• 한국표면공학회지
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• 제30권4호
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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.

• 한국수소및신에너지학회논문집
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• 제14권4호
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• pp.327-334
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• 2003

경수소와 중수소를 사용하여 Ti1.0Mn0.9V1.1합금의 경우 313K와 353 K에서, $Ti_{1.0}Cr1.5V_{1.1}$합금의 경우 313 K와 338K에서 각각 수소 동위체 효과를 조사하였다. 합금의 결정구조, 각 상의 존재량, 격자상수 등은 Rietveld method에 의해 결정되었다. 두 합금 모두 용도에 관계 없이 중수소의 흡장량이 경수소에 비하여 많았고, 이들 합금의 수소 동위체 효과는 LaNis 합금에 비하여 대단히 크게 나타났다. 실험 온도 범위에서 $Ti_{1.0}Mn_{0.9}V_{1.1}$합금의 경수소화물은 중수소화물에 비하여 안정하였고, Ti1.0Cr1.5V1.7합금에 있어서는 중수소화물이 더욱 안정하였다. 또한 $Ti_{1.0}Cr_{1.5}V_{1.7}$합금이 $Ti_{1.0}Mn_{0.9}V_{1.1}$합금보다 많은 량의 경수소와 중수소를 흡장하였다.

• 한국수소및신에너지학회논문집
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• 제21권4호
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• pp.340-345
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• 2010

For the conversion into hydrogen society, not only studying facilities of hydrogen production, storage, transportation and charging system but also developing technique of ensuring safety are essentially needed. Hence, for the first step of that, evaluated the hydrogen embrittlement of Inconel alloy 617, Ni-based super heat-resisting alloy, by small punch test. Prepared the various specimens through changing electrochemical charging time and measured the toughness degradation of the specimens by small-punch test. The analysis of hydrogen embrittlement behavior were carried out by investigating the fractured surface of specimens. This study has significance on revealing mechanism of hydrogen embrittlement behavior and the factor affecting hydrogen embrittlement in the future study.

• 한국수소및신에너지학회논문집
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• 제4권1호
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• pp.31-39
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• 1993

In order to improve the hydrogen storage capacity and the activation property of the $MmNi_{4.5}Al_{0.5}$ alloy, the multiphase alloy system are prepared by adding the excess Zr in $MmNi_{4.5}Al_{0.5}$ alloy. It is estimated from the X-ray diffraction pattern and the energy dispersive X-ray analysis that the 2nd phases in $MmNi_{4.5}Al_{0.5}Zr_x$ alloys are $ZrNi_3$, ${\beta}$-Zr. Their morphology is also examined by the scanning electron microscope, and it shows the needle-like precipitation. As the Zr contents increase, the activation time and the plateau pressure decrease, sloping of the plateau pressure increase. Amount of the 2nd phases increase with Zr contents in $MmNi_44.5Al_{0.5}Zr_x$ alloys. The $MmNi_44.5Al_{0.5}Zr_{0.05}$ alloy, which shows the maximum storage capacity and the strong resistance to intrinsic degradation, is considered as a proper alloy for hydrogen storage.

• 한국수소및신에너지학회논문집
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• 제14권2호
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• pp.97-104
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• 2003

The structural transitions of the matrix and the second phases of $Ti_{1.0}Mn_{0.9}V_{1.1}$ and $Ti_{1.0}Cr_{1.5}V_{1.7}$ alloys upon hydrogenation have been investigated at 293K. The effect of hydrogen isotope on their crystal structures has been also discussed. The crystal structures, Phase abundance and lattice parameters of the hydrides were determined by the Rietveld method using X-ray diffraction data. At the experimental temperature, the $Ti_{1.0}Mn_{0.9}V_{1.1}$ alloy and $Ti_{1.0}Cr_{1.5}V_{1.7}$ alloy revealed different structural transition processes upon hydrogenation although the crystal structures of these two alloys are both BCC at room temperature. The second phases such as Ti-rich phase with $NiTi_2$ structure and $\alpha$-Ti with HCP structure absorbed hydrogen at relatively low hydrogen pressures and the phase abundance remained almost constant. This means that it is desirable to decrease the amount of the second phases as far as possible in order to increase the effective hydrogen storage capacities of the alloys. The crystal structures of corresponding isotope hydrides, the phase abundance and the lattice parameters did not depend on the kind of hydrogen isotope, but only on the hydrogen content.

• 한국수소및신에너지학회논문집
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• 제17권2호
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• pp.125-132
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• 2006

The alloys which compositions were represented by the formula, $Ti_{(0.22+X)}Cr_{(0.28+1.5X)}V_{(0.5-2.5X)}$ ($0{\leq}X{\leq}0.12$), had the total hydrogen storage capacity higher than 3 wt% and the effective hydrogen storage capacity higher than 1.4 wt%. Particularly, among all the tested alloys, the $Ti_{0.32}Cr_{0.43}V_{0.25}$ alloy exhibited the best effective hydrogen storage capacity of 1.65 wt%. Furthermore, the reversible bcc${\leftrightarrow}$fcc structural transition was observed with hydrogenation and dehydrogenation, which predicted the possibility of pressure cycling. EDS analysis revealed micro-segregation, which suggested the necessity of microstructure homogenization by heat treatment. The $Ti_{0.32}Cr_{0.43}V_{0.25}$ alloy was selected for heat treatment and for other related studies. The results showed that the total and the effective hydrogen storage capacity increased to 3.7 wt% and 2.3 wt%, respectively. The flatness of the plateau region was also greatly improved and heat of hydride formation was determined to be approximately -36 kJ/mol $H_2$.

