WO2003054240A1 - Alliage de stockage d'hydrogene et poudre d'alliage de stockage d'hydrogene, son procede d'obtention, et electrode negative pour un element accumulateur nickel-hydrogene - Google Patents

Alliage de stockage d'hydrogene et poudre d'alliage de stockage d'hydrogene, son procede d'obtention, et electrode negative pour un element accumulateur nickel-hydrogene Download PDF

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Publication number
WO2003054240A1
WO2003054240A1 PCT/JP2002/013062 JP0213062W WO03054240A1 WO 2003054240 A1 WO2003054240 A1 WO 2003054240A1 JP 0213062 W JP0213062 W JP 0213062W WO 03054240 A1 WO03054240 A1 WO 03054240A1
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Prior art keywords
hydrogen storage
alloy
storage alloy
phase
powder
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PCT/JP2002/013062
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English (en)
Japanese (ja)
Inventor
Kiyofumi Takamaru
Hiroki Hayashi
Hideaki Ikeda
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Santoku Corporation
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Application filed by Santoku Corporation filed Critical Santoku Corporation
Priority to AU2002354479A priority Critical patent/AU2002354479A1/en
Priority to JP2003554939A priority patent/JP4647910B2/ja
Publication of WO2003054240A1 publication Critical patent/WO2003054240A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
    • C01B3/0047—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof
    • C01B3/0057—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof also containing nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0433—Nickel- or cobalt-based alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/383—Hydrogen absorbing alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

