• Clean Technology
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• v.27 no.3
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• pp.223-231
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• 2021

In order to address many issues associated with large volume changes of silicon, which has very low electrical conductivity but offers about 10 times higher theoretical capacity than graphite (Gr), a silicon nanoparticles/hollow carbon (SiNP/HC) composite having bimodal-mesopores was prepared using silica nanoparticles as a template. A control SiNP/C composite without a hollow structure was also prepared for comparison. The physico-chemical and electrochemical properties of SiNP/HC were analyzed by X-ray diffractometry, X-ray photoelectron spectroscopy, nitrogen adsorption/desorption measurements for surface area and pore size distribution, scanning electron microscopy, transmission electron microscopy, galvanostatic cycling, and cyclic voltammetry tests to compare them with those of the SiNP/C composite. The SiNP/HC composite showed significantly better cycle life and efficiency than the SiNP/C, with minimal increase in electrode thickness after long cycles. A hybrid composite, SiNP/HC@Gr, prepared by physical mixing of the SiNP/HC and Gr at a 50:50 weight ratio, exhibited even better cycle life and efficiency than the SiNP/HC at low capacity. Thus, silicon/carbon composites designed to have hollow spaces capable of accommodating volume expansion were found to be highly effective for long cycle life of silicon-based composites. However, further study is required to improve the low initial coulombic efficiency of SiNP/HC and SiNP/HC@Gr, which is possibly because of their high surface area causing excessive electrolyte decomposition for the formation of solid-electrolyte-interface layers.

• Applied Chemistry for Engineering
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• v.29 no.6
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• pp.759-764
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• 2018

3D porous carbon electrodes (cNPIM), prepared by solution casting of a polymer of intrinsic microporosity (PIM-1) followed by nonsolvent-induced phase separation (NIPS) and carbonization are presented. In order to effectively control the pore size of 3D porous carbon structures, cNPIM was prepared by varying the THF ratio of mixed solvents. The SEM analysis revealed that cNPIMs have a unique 3D macroporous structure having a gradient pore structure, which is expected to grant a smooth and easy ion transfer capability as an electrode material. In addition, the cNPIMs presented a very large specific surface area ($2,101.1m^2/g$) with a narrow micropore size distribution (0.75 nm). Consequently, the cNPIM exhibits a high specific capacitance (304.8 F/g) and superior rate capability of 77% in an aqueous electrolyte. We believe that our approach can provide a variety of new 3D porous carbon materials for the application to an electrochemical energy storage.

• Clean Technology
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• v.24 no.4
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• pp.332-338
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• 2018

Currently graphite is used as an anode active material for lithium ion battery. However, since the maximum theoretical capacity of graphite is limited to $372mA\;h\;g^{-1}$, a new anode active material is required for the development of next generation high capacity and high energy density lithium ion battery. The maximum theoretical capacity of Si is $4200mA\;h\;g^{-1}$, which is about 10 times higher than the maximum theoretical capacity of graphite. However, since the volume expansion rate is almost 400%, the irreversible capacity increases as the cycle progresses and the discharge capacity relative to the charge is remarkably reduced. In order to solve these problems, it is possible to control the particle size of the Si anode active material to reduce the mechanical stress and the volume change of the reaction phase, thereby improving the cycle characteristics. Therefore, in order to minimize the decrease of the charge / discharge capacity according to the volume expansion rate of the Si particles, the improvement of the cycle characteristics was carried out by pulverizing Si by a dry method with excellent processing time and cost. In this paper, Si is controlled to nano size using vibrating mill and the physicochemical and electrochemical characteristics of the material are measured according to experimental variables.

• Transactions of the Korean hydrogen and new energy society
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• v.32 no.6
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• pp.442-454
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• 2021

The porous transport layer (PTL) is essential to effectively remove oxygen and hydrogen gas from the electrode surface at high current density operation conditions. In this study, the effect of PTL with different characteristics such as pore size, pore gradient, interfacial coating was investigated by multi-layered sintered mesh. A water electrolysis single cell of active area of the 34.56 cm² was constructed, and IV performance and impedance analysis were conducted in the range of 0 to 2.0 A/cm². It was confirmed that the multi-layered sintered mesh PTL, which have an average pore size of 25 to 57 ㎛ and a larger pore gradient, removed bubbles effectively and thus seemed to improve IV performance. Also, it was confirmed that the catalytic metals such as Ni, NiMo coating on the PTL reduced activation overpotential, but increased mass transport overpotential.

