• 한국수소및신에너지학회논문집
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• 제15권2호
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• pp.144-151
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• 2004

The effect of the cobalt content on the thermodynamic and, heat and mass transfer properties of the $MmNi_{5-y}B_{y-z}C_z(y=0.5{\sim}1.5,\;z=0.5)$hydrogen storage alloys has been studied systematically. The P-C isotherms curves show that with increasing cobalt content in the alloys, the plateau pressure of the hydrogen absorption and desorption and enthalpy(${\Delta}H$) increases steeply and the plateau region becomes flat, while entropy(${\Delta}S$) decreases. Also at the constant cobalt content the hydrogen transfer rate decreases with the reaction temperature, while the initial reaction kinetics increases. But the initial reaction with hydrogen completes within 1min, although the reaction proceeds about 30minutes thereafter.

• 대한금속재료학회지
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• 제47권7호
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• pp.433-439
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• 2009

Ti and Ti based hydrogen storage alloys have been thought to be the third generation of alloys with a high hydrogen capacity, which makes it difficult to handle because of high reactivity. In order to solve the problem, the activation of a wide range of hysteresis of hydriding/dehydriding and without degradation of hydrogen capacity due to the hydriding/dehydriding cycle have to be improved in order to be aplied. Ti-Cr alloys have a high capacity about 0.8 wt.% in an ambient atmosphere. When the Ti-Cr alloys are added to Nb and Ta elements, they formed a laves phase in the alloy system. The Nb element was expected to make easy diffuse hydrogen in the Ti-Cr storage alloy, which was a catalytic element. In this study, the Ti-Nb-Cr ternary alloy was prepared by melt spinning. As-received specimens were characterized using XRD (X-ray Diffraction), SEM (Scanning Electron Microscopy) with EDX (Energy Dispersive X-ray) and TG/DSC (Thermo Gravimetric Analysis/Differential Scanning Calorimetry). In order to examine hydrogenation behavior, the PCI (Pressure-Composition-Isotherm) was performed at 293, 323, 373 and 423 K.

• 한국수소및신에너지학회논문집
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• 제4권1호
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• pp.31-39
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• 1993

In order to improve the hydrogen storage capacity and the activation property of the $MmNi_{4.5}Al_{0.5}$ alloy, the multiphase alloy system are prepared by adding the excess Zr in $MmNi_{4.5}Al_{0.5}$ alloy. It is estimated from the X-ray diffraction pattern and the energy dispersive X-ray analysis that the 2nd phases in $MmNi_{4.5}Al_{0.5}Zr_x$ alloys are $ZrNi_3$, ${\beta}$-Zr. Their morphology is also examined by the scanning electron microscope, and it shows the needle-like precipitation. As the Zr contents increase, the activation time and the plateau pressure decrease, sloping of the plateau pressure increase. Amount of the 2nd phases increase with Zr contents in $MmNi_44.5Al_{0.5}Zr_x$ alloys. The $MmNi_44.5Al_{0.5}Zr_{0.05}$ alloy, which shows the maximum storage capacity and the strong resistance to intrinsic degradation, is considered as a proper alloy for hydrogen storage.

• 한국수소및신에너지학회논문집
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• 제10권4호
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• pp.197-210
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• 1999

The hydrogen storage performance and electrochemical properties of $Zr_{1-X}Ti_X(Mn_{0.2}V_{0.2}Ni_{0.6})_{1.8}$(X=0.0, 0.2, 0.4, 0.6) alloys are investigated. The relationship between discharge performance and alloy characteristics such as P-C-T characteristics and crystallographic parameters is also discussed. All of these alloys are found to have mainly a C14-type Laves phase structure by X-ray diffraction analysis. As the mole fraction of Ti in the alloy increases, the reversible hydrogen storage capacity decreases while the equilibrium hydrogen pressure of alloy increases. Furthermore, the discharge capacity shows a maxima behavior and the rate-capability is increased, but the cycling durability is rapidly degraded with increasing Ti content in the alloy. In order to analyze the above phenomena, the phase distribution, surface composition, and dissolution amount of alloy constituting elements are examined by S.E.M., A.E.S. and I.C.P. respectively. The decrease of secondary phase amount with increasing Ti content in the alloy explains that the micro-galvanic corrosion by multiphase formation is little related with the degradation of the alloys. The analysis of surface composition shows that the rapid degradation of Ti-substituted Zr base alloy electrode is due to the growth of oxygen penetration layer. After comparing the radii of atoms and ions in the electrolyte, it is clear that the electrode surface becomes more porous, and that is the source of growth of oxygen penetration layer while accelerating the dissolution of alloy constituting elements with increasing Ti content. Consequently, the rapid degradation (fast growth of the oxygen-penetrated layer) with increasing Ti substitution in Zr-based alloy is ascribed to the formation of porous surface oxide through which the oxygen atom and hydroxyl ion with relatively large radius can easily transport into the electrode surface.

