• 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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• 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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• 제33권1호
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• pp.8-18
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• 2022

With rapid industrialization and population growth, fossil fuel use has increased, which has a significant impact on the environment. Hydrogen does not cause contamination in the energy production process, so it seems to be a solution, but it is essential to find an appropriate storage method due to its low efficiency. In this study, Mg-based alloys capable of ensuring safety and high volume and hydrogen storage density per weight was studied, and Mg₂NiH_x synthesized with Ni capable of improving hydrogenation kinetics. In addition, in order to improve thermal stability, a hydrogen storage composite material synthesized with CaO was synthesized to analyze the change in hydrogenation reaction. In order to analyze the changes in the metallurgical properties of the materials through the process, XRD, SEM, BET, etc. were conducted, and hydrogenation behavior was confirmed by TGA and hydrogenation kinetics analysis. In addition, in order to evaluate the impact of the process on the environment, the environmental impact was evaluated through "Material Life Cycle Assessments" based on CML 2001 and EI99' methodologies, and compared and analyzed with previous studies. As a result, the synthesis of CaO caused additional power consumption, which had a significant impact on global warming, and further research is required to improve this.

• 대한금속재료학회지
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• 제50권10호
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• pp.769-774
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• 2012

Mg-x wt% $Fe_2O_3-y$ wt% Ni samples were prepared by reactive mechanical grinding in a planetary ball mill, and their hydrogen-storage properties were investigated and compared. Activations of $Mg-5Fe_2O_3-5Ni$ was completed after one hydriding (under 12 bar $H_2$) - dehydriding (in vacuum) cycle at 593 K. At n = 2, $Mg-5Fe_2O_3-5Ni$ absorbed 3.43 wt% H for 5 min, 3.57 wt% H for 10 min, 3.76 wt% H for 20 min, and 3.98 wt% H for 60 min. Activated $Mg-10Fe_2O_3$ had the highest hydriding rate, absorbing 2.99 wt% H for 2.5 min, 4.86 wt% H for 10 min, and 5.54 wt% H for 60 min at 593 K under 12 bar $H_2$. Activated $Mg-10Fe_2O_3-5Ni$ had the highest dehydriding rate, desorbing 1.31 wt% H for 10 min, 2.91 wt% H for 30 min, and 3.83 wt% H for 60 min at 593 K under 1.0 bar $H_2$.

• 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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• 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.

• 한국수소및신에너지학회논문집
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• 제21권1호
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• pp.58-63
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• 2010

Mg and Ma-based alloys are promising hydrogen storage materials for renewable clean energy applications. It has high hydrogen storage capacity (7.6wt.%), lightweight and low economical materials. However, commercial applications of the Mg hydride are currently hindered by its high operating temperature, and very slow reaction kinetics. In this work, we are aimed at studying the hydrogenation properties of the $MgH_x-V_2O_5$ composite prepared by hydrogen induced mechanical alloying. The absorption capacity of the sample is found to be about 4.7wt.% at 623K under 3 MPa $H_2$ pressure. The absorption characteristics observed have been compared with prepared $MgH_x$.

• 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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• 제13권4호
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• pp.270-278
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• 2002

Mg and Mg alloys are attractive hydrogen storage materials because of their lightweight and high absorption capacity. Their range of applications could be further extended if their hydrogenation properties and degradation behavior could be improved, The main emphasis of this study was to find an economic manufacturing method for Mg-Ti-Ni-H systems, and to investigate their hydrogenation properties, In order to examine hydrogenation behavior, a Sieverts type automatic pressure-composition-isotherm(PCI) apparatus was used and the experiments were performed at 423, 473, 523, 573, 623 and 673K. The results of thermogravimetric analysis(TGA) reveal that the absorbed hydrogen contents are around 2.5 wt% for ($Mg_9Ti_1$)-10 wt% Ni. With increased Ni content, the absorbed hydrogen content decreases to 1.7 wt%, whereas the dehydriding starting temperatures are lowered by some 70-100K. The results of PCI on ($Mg_9Ti_1$)-20 wt% Ni show that its hydrogen capacity is around 5.3 wt% and its reversible capacity and plateau pressure are also excellent at 523K and 573K. In addition, the reaction enthalpy, $\Delta$HD.plateau, is $30.6{\pm}5.7kJ/molH_2$.

• 한국전기화학회:학술대회논문집
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• 한국전기화학회 2005년도 수소연료전지공동심포지움 2005논문집
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• pp.335-340
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• 2005

Amorphous $MgNi_{1-x}Ti_x$ alloys with the composition of x=0.02, 0.03, 0.05 and 0.07 were synthesized by mechanical alloying. The synthesized alloys were investigated by electrochemical test, XRD and SEM. As increasing Ti concentration, the initial discharge capacity was raised more than that of nanocrystalline Mg-Ni 289 mAh/g, but the electrodes were degraded faster. Comparing to other synthesized alloys, $MgNi_{0.95}Ti_{0.05}$ alloy showed the highest initial discharged capacity 474 mAh/g and maintained $54\%$ of the initial capacity after 10 cycles.