Definitions

  • Hydrogen storage alloys Hydrogen storage alloys, hydrogen storage alloy powders, their production methods, and negative electrodes for nickel-metal hydride secondary batteries
  • the present invention is useful as an electrode material for nickel-metal hydride secondary batteries and the like.
  • the present invention relates to the powder, a method for producing the powder, and a negative electrode for a nickel-metal hydride secondary battery.
  • a metal oxide monohydrogen battery in which the hydrogen negative electrode is made of a hydrogen storage alloy.
  • Such batteries inherently have a high energy density, are excellent in volumetric efficiency, can operate safely, and are excellent in characteristics and reliability.
  • the AB 5 SET-containing storage alloy is mainly used as a negative electrode material of the battery, usually, in order to improve the characteristics of the battery, high hydrogen storage capacity, a variety of such low pressures, corrosion resistance, Blato one flatness Characteristics are required. Since some of these properties are contradictory, research has been conducted on improving the other property without sacrificing one property, and some of them have been put to practical use.
  • nickel-metal hydride secondary batteries have been used for batteries requiring high-rate discharge, such as power tool applications, and further improvement in the properties of the hydrogen storage alloy used for these batteries is required. Disclosure of the invention
  • An object of the present invention is to be useful as an electrode material of a nickel-metal hydride secondary battery.
  • An object of the present invention is to provide a hydrogen storage alloy having good life characteristics and good balance and excellent recyclability, a powder thereof, a method for producing the same, and a negative electrode for a nickel-metal hydride secondary battery using the hydrogen storage alloy powder. .
  • the present inventors have conducted intensive studies on the correlation between the composition and structure of the alloy and the corrosion resistance and activity in order to solve the above-mentioned problems.
  • the B-site component of the alloy is set to a specific range
  • the B-site Completed the present invention by finding that the above problems can be solved by using a hydrogen storage alloy in which the amount of A1 and Mn in the components is in a specific range and a fine second phase is uniformly deposited over the entire matrix. did.
  • an alloy having a composition represented by the formula (1), wherein the content of A1 and Mn in the crystal grain boundaries and in the crystal grains of the mother phase constituting the alloy is A hydrogen-absorbing alloy having a second phase that is larger than the contents of A1 and Mn and has a particle size of 10 m or less is obtained.
  • R represents a rare earth element containing yttrium or a mixed element thereof
  • M represents Mg, Fe, Cu, Zr, Ti, Mo, W, B or a mixture thereof.
  • A represents 3.50 ⁇ a ⁇ 4.95
  • B is 0.10 ⁇ b ⁇ 0.50
  • c is 0.35 ⁇ c ⁇ 0.55
  • d is 0.10 ⁇ d 0.45
  • e is 0 ⁇ e ⁇ 0.10
  • an alloy powder having a composition represented by the above formula (1), a particle size of 10 ⁇ or more, and a grain boundary and at least one second phase inside the alloy particle.
  • a hydrogen storage alloy powder comprising:
  • a hydrogen storage alloy powder which is an alloy powder having an average particle diameter of 5 to: L00 m and contains the alloy powder.
  • the molten alloy is cooled and solidified to obtain a piece having an average thickness of 0.05 to 0.5 mm, which is obtained.
  • 900 pieces The method for producing a hydrogen-absorbing alloy is characterized by performing a heat treatment at ⁇ 1100 ° C. for 30 minutes to 10 hours.
  • the alloy melt is cooled and solidified to obtain a piece having an average thickness of 0.05 to 0.5 mm. After the heat treatment of the pieces at 900 to 1100 ° C for 30 minutes to 10 hours, a method of producing the above-mentioned alloy powder which is pulverized is performed.
  • a negative electrode for a nickel-metal hydride secondary battery including the above alloy powder and a conductive material as a negative electrode material.
  • FIG. 1 is a copy of an electron micrograph showing a cross section and a view of the hydrogen-absorbing piece prepared in Example 1-1.
  • FIG. 2 is a copy of an electron micrograph showing a cross-sectional structure of the hydrogen storage alloy powder prepared in Example 2-1.
  • the hydrogen storage alloy of the present invention has a composition represented by the above formula (1).
  • R in the formula (1) represents a rare earth element containing yttrium or a mixed element of two or more thereof.
  • R in the formula (1) represents a rare earth element containing yttrium or a mixed element of two or more thereof.
  • La is 40 to; L00 wt%, Ce is 0 to 50 mass%, Pr is that 0 to 50 weight 0/0, Nd is 0 to 50 mass 0/0 preferable.
  • A which indicates the amount of Ni in the formula (1), is 3.50 ⁇ a ⁇ 4.95, preferably 3.90 ⁇ a ⁇ 4.75.
  • B indicating the amount of Co is 0.10 ⁇ b ⁇ 0.50, preferably 0.20 ⁇ b 0.50. If it exceeds 0.50, the alloy price will increase, and if it is less than 0.10, the corrosion resistance will inevitably decrease.
  • C indicating the amount of A1 is 0.35 ⁇ c ⁇ 0.55, preferably 0.35 ⁇ c ⁇ 0.50.
  • D indicating the amount of Mn is 0.10 ⁇ d ⁇ 0.45, preferably 0.15 ⁇ d ⁇ 0.30.
  • the amount of A1 and Mn is good within the above range, but in order to further improve the desired object of the present invention, the composition is set so that the c / d indicating the abundance ratio of A1 and Mn is 0.7 or more. It is particularly preferred to adjust
  • M in the formula (1) is an additive element for adjusting the hydrogen storage characteristics of the alloy, and includes Mg, Fe, Indicate Cu, Zr, Ti, Mo, W, B or a mixture of two or more thereof.
  • E indicating the amount of M is 0 ⁇ e ⁇ 0.10. If e exceeds 0.10, it is not possible to improve the properties corresponding to the added amount, and recycling may be difficult.
  • a + b + c + d + e ⁇ Z) f indicating the B-site element ratio is 510 to 5.50, preferably 5.20 to 5.40. If this value is less than 5.10, it becomes difficult to disperse the fine second phase in the alloy structure, and if it exceeds 5.50, a decrease in capacity when used as a battery material is inevitable.
