• 한국재료학회지
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• 제5권1호
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• pp.112-122
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• 1995

Metal hydride alloys of TiFe based system have been produced by mechanical alloying(MA) method and their electrochemical characteristics have been evaluated for application for Ni/MH battery electrode. These alloys became amorphous after 36hrs ball milling and easily activated electrochemically. All MA amorphous alloys reached at the first charge/discharge cycle the maximum capacity which was 2-3 times higher than the crystalline state. But their cyclic lives were much inferior to the crystalline state. Alloying elements such as Ni, Co, Cr, Mo substituting Fe greatly improved the capacity and 180 mAh/g capacity was obtained in an alloy of TiFe_{0.6}Ni_{0.1}Co_{0.1}Cr_{0.1}Mo_{0.1}$.

• 한국수소및신에너지학회논문집
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• 제17권1호
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• pp.31-38
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• 2006

There are two types of metal hydride electrodes as a negative electrode in a Ni-MH battery, $AB_2$ Zr-based Laves phases and $AB_5$ LM(La-rich mischmetal)-based alloys. The $AB_5$ alloy electrodes have characteristic properties such as a large discharge capacity per volume, easiness in activation, long cycle life and a low cost of alloy. However they have a relatively small discharge capacity per weight. The $AB_2$alloy electrodes have a much higher discharge capacity per weight than $AB_5$ alloy electrodes, however they have some disadvantages of poor activation behavior and cycle life. Therefore, in order to improve the discharge capacity of the $AB_5$ alloy electrode the Zr, Ti and V which are the alloying elements of the $AB_2$ alloys were added to the $LaNi_{3.6}Ai_{0.4}Co_{0.7}Mn_{0.3}$ alloy which was chosen as a $AB_5$ alloy with a high capacity. The addition of Zr, Ti and V to $LaNi_{3.6}Ai_{0.4}Co_{0.7}Mn_{0.3}$ alloy improved the activation to be completed in two cycles. The discharge capacities of Zr 0.02, Ti 0.02 and V 0.1 alloys in $LaNi_{3.6}Ai_{0.4}Co_{0.7}Mn_{0.3}M_y$ (M = Zr, Ti, V) were respectively 346, 348 and 366 mAh/g alloy. The alloy electrodes, Zr 0.02, Ti 0.05 and V 0.1 in $LaNi_{3.6}Ai_{0.4}Co_{0.7}Mn_{0.3}M_y$ (M = Zr, Ti, V), have shown good cycle property after 200 cycles. The rate capability of the $LaNi_{3.6}Ai_{0.4}Co_{0.7}Mn_{0.3}M_y$ (M = Zr, Ti, V) alloy electrodes were very good until 0.6 C rate and the alloys, Zr 0.02, Ti 0.05 and V 0.1, have shown the best result as 92 % at 2.4 C rate. The charge retention property of the $LaNi_{3.6}Ai_{0.4}Co_{0.7}Mn_{0.3}M_y$ (M = Zr, Ti, V) alloys was not good and the alloys with M content from 0.02 to 0.05 showed better charge retention properties.

• 한국수소및신에너지학회논문집
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• 제9권4호
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• pp.135-141
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• 1998

Fe-Ti계 수소저장합금 전극의 방전특성을 개선하기 위하여 Ni을 첨가한 $TiFe_{1-x}Ni_x$ 합금을 제조하여 방전특성과 열처리 온도에 따른 변화를 조사하였다. 합금의 조성은 x = 0.1에서 0.6까지 0.1 단위씩 변화시킨 6가지 조성을 선택하여 각각에 대한 초기방전용량과 충방전사이클에 따른 용량변화를 조사하였다. 초기방전용량은 Ni의 조성이 클수록 증가하다가 x = 0.6 에서 다시 감소하였으며 Ni의 조성이 증가함에 따라 사이클특성은 전반적으로 매우 악화되었다. 열처리온도가 사이클 특성에 미치는 영향을 조사하기 위하여 초기용량이 가장 우수한 $TiFe_{0.5}Ni_{0.5}$ 합금에 대하여 $700{\sim}900^{\circ}C$ 의 온도범위에서 열처리를 시행한 후 방전특성을 조사하였다. 열처리에 의해서 초기용량은 감소되지만 사이클 특성은 현저히 개선되었다. $700{\sim}850^{\circ}C$의 온도범위에서 1시간 열처리한 전극의 경우에 사이클이 진행되면서 방전용량이 크게 회복되었으며, 열처리한 표면조직을 SEM 으로 관찰해 본 결과 이는 충분한 전극강도 및 기공율에 기인한 것으로 생각되었다. $900^{\circ}C$에서 1시간 열처리한 전극은 충분한 기공율을 갖지 못하여 방전특성이 좋지 않음을 알 수 있었다.

