• 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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• 제4권1호
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• pp.41-50
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• 1993

The hydrogen absorption and desorption characteristics of microencapsulated (CFM)$Ni_{4.7}Al_{0.2}Fe_{0.1}$ and $MmNi_4Fe$ powder with Ni and/or Cu by means of chemical plating method have been investigated. Initial hydrogen absorption rate and activation property were increased remarkably by encapsulation and subsequent compacting. Pellets abtained by compacting of Cu-encapsulated fine powder have fairly good strength even after 30 cycles of hydriding and dehydriding. Encapsulated alloy powder and their compacts show a good resistance to degradation by $O_2$ or CO in hydrogen.

• 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.

• 한국수소및신에너지학회논문집
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• 제8권4호
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• pp.161-171
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• 1997

$AB_2$ type Zr-based Laves phase alloys have been studied for potential application as negative electrode in Ni/MH batteries. However, They have a serious disadvantage of poor activation behavior in KOH solution. In this work, a new method of alloy design method was tried for improving Zr-based alloy activation. this method has focused on phase controlling to make multi-phase microstructure. In the case of multi-phase Zr-V-Mn-Ni shows good performance in activation, but activation mechanism has not been known. So, we were in search of elucidating this mechanism, Using morphological and electrochemical analysis, we could find that surface morphology and electocatalytic activity of the alloy change during immersion in KOH solution. V-rich second phases are selectively corroded and dissolved and then become Ni-rich phases. Resulting from these surface reaction in KOH solution, self-hydrogen charging occurs through Ni-rich phase. However, the alloy has poor cyclic durability because of such a corrosion mechanism. Therefore, finally we developed durable alloys by substitution of other alloying element.

• 한국수소및신에너지학회논문집
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• 제10권3호
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• pp.177-184
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• 1999

The charge-discharge characteristics of the $Mg_2Ni-x$ wt.%Nd (x = 0~3) electrodes were investigated. The electrodes were prepared by the mechanical grinding of the induction-melted $Mg_2Ni$ alloy powders with Ni and/or Nd using planetary ball mill apparatus. The discharge capacity of the $Mg_2Ni$ alloy increased with the increase in the nickel content. The electrode possessing 100 wt.% nickel powder showed the initial capacity of 760 mAh/g and the capacity decay with the cycle number was less than that of the 55 wt.% nickel powder. The Nd was added to this composition. It was found that the $Mg_2Ni-100$ wt.%Ni -0.2 wt.%Nd alloy showed an excellent charge-discharge cycle characteristics compared with the other reported Mg-Ni alloy system. The discharge capacity was 400 mAh/g after 70 cycles. Such an improved cycle life seems to be attributed to the improvement in the corrosion characteristics of the alloy. The anodic polarization curve of the $Mg_2Ni-100$ wt.%Ni-0.2 wt.%Nd alloy exhibited better passivating behavior than that of the $Mg_2Ni-100$ wt.%Ni.

• 한국수소및신에너지학회논문집
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• 제3권2호
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• pp.9-15
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• 1992

Electroless copper plating method using an alkaline bath have been employed in copper coating of the (LM)Ni4.5Co0.1MnO.2A10.2 hydrogen storage alloy powders for electrode preparation. The plating were conducted without any pretreatment of alloy powders. For the preparation of the electrodes, about 0.12g of the copper coated alloy powder (copper to alloy ratio 1/3 by weight) was compacted with pressure of 6 tons/cm2 at room temperature. The disk-type compacts had a diameter of 10mm and thickness of about 0.24mm. The electrode characteristics were examined through SEM observations and electrochemical measurements in a half cell. The electrochemical measurement showed that the maximum discharge capacity of the electrodes prepared by using alkaline bath were 245mAh per gram of coated alloy (327mAh per gram of alloy) and appeared a considerable degradation with increasing number of cycles. The decrease of the discharge capacity after 100 cycles was about 30% It can be suggested that, with a slight of improvement, this electroless copper plating method could be applied to the preparation of the rare earth-nickel based alloy electrode.

• 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.

• 전기화학회지
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• 제11권4호
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• pp.289-296
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• 2008

산업용 밀폐형 니켈수소전지에 사용되는 수산화니켈 및 수소저장합금 전극에 대해 반쪽전지 시험에 의한 전기화학적 특성을 조사하고, 대용량 밀폐형 니켈수소전지를 제작하여 전지의 충전 효율 및 내압 특성에 대해 평가하였다. 전기화학적 특성 실험은 전지의 충방전 사이클에 따른 전지 내압 상승 억제를 목표로 수산화니켈 전극 및 수소저장합금 전극에 대해 전위주사법을 이용하여 수행하였다. 전위주사법 실험 결과, 수산화니켈 전극의 프로톤 산화 환원 반응 양태, 산소발생 거동, 그리고 수소저장합금 전극의 수소화 반응 특성을 명확히 파악할 수 있었다. 또한 산소 과전압이 높은 수산화니켈 분말과 수소 활성화 특성이 우수한 수소저장합금 분말을 사용하여 제작한 130 Ah 니켈수소전지의 충전 효율은 1 C 전류로 충전 시 98% 수준이 얻어 졌으며 과충전 시 전지 내압이 4 atm 이하로 유지됨을 확인하였다. 그리고 충방전 사이클에 의한 전지 보존 용량도 약 400 사이클에서 약 95% 수준으로 그 특성이 우수함을 알 수 있었다.

• 한국수소및신에너지학회논문집
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• 제4권2호
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• pp.29-40
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• 1993

Intensive studies on the electrochemical characteristics of TiFe type alloy electrodes have been carried out to clarify the mechanism of electrochemical hydrogen absorption and desorption. It was found that electrochemical activation of the TiFe type alloys is difficult and that charge efficiencies are very low even after a decade of activation cycles. However, by the pretreatment of the powders such as gas activation and/or Ni chemical plating, charge efficiencies fairly increased, especially for the $TiFe_{0.8}Ni_{0.2}$ alloy. It was considered that difficulties to activation and lower charge efficies of the alloys are due to the presence of the passivation films, which prohibit inward diffusion of hydrogen and promote the combination of adsorbed hydrogen atom to gas bubbles during the electrochemical charge. In addition, lower diffusivity of hydrogen in the alloys may be played an important role lowering the charge efficiencies.

• 한국수소및신에너지학회논문집
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• 제23권5호
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• pp.429-436
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• 2012

Mg and Mg-based alloys are regarded as strong candidate hydrogen storage materials since their hydrogen capacity exceeds that of known metal hydrides. One of the approaches to improve kinetic is addition of metal oxide. In this paper, we tried to improve the hydrogenation properties of Mg-based hydrogen storage composites. The effect of transition metal oxides, such as $Nb_2O_5$ on the kinetics of the Magnesium hydrogen absorption kinetics was investigated. $MgH_x$-5wt.% $Nb_2O_5$ composites have been synthesized by hydrogen induced mechanical alloying. The powder fabricated was characterized by X-ray diffraction (XRD), Field Emission-Scanning Electron Microscopy (Fe-SEM), Energy Dispersive X-ray (EDX), BET and simultaneous Thermo Gravimetric Analysis / Differential Scanning Calorimetry (TG/DSC) analysis. The Absorption / desorption kinetics of $MgH_x$-5wt.% $Nb_2O_5$ (type I and II) are determined at 423, 473, 523, 573 and 623 K.