• Transactions of the Korean hydrogen and new energy society
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• v.7 no.1
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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.

• Transactions of the Korean hydrogen and new energy society
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• v.8 no.4
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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.

• Transactions of the Korean hydrogen and new energy society
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• v.33 no.1
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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.

• Korean Journal of Metals and Materials
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• v.50 no.10
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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 $H_2$.

• Journal of the Korean Electrochemical Society
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• v.1 no.1
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• pp.45-51
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• 1998

[ $AB_2-type$ ] alloy, one kind of hydrogen storage alloys used as an anode of Ni-MH batteries, has large discharge capacity but has remaining problems regarding initial activation, cycle life and self-discharge. This study investigates the effects of Cr-addition and fluorination after La-addition on $Zr_{0.7}Ti_{0.3}V_{0.4}Mn_{0.4}Ni_{1.2}$, composition $AB_2-type$ alloy. EPMA and SEM surface analysis techniques were used and the crystal structure was characterized by XRD analysis. In addition, electrodes were fabricated out of the alloys and characterized by constant current cycling test, electrochemical impedance spectroscopy and potentiodynamic polarization. Cr-addition was found to be effective to cycle life and self-discharge but ineffective to initial activation due to formation of stable oxide film on surface. Fluorination after La-addition to the alloys improved initial activation remarkably due to formation of highly reactive particles on surface.

• Transactions of the Korean hydrogen and new energy society
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• v.11 no.4
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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.

• Transactions of the Korean hydrogen and new energy society
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• v.21 no.1
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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 $MgH_x$.

• Transactions of the Korean hydrogen and new energy society
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• v.17 no.1
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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.

• Transactions of the Korean hydrogen and new energy society
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• v.13 no.4
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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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• 2005.07a
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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.