• 한국수소및신에너지학회논문집
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• 제24권5호
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• pp.367-372
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• 2013

Hydrogen storage as a metal hydride is the most promising alternative because of its relatively large hydrogen storage capacities near room temperature. TiMn2-based C14 Laves phases alloys are one of the promising hydrogen storage materials with easy activation, good hydriding-dehydriding kinetics, high hydrogen storage capacity and relatively low cost. In this work, multi-component, hyper-stoichiometric $Ti_{0.85}Zr_{0.13}(Fe_x-V)_{0.56}Mn_{1.47}Ni_{0.05}$ C14 Laves phase alloys were prepared by a vacuum induction melting for a hydrogen storage tank. Since pure vanadium (V) is quite expensive, the substitution of the V element in these alloys has been tried and some interesting results were achieved by replacing V by commercial ferrovanadium (FeV) raw material. In addition, the melt-spinning process, which was applied to the manufacturing of some of these alloys, could make the plateau slopes much flatter, which resulted in the increase of reversible hydrogen storage capacity. The improvement of sloping properties of melt-spun $Ti_{0.85}Zr_{0.13}(Fe_x-V)_{0.56}Mn_{1.47}Ni_{0.05}$ alloys was mainly attributed to the homogeneity of chemical composition.

• 한국수소및신에너지학회논문집
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• 제19권6호
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• pp.482-489
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• 2008

Ti-Cr alloys consist of BCC solid solution, C36, C14 and C15 Laves phase at high temperature. Among others, the BCC solid solution phase was reported to have a high hydrogen storage capacity. However, activation, wide range of hysteresis at hydrogenation/dehydrogenation, and degradation of hydrogen capacity due to hydriding/dehydriding cycles must be improved for its application. In this study, to improve such problems, we added a Nb. For attaining target materials, Ti-10Cr-xNb(x=1, 3, 5wt.%) specimens were prepared by arc melting. The arc melting process was carried out under argon atmosphere. 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 423K.

• 한국재료학회지
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• 제7권3호
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• pp.234-243
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• 1997

아크용해로와 진공유도로를 사용하여 니켈-수소 전지의 음극용으로 주목받고 있는 AB2 타입의 ZrV /sub x/Mn/sub 1-x/Ni/sub 1.0/, ZrV/sub x/Mn/sub 0.8-x/Ni/sub 1.2/, ZrV/sub x/Mn/sub 0.6-x/Ni/sub 1.4/합금을 용해하였다. 이들 합금은 용해한 상태에서 C14과 C15의 혼합상을 갖는 것으로 나타났으며 합금조성 및 열처리에 따라 혼합상분율이 크게 변화하였다. 이들의 결정상 및 상분율은 합금원소들의 평균원자반경비(r/sub A//r/sub B)에 따라 결정되는 것으로 밝혀졌으며 특히 열처리한 합금의 경우에는 평균원자반경비가 1.254일때를 경계로 하여 두 상의 명확간 안정구역이 설정되었다. 가압한 분위기에서 아크용해한 경우 합금성분의 손실은 미미하였으나 진공유도로를 사용하여 용해한 경우 Mn이 다량 휘발감소하여 조성이 크게 변화하였다.

• 한국수소및신에너지학회논문집
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• 제5권1호
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• pp.1-8
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• 1994

Lattice structure, hydrogen absorption characteristics, discharge capacity and cycle life of $V_{22}Ti_{16}Zr_{16}Ni_{39}X_7$(X= Cr, Co, Fe, Mn, Al) alloys were investigated. The matrix phases of these alloys were the C14 Laves phase. Chromium-containing alloy had a vanadium-rich phase in addition to the Laves phase. The chromium, maganese, or aluminum-containing alloys had lower hydrogen equilibrium pressure and larger hydrogen absorption content than the cobalt or iron-containing alloys. The discharge capacities of these alloys were 270~330mAh/g. The discharge capacity according to the alloying element X decreased in the order of Mn>Cr>Co, Al)Fe. The charge/discharge cycle lives of the chromium, cobalt or iron-containing alloys were longer than those of maganese or aluminum-containing alloys due to the lower vanadium dissolution rate.