• 대한금속재료학회지
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• 제49권3호
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• pp.264-269
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• 2011

Hydrogen and hydrogen energy have been recognized as clean energy sources and high energy carrier. Mg and Mg alloys are attractive hydrogen storage materials because of their lightweight and low cost materials with high hydrogen capacity (about 7.6 wt.%). However, the commercial applications of the Mg hydrides are currently hinder by its high absorption/desorption temperature, and very slow reaction kinetics. However, Ti and Ti based hydrogen storage alloys have been thought to be the third generation of alloys with a high hydrogen capacity, which makes it difficult to handle because of high reactivity. One of the most methods to develope kinetics was addition of transition metal. Therefore, Mg-Ti-Cr-Nb alloy was fabricated to add TiCrNb by hydrogen induced mechanical alloying. TiCrNb systems have included transition metals, low operating temperatures and hydrogen storage materials. As-received specimens were characterized using X-ray Diffraction analysis (XRD), Scanning Electron Microscopy (SEM) and Thermo Gravimetric analysis/Differential Scanning Calorimetry (TG/DSC). $Mg-TiCr_{10}Nb$ systems were evaluated for hydrogen kinetics by Sievert's type Pressure-Composition-Isotherm (PCI) equipment. The operating temperature range was 473, 523, 573 and 623 K.

• 전기저널
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• 8호통권128호
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• pp.54-60
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• 1987

• 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.

• Nuclear Engineering and Technology
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• 제56권3호
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• pp.824-831
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• 2024

In order to investigate the occurring processes during long-term dry storage of spent fuel assemblies, a joined project called SPIZWURZ, between the Karlsruhe Institute of Technology and the Gesellschaft für Anlagen-und Reaktorsicherheit (GRS), was started. Aim of the SPIZWURZ project is the determination and quantification of the influence of texture and elastic strain on diffusion and solubility of hydrogen in three different zirconium alloys used in western Europe during a long-term cooling transient (1 K/d) starting at 400 ℃. The strain in the cladding of an irradiated spent fuel rod shall be measured. Models predicting the formation of radial oriented hydrides will be validated, improved, and implemented in the GRS fuel rod performance code TESPA-ROD. This paper describes the SPIZWURZ project and already obtained first results.

• 대한금속재료학회지
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• 제56권11호
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• pp.829-834
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• 2018

Although magnesium-based alloys are attractive materials for hydrogen storage applications, their activation properties, hydrogenation/dehydrogenation kinetics, thermodynamic equilibrium parameters, and degradation characteristics must be improved for practical applications. Further, magnesium poses several risks, including explosion hazard, environmental pollution, insufficient formability, and industrial damage. To overcome these problems, CaO-added Mg alloys, also called Eco-Mg (environment-conscious Mg) alloys, have been developed. In this study, $Eco-MgH_x$ composites were fabricated from Mg-CaO chips by hydrogen-induced mechanical alloying in a high-pressure atmosphere. The balls-to-chips mass ratio (BCR) was varied between a low and high value. The particles obtained were characterized by X-ray diffraction (XRD), and the absorbed hydrogen was quantified by thermogravimetric analysis. The XRD results revealed that the $MgH_2$ peaks broadened for the high BCR. Further, PSA results revealed particles size were decreased from $52{\mu}m$ to $15{\mu}m$.

• 한국수소및신에너지학회논문집
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• 제3권2호
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• pp.45-54
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• 1992

An applicability microencapsulation, using electroless copper plating, of hydrogen storage alloy powder as an anode material for nickel-hydrogen secondary batteries was investigated. Alloys employed were $LaNi_{4.7}Al_{0.3}$ and $MmNi_{4.5}Al_{0.5}$(Mm=mischmetal) which have an appropriate equilibrium pressure and capacity. The microencapsulation of the alloy powder was found to accelerate initial activation of electrodes and to increase capacity which is about 285mAh/g for $LaNi_{4.7}Al_{0.3}$. In addition, other charge and discharge characteristics, such as polarization and flatness of charge and discharge potential, were improved due to the role of copper layer as a microcurrent collector and an oxidation barrier of the alloy powder. $MmNi_{4.5}Al_{0.5}$ alloy showed lower capacity than $LaNi_{4.7}Al_{0.3}$ because of higher equilibrium pressure. Cyclic characteristics of both alloys were somewhat poor because of mainly shedding and partial oxidation of alloy powder during the cycling. However, it was considered that the microencapsulation method is effective to improve the performances of the hydrogen storage alloy electrodes.