• 한국수소및신에너지학회논문집
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• 제5권2호
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• pp.99-109
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• 1994

To develop high capacity hydrogen storage alloys for secondary Ni/MH batteries, electrochemical charge/discharge characteristics of $Zr_{1-x}Ti_xMn_{1-y}V_yNi_{1-z}M_z$ (M=Al,Co,Fe) alloys were investigated, in which $0.2{\leq}x{\leq}0.6$, $0.2{\leq}y{\leq}0.8$, $0.2{\leq}z{\leq}0.4$. With increasing Ti content(x) and/or decreasing V content(y), lattice constants and maximum theoretical capacities of the alloys were decreased and equilibrium pressure of hydrogen absorption were increased. Electrochemical discharge capacities were increased with increasing Ti content(x). Especially, the alloys of x= 0.4~0.6 showed better charge/discharge efficiencies than those of x<0.4. Discharge capacities of $Zr_{0.4}Ti_{0.6}Mn_{0.4}V_{0.6}Ni_{0.8}Fe_{0.2}$, $Zr_{0.4}Ti_{0.6}Mn_{0.4}V_{0.6}Ni_{0.8}Al_{0.2}$ and $Zr_{0.5}Ti_{0.5}Mn_{0.4}V_{0.6}Ni_{0.6}Co_{0.4}$ were 385, 328 and 333mAh/g, respectively. These alloys were fully activated within five charge/discharge cycles and had a good charge and discharge rate capabilities and temperature characteristics.

• 한국수소및신에너지학회논문집
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• 제7권1호
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• pp.11-18
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• 1996

The Laves phase alloy hydrides have some promising properties as electrode materials in reversible metal hydride batteries. In this work, the hydrogen storage performance, crystallographic parameters, surface morphology, surface area and electrochemical characteristics of the non-stoichiometric $ZrMn_{0.3}V_{0.7}Ni_{1.4+{\alpha}}$, $ZrMn_{0.5}V_{0.5}Ni_{1.4+{\alpha}}$($\alpha$ =0.0, 0.2, 0.4, 0.6) alloys were examined. These as-cast alloys were found to have mainly a cubic C15-type Laves phase structure by X -ray diffraction analysis. The equilibrium pressure of the alloy were increased as $\alpha$ increased in both two types alloy. In case of $ZrMn_{0.5}V_{0.5}Ni_{1.4+{\alpha}}$ alloys, discharge efficiency and the rate capability of the alloy were decreased as $\alpha$ increased but, these values were increased in case of $ZrMn_{0.3}V_{0.7}Ni_{1.4+{\alpha}}$ alloys. The differences of these electrode properties observed were dependent on the reaction surface area and the catalytic activity of unit area of the each electrode.

• 한국수소및신에너지학회논문집
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• 제7권1호
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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.

• 한국수소및신에너지학회논문집
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• 제7권2호
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• pp.157-164
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• 1996

The AB5-type metal hydride electrodes using $(LM)Ni_{4.49}Co_{0.1}Mn_{0.205}Al_{0.205}$(LM : Lanthaniumrich Mischmetal) alloy powders(${\leq}200$mesh) which were coated with 25wt% copper in an acidic bath were prepared with or without addition of 10wt% PTFE as a binder. Prior to electrochemical measurements, the electrodes were sintered at $40^{\circ}C$ for 1 and 2hrs in vacuum with Mm(mischmetal) and sponge type Ti getters. The properties such as maximum capacity, cycle life and mechanical strength of the negative electrode have been investigated. The surface analysis of the electrode was also obtained before and after charge-discharge cycling using scanning electron microscope(SEM). From the observations of electrochemical behavior, it was found that the sintered electrode shows a lower maximum discharge capacity compared with non-sintered electrode but it shows a better cycle life. For the both electrodes with or without addition of PTFE binder, the values of mechanical strength were obtained, and their values increased with increasing sintering time. However, there is little difference of discharge capacity for both electrodes.