• 한국수소및신에너지학회논문집
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• 제13권3호
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• pp.181-189
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• 2002

A series of multicomponent $Zr_{0.8}Ti_{0.2}Mn_{0.4}V_{0.6}Ni_{1-x}Fe_{x}$ (x=0.00, 0.08, 0.15, 0.22, and 0.30) alloys are prepared and their oystal structure and P-C-T curves are examined. The electrochemical properties of these allqys such as activation conditions, discharge capacity, cycling performance are also investigated. $Zr_{0.8}Ti_{0.2}Mn_{0.4}V_{0.6}Ni_{1-x}Fe_{x}$ (x=0.00, 0.08, 0.15, 0.22 and 0.30) have the C14 Laves phase hexagonal structure. The electrode was activated by the hot-charging treatment. The best activation conditions were the current density 120 mA/g and the hot-charging time 12h at $80^{\circ}C$ in the case of the alloy with x=0.00. The discharge capacity increased rapidly until the fourth cycle and then decreased. The discharge capacity increased again from the 13th cycle, arriving at 234 mAh/g at the 50th cycle. The discharge capacily just after activation decreases with the increase in the amount of the substituted Fe but the cycling performance is improved. The discharge capacity after activation of the alloy with x=0.00 is 157 mAh/g at the current density 120 mA/g. $Zr_{0.8}Ti_{0.2}Mn_{0.4}V_{0.6}Ni_{0.85}Fe_{0.15}$ is a good composition with a medium quantity of discharge capacities and a good cycling performance. The ICP analysis of the electrolyte for these electrodes after 50 charge-discharge cycles shows that the concentrations of V and Zr are relatively high. Another series of multicomponent $Zr_{0.8}Ti_{0.2}Mn_{0.4}V_{0.6}Ni_{0.85}M_{0.15}$ (M = Fe, Co, Cu, Mo and Al) alloys are prepared. They also have the C14 Laves phase hexagonal structure. The alloys with M = Co and Fe have relatively larger hydrogen storage capacities. The discharge capacities just after activation are relatively large in the case of the alloys with M = Al and Cu. They are 212 and 170 mAh/g, respectivety, at the current density 120mA/g. The $Zr_{0.8}Ti_{0.2}Mn_{0.4}V_{0.6}Ni_{0.85}Co_{0.15}$ alloy is the best one with a relatively large discharge capacity and a good cycling performance.

• 한국수소및신에너지학회논문집
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• 제12권1호
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• pp.29-38
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• 2001

Zr-Mn-Ni 3성분계 합금으로서 $ZrMn_2Ni_x$ (x=0.0, 0.3, 0.6, 0.9 and 1.2) 합금을 제작하여 이들의 수소저장특성과 전기화학적 특성을 조사한 결과 $ZrMn_2Ni_x$ 모든 조성에서 C14 Laves phase가 형성되었다. 여러 합금 중에서 $ZrMn_2Ni_{0.6}$ 합금이 비교적 활성화가 빨리 이루어졌고(약 11회 싸이클 후), 방전용량이 가장 컸다(최대 45mAh/g). 모든 합금에서 6M KOH 전해질에 Zr이 가장 잘 용해되었다. $ZrMn_2Ni_{0.6}$ 합금은 다른 합금들에 비해 Mn과 Ni이 더 많이 용해되었다. $ZrMn_2Ni_{0.6}$ 합금이 비교적 활성화가 빨리 이루어지고 방전용량이 컸는데, 이에 따른 활발한 충 방전으로 인하여 Zr, Mn, Ni이 많이 용해되어 나온 것으로 사려된다.

• 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.

• 한국분말재료학회지
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• 제18권2호
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• pp.149-158
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• 2011

Electro-Discharge Sintering (EDS) employs a high-voltage/high-current-density pulse of electrical energy, discharged from a capacitor bank, to instantaneously consolidate powders. In the present study, a single pulse of 0.57-1.1 kJ/0.45 g-atomized spherical $Ti_{52}Zr_{28}Ni_{20}$ powders in size range of 10~30 and $30\sim50{\mu}m$ consisting of ${\beta}$-(Ti, Zr) and icosahedral phases were applied to examine the structural evolution of icosahedral phase during EDS. Structural investigation reveals that high electrical input energy facilitates complete decomposition of icosahedral phase into C14 laves and ${\beta}$-(Ti, Zr) phases. Moreover, critical input energy inducing decomposition of the icosahedral phase during EDS depends on the size of the powder. Porous Ti and W compacts have been fabricated by EDS using rectangular and spherical powders upon various input energy at a constant capacitance of $450{\mu}F$ in order to verify influence of powder shape on microstructure of porous compacts. Besides, generated heat (${\Delta}H$) during EDS, which is measured by an oscilloscope, is closely correlated with powder size.