  • the hydrogen storage alloy of the present invention has the above-described composition, and its structure is such that, in order to obtain desired characteristics, the amount of A1 and the amount of ⁇ are within the crystal grain boundaries and within the crystal grains of the parent phase constituting the alloy.
  • the form of this second phase is different from the second phase contained in the conventional hydrogen storage alloy, and often shows a spherical shape or an elliptical spherical shape.
  • the size of the second phase is preferably from 0.05 to 10 m, more preferably from 0.05 to 5 ⁇ m , and even more preferably from 0.05 to 2 ⁇ , so as to be uniformly distributed inside the alloy powder.
  • the narrowest interval between the second phases existing in the hydrogen storage alloy is preferably 10 111 or less, particularly 5 111 or less, and more preferably 2 111 or less, and there is no need for the interval.
  • the presence of the second phase can be determined using an electron microscope or ⁇ .
  • that the amount of A1 and Mn is larger than the amount of A1 and Mn of the parent phase means that the average of A1 and Mn contained in the parent phase is larger than the average value of A1 and Mn contained in the second phase. It means that the amount is significant and significant.
  • the amount of A1 and Mn in the second phase is preferably at least 2% higher than the average of that of the mother phase.
  • the range of X is desirably in the range of 6 to;
  • the method for producing the hydrogen storage alloy of the present invention is not particularly limited as long as the composition of the obtained alloy and the particle size, shape and dispersion state of the second phase can be controlled as described above.
  • the production method of the present invention is preferred.
  • an alloy raw material having a composition represented by the above formula (1) is melted, and then the alloy melt is cooled and solidified to obtain a piece having a specific average thickness. It is characterized in that the piece is heat-treated under specific conditions.
  • the alloy raw material having the composition represented by the formula (1) is not particularly limited as long as the obtained alloy composition is a mixture of metals and alloys satisfying the formula (1).
  • a mixture of each metal having the composition shown in (1) can be used.
  • the alloy melt of the alloy raw material is subjected to a known method such as high-frequency melting in an inert gas atmosphere using an alumina tube. You can get more.
  • the above-mentioned alloy melt is solidified by cooling to obtain a piece having an average thickness of 0.05 to 0.5 mm.
  • the cooling rate is high, the crystal grain size becomes finer, and if the cooling rate is slow, the crystal grain size becomes coarse. Since the crystal grain size is not uniform at the time of producing the piece and the shape and precipitation state of the second phase are not uniform, a heat treatment is performed under specific conditions in a subsequent step. Therefore, if the cooling rate at the time of producing the piece is too slow, the crystal diameter becomes large during the heat treatment described later, and it becomes difficult to make the dispersion state of the second phase uniform, which is not preferable.
  • the cooling rate is too high, the crystals become finer and the dispersed state becomes better. It is not preferable because it becomes difficult to control the heat treatment conditions and the productivity decreases. Further, when the cooling rate is further increased to become amorphous, it is difficult to precipitate the second phase in the crystal grains even if heat treatment is subsequently performed for crystallization, which is not preferable.
  • the above-mentioned strip be performed by a strip casting method using a single Rhono twin roll, a centrifugal method, a rotary disk manufacturing method, or the like that can obtain a suitable cooling rate.
  • the cooling conditions are usually about 10 to 3000 ° CZ seconds, preferably 10 to 500 ° CZ seconds, and more preferably 10 to 200 ° C / second.
  • the thickness of the obtained piece is controlled in the range of 0.05 to 0.5 mm in order to eliminate the variation of the crystal grain size in the cross-sectional direction of the piece and to make the crystal grain size after heat treatment described later uniform. There is a need. In this case, by exploring the above method, columnar crystals grow in the thickness direction of the obtained piece. In single-sided cooling such as single roll strip casting, the crystal grain size of the surface that is woven into the cooling medium is the smallest, and the crystal diameter increases toward the opposite surface.
  • the crystal grain size on the surface that is infested with the cooling medium is small, and the crystal grain size increases toward the center of the piece. ⁇ If the thickness of the piece exceeds 0.5 mm, the difference in grain size between the portion with a small crystal grain size and the portion with a large crystal grain size becomes too large, making it difficult to obtain the desired weave even by the heat treatment described below. Become.
  • the piece obtained above is subjected to a specific heat treatment to obtain the hydrogen storage alloy of the present invention.
  • the higher the heat treatment ⁇ and the longer the heat treatment time the smaller the grain size difference of each crystal in the piece, but the crystal grain size becomes too large and the desired characteristics may not be obtained. . Therefore, in the production method of the present invention, it is necessary to set the heat treatment conditions at 900 to 1100 ° C. for 30 minutes to 10 hours.
  • the hydrogen storage alloy powder of the present invention has a composition represented by the above formula (1), and has a particle size of 10 m or more. Alloy powder containing a grain boundary and at least a second phase inside the alloy (hereinafter, this alloy powder is referred to as a first powder), and an average particle size of 5 to 100 ⁇ m. m, and an alloy powder containing the first powder (hereinafter, this alloy powder is referred to as a second powder).
  • the composition and the second phase the same composition and the second phase as described in the hydrogen storage alloy of the present invention described above are preferably used.
