• Korean Chemical Engineering Research
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• v.60 no.2
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• pp.175-183
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• 2022

With the expansion of the automobile market, the demand for Nd as an essential rare earth material for automobile motors is rapidly increasing. Research on the calcio-thermic reduction process between Nd₂O₃ and calcium-based alloys has been extensively studied in order to manufacture Nd. In this study, Ca-Cu, as a reducing for Nd₂O₃, was prepared by electrolysis in CaCl₂ molten salt. Cu wire and graphite were employed as a working electrode and a counter electrode for electrolysis reaction, respectively. The reference electrode was manufactured by putting Ag wire in a mixture of AgCl and CaCl₂ at a ratio of 1:99 mol%. The cyclic voltammetry results showed that the deposition of Ca²⁺ on the surface of working electrode was observed from a potential of -1.8 V, and the reduction potential of Ca²⁺ decreased as the reaction temperature increased. The diffusion coefficient of Ca²⁺ calculated by the chronoamperometry experiment was found to be 5.4(±6.8)×10^-6 cm²/s. In addition, Ca-Cu liquid alloy was prepared by applying a constant potential to Cu electrodes. The element ratio of Ca-Cu alloy formed by applying a potential of -2.0 V was found to Ca:Cu=1:4.

• Journal of the Korean Electrochemical Society
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• v.11 no.4
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• pp.313-318
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• 2008

The influence of the particle size of platinum(Pt) on the stability and activity was studied. The particle size of platinum was controlled in the range of $3.5{\sim}9\;nm$ by heat treatment of commercial Pt/C and confirmed by XRD and TEM. An accelerated degradation test was performed to evaluate the stability of platinum catalysts. Oxygen reduction reaction was monitored for the measurement of activity. As increasing the Pt particle size, the stability of Pt/C electrode was enhanced and the activity was reduced. It was confirmed that the stability of Pt/C electrode was in inverse proportion to the activity. PtCo/C alloy catalyst was used to improve the activity and stability of large-sized platinum particle. The maximum power density of commercial Pt/C was $507.6\;mV/cm^2$ and PtCo/C alloy catalyst was $585.8\;mV/cm^2$. The decrement of electrochemical surface area showed Pt/C(60%) and PtCo/C alloy catalyst(24%). It was possible to enhance both of stability and activity of catalyst by the combination of particle size control and alloying.

• Journal of the Korean Chemical Society
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• v.59 no.1
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• pp.36-44
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• 2015

This article describes synthesis and electrochemical properties of layer-by-layer self-assembled multilayer film composed of polyaniline (PANi), graphene oxide (GO) and phytic acid (PA), whereby the GO was electrochemically reduced to ERGO, resulting in $(PANi/ERGO/PANi/PA)_{10}$ film electrode. Especially, we examined the possibility to improve the volumetric capacitive property of $(PANi/ERGO)_{20}$ film electrode via combining a spherical hexakisphosphate PA nanoparticle into the multilayer film that would dope PANi properly and also increase the porosity and surface area of the electrode. The electrochemical performances of the multilayer film electrodes were investigated using a three-electrode configuration in 1 M $H_2SO_4$ electrolyte. As a result, the $(PANi/ERGO)_{20}$ electrode showed the volumetric capacitance of $666F/cm^3$ at a current density of $1A/cm^3$, which was improved to the volumetric capacitance of $769F/cm^3$ for the $(PANi/ERGO/PANi/PA)_{10}$ electrode, in addition to the cycling stability maintained to 79.3% of initial capacitance after 1000 cycles. Thus, the electrochemical characteristics of the $(PANi/ERGO)_{20}$ electrode, which was densely packed by ${\pi}-{\pi}$ stacking between the electron-rich conjugate components, could have been improved through structural modification of the multilayer film via combining a spherical hexakisphosphate PA nanoparticle into the multilayer film.

