• 한국수소및신에너지학회논문집
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• 제6권1호
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• pp.35-41
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• 1995

The MmNi-based alloy electrode was studied for use as a negative electrode in Ni-MH battery. Alloys with $MmNi_5-_xM_x$(M=Co,Al,Mn) composition were synthesized, and their electrode charateristics of activation rate, temperature dependence, electrode capacity and cycle life were investigated. With increasing Al content and decreasing Mn content in the alloys, the discharge capacity increased while the cycle life decreased. As x in $MmNi_5-_xM_x$ increased from 1.5 to 2.0, decreasing the Ni content, the discharge capacity, the low temperature property and the rate capability decreased. However its cycle life was improved. Increasing Co content resulted in a prolonged cycle life and decrease of high rate discharge capacity. It can be concluded that the most promising alloy in view of discharge capacity and cycle life is $MmNi_{3.5}Co_{0.7}Al_{0.5}Mn_{0.3}$.

• 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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• 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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• 제7권2호
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• pp.181-191
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• 1996

기계적인 합금화는 planetary mill을 사용하여 이루어졌으며, 시료의 조성은 Mg-10wt.%Ni과 Mg-25wt.%Ni이었다. 수소화물 형성 분해 cycling에 의해 혼합물 내에 $Mg_2Ni$상이 형성되었다. Mg-10wt.%Ni, Mg-25wt.%Ni은 583K, $0{\sim}8barH_2$에서 각각 n=7, n=6정도 후 활성화가 완료되었으며, 583K, $8barH_2$에서 10분 동안에 Mg-10wt.%Ni과 Mg-25wt.%Ni 시료에 의해 흡수된 수소의 중량 퍼센트 Ha(10min)은 각각 4.99, 4.52이었다. Mg-10wt.%Ni과 Mg-25wt.%Ni 혼합물은, 다른 Mg의 합금이나 혼합물에 비해 수소화물 형성 속도는 훨씬 높고, 수소화물 분해 속도와 수소 저장 용량은 비교적 높은 우수한 수소 저장 특성을 가진 수소 저장 재료라 판단된다. 기계적인 합금 처리와 수소 화합물 형성 분해 cycling의 효과는 핵 생성 site를 만들어 주고 입자의 크기를 줄이는 것으로 생각된다.

• 전기화학회지
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• 제3권2호
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• pp.121-126
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• 2000

[ $AB_5$ ] 수소저장합금인 $LaNi_5$, 합금분말에 Ni 및 Cu 무전해 도금의 영향을 전기 화학적 실험을 통하여 고찰하였다. 전기 화학적 실험은 정전류 충$\cdot$방전 실험, 순환전류전위 실험, 교류 임피던스 실험 등을 실시하여 도금하지 않은 $LaNi_5$ 전극과 Ni 및 Cu 무전해 도금한 전극간의 특성을 비교 연구하였다. 현상학적인 분석으로는 SEM을 이용하여 분말상의 미세조직을 관찰하였으며 X-선 회절시험을 실시하였다 무전해 도금을 실시하여 Ni 및 Cu박막이 피복된 수소저장 합금은 활성화 특성파 싸이클 수명 등의 특성이 개선되었으며 도금하지 않은 전극에 비하여 반응속도가 증가하였다. 또한 충$\cdot$방전이 반복됨에 따라 전극과 전해질 계면에서의 전하이동저항이 현저하게 감소하였다. 따라서 본 연구에서 실시한 $LaNi_5$, 활물질에 Ni및 Cu 무전해 도금을 실시하면 초기 활성화반응을 촉진시키며 $LaNi_5$활물질이 전해질과의 직접 접촉을 피하게 되어 전극의 수명을 증가시키는 것을 알 수 있었다.

• 한국수소및신에너지학회논문집
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• 제6권2호
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• pp.85-90
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• 1995

Activation behavior, hydriding rate and disintegration were tested for hydrogen storage alloy particles fixed in an adhesive after treating with inorganic solution. Commertial adhesive as a binder was used. Chemical-treated particles showed the best characteristics for activation and a little effect of prevention the break down of the powders themselves after several repeated operations. Furthermore activation characteristics were found to show a similar trend to chemical-treated powders even in the fixed one with an adhesive, except for a slight decrease in reaction velocity.

