M=Ni, Mg), which are easy to adsorb lithium polysulfide, are added to the CNT/S electrode to suppress the shuttle reaction in lithium-sulfur batteries, which is a result of suppressing the loss of active sulfur material due to the excellent adsorption of lithium polysulfide by metal oxides. The MO_x@CNT/S electrode exhibited higher capacity characteristics and cycle stability than the CNT/S electrode without metal oxides. Among the MO_x@CNT/S electrodes, the NiO@CNT/S electrode displayed a high discharge capacity of 780 mAh g^-1 at 1 C and an extreme capacity decrease to 134 mAh g^-1 after 200 cycles. Although the MgO@CNT/S electrode exhibited a low discharge rate of 544 mAh g^-1 in the initial cycle, it showed good cycle stability with 90% of capacity retention up to 200 cycles. Further, to achieve high capacity and cycle stability, the Ni_0.7Mg_0.3O@CNT/S electrode, mixed with Ni:Mg in the ratio of 0.7:0.3, manifested an initial discharge rate of 755 mAh g^-1 (1 C) and a capacity retention rate of more than 90% after 200 cycles. Therefore, applying binary metal oxides to CNT/S provides a freestanding electrode for developing economical and high-performance Li-S batteries, effectively improving lithium polysulfide's high capacity characteristics and dissolution.

• Journal of the Korean Electrochemical Society
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• v.24 no.3
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• pp.42-51
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• 2021

Dissociation into Lithium-polysulfide electrolyte due to repeated cycles during the Lithium/Sulfur battery reaction is a major problem of reduced battery lifespan. We searched for a porous carbon with a large specific surface area that infiltrated S to prevent liquid Lithium-polysulfide from being dissolved in electrolyte, induce adsorption of Lithium-polysulfide, and further increase conductivity. In order to obtain porous carbon spheres with a large specific surface area, the carbon spheres of 1939 m²/g were raised to 2200 m²/g through additional KOH treatment. In addition, through heat treatment with S, a carbon sulfur compound containing 75 wt% of S was fabricate and material analysis was conducted on the possibility of using the cathode material. The electrochemical characteristics of the Reference (622; sulfur: 60%, conductive material: 20%, binder: 20%) pouch cell and the pouch cell made using 75wt% of carbon sulfur compound were analyzed. 75wt% of carbon sulfur pouch cell showed a 20% increase in lifespan and 10% improvement in C-rate compared to the Reference pouch cell after 50 cycles.

• Bulletin of the Korean Chemical Society
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• v.27 no.9
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• pp.1310-1314
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• 2006

Sulfur-substituted $LiMn_{0.9}Cr_{0.1}O_{2-x}S_x$ $(0\;\leq\;x\;\leq\;0.1)$ layered oxides have been prepared by solid state reaction under inert atmosphere. From powder X-ray diffraction analyses, all the present lithium manganates were found to be crystallized with monoclinic-layered structure. Electrochemical measurements clearly demonstrated that, in comparison with the pristine $LiMn_{0.9}Cr_{0.1}O_2$, the sulfur-substituted derivatives exhibit smaller discharge capacities for the entire cycle range but the recovery of discharge capacity after the initial several cycles becomes faster upon sulfur substitution. The effect of the sulfur substitution on the chemical bonding nature of $LiMn_{0.9}Cr_{0.1}O_{2-x}S_x$has been investigated using X-ray absorption spectroscopic (XAS) analyses at Mn and Cr K-edges. According to Mn K-edge XAS results, the trivalent oxidation state of manganese ion remains unchanged before and after the substitution whereas the local structure around manganese ions becomes more distorted with increasing the substitution rate of sulfur. On the other hand, the replacement of oxygen with sulfur has negligible influence on the local atomic arrangement around chromium ions, which is surely due to the high octahedral stabilization energy of $Cr^{+III} $ ions. Based on the present experimental findings, we have suggested that the decrease of discharge capacity upon sulfur substitution is ascribable to the enhanced structural distortion of $MnO_6$ octahedra and/or to the formation of covalent Li-S bonds, and the accompanying improvement of cyclability would be related to the depression of Mn migration and/or to the pillaring effect of larger sulfur anion.

• Transactions of the Korean hydrogen and new energy society
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• v.21 no.4
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• pp.278-285
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• 2010

The Sulfur-Iodine (SI) thermochemical hydrogen production process of a closed cycle consists of three sections, which are so called the Bunsen reaction section, the $H_2SO_4$ decomposition section and the HI decomposition section. To identify the role of oxygen that can be supplied to the Bunsen reaction section via the $H_2SO_4$ decomposition section, Bunsen reactions with a $SO_2,\;SO_2-O_2$ mixture and $SO_2-N_2$ mixture as feed gases were carried out using a stirred reactor in the presence of $I_2/H_2O$ mixture. As the results, the amounts of $I_2$ unreacted under the feed of mixture gases were higher than those under the feed of $SO_2$ gas only, and the amount of HI produced was relatively decreased. The results of Bunsen reaction using $SO_2-O_2$ mixture were similar to those using $SO_2-N_2$ mixture. It may be concluded that an oxygen in $SO_2-O_2$ mixture has a role as a carrier gas like a nitrogen in $SO_2-N_2$ mixture. The effects of oxygen were decreased with increasing temperature and decreasing oxygen content in $SO_2-O_2$ mixture.

