• Journal of the Korean Institute of Illuminating and Electrical Installation Engineers
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• v.20 no.6
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• pp.69-74
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• 2006

The effects of mechanical grinding(MG) treatment on the hydrogen storage of $Mg_2Ni$ alloy and $Mg_2Ni$ composite alloy($Mg_2Ni+graphite$) were investigated by pressure-composition-temperature(PCT) measurement, the micro-electrode technique of electrochemistry and etc, in which PCT was measured at high temperature(around $300[^{\circ}C]$) of gas phase and a carbon-filament micro-electrode for electrochemical evaluation was manipulated to make electrical contact with the particle in 1M KOH aqueous solution. It was found that the hydrogenation properties of $Mg_2Ni$ and graphite composite particle were greatly improved by the mechanical grinding treatment by which the $Mg_2Ni$ and graphite composite alloys could be changed into microstructure and nano-level particles. namely; the hydrogen dissociation pressure of PCT measurement was decreased from 0.55[MPa] to 0.42[MPa] and hydrogenation peaks by micro-electrode were also observed more clearly on the same sample.

• Transactions of the Korean hydrogen and new energy society
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• v.9 no.1
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• pp.8-15
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• 1998

The catalytic hydrogenation of carbon dioxide has been studied for the fixation of carbon dioxide to mitigate global warming problems, but it needed hydrogen, which the price is still high. Recently, the electrochemical reduction of carbon dioxide has been drawn attractions because carbon dioxide could be converted to the valuable chemicals such as methane, ethane and alcohols electrochemically in the electrolyte solution using a catalytic electrode. This system is simple because the water electrolysis and hydrogenation take place at the same time using the surplus electricity at midnight. In this work, a continuous electrochemical reduction system was fabricated, which was composed of the reduction electrode (copper or perovskite type, $2{\times}2cm^2$), reference electrode(platinum, $2{\times}6cm^2$), standard electrode(Ag/AgCl), and potassium bicarbonate electrolyte solution saturated with carbon dioxide. The quality and quantity of the products and reduction current were analyzed, according to the electrolyte concentration and electrode type.

• Journal of the Korean Electrochemical Society
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• v.9 no.2
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• pp.95-99
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• 2006

Electrochemical properties were studied for a single particle of active material of hydrogen storage alloy $(MmNi_{3.55}Co_{0.75}Mn_{0.4}Al_{0.3})$ and nickel hydroxides $(NiOH)_2$ for the secondary Nickel Metal Hydride (Ni-MH) batteries using the microelectrode, which was manipulated to make electrical contact with an active material particle for cyclic voltammograms (CV) and potential-step experiments. As a result of CV test, it was found that three kinds of hydrogen oxidation peaks at -0.9, -0.75 and -0.65 V and hydrogen evolution peak at -0.98 V for hydrogen storage alloy were separately observed and two kinds of peaks of proton oxidation/reduction at 0.45 and 0.32 V and oxygen evolution reaction (OER) at 0.6 V for nickel hydroxides were also more clearly observed. Furthermore hydrogen diffusion coefficient within a single particle was also found to vary the order between $10^{-9}\;and\;10^{-10}cm^2/s$ over the course of hydrogenation and dehydrogenation process for potential-step experiments.

• Journal of the Korean Chemical Society
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• v.35 no.2
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• pp.165-171
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• 1991

The electrochemical reduction of carbon-6-dibromo groups on 6,6-dibromo penicillanic acid 1,1-oxide(DBPA) was investigated by direct current, differential pulse polarography, cyclic voltammetry and controlled potential coulometry. The irreversible two electrons transfer on the reductive debromination of each bromo group proceeded by EC,EC mechanism at the two electrode reduction steps(-0.48, -1.62 volts). The 6-bromo-PA and 6,6-dihydro-PA was synthesized by controlled potential electrolysis. Upon the basis of results on the products analysis and interpretation of polarograms obtained at various pH, electrochemical reaction mechanism was suggested.