• 한국수소및신에너지학회논문집
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• 제8권1호
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• pp.11-21
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• 1997

$ZrV_{0.7}Mn_{0.5}Ni_{1.2}$ alloy is attractive for anode material in Ni/MH secondary battery because of its large hydrogen storage capacity in gas-solid reaction and long cycling durability in KOH electrolyte. In this work, in order to further improve the discharge performance of this alloy electrode, the alloy was annealed by optimal condition which is for 12 hours at $1000^{\circ}C$. The alloy annealed under optimal condition had higher rate capability and discharge capacity than as-cast one. The microstructure of the as-cast and annealed alloy was investigated by scanning electron microscopy and energy dispersive spectroscopy. Ni content in the matrix was increased, being this homogenized after annealing. Additionally, The measurement of the surface area by B.E.T. analysis showed that there was little difference as-cast and annealed alloy. Therefore, improvement in the rate capability of the annealed alloy is due to increase of Ni content in the matrix.

• 한국수소및신에너지학회논문집
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• 제7권1호
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• pp.19-28
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• 1996

Ti-Mn based hydrogen storage alloy were modified by substituting alloying elements such as Zr, V and Ni in order to design a high capacity MH electrode for Ni/MH rechargeable battery. When V was substituted in Ti-Mn binary system, the crystal structure was maintained as $Cl_4$ Laves phase at a composition of $Ti_{0.2}V_{0.4}Mn_{0.4}$ and $Ti_{0.4}V_{0.2}Mn_{0.4}$ and equilibrium pressure decreased below 1 atm without decreasing hydrogen storage capacity considerably. It was found that Ni should be included in Ti-V-Mn alloy in order to hydrogenate it electrochemically in KOH electrolyte. But substitution of Ni for Mn in Ti-V-Mn system caused the increase of equilibrium pressure above 1atm and decrease of hydrogen storage capacity. Zr was able to increase the reversible hydrogen storage capacity of Ti-V-Mn-Ni alloy without considerable change of hydrogenation properties. The electrochemical discharge capacity of Ti-Zr-V-Mn-Ni system were in the range of 350 - 464mAh/g and among them $Ti_{0.8}Zr_{0.2}V_{0.5}Mn_{0.5}Ni_{1.0}$ alloy had $Cl_4$ Laves single phase and very high electrochemical discharge capacity of 464mAh/g.

• 한국수소및신에너지학회논문집
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• 제12권3호
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• pp.177-189
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• 2001

T hydrogen absorption-desorption behavior induced by thermal or hydrogen pressure cycling in a closed system was observed in hydrogen storage alloys, $(La-R-Mm)Ni_{4.5}Fe_{0.5}$, $MmNi_4Fe_{0.85}Cu_{0.15}$ and $(Ce-F-Mm)Ni_{4.7}Al_{0.2}Fe_{0.1}$. Thereby (La-R-Mm), Mm and (Ce-F-Mm) refer to La-rich mischmetal, mischmetal and Ce-free mischmetal respectively. As the results, it is found that the alloy stabilities during thermal cycling varies with alloy composition change. The highest stability occurs in $MmNi_4Fe_{0.85}Cu_{0.15}$ and the lowest stability in $(La-R-Mm)Ni_{4.5}Fe_{0.5}$. Comparing hydrogen pressure cycling with thermal cycling, pressure cycling causes severer degradation of the alloy $(Ce-F-Mm)Ni_{4.7}Al_{0.2}Fe_{0.1}$ than thermal cycling. When the 1500 times-cycled alloy is annealed at $400^{\circ}C$ for 3hrs under 1 atm of hydrogen pressure the hydrogen storage capacity is recovered only partially but not completely to the initial capacity. The amount of capacity loss after annealing is larger in the hydrogen pressure cycled samples than in the thermal cycled, suggesting an incoming of impure gas during hydrogen pressure cycling.

• 한국수소및신에너지학회논문집
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• 제5권1호
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• pp.51-57
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• 1994

Compaction techniques of hydrogen storage alloy 'powders, to solve the problems due to disintegration during the cyclic hydriding and dehydriding, by using polytetrafluoroethylene (PTFE) and silicon sealant as a polymer binder were studied. Optimum conditions of compaction were as follows. Binder content, 10 % for PTFE and 5 % for silicon sealant ; particle size of alloy powders, $-25{\mu}m$ ; compacting pressure, $4ton/cm^2$. Compacts obtained were easily activated and had a good strength even after 30 cycles of hydriding and dehydriding. PTFE added compacts showed very good rate capability, however, in the silicon added compacts hydrogen absorption rate was somewhat slow because of higher elasticity and adhesiveness of the binder.