• Korean Chemical Engineering Research
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• v.46 no.3
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• pp.633-638
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• 2008

The bunsen reaction, part of IS(Iodine-sulfur) cycle that one of the hydrogen production by the thermochemical water splitting, was investigated. It was observed that $H_2SO_4$ was uniformly generated and generation of $H_2SO_4$ was independent of iodine input. However, generation of HI was decreased with increasing iodine input. It was thought that HI and unreacted iodine were formed complex compound such as $HI_3$ $HI_5$ or $HI_7$. The complex compound accelerated liquid-liquid separation properties in the product. It was also revealed that reaction kinetics was increased with increasing iodine input. Liquid-liquid separation properties were improved with increasing iodine input and reaction temperature. Moreover, no side reaction was occurred at all reaction conditions.

• Proceedings of the Korean Society of Crop Science Conference
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• 2017.06a
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• pp.187-187
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• 2017

Cadmium (Cd) pollution is rapidly increasing in worldwide due to industrialization and urbanization. In addition to its negative effects on the environment, Cd pollution adversely affects human health. Rice (Oryza sativa L.) is an important agricultural crop worldwide, including South Korea, and studies have examined its ability to alleviate Cd uptake from the soil into plants. However, information about the relationship between sulfur (S) and antioxidants in rice seedlings is still limited with regard to Cd phytotoxicity. We therefore investigated the changes in reactive oxygen species (ROS) and antioxidants in rice (Oryza sativa L. 'Dongjin') seedlings exposed to toxic Cd, S treatment, or both. The exposure of rice seedlings to $30{\mu}M$ Cd inhibited plant growth; increased the contents of superoxide, hydrogen peroxide, and malondialdehyde (MDA); and induced Cd uptake by the roots, stems, and leaves. Application of S to Cd-stressed seedlings decreased Cd-induced oxidative stress by increasing the capacity of the glutathione (GSH)-ascorbate (AsA) cycle, promoted S assimilation by increasing cysteine, GSH, and AsA contents in treated plants, and decreased Cd transfer from the roots to the stems and leaves. In conclusion, S application of plants under Cd stress promoted Cys and GSH biosynthesis and GSH-AsA cycle activity, thereby lowering the rate of Cd transfer to plant shoots and promoting the scavenging of the ROS that resulted from Cd toxicity, thus alleviating the overall Cd toxicity. Therefore, these results provide insights into the role of S in regulating the tolerance, uptake, and translocation of Cd in rice seedlings. The results of this study indicate that S application should have potential as a tool for mitigating Cd-stress in cereal crops, especially rice.

• Journal of the Korean Society of Marine Environment & Safety
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• v.24 no.6
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• pp.834-840
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• 2018

In this study, the characteristics of air pollutant emissions from ships' engines have been investigated by conducting E2 and E3 cycle mode tests. A engine 360Ps (Doosan L126TIH engine) and 400kW dynamometer Horiba-Schenck were utilized for engine tests. The FTIR analyzer and SPC were used to measure exhaust gas (NOx, SOx etc.) and PM (particulate matter), respectively. The results showed that the emissions of THC and CO produced from engine were increased with the increase of sulfur content in fuel oils at E2 and E3 cycle modes. The kinetic viscosity of the fuel increased as the sulfur content of the fuel increased, thereby the specific fuel oil consumption (SFC) of the engine improved. This result is considered to be due to improved combustion conditions due to increased average diameters of sprayed particles and due to increased kinetic viscosity under constant fuel injection pressure in this study. In the case of NOx emission, this study showed no significant change in amount of sulfur content.

• Korean Chemical Engineering Research
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• v.46 no.5
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• pp.845-851
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• 2008

Oxidative desulfurizaton of model sulfur compounds and Industrial diesel fuel(LCO; Light Cycle Oil) over Ti-grafted SBA-15 catalyst was studied in a batch reactor with tert-Butyl Hydroperoxide(TBHP) as oxidant. Effects of Ti loading, TBHP/Sulfur mole ratio, reaction temperature on ODS activity and kinetic parameters were investigated. Ti-grafted SBA-15 catalyst showed higher sulfur removal activity in the oxidative desulfurization reaction of refractory sulfur compounds(DBT and 4, 6-DMDBT) and LCO, suggesting that Ti-grafted SBA-15 catalyst could be a good candidate for ODS catalyst.