  • the narrowest interval between the second phases is preferably 10 / m or less, particularly 5 ⁇ or less, and more preferably 2 m or less, and there may be no interval.
  • the composition of the second powder preferably has a composition represented by all of the formula (1), and powders other than the first powder in the second powder also have at least a second grain boundary with the grain boundary inside the alloy particles. It is preferable to include two phases.
  • the crystal grain size is preferably 5 ⁇ m or more, and more preferably 5 to 50 ⁇ m. It is preferable that the average particle size is 1/2 or less.
  • the surface may be covered with plating or a high-molecular polymer, or acid, Known treatments such as a surface treatment with a solution such as aluminum can be applied.
  • the first and second powders of the present invention can be obtained by, for example, the production method of the present invention in which the hydrogen storage alloy of the present invention is produced, and then the obtained heat-treated pieces are pulverized.
  • the step of pulverizing the piece after the heat treatment is not particularly limited as long as the alloy oxidation does not proceed during the pulverization of the piece and a specific particle size can be obtained.
  • a wet pulverization method using low oxygen water a dry pulverization method such as a pin mill / disk mill, and a hydrogen pulverization method using hydrogen gas are preferably exemplified.
  • the negative electrode for a nickel-metal hydride secondary battery of the present invention is not particularly limited as long as it contains the first or second powder and a conductive material as a negative electrode material. May contain other materials to achieve purpose! / ,.
  • the negative electrode for a nickel-metal hydride secondary battery of the present invention uses, for example, a first or second powder pulverized to a specific particle size and a conductive material, and mixes with a binder, a conductive auxiliary, and the like by a known method. It can be prepared by molding.
  • the conductive material, the binder, the conductive auxiliary agent, and the like are not particularly limited, and may be used.
  • the hydrogen storage alloy and the powder thereof of the present invention have a specific composition, a specific texture, and are therefore useful as an electrode material for a nickel hydrogen secondary battery. Excellent initial activity, high rate discharge characteristics, corrosion resistance and longevity characteristics, good balance, and with a small amount of Co, these characteristics can be obtained. . Further, according to the production method of the present invention, such a hydrogen storage alloy and its powder can be industrially easily obtained.
  • the negative electrode for a nickel-metal hydride secondary battery of the present invention uses the above-mentioned hydrogen-absorbing alloy powder of the present invention as an active material.
  • Example 1-1 ⁇ : L-6 and Comparative Example 1-:! ⁇ 1-2
  • Rare earth metals having the compositions shown in Table 1 (Examples 1-1 to 1-4; Mish Metal manufactured by Santoku Co., Ltd. were used) were used as A sites, and the A site was set to 1 for ⁇ Ni, Co, A raw material metal or an alloy was blended so that the atomic ratio of Mn and Al and the X of ABx became the values shown in Table 1, and were subjected to high frequency melting in an argon atmosphere using an alumina loop to prepare an alloy melt.
  • the obtained alloy melt was continuously supplied to a single roll via a tundish, and rapidly cooled at a cooling rate of 100 ° C / sec by a strip casting method to prepare a piece having a thickness of 0.2 mm. .
  • the obtained piece was ripened in an argon gas atmosphere under the conditions shown in Table 1 to prepare a hydrogen storage alloy.
  • the composition of the obtained hydrogen storage alloy was quantitatively analyzed by X-ray fluorescence spectroscopy (Nippon Kogyo Co., Ltd .: fc SMX-10), and it was confirmed that the composition was the same as the composition.
  • the alloy structure was observed with a scanning electron microscope, and the presence or absence of the second phase, the morphology of the second phase, the particle size of the second phase, and the narrowest interval between the second phases were measured.
  • the amounts of A1 and Mn in the parent phase and the second phase were measured by EPMA (JEOL JXL8800) quantitative analysis from the observed alloy structure, and the average total amount of A1 and Mn in the parent phase (b ), The increase in the total amount (s) of A1 and Mn in the second phase was calculated. Table 1 shows the results.
  • FIG. 1 shows a copy of an electron micrograph showing a cross-sectional structure of the hydrogen storage alloy ⁇ prepared in Example 1-1, taken along a cross section perpendicular to the thickness direction.
  • Example 2- ! ⁇ 2-6 and Comparative Examples 2-1 ⁇ 2-2
  • the hydrogen storage alloy prepared in Examples 1-1 to 1-6 or Comparative Example 1-1-1-2 was mechanically pulverized to prepare a hydrogen storage alloy powder having an average particle diameter of 60 m or less.
  • Example 1-1-1-6 and Comparative Example 1-1-1- It was confirmed that the composition was the same as the hydrogen storage alloy composition prepared in 2. Further, the alloy powder yarn was observed with a scanning electron microscope, and the presence or absence of the second phase and the grain boundary, and the crystal size of the crystal grains in the alloy powder in the minor axis direction were measured. In addition, the minimum particle size and the average particle size of the alloy powder were measured using a particle size meter. Table 2 shows the results.
  • FIG. 2 shows a copy of an electron micrograph showing the cross-sectional structure of the hydrogen storage alloy powder prepared in Example 2-1.
  • the capacity at the time of discharging at 1 C at the 11th cycle was measured, and the ratio of the value at this time to the discharge capacity at the 10th cycle was evaluated.
  • the corrosion resistance after the 12th cycle, the battery was discharged again with a discharge current of 0.2 C, and the capacity retention ratio at the 600th cycle with respect to the discharge at the 10th cycle was evaluated.

