• Journal of Hydrogen and New Energy
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• v.10 no.2
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• pp.141-149
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• 1999

Recently the Ni/MH secondary battery has been studied extensively to achieve higher energy density, longer cycle life and faster charging-discharging rate etc. In this work, the electrode properties of $(LM)Ni_{4.49}Co_{0.1}Mn_{0.205}Al_{0.205}$ alloy and $Ti_{0.6}Zr_{0.4}V_{0.6}Ni_{1.4}$ alloy with addition of Pd were investigated. These alloys did not show any change in XRD pattern by Pd addition. As Pd was added as alloy element, the activation behavior was not affected significantly in both $AB_2$ type and $AB_5$ type electrodes and, On charging and discharging in high current density, Discharge capacity with increasing of Pd content was more decreased. But cycle life was showed increasing. Especially the electrode of $Ti_{0.6}Zr_{0.4}V_{0.6}Ni_{1.4}+0.5wt%$ Pd alloy was not almost decreased discharge capacity for 400cycles.

• 한국전기화학회:학술대회논문집
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• 1998.10a
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• pp.96-96
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• 1998

• Journal of Hydrogen and New Energy
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• v.17 no.4
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• pp.418-424
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• 2006

In order to improve the activation properties of the $AB_2$ type hydrogen storage alloys for Ni-MH battery, the alloy surface was modified by employing high energy ball milling. The $Zr_{0.54}Ti_{0.45}V_{0.54}Ni_{0.87}Cr_{0.15}Co_{0.21}Mn_{0.24}$ alloy powder was ball milled for various period by using the high energy ball mill. As the ball milling time increased, activation of the $AB_2$ type composite powder electrodes were enhanced regardless of additives. When the ball milling time was small discharge capacities of the $AB_2$ type composite powder electrodes increased with the milling time. On the other hand for large milling time it decreased with increasing milling time. The maximum discharge capacity was obtained by ball milling for 3-4 min.

• 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.

• Journal of Hydrogen and New Energy
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• v.10 no.4
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• pp.225-232
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• 1999

The $Mg_2Ni$ hydrogen storage alloys which have much higher theoretical discharge capacity than $AB_5$ and $AB_2$ type alloys were synthesized by mechanical alloying with some additives and subjected to the electrochemical measurements. Two different processes were employed to the synthesis of $Mg_2Ni$ alloys with using the high energy ball mill SPEX 8000. One was only ball milling, 12 hrs, the Mg and Ni powders for 12 hrs with additives such as $AB_5$, Ni, Co and Cu powders. In the other process the Mg and Ni powders were ball milled for 1 hr first and then heat treated at $300{\sim}400^{\circ}C$ for 1 hr to get $Mg_2Ni$ alloy, and finally the $Mg_2Ni$ alloy powders were ball milled with the additives for 12 hrs. The alloy powders prepared were compacted at room temperature under $7.64tons/cm^2$ into disk type electrodes for the electrochemical measurements. The experimntal results showed that the electrodes prepared with the heat treated alloy powders had a higher discharge capacities than those without heat treatment. The addition of Ni caused an increase of the discharge capacity and the addition of Co improved the cycling characteristics. The electrode prepared by ball milling of $Mg_2Ni$ and 10wt% Ni powders has showed the highest discharge capacity, 546mAh/g.alloy, which was 55% of the theoretical capacity.

• Korean Journal of Materials Research
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• v.7 no.3
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• pp.234-243
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• 1997

The crystal structure of arc melted $ZrV_{x}Mn_{1-x}Ni_{1.0},\;ZrV_{x}Mn_{0.8-x}Ni_{1.2},\;ZrV_{x}Mn_{0.6-x}Ni_{1.4}$ alloys which are known to have AB2 type Laves structure was investigated. They had mixed phases of C14 and C15. The radius ratio ($r_{A}/r_{B}$) of atoms in A site to that of B site was found to be an important parameter in explaining the omposition dependence of the crystal structure The C15 structure showed a linear increase with the ratio in as-cast conditions. However, the annealed alloys revealed a definite ratio at which the stability of both phases are divided distinctly. The composition of the alloys could be closely controlled by maintaining the argon pressure in the chamber over 1 arm during arc melting. In contrast, the alloy ingot melted in VIM showed a significant loss of hln.