• Journal of the Korean Electrochemical Society
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• v.5 no.3
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• pp.111-116
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• 2002

Electrochemical scanning tunneling microscopy was employed to study the evolution of surface morphology during electrochemical preparation of Si(111)-H from Si(111) oxide. Anodic dark current of cyclic voltammogram in 0.2M $NH_4F$ solution (pH 4.7) decreased as the number of cycles increased and remained nearly constant after the second cycle. Then, the Si(111) oxide was entirely stripped, which was followed by H termination on the Si(111) surface. Hydrides at kink and step sites were etched more rapidly than on the terrace, which remained triangle pits with [112] oriented steps where existed stable monohydride. Then, triangle pits deepened. During chronomamperometry at 0.4V anodic dark current shoulder appeared and decreased slowly, indicated the stripping of Si(111) oxide and the formation of stable (112) oriented steps with monohydride. Additionally, the etching mechanism of Si(111)-H in 0.2M $NH_4F(pH 4.7)$ solution at +0.4V was discussed.

• Journal of the Korean Institute of Illuminating and Electrical Installation Engineers
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• v.20 no.2
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• pp.24-28
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• 2006

Electrochemical hydrogenation/dehydrogenation properties were studied for a single particle of a Mm-based(Mm : misch metal) hydrogen storage alloy($MmNi_{3.55}Co_{0.75}Mn_{0.4}Al_{0.3}$) for the anode of Ni-MH batteries. A carbon fiber microelectrode was manipulated to make electrical contact with an alloy particle, and the cyclic voltammetry and the galvanostatic charge/discharge experiments were performed. A single particle of the alloy showed the discharge capacity of 280[mAh/g], the value being 90[%] of the theoretical capacity. Data were compared with that of the composite film consisting of the alloy particles and a polymer binder, which is more practical form for Ni-MH batteries. Additionally, pulverization of the alloy particles are directly observed. Compared with the conventional composite film electrodes, the single particle measurements using the microelectrode gave more detailed, true information about the hydrogen storage alloy.

• Transactions of the Korean hydrogen and new energy society
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• v.7 no.1
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• pp.19-28
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• 1996

Ti-Mn based hydrogen storage alloy were modified by substituting alloying elements such as Zr, V and Ni in order to design a high capacity MH electrode for Ni/MH rechargeable battery. When V was substituted in Ti-Mn binary system, the crystal structure was maintained as $Cl_4$ Laves phase at a composition of $Ti_{0.2}V_{0.4}Mn_{0.4}$ and $Ti_{0.4}V_{0.2}Mn_{0.4}$ and equilibrium pressure decreased below 1 atm without decreasing hydrogen storage capacity considerably. It was found that Ni should be included in Ti-V-Mn alloy in order to hydrogenate it electrochemically in KOH electrolyte. But substitution of Ni for Mn in Ti-V-Mn system caused the increase of equilibrium pressure above 1atm and decrease of hydrogen storage capacity. Zr was able to increase the reversible hydrogen storage capacity of Ti-V-Mn-Ni alloy without considerable change of hydrogenation properties. The electrochemical discharge capacity of Ti-Zr-V-Mn-Ni system were in the range of 350 - 464mAh/g and among them $Ti_{0.8}Zr_{0.2}V_{0.5}Mn_{0.5}Ni_{1.0}$ alloy had $Cl_4$ Laves single phase and very high electrochemical discharge capacity of 464mAh/g.

• Journal of Powder Materials
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• v.13 no.5 s.58
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• pp.327-335
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• 2006

