• Korean Chemical Engineering Research
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• v.55 no.4
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• pp.483-489
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• 2017

The loss of the sulfur cathode material through dissolution of the polysulfide into electrolyte causes a significant capacity reduction of the lithium-sulfur cell during the charge-discharge reaction, thereby debilitating the electrochemical performance of the cell. We addressed this problem by using a chemical and physical approach called reduction of polysulfide dissolution through direct coating functional inorganic (graphene oxide) or organic layer (polyethylene oxide) on electrode, since the deposition of external functional layer can chemically interact with polysulfide and physically prevent the leakage of lithium polysulfide out of the electrode. Through this approach, we obtained a composite electrode for a lithium-sulfur battery (sulfur: 60%) coated with uniform and thin external functional layers where the thin external layer was coated on the electrode by solution coating and drying by a subsequent heat treatment at low temperature (${\sim}80^{\circ}C$). The external functional layer, such as inorganic or organic layer, not only alleviates the dissolution of the polysulfide electrolyte during the charging/discharging through physical layer formation, but also makes a chemical interaction between the polysulfide and the functional layer. As-formed lithium-sulfur battery exhibits stable cycling electrochemical performance during charging and discharging at a reversible capacity of 700~1187 mAh/g at 0.1 C (1 C = 1675 mA/g) for 30 cycles or more.

• Journal of Hydrogen and New Energy
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• v.13 no.4
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• pp.259-269
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• 2002

A battery based on the lithium/elemental sulfur redox couple has the advantage of high theoretical specific capacity of 1,675 mAh/g-sulfur. However, Li/S battery has bad cyclic durability at room temperature due to sulfur active material loss resulting from lithium polysulfide dissolution. To improve the cycle life of Li/S battery, PEGDME (Poly(ethylene glycol) dimethyl ether) 500 containing 1M LiTFSI salt which has high viscosity was used as electrolyte to retard the polysulfide dissolution and nano-sized $Mg_{0.6}Ni_{0.4}O$ was added to sulfur cathode as additive to adsorb soluble polysulfide within sulfur cathode. From experimental results, the improvement of the capacity and cycle life of Li/S battery was observed( maximum discharge capacity : 1,185 mAh/g-sulfur, C50/C1 = 85 % ). Through the charge-discharge test, we knew that PEGDME 500 played a role of preventing incomplete charge-discharge $behavior^{1,2)$. And then, in sulfur dissolution analysis and rate capability test, we first confirmed that nano-sized $Mg_{0.6}Ni_{0.4}O$ had polysulfide adsorbing effect and catalytic effect of promoting the Li/S redox reaction. In addition, from BET surface area analysis, we also verified that it played the part of increasing the porosity of sulfur cathode.

• Korean Chemical Engineering Research
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• v.60 no.2
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• pp.184-192
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• 2022

Porous NiO synthesized via hydrothermal synthesis was used in the electrodes of lithium-sulfur batteries to inhibit the elution of lithium polysulfide. The electrode of the lithium-sulfur battery was manufactured as a freestanding flexible electrode using an economical and simple vacuum filtration method without a current collector and a binder. The porous NiO-added S/CNT/NiO electrode exhibited a high initial discharge capacity of 877 mA h g^-1 (0.2 C), which was 125 mA h g^-1 higher than that of S/CNT, and also showed excellent retention of 84% (S/CNT: 66%). This is the result of suppressing the dissolution of lithium polysulfide into the electrolyte by the strong chemical bond between NiO and lithium polysulfide during the charging and discharging process. In addition, for the flexibility test of the S/CNT/NiO electrode, the 1.6 × 4 cm² pouch cell was prepared and exhibited stable cycle characteristics of 620 mA h g^-1 in both the unfolded and folded state.

• Clean Technology
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• v.28 no.2
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• pp.97-102
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• 2022

Lithium sulfur (Li-S) batteries have attracted considerable attention as a promising candidate for next-generation power sources due to their high theoretical energy density, low cost, and eco-friendliness. However, the poor electrical conductivity of sulfur and its insoluble discharging products (Li₂S₂/Li₂S), large volume changes, severe self-discharge, and dissolution of lithium polysulfide intermediates result in rapid capacity fading, low Coulombic efficiency, and safety risks, hindering Li-S battery commercial development. In this study, a three-dimensionally (3D) connected hierarchical porous carbon framework (HPCF) derived from waste sunflower seed shells was synthesized as a sulfur host for Li-S batteries via a chemical activation method. The natural 3D connected structure of the HPCF, originating from the raw material, can effectively enhance the conductivity and accessibility of the electrolyte, accelerating the Li⁺/electron transfer. Additionally, the generated micropores of the HPCF, originated from the chemical activation process, can prevent polysulfide dissolution due to the limited space, thereby improving the electrochemical performance and cycling stability. The HPCF/S cell shows a superior capacity retention of 540 mA h g^-1 after 70 cycles at 0.1 C, and an excellent cycling stability at 2 C for 700 cycles. This study provides a potential biomass-derived material for low-cost long-life Li-S batteries.

• Carbon letters
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• v.19
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• pp.40-46
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• 2016

Nitrogen-atom doped graphene oxide was considered to prevent the dissolution of polysulfide and to guarantee the enhanced redox reaction of sulfur for good cycle performance of lithium sulfur cells. In this study, we used urea as a nitrogen source due to its low cost and easy preparation. To find the optimum urea content, we tested three different ratios of urea to graphene oxide. The morphology of the composites was examined by field emission scanning electron microscope. Functional groups and bonding characterization were measured by X-ray photoelectron spectroscopy. Electrochemical properties were characterized by cyclic voltammetry in an organic electrolyte solution. Compared with thermally reduced graphene/sulfur (S) composite, nitrogen-doped graphene/S composites showed higher electroactivity and more stable capacity retention.

• 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 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.