• Journal of Hydrogen and New Energy
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• v.28 no.5
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• pp.459-464
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• 2017

The volume expansions of $Ti_{0.95}Zr_{0.05}V_{0.4}Mn_{1.45}Fe_{0.1}Cr_{0.05}$ alloy during hydrogenation with various conditions have been investigated. The theoretical volume expansion measured with XRD for this alloy with hydrogenation was 21%. The apparent volume expansion of this alloy ingot with hydrogenation was composed of two effects. One is a hydrogenation and the other is a pulverization. The apparent volume of free alloy powder was 1.8 times greater than that of an ingot, implying the pulverization effect on the apparent volume expansion is 80%. The apparent volume expansion of the alloy ingot with hydrogenation under a unconstrained condition was about 80 (${\pm}15$)%, much smaller than that of free alloy powder which expected as 118%. In addition, The apparent volume expansion of the alloy ingot with hydrogenation under a constrained condition(Al container) was about 50%, much smaller than that of the unconsrained. This reduced apparent volume expansion of the alloy ingot could be attributed to an arrangement of alloy powder keeping its original shape of the ingot even after hydrogenation.

• Journal of Hydrogen and New Energy
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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.

• Journal of Surface Science and Engineering
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• v.30 no.4
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• pp.262-271
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• 1997

Nickel-matal hydride(Ni-MH) batteries are receiving attention as non-pollunting. high performance rehargeable energy stoage system. The performance of Ni-Mh is significantly influenced by the hydrogen storage alloy materiels used as an anode material. Recently, having discharge capacities higher than the $AB_5$-type hydrogen storage alloys, the Zr-based $AB_2$-Type hydrogen storage alloys has remaining problems regarding cycle life and self-dischareg. These problems need to be solved by improvements in the alloy design and/or surface treatment. This work investiggates the effects the effects of surface property by fluorination on $Zr_{0.7}Ti_{0.3}V_{0.4}Mn_{0.4}Ni{1.2}$ composittion $AB_2$-Type hydrogen storage alloys. EPMA, SEM and AES techniques were used for surface analysis, and the crystal structure was characterized by constant current cycling test and potential sweep methods. Fluorination was found to be effective when La-was incorporated into the alloy, and has unique morphology, higher reactivity, and at the same time formed a protective film. Through, fluorination, the cycle life of an electrode was found to increase significantly, charge/discharge characteristics of the electrode the potential difference between the charge/discharge plateau, i.e polarization(overpotential)were improved.

• Journal of Hydrogen and New Energy
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• v.12 no.1
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• pp.29-38
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• 2001

The alloys $ZrMn_2Ni_x$ (x=0.0, 0.3, 0.6, 0.9 and 1.2) as the alloys of Zr-Mn-Ni three component system were prepared and their hydrogen-storage properties and their electrochemical properties were investigated. The C14 Laves phase formed in all the alloys $ZrMn_2Ni_x$. Among these alloys $ZrMn_2Ni_{0.6}$ was activated relatively easily(after about 11 charge-discharge cycles), and had the largest discharge capacity(max. 45mAh/g). For all the alloys Zr was dissolved most easily into the 6M KOH solution. More Mn and Ni were dissolved from the $ZrMn_2Ni_{0.6}$ alloy than from the other alloys. Due to the active charge and discharge of the $ZrMn_2Ni_{0.6}$ alloys, related to the easier activation and the larger discharge capacity, Zr, Mn and Ni in this alloy were considered to be dissolved more easily into the 6M KOH solution, compared with the other alloys.