• 한국수소및신에너지학회논문집
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• 제5권1호
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• pp.9-17
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• 1994

Activation behavior, hydriding rate and disintegration were studied for a compact in pellet form and hydrogen storage alloy particles treated with newly developed inorganic solution. Cylindrical disc of 12.95mm diameter and of 7.1mm thickness was prepared by compressing(8ton) a mixture of $MmNi_{4.5}Al_{0.47}$ and PTFE. Chemical treatment of particles with 1mol of solution was performed at room temperature for several hours until the pH of solution did not change. Chemical treatment made much accelerated activation without any incubation period which generally exists in the untreated alloys and the hydriding reaction rate after full activation also was improved.

• 전기화학회지
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• 제1권1호
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• pp.45-51
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• 1998

Ni-MH 전지의 음극으로 쓰이는 수소저장합금(MH)의 한 종류인 $AB_2$계 합금은 수소저장량이 큰 장점이 있으나 초기활성화나 싸이클 수명 및 자기방전 특성이 나쁜 단점이 있다. 본 연구에서는 Zr-Ti-V-Mn-Ni계 합금에 비화학양론적으로 Cr을 소량 첨가했을 때와 La을 첨가하여 불화처리 했을 때의 초기활성화, 싸이클 수명 및 자기방전에 미치는 영향을 조사하였다 EPMA 및 SEM을 이용하여 합금의 표면을 분석하였으며 XRD 분석으로 결정구조를 관찰하였다. 또한 합금으로 전극을 제조하여 정전류 시험법, 임피던스법과 전위주사법 등에 의해 전극특성을 조사하였다. Cr이 첨가될수록 전극표면에 안정한 산화막이 형성되어 V등의 전해질로의 용해를 막아주어 충, 방전에 따른 수명특성 및 자기방전 특성을 향상시키지만 초기 전하이동 반응이 저해되어 초기활성화 특성이 악화되었다. La을 첨가 후 불화처리하면 표면에 반응성이 좋은 입자를 형성하여 전극의 초기 활성화가 크게 향상되었다.

• 한국수소및신에너지학회논문집
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• 제22권6호
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• pp.787-793
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• 2011

A 76.5wt%Mg - 23.5wt%Ni (Mg-23.5Ni) sample was prepared by reactive mechanical grinding (RMG) and its hydriding and dehydriding properties were then investigated. Activation of the Mg-23.5Ni sample was completed only after two hydriding (under 12 bar $H_2$) - dehydriding (under 1.0 bar $H_2$) cycles at 593K. The reactive mechanical grinding of Mg with Ni is considered to facilitate nucleation and shorten diffusion distances of hydrogen atoms. After hydriding - dehydriding cycling, the Mg-23.5Ni sample contained Mg2Ni phase.

• 한국수소및신에너지학회논문집
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• 제11권4호
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• pp.189-202
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• 2000

$AB_2$ type Zr-based Laves phases alloys have been studied for potential application as a negative electrode in a Ni-MH battery. The $AB_2$-type electrodes have a much higher energy density than $AB_5$-type electrodes per weight, however they have some disadvantages such as poor activation behavior and cycle life etc. Nonetheless, the $AB_2$-type electrodes have been studied very extensively due to their high energy density. In this study, in order to develop the cycle life, the Mn of $AB_2$ alloy composition was substituted partially by Mo. The alloys were melted by arc furnace and remelted 4-5 times for homogeneity. The alloy powder was used below 200-325 mesh for experiments. The structures and phases of the alloys were analyzed by XRD, SEM and EDS, and measured the curve of a pressure-composition isotherms. The electrodes were prepared by cold pressing of the copper-coated(25 wt%) alloy powders, and tested by a half cell. The results are summarized as follows. The cycle life was improved with the increase of Mo amount in $Zr_{1-x}Ti_xV_{0.4}Ni_{1.2}Mn_{0.4}Mo_y$(x=0.3, 0.4) and the activation was faster, whereas the discharge capacity decreased.