• 한국수소및신에너지학회논문집
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• 제32권3호
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• pp.156-162
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• 2021

Mg hydride has a relatively high hydrogen storage amount of 7.6wt%, and inexpensive due to abundant resources, but has high reaction temperature and long reaction time because of treble oxidation reactivity and upper activation energy. Their range of applications could be further extended if their hydrogenation kinetics and degradation behavior could be improved. Therefore, the effect of CaO has improved the hydrogenation kinetics and slowed down the degradation. This study focused on investigating whether to improve the hydrogenation kinetics by synthesizing Mg₂NiH_x-5wt% CaO composites. The Mg₂NiH_x-5wt% CaO composites have been synthesized by hydrogen induced mechanical alloying. The synthesized composites were characterized by performing X-ray diffraction, Scanning Electron Microscopy, Brunauer-Emmett-Teller, Thermogravimetric, and Sivert's type automatic pressure-composition-temperature analysis. Hydriding kinetics were performed using an automatic PCT measurement system and evaluated over the temperature range of 423 K, 523 K, and 623 K. As a result of calculating the hydrogen adsorption amount through the hydrogenation kinetics curve, it was calculated as about 0.42wt%, 0.91wt%, and 1.15wt%, the highest at 623 K and the lowest at 423 K.

• 한국수소및신에너지학회논문집
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• 제6권2호
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• pp.65-73
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• 1995

Negative electrode was prepared by mixing $Ti_{0.7}Zr_{0.3}Cr_{0.3}Mn_{0.3}V_{0.6}Ni_{0.8}$ alloy powder with copper or nickel powder and pressing in the air. The cycled electrodes were analyzed with SEM, potentiostat and electrochemical impedance spectroscopy. It was found that the Cu-compacted electrode showed better low temperature dischargeability and higher rate capability than Ni-compacted electrode. From SEM analysis of the cycled electrode compacted with copper powder, it was observed that the surface of MH particles was covered with copper grains and whisker precipitated from electrolyte after dissolution during cell test. It is found that the improved electrode characteristics are attributed to the copper layer on MH particles deposited by dissolution and precipitation(DP) process.

• 한국수소및신에너지학회논문집
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• 제2권1호
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• pp.15-21
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• 1990

Nickel-hydrogen battery systems with metal hydride alloys are expected to have both higher energy density and lower pollution than nickel-cadmium cells. Nickel-hydrogen storage cells are expected to be well-suited for use in space crafts for a large capacity power storage system. Their major advantages are not only a capability of deep DOD(depth of discharge) using but also with excellent durability under excessive overcharging and overdischarging. In this study, the charge/discharge capacities, anodic polarization characteristics and durability for the continious charge/diacharge cycling of the $Ti_{1-X}Zr_XVNi$ and $Ti_{1-X}Zr_XV_{0.5}Ni_{1.5}$ alloys were measured by electrochemical method. The electrode properties of the copper or nickel plated $Ti_{1-X}Zr_XV_{0.5}Ni_{1.5}$ alloys were examined with a battery charge/discharge testing system in the temperature range of -5 to $25^{\circ}C$.

• 한국수소및신에너지학회논문집
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• 제10권1호
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• pp.49-57
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• 1999

In order to study the effect of high energy ball milling on the $Mg_2Ni+Ni$, $Mg_2Ni+0.5Ni+0.5Al$ powders, we have investigated on the discharge properties, microstructures. The powder size of samples decreased as ball milling time. From the XRD results, the crystal structure of $Mg_2Ni+Ni$ mixed powders were changed to amorphous or nano-structure after 60hr ball milling. The discharge capacities of both $Mg_2Ni+Ni$ and $Mg_2Ni+0.5Ni+0.5Al$ powders increased, with increasing ballmilling time, the maximum capacity(342mAh/g) was shown for the 60 hrs ballmilled $Mg_2Ni+Ni$ sample. The capacity decreased drastically after a few charge-discharge cycles.

• 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.185-189
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• 1999

Effects of alloy modification with the $Zr_{0.6}Ti_{0.4}V_{0.4}Ni_{1.2}Mn_{0.4}$ alloy for an electrode use have been investigated. For the alloy composition, a part of Mn was substituted by Co, Cr and Fe. The experimental results showed that Co accelerated activation of alloy, and Fe and Cr improved the discharge capacity. These results agree with P-C-T curves of each alloy. But substituting Fe for Mn showed the decrease of the discharge capacity when discharged at high rate (60mA, about 1C rate). Considering both the discharge capacity and the high rate discharge property, $Zr_{0.6}Ti_{0.4}V_{0.4}Ni_{1.2}Mn_{0.3}Cr_{0.1}$ alloy was found to be the best alloy among the alloys subjected to the test.

• 한국수소및신에너지학회논문집
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• 제10권4호
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• pp.219-224
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• 1999

Effects of alloy modification for the $Zr_{0.7}Ti_{0.3}V_{0.4}Ni_{1.2}Mn_{0.4}$ alloy as an electrode materials have been investigated. When Ti in the alloy was partially substituted by Zr, the hydrogen storage capacity and subsequently the discharge capacity increased significantly, however, the activation characteristic and rate capability decreased. By substituting Mn with other elements (Cr, Co and Fe) in the alloy, discharge capacity decreased but the cycle life and rate capability were improved. Considering both the discharge capacity, the high rate discharge property and cycle life, the $Zr_{0.7}Ti_{0.3}V_{0.4}Ni_{1.2}Mn_{0.3}Cr_{0.1}$ alloy among the alloys subjected to the test was found to be a prominent alloy for a practical usage.