• Journal of the Korean Chemical Society
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• v.33 no.6
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• pp.633-643
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• 1989

The R$Rh_2(ap)_4$(2,2-trans) isomer (ap = 2-anilinopyridinate), which has two anilino nitrogens and two pyridyl nitrogens bound to each rhodium ion trans to their own kind, shows activation towards the one electron reduction of dioxygen at -0.40 V vs SCE. The ESR spectrum taken at 123 K proves the formation of a $[Rh_2(ap)_4(O_2)]$ ion with oxygen axially bound to one rhodium ion and the complex is at a RhⅡ2 oxidation state. The complex will form [$Rh_2(ap)_4(O_2)(CH_3CN)]^-$ in presence of $CH_3CN/CH_2Cl_2$ mixture without breaking the Rh-$O_2^-$ bond. When oxidized at -0.25 and 0.55 V, $[Rh_2(ap)_4(O_2)]$ will undergo two one electron oxidations to form $Rh_2(ap)_4(O_2)[Rh_2(ap)_4(O_2)]^+$. Both species have an axially bound superoxide ion but the former is at $Rh^{II}Rh^{III }$and the later at $Rh^{III}_2$ oxidation states. The ESR spetra and $CH_3CN$ addition study, on the other hand, show that the later complex is better described as $[Rh_{II}Rh^{III}(ap)_4(O_2)]^+$ with the odd electron localized on rhodium ion and the complex has an axially coordinated molecular oxygen. The electrochemical and ESR studies also show that the degree of dioxygen activation is a function of electrochemical redox potential.

• Journal of the Korean Electrochemical Society
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• v.11 no.1
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• pp.42-46
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• 2008

Even though fuel cell have high efficiency when pure hydrogen from gas tank is used as a fuel source, it is more beneficial to generate hydrogen from city gas (mainly methane) in residential application such as domestic or office environments. Thus hydrogen is generated by reforming process using hydrocarbon. Unfortunately, the reforming process for hydrogen production is accompanied with unavoidable impurities. Impurities such as CO, $CO_2$, $H_2S$, $NH_3$, $CH_4$, and $CH_4$ in hydrogen could cause negative effects on fuel cell performance. Those effects are kinetic losses due to poisoning of the electrode catalysts, ohmic losses due to proton conductivity reduction including membrane and catalyst ionomer layers, and mass transport losses due to degrading catalyst layer structure and hydrophobic property. Hydrogen produced from reformer eventually contains around 73% of $H_2$, 20% or less of $CO_2$, 5.8% of less of $N_2$, or 2% less of $CH_4$, and 10ppm or less of CO. This study is aimed at investigating the effect of carbon dioxide on fuel cell performance. The performance of PEM fuel cell was investigated using current vs. potential experiment, long run(10 hr) test, and electrochemical impedance measurement when the concentrations of carbon dioxide were 10%, 20% and 30%. Also, the concentration of impurity supplied to the fuel cell was verified by gas chromatography(GC).

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.8 no.1
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• pp.1-7
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• 2010

In the present work, an electrowinning process in the LiCl-KCl/Cd system is considered to model and analyze the electrotransport of the actinide and rare-earth elements. A simple dynamic modeling of this process was performed by taking into account the material balances and diffusion-controlled electrochemical reactions in a diffusion boundary layer at an electrode interface between the molten salt electrolyte and liquid cadmium cathode. The proposed modeling approach was based on the half-cell reduction reactions of metal chloride occurring on the cathode. This model demonstrated a capability for the prediction of the concentration behaviors, a faradic current of each element and an electrochemical potential as function of the time up to the corresponding electrotransport satisfying a given applied current based on a galvanostatic electrolysis. The results of selected case studies including five elements (U, Pu, Am, La, Nd) system are shown, and a preliminary simulation is carried out to show how the model can be used to understand the electrochemical characteristics and provide better information for developing an advanced electrowinner.

• Journal of the Korean Electrochemical Society
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• v.19 no.2
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• pp.39-44
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• 2016

Oxygen reduction reaction in the fuel cell (ORR) plays a dominant role in the overall reaction. In addition, the low compatibility between the membrane and the binder consisted of different materials, greatly reduces the efficiency of the fuel cell performance. In view of these two problems, geometrically modified copolymers with 9.9_Bis (4-hydroxyphenyl) were synthesized via condensation reaction instead of conventional biphenol and were adopted as hydrocarbon ionomer binders. By utilizing these binders, two kinds of MEAs using fluorinated Nafion membrane and hydrocarbon based membrane were manufactured in order to electrochemical performance evaluation. With current-voltage curves, there was no significant difference in the 0.6 V when two types of membrane were applied. Also, tafel slope became considerably lower as compared to the Nafion membrane. Thus, it is determined that the new hydrocarbon binder is expected to contribute the improvement in performance of fuel cells.

