• 한국수소및신에너지학회논문집
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• 제8권4호
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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.

• 한국수소및신에너지학회논문집
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• 제7권1호
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• pp.117-120
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• 1996

• 한국수소및신에너지학회논문집
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• 제10권2호
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• pp.141-149
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• 1999

현재 수소저장 합금을 이용하여 2차전지의 음극으로 개발되고 있는 $AB_5$ type의 $(LM)Ni_{4.49}Co_{0.1}Mn_{0.205}Al_{0.205}$ 조성의 수소저장합금과 $AB_2$ type의 $Ti_{0.6}Zr_{0.4}V_{0.6}Ni_{1.4}$ 조성의 수소저장합금에 Pd를 0, 0.5, 1, 2 wt% 첨가한 조성을 진공 중에서 arc 용해를 하였다. 용해된 합금의 조직과 결정구조를 SEM, XRD로 조사하였다. Pd 가 첨가되었음에도 조직이나 결정구조의 변화는 보이지 않았다. 미세한 구리분말을 합금분말 대비 3:1로 첨가하여 pellet형태의 전극을 제조하여 전극특성을 조사한 결과 Pd 첨가에 따른 초기 활성화와 급속 충방전 특성은 크게 변하지 않았다. 그러나 싸이클 수명에 있어서는 Pd를 첨가한 전극들이 Pd를 첨가하지 않는 전극에 비해 우수하였다. $AB_5$ type 조성의 합금에서는 Pd를 2wt% 첨가한 전극, 그리고 $AB_2$ type 조성의 합금에서는 Pd를 0.5wt% 첨가한 전극에서 싸이클 특성이 가장 우수하게 나타났다.

• 한국수소및신에너지학회논문집
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• 제7권2호
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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.

• 한국수소및신에너지학회논문집
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• 제7권2호
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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.

• 한국수소및신에너지학회논문집
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• 제9권4호
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• pp.161-167
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• 1998

Ni/MH 2차전지의 음극용 금속간화합물전극의 부식특성에 미치는 합금원소와 결합제의 영향을 조사하였다. 전극의 재료는 $(LM)Ni_{4.49}Co_{0.1}Mn_{0.205}Al_{0.205}$와 $(LM)Ni_{3.6}Co_{0.7}Mn_{0.3}Al_{0.4}$의 $AB_5$ type합금을 모재로 하였다. 여기에 Si sealant 또는 PTFE를 결합제로 첨가한 것과 원재료 분말에 구리를 20% 무전해도금한 것을 냉간 압착하여 전극을 제조하였다. 부식특성을 조사하기위해 탈공기된 6M의 KOH 용액에서 동전위법과 순환전위법을 이용하여 부식전류와 전류밀도를 측정하였다. 모재에 Co가 많이 함유되면 전극의 내식성을 향상시키고 Ni이 많이 함유되면 충전과 방전을 반복하는 동안에 전극의 안정성을 저하시켰다. 부식전류밀도는 Si sealant를 결합제로 사용한 전극의 경우가 PTFE를 사용한 전극의 경우보다 낮았고 Cu가 도금된 전극은 내식성에서 가장 우수하게 나타났다.

• 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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• 제13권3호
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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.