• Clean Technology
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• v.26 no.4
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• pp.329-335
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• 2020

Methanol synthesized from renewable hydrogen and captured CO2 has recently attracted great interest as a sustainable energy carrier for large-scale renewable energy storage. In this study, molten carbonate fuel cell's performance was investigated with the direct conversion of methanol into syngas inside the anode chamber of the cell. The internal reforming of methanol may significantly improve system efficiency since the heat generated from the electrochemical reaction can be used directly for the endothermic reforming reaction. The porous Ni-10 wt%Cr anode was sufficient for the methanol steam reforming reaction under the fuel cell operating condition. The direct supply of methanol into the anode chamber resulted in somewhat lower cell performance, especially at high current density. Recycling of the product gas into the anode gas inlet significantly improved the cell performance. The analysis based on material balance revealed that, with increasing current density and gas recycling ratio, the methanol steam reforming reaction rate likewise increased. A methanol conversion more significant than 90% was achieved with gas recycling. The results showed the feasibility of electricity and syngas co-production using the molten carbonate fuel cell. Further research is needed to optimize the fuel cell operating conditions for simultaneous production of electricity and syngas, considering both material and energy balances in the fuel cell.

• Journal of the Korean Electrochemical Society
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• v.23 no.2
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• pp.25-38
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• 2020

Photoelectrochemical water splitting has been considered as the most promising technology for generating hydrogen energy. Transition metal dichalcogenide (TMD) compounds have currently attracted tremendous attention due to their outstanding ability towards the catalytic water-splitting hydrogen evolution reaction (HER). Herein, we report the synthesis method of various transition metal dichalcogenide including MoS₂, MoSe₂, WS₂, and WSe₂ nanosheets as excellent catalysts for solar-driven photoelectrochemical (PEC) hydrogen evolution. Photocathodes were fabricated by growing the nanosheets directly onto Si nanowire (NW) arrays, with a thickness of 20 nm. The metal ion layers were formed by soaking the metal chloride ethanol solution and subsequent sulfurization or selenization produced the transition metal chalcogenide. They all exhibit excellent PEC performance in 0.5 M H₂SO₄; the photocurrent reaches to 20 mA cm^-2 (at 0 V vs. RHE) and the onset potential is 0.2 V under AM1.5 condition. The quantum efficiency of hydrogen generation is avg. 90%. The stability of MoS₂ and MoSe₂ is 90% for 3h, which is higher than that (80%) of WS₂ and WSe₂. Detailed structure analysis using X-ray photoelectron spectroscopy for before/after HER reveals that the Si-WS₂ and Si-WSe₂ experience more oxidation of Si NWs than Si-MoS₂ and Si-MoSe₂. This can be explained by the less protection of Si NW surface by their flake shape morphology. The high catalytic activity of TMDs should be the main cause of this enhanced PEC performance, promising efficient water-splitting Si-based PEC cells.

• Applied Chemistry for Engineering
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• v.7 no.6
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• pp.1078-1086
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• 1996

The peroxo-polytungstic acid was formed by the direct reaction of tungsten powder with the hydrogen peroxide solution. Peroxo-polytungstic powder were prepared by rotary evaporator using the fabricated on to ITO coated glass as substrate by dip-coating method using $2g/10mL(W-IPA/H_2O)$ sol solution. A substrate was dipped into the sol solution and after a meniscus had settled, the substrate was withdrawn at a constant rate of the 3mm/sec. Thicker layer could be built up by repeated dipping/post-treatment 15 times cycles. The layers dried at the temperature of $65{\sim}70^{\circ}C$ during the withdrawn process, and then tungsten oxides thin film was formed by final heating treatment at the temperature of $230{\sim}240^{\circ}C$ for 30min. A linear rotation between the thickness of thin film and the number of dipping/post-treatment cycles for tungsten oxides thin films made by dip-coating was found. The thickness of thin film had $60{\AA}$ after one dipping. From the patterns of XRD, the structure of tungsten oxides thin film identified as amorphous one and from the photographs of SEM, the defects and the moderate cracks were observed on the tungsten oxides thin film, but the homogeneous surface of thin films were mostly appeared. The electrochemical characteristic of the $ITO/WO_3$ thin film electrode were confirmed by the cyclic voltammetry and the cathodic Tafel polaization method. The coloring bleaching processes were clearly repeated up to several hundreds cycles by multiple cyclic voltammetry, but the dissolved phenomenon of thin film revealed in $H_2SO_4$ solution was observed due to the decrease of the current densities. The diffusion coefficient was calculated from irreversible Randles-Sevick equation from the data obtained by the cyclic voltammetry with various scan rates.