• Resources Recycling
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• v.27 no.4
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• pp.29-35
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• 2018

In this study, the electrochemical redox behavior of neodymium in non-aqueous electrolytes was investigated to confirm the possibility of neodymium metallurgy at room temperature. The non-aqueous electrolytes include ionic liquids such as $[C_4mim]PF_6$, $[C_4mim]Cl$, and $[P_{66614}]PF_6$, ethanol which are highly soluble in neodymium salts, and mixed electrolytes based on carbonate with highly electrochemical stability. The electrochemical redox properties of neodymium were better than those of other electrolytes in the case of the mixed electrolyte based on ethylene carbonate (EC)/di-ethylene carbonate (DEC). Ethanol was added to improve the physical properties of the mixed electrolyte. Thorough the analysis about ionic conductivity of EC/DEC ratio, ethanol content and $NdCl_3$ concentration, the best electrolyte composition was 50 vol% content of ethanol and 0.5 M of $NdCl_3$. Using cyclic voltametry and linear sweep voltametry, a current peak estimated at -3.8 V (vs. Pt-QRE) was observed as a limiting current of neodymium reduction. Potentiostatic electrolysis for 18 hours at room temperature at -6 V (vs. Pt-QRE) confirmed that metallic neodymium was electrodeposited.

• Korean Chemical Engineering Research
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• v.56 no.6
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• pp.884-889
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• 2018

In this study, polyaniline $(PANI)/WO_3$ electrode was prepared as an anode of a lithium ion capacitor, and its electrochemical characteristics were measured and analyzed. When PANI was electrochemically deposited on the surface of $WO_3$ electrode, the capacity of $PANI/WO_3$ was improved with increase of the deposited amounts of PANI. Furthermore, the effect of light irradiation on capacity and coulombic efficiency was examined by irradiating sunlight during charging and discharging. When the light was irradiated to the $WO_3$ electrode and the $PANI/WO_3$ electrode, those capacities and coulombic efficiencies were increased compared to that measured under the dark condition. It is attributed to the photocatalytic property of $WO_3$ that can generate photoelectrons by light irradiation. In $PANI/WO_3$ electrode, PANI also can be excited under the light irradiation with affecting the electrochemical property of electrode. The photoelectrons improve the capacity by participating in the intercalation of $Li^+$ ions, and also improve the coulombic efficiency by facilitating electrons' transport. Under the dark condition, the capacity of $PANI/WO_3$ was gradually reduced with increase of cycles due to a poor stability of PANI. However, the stability of PANI was significantly improved by the light irradiation, which is attributed to the oxidation-reduction reaction originated from the photogenerated electrons and holes in $PANI/WO_3$.

• Journal of the Korean Electrochemical Society
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• v.22 no.2
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• pp.69-78
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• 2019

Lithium metal anode with the highest theoretical capacity to replace graphite anodes are being reviewed. However, the dendrite growth during repeated oxidation/reduction reaction on lithium metal surface, which results in poor cycle performance and safety issue has hindered its successful implementation. In our previous work, we solved this problem by using surface modification technique whereby a surface pattern on lithium metal anode is introduced. Although the micro-patterned Lithium metal electrode is beneficial to control Li metal deposition efficiently, it is difficult to control the mossy-like Li granulation at high current density ($>2.0mA\;cm^{-2}$). In this study, we introduce vinylene carbonate (VC) electrolyte additive on micro patterned lithium metal anode to suppress the lithium dendrite growth. Owing to the synergetic effect of micro-patterned lithium metal anode and VC electrolyte additive, lithium dendrite at a high current density is dense. As a result, we confirmed that the cycle performance was further improved about 6 times as compared with the reference electrode.