• 한국수소및신에너지학회논문집
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• 제8권2호
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• pp.79-90
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• 1997

Extensive work has been done on investigating the inner cell pressure characteristics of sealed type Ni-MH battery in which Zr-Ti-Mn-V-Ni alloy is used as anode. The inner cell pressure of this type Ni-MH battery much more increases with the charge/discharge cycling than that of the other type Ni-MH battery where commercialized $AB_5$ type alloy is used as anode. The increase of inner cell pressure in the sealed type Ni/MH battery using Zr-Ti-Mn-V-Ni alloy system is mainly due to the accumulation of oxygen gas during charge/discharge cycling. The accumulation of oxygen gas arises mainly due to the low rate of oxygen recombination on the MH electrode surface during charge/discharge cycling. The difference of oxygen recombination rate between $AB_5$ type electrode and Zr-Ti-Mn-V-Ni electrode is caused by the difference of electrode reaction surface area resulting from different particle size after their activation and the difference of surface catalytic activity for oxygen recombination reaction, respectively. After EIS analysis, it is identified that the surface catalytic activity affects much more dominantly on the oxygen recombination reaction than the reaction surface area does. In order to suppress the inner cell pressure of Ni-MH battery where Zr-Ti-Mn-V-Ni is used as anode, it is suggested that the surface catalytic activity for oxygen recombination should be improved.

• 한국수소및신에너지학회논문집
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• 제8권3호
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• pp.137-141
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• 1997

The effects of Ag addition to Zr-based hydrogen storage alloys ($Zr_{0.7}Ti_{0.3}V_{0.4}Ni_{1.2}Mn_{0.4}$, $Zr_{0.7}Ti_{0.3}V_{0.4}Ni_{1.2}Mn_{0.3}Cr_{0.1}$ and $Zr_{0.6}Ti_{0.4}V_{0.4}Ni_{1.2}Mn_{0.3}Fe_{0.1}$) on the electrode properties were examined. Ag-free and Ag-added Ze-based alloys were prepared by arc melting, crushed mechanically, and subjected to the electrochemical measurement. In $Zr_{0.7}Ti_{0.3}V_{0.4}Ni_{1.2}Mn_{0.4}$ alloy, 0.08 wt% Ag addition to the alloy improved the activation rate. Also Ag addition improved both activation property and discharge capacity in $Zr_{0.7}Ti_{0.3}V_{0.4}Ni_{1.2}Mn_{0.3}Cr_{0.1}$. For these Ag-added alloys, discharge capacities with the change of charge-discharge current density(10mA, 15mA and 30mA) are almost constant. Showing very high rate capability, discharge capacity of $Zr_{0.6}Ti_{0.4}V_{0.4}Ni_{1.2}Mn_{0.3}Fe_{0.1}$ alloy increased by Ag addition to the alloy. When the amount of Ag addition in $Zr_{0.7}Ti_{0.3}V_{0.4}Ni_{1.2}Mn_{0.4}$ alloy increased too much, the electrode properties became worse. Unveiling mechanism of effect of Ag addition is now progressing in our laboratory.

• 한국재료학회지
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• 제20권10호
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• pp.543-549
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• 2010

The hydrogen energy had recognized clean and high efficiency energy source. The research field of hydrogen energy was production, storage, application and transport. The commercial storage method was using high pressure tanks but it was not safety. However metal hydride was very safety due to high chemical stability. Mg and Mg alloys are attractive as hydrogen storage materials because of their lightweight and high absorption capacity (about 7.6 wt%). Their range of applications could be further extended if their hydrogenation properties and degradation behavior could be improved. The main emphasis of this study was to find an economical manufacturing method for Mg-Ti-Ni-H systems, and to investigate their hydrogenation properties. In order to examine their hydrogenation behavior, a Sievert's type automatic pressure-compositionisotherm (PCI) apparatus was used and experiments were performed at 423, 473, 523, 573, 623 and 673 K. The results of the thermogravimetric analysis (TGA) revealed that the absorbed hydrogen contents were around 2.5wt.% for (Mg8Ti2)-10 wt.%Ni. With an increasing Ni content, the absorbed hydrogen content decreased to 1.7 wt%, whereas the dehydriding starting temperatures were lowered by some 70-100 K. The results of PCI on (Mg8Ti2)-20 wt.%Ni showed that its hydrogen capacity was around 5.5 wt% and its reversible capacity and plateau pressure were also excellent at 623 K and 673 K.