• Journal of the Korean Electrochemical Society
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• v.10 no.4
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• pp.283-287
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• 2007

KIER has been developing the anode-supported flat tubular solid oxide fuel cell unit bundle for the intermediate temperature($700{\sim}800^{\circ}C$) operation. Anode-supported flat tubular cells have Ni/YSZ cermet anode support, 8 moi.% $Y_2O_3$ stabilized $ZrO_2(YSZ)$ thin electrolyte, and cathode multi-layer composed of Sr-doped $LaSrMnO_3(LSM)$, LSM-YSZ composite, and $LaSrCoFeO_3(LSCF)$. The prepared anode-supported flat tubular cell was joined with ferritic stainless steel cap by induction brazing process. Current collection for the cathode was achieved by winding Ag wire and $La_{0.6}Sr_{0.4}CoO_3(LSCo)$ paste, while current collection for the anode was achieved by using Ni wire and felt. For making stack, the prepared anode-supported flat tubular cells with effective electrode area of $90\;cm^2$ connected in series with 12 unit bundles, in which unit bundle consists of two cells connected in parallel. The performance of unit bundle in 3% humidified $H_2$ and air at $800^{\circ}C$ shows maximum power density of $0.39\;W/cm^2$ (@ 0.7V). Through these experiments, we obtained basic technology of the anode-supported flat tubular cell and established the proprietary concept of the anode-supported flat tubular cell unit bundle.

• Analytical Science and Technology
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• v.22 no.5
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• pp.432-438
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• 2009

In order to develop the analytical method for the pharmaceutical tablets containing ranitidine HCl by square wave voltammetry (SWV), $5.00{\times}10^{-5}M$ ranitidine HCl solutions prepared with phosphate buffers of various pH values were investigated by SWV. The well defined main peak due to the electrochemical reduction of $-NO_2$ in the structure of ranitidine moved towards the cathodic direction by -70 mV/pH as the pH values were increased indicating the involvement of hydrogen in its reduction. The calibration curve, the plot of peak currents (Ip) vs. concentrations of ranitidine HCl in the range between $1.00{\times}10^{-7}M$ and $1.00{\times}10^{-5}M$ showed linearity with slopes of $232,530{\mu}A/M$ (pH 6.14), $289,015{\mu}A/M$ (pH 7.07) and $232,843{\mu}A/M$ (pH 8.01). When one pharmaceutical tablet was simply dissolved in the phosphate buffer with a pH value of 6.14 and determined by standard addition method using SWV, the within-day precision study (n=4) resulted in the contents of ranitidine HCl as $171{\pm}2.1mg$ ($102{\pm}1.3%$ of the specified contents, RSD of 1.2%) in a tablet of Curan$^{(R)}$. The inter-day precision for 5 days was 1.1% of RSD. For Zantac$^{(R)}$ the within-day precision study (n=4) showed the contents of ranitidine HCl as $167{\pm}0.8mg$ ($99{\pm}0.5%$ of the specified contents, RSD of 0.5%) in a tablet and the inter-day precision for 5 days was 0.3% of RSD.

• Clean Technology
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• v.26 no.2
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• pp.137-144
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• 2020

Metal-impregnated activated carbons were prepared via ultrasonic-assisted impregnation method for regeneration and low ammonia concentration. Magnesium and copper were selected as metals, while chloride (Cl^-) and nitrate (NO₃^-) precursors were used to impregnate the surface of activated carbon. The physical and chemical properties of the prepared adsorbents were characterized by TGA, BET, and NH₃-TPD. The ammonia breakthrough test was carried out using a fixed bed and flowing ammonia gas (1000 mg L^-1 NH₃, balanced N₂) at 100 mL min^-1, under conditions of temperature swing adsorption (TSA) and pressure swing adsorption (PSA, 0.3, 0.5, 0.7, 0.9 Mpa). The adsorption and desorption performance of ammonia were in the order of AC-Mg(Cl) > AC-Cu(Cl) > AC-Mg(N) > AC-Cu(N) > AC through NH₃-TPD and TSA and PSA processes. AC-Mg(Cl) using MgCl₂ showed the average adsorption amount of 2.138 mmol/g at TSA process. Also, AC-Mg(Cl) showed the highest initial adsorption amount of 3.848 mmol/g at PSA 0.9 Mpa. When metal impregnated the surface of the activated carbon, it was confirmed that not only physical adsorption, but also chemical adsorption increased, making enhancement in adsorption and desorption performances possible. Also, the prepared adsorbents showed stable adsorption and desorption performances despite repeated processes, confirming their applicability in the TSA and PSA processes.