• Transactions of the Korean hydrogen and new energy society
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• v.8 no.4
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• pp.181-185
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• 1997

The electrochemical properties of the $AB_2$-type (Zr-Ti-V-Ni-Cr-Co-Mn) metal hydride electrodes prepared by ball milling with $AB_5-type\{(LM)Ni_{3.6}Al_{0.4}Co_{0.7}Mn_{0.3}\}$(LM : Lanthanum-rich mischmetal) alloy powder as a surface activator were investigated. By ball milling with $AB_5$ type alloy powder, the activation of $AB_2$ type metal hydride electrode was accelerated resulting in an increase of discharge capacity from 35% to 85% of the maximum capacity at the first cycle. As the amount of surface activator increased the activation rate increased, whereas the discharge capacity increased with 10wt% and decreased with 20wt% addition of the surface activator. When the amount of the surface activator was kept constant as 10wt%, the discharge capacity and the activation rate increased with ball milling time up to 20 hours. However beyond 20 hours of ball milling time, they decreased drastically due to the nano-crystallization or amorphorzation of the alloy powder.

• Transactions of the Korean hydrogen and new energy society
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• v.7 no.1
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• pp.117-120
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• 1996

• Transactions of the Korean hydrogen and new energy society
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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.

• Transactions of the Korean hydrogen and new energy society
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• v.7 no.2
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• pp.157-164
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• 1996

The AB5-type metal hydride electrodes using $(LM)Ni_{4.49}Co_{0.1}Mn_{0.205}Al_{0.205}$(LM : Lanthaniumrich Mischmetal) alloy powders(${\leq}200$mesh) which were coated with 25wt% copper in an acidic bath were prepared with or without addition of 10wt% PTFE as a binder. Prior to electrochemical measurements, the electrodes were sintered at $40^{\circ}C$ for 1 and 2hrs in vacuum with Mm(mischmetal) and sponge type Ti getters. The properties such as maximum capacity, cycle life and mechanical strength of the negative electrode have been investigated. The surface analysis of the electrode was also obtained before and after charge-discharge cycling using scanning electron microscope(SEM). From the observations of electrochemical behavior, it was found that the sintered electrode shows a lower maximum discharge capacity compared with non-sintered electrode but it shows a better cycle life. For the both electrodes with or without addition of PTFE binder, the values of mechanical strength were obtained, and their values increased with increasing sintering time. However, there is little difference of discharge capacity for both electrodes.

• Transactions of the Korean hydrogen and new energy society
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• v.7 no.2
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• pp.137-145
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• 1996

The Zr-based $AB_2$ type Laves phase hydrogen storage alloys have some promising properties, long cycle life, high discharge capacity, as electrode materials in reversible metal hydride batteries. However, when these alloys are used as negative electrode for battery, there is a problem that their rate capabilities are worse than those of commercialized $AB_5$ type hydrogen storage alloys. In this work, we tried to develop the Zr-based $AB_2$ type Laves phase hydrogen storage alloys which have high capacity and, especially, high rate capability.

• Transactions of the Korean hydrogen and new energy society
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• v.9 no.4
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• pp.161-167
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• 1998

It has been investigated the effects of alloying elements and binders on the corrosion behavior of metal hydride electrodes for anode of Ni/MH secondary battery. The $AB_5$-type alloys, $(LM)Ni_{4.49}Co_{0.1}Mn_{0.205}Al_{0.205}$ and $(LM)Ni_{3.6}Co_{0.7}Mn_{0.3}Al_{0.4}$, were used for the experiments. The electrodes were prepared by mixing and cold-pressing of alloy powders with Si sealent or PTFE powders, or cold-pressing the electroless copper coated alloy powders. The amount of copper coating was 20wt%. In order to examine corrosion behavior of the electrodes, the corrosion current and the current density, in 6M KOH aqueous solution after removal of oxygen in the solution, were measured by potentiodynamic and cyclic voltamo methods. The results showed that Co in the alloy increased corrosion resistance of the electrode whereas Ni decreased the stability of the electrode during the charge-discharge cycles. The electrode used Si sealant as a binder showed a lower corrosion current density than the electrode used PTFE and the electrode used Cu-coated alloy powders showed the best corrosion resistance.

• 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.3
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• pp.181-189
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• 2002

A series of multicomponent $Zr_{0.8}Ti_{0.2}Mn_{0.4}V_{0.6}Ni_{1-x}Fe_{x}$ (x=0.00, 0.08, 0.15, 0.22, and 0.30) alloys are prepared and their oystal structure and P-C-T curves are examined. The electrochemical properties of these allqys such as activation conditions, discharge capacity, cycling performance are also investigated. $Zr_{0.8}Ti_{0.2}Mn_{0.4}V_{0.6}Ni_{1-x}Fe_{x}$ (x=0.00, 0.08, 0.15, 0.22 and 0.30) have the C14 Laves phase hexagonal structure. The electrode was activated by the hot-charging treatment. The best activation conditions were the current density 120 mA/g and the hot-charging time 12h at $80^{\circ}C$ in the case of the alloy with x=0.00. The discharge capacity increased rapidly until the fourth cycle and then decreased. The discharge capacity increased again from the 13th cycle, arriving at 234 mAh/g at the 50th cycle. The discharge capacily just after activation decreases with the increase in the amount of the substituted Fe but the cycling performance is improved. The discharge capacity after activation of the alloy with x=0.00 is 157 mAh/g at the current density 120 mA/g. $Zr_{0.8}Ti_{0.2}Mn_{0.4}V_{0.6}Ni_{0.85}Fe_{0.15}$ is a good composition with a medium quantity of discharge capacities and a good cycling performance. The ICP analysis of the electrolyte for these electrodes after 50 charge-discharge cycles shows that the concentrations of V and Zr are relatively high. Another series of multicomponent $Zr_{0.8}Ti_{0.2}Mn_{0.4}V_{0.6}Ni_{0.85}M_{0.15}$ (M = Fe, Co, Cu, Mo and Al) alloys are prepared. They also have the C14 Laves phase hexagonal structure. The alloys with M = Co and Fe have relatively larger hydrogen storage capacities. The discharge capacities just after activation are relatively large in the case of the alloys with M = Al and Cu. They are 212 and 170 mAh/g, respectivety, at the current density 120mA/g. The $Zr_{0.8}Ti_{0.2}Mn_{0.4}V_{0.6}Ni_{0.85}Co_{0.15}$ alloy is the best one with a relatively large discharge capacity and a good cycling performance.