In the development of new hydrogen absorbing materials for a next generation of metal hydride electrodes for rechargeable batteries, metastable Mg-Ni-based compounds find currently special attention. Amor phous-nanocrystalline $Mg_{63}Ni_{30}Y_7$ and $Mg_{50}Ni_{30}Y_{20}$ alloys were produced by mechanical alloying and melt-spinning and characterized by means of XRD, TEM and DSC. On basis of mechanically alloyed Mg-Ni-Y powders, complex hydride electrodes were fabricated and their electrochemical behaviour in 6M KOH (pH=14,8) was investigated. The electrodes made from $Mg_{63}Ni_{30}Y_7$ powders, which were prepared under use of a SPEX shaker mill, with a major fraction of nanocrystalline phase reveal a higher electrochemical activity far hydrogen reduction and a higher maximum discharge capacity (247 mAh/g) than the electrodes from alloy powder with predominantly amorphous microstructure (216 mAh/g) obtained when using a Retsch planetary ball mill at low temperatures. Those discharge capacities are higher that those fur nanocrystalline $Mg_2Ni$ electrodes. However, the cyclic stability of those alloy powder electrodes was low. Therefore, fundamental stability studies were performed on $Mg_{63}Ni_{30}Y_7$ and $Mg_{50}Ni_{30}Y_{20}$ ribbon samples in the as-quenched state and after cathodic hydrogen charging by means of anodic and cathodic polarisation measurements. Gradual oxidation and dissolution of nickel governs the anodic behaviour before a passive state is attained. A stabilizing effect of higher fractions of yttrium in the alloy on the passivation was detected. During the cathodic hydrogen charging process the alloys exhibit a change in the surface state chemistry, i.e. an enrichment of nickel-species, causing preferential oxidation and dissolution during subsequent anodization. The effect of chemical pre-treatments in 1% HF and in $10\;mg/l\;YCl_3/1%\;H_2O_2$ solution on the surface degradation processes was investigated. A HF treatment can improve their anodic passivation behavior by inhibiting a preferential nickel oxidation-dissolution at low polarisation, whereas a $YCl_3/H_2O_2$ treatment has the opposite effect. Both pre-treatment methods lead to an enhancement of cathodically induced surface degradation processes.

• Journal of the Korean Electrochemical Society
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• v.11 no.4
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• pp.289-296
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• 2008

Electrochemical studies were performed by a half-cell test for the nickel hydroxide (cathode) and hydrogen storage alloy(anode) electrodes for the sealed Ni-MH batteries applicable to industrial use. The electrodes were fabricated and checked a charge efficiency and an internal pressure of the battery during charge-discharge cycling. In order to reduce the internal pressure of the sealed Ni-MH battery, cyclic voltammetry (CV) were performed on the electrodes of nickel hydroxide(cathode) and hydrogen storage alloy(anode), respectively. The results of the test showed clearly the oxidation/reduction and oxygen evolution reaction in a nickel hydroxide electrode and the hydrogenation behavior of a hydrogen storage electrode. The sealed Ni-MH battery of 130Ah was fabricated by using nickel hydroxide of a high over-voltage for an oxygen gas evolution and hydrogen storage alloy of a good performance for activation The battery showed a good characteristics such as a high charge efficiency of 98% at 1 C charge current, a low level internal pressure of 4 atm on a continuous over-charging and a large preservation capacity of 95% at 400 cycle.

• Journal of the Korean Institute of Illuminating and Electrical Installation Engineers
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• v.20 no.7
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• pp.46-52
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• 2006

The effects of surface treatment on the hydrogen storage properties of a $Mg_2Ni$ alloy particle were investigated by the microvoltammetric technique, in which a carbon-filament microelectrode was manipulated to make electrical contact with the particle in a KOH aqueous solution. It was found that the hydrogen storage properties of $Mg_2Ni$ at room temperature were improved by the surface treatment with a nickel plating solution. The sodium salts(sodium phosphate and sodium dihydrogen citrate) contained in the nickel plating solution made the alloy form an amorphous-like state, resulting in an improved hydrogen charge/discharge capacity at room temperature as high as about 150[mAh/g] from the original value of 17[mAh/g]. Potential-step experiment was carried out to determine the apparent chemical diffusion coefficient of hydrogen atom($D_{app}$) in the alloy. Since the alloy particle we used here was a dense, conductive sphere, the spherical diffusion model was employed for data analysis. $D_{app}$ was found to vary the order between $10^{-8}{\sim}10^{-9}[cm^2/s]$ over the course of hydrogenation and dehydrogenation process.