• 한국전기전자재료학회논문지
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• 제21권7호
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• pp.610-614
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• 2008

In this work, the electrical and optical properties of the two different p-type GaN electrode schemes, ZnNi/ITO and ZnNi/Au, were compared each other, and applied to the top-emitting GaN/InGaN light-emitting diodes (LEDs). The ZnNi/ITO electrode showed much higher transmittance (90%) and slightly lower contact resistance $(1.27{\times}10^{-4}{\Omega}cm^2)$ than those (77%, $(2.26{\times}10^{-4}{\Omega}cm^2)$) of the ZnNi/Au at a wavelength of 460 nm. In addition, GaN LEDs having ZnNi/ITO showed accordingly higher light output power and luminous intensity than those having ZnNI/Au did at the current levels up to 1 A.

• 한국재료학회지
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• 제9권4호
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• pp.386-391
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• 1999

The charge-discharge, the high-rate dischargeability, and the self discharge characteristics of the electrodes composed of rapidly solidified ZrV\ulcornerMn\ulcornerMo\ulcornerNi\ulcorneralloy, which has the form of partial substitution of Mn, Mo, Ni for V in $ZrV_2$ were studied. The alloys were prepared using Arc & RSP(Rapid Solidification Process) at the rotating roller speed of 2000 and 5000 rpm. Some of them were received heat treatment at$ 560 ^{\circ}C$ for 1 hour after the solidification to investigate the effect of the heat treatment. It was fond that cycle life was significantly improved by RSP, whereas discharge capacity, activation rte and high rate dischargeability were decreased compared with the conventional arc melting method. The capacity loss seems to be due to the loss of the crystallinity and the increase of the cycle life ascribed to the presence of the amporphous phase as well as the refined grain size of less than 0.2$\mu\textrm{m}$. Heat treatment of the alloy cooled at 2000 rpm improved the cycle life. In case of the alloys cooled at 5000 rpm, both the discharge capacity and the activation rate were significantly improved by the heat treatment.

• 한국표면공학회지
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• 제30권4호
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• pp.262-271
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• 1997

Nickel-matal hydride(Ni-MH) batteries are receiving attention as non-pollunting. high performance rehargeable energy stoage system. The performance of Ni-Mh is significantly influenced by the hydrogen storage alloy materiels used as an anode material. Recently, having discharge capacities higher than the $AB_5$-type hydrogen storage alloys, the Zr-based $AB_2$-Type hydrogen storage alloys has remaining problems regarding cycle life and self-dischareg. These problems need to be solved by improvements in the alloy design and/or surface treatment. This work investiggates the effects the effects of surface property by fluorination on $Zr_{0.7}Ti_{0.3}V_{0.4}Mn_{0.4}Ni{1.2}$ composittion $AB_2$-Type hydrogen storage alloys. EPMA, SEM and AES techniques were used for surface analysis, and the crystal structure was characterized by constant current cycling test and potential sweep methods. Fluorination was found to be effective when La-was incorporated into the alloy, and has unique morphology, higher reactivity, and at the same time formed a protective film. Through, fluorination, the cycle life of an electrode was found to increase significantly, charge/discharge characteristics of the electrode the potential difference between the charge/discharge plateau, i.e polarization(overpotential)were improved.