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Abstract

L'invention concerne un alliage de stockage d'hydrogène ayant une composition représentée par la formule (I) : RNiaCobAlcMndMe ----, dans laquelle R représente un élément de terres rares comprenant Y ou analogue, M représente Mg, Fe ou analogue, et 3,50 ≤ a ≤ 4,95, 0,10 ≤ b ≤ 0,50, 0,35 ≤ c ≤ 0,55, 0,10 ≤ d ≤ 0,45 et 0 ≤ e ≤ 0.10, à condition que 5,10 ≤ a+b+bd+e ≤ 5,50, et ayant un diamètre particulaire de 10 νm ou inférieur et, au niveau d'une limite du grain et dans un grain de la phase de base constituant l'alliage, une seconde phase ayant une teneur en Al et une teneur en Mn supérieure à celles de la phase de base. L'alliage de stockage d'hydrogène sert de matière d'électrode pour un élément accumulateur faisant preuve d'une teneur en cobalt réduite, et offre également un bon équilibre du niveau des activités, notamment de l'activité initiale et des caractéristiques de décharge, en terme de résistance à la corrosion, de caractéristiques de durée de vie. L'invention est également excellente en termes de recyclabilité.
PCT/JP2002/013062 2001-12-13 2002-12-13 Alliage de stockage d'hydrogene et poudre d'alliage de stockage d'hydrogene, son procede d'obtention, et electrode negative pour un element accumulateur nickel-hydrogene WO2003054240A1 (fr)

Priority Applications (2)

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AU2002354479A AU2002354479A1 (en) 2001-12-13 2002-12-13 Hydrogen storage alloy and hydrogen storage alloy powder, method for production thereof, and negative electrode for nickel-hydrogen secondary cell
JP2003554939A JP4647910B2 (ja) 2001-12-13 2002-12-13 水素吸蔵合金粉末、その製造法及びニッケル水素二次電池用負極

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JP2001380048 2001-12-13
JP2001-380048 2001-12-13

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1652947A1 (fr) * 2003-08-08 2006-05-03 Mitsui Mining & Smelting Co., Ltd. Alliage d'occlusion d'hydrogene a faible teneur en co
CN1297021C (zh) * 2005-05-31 2007-01-24 钢铁研究总院 一种高容量镍氢电池用负极材料
WO2007040277A1 (fr) * 2005-10-06 2007-04-12 Mitsui Mining & Smelting Co., Ltd. ALLIAGE À FAIBLE TENEUR EN Co ABSORBANT L'HYDROGÈNE
JP2008053223A (ja) * 2006-07-25 2008-03-06 Matsushita Electric Ind Co Ltd ニッケル水素電池用負極活物質およびニッケル水素電池、およびニッケル水素電池用負極活物質の処理方法
WO2008093437A1 (fr) 2007-01-30 2008-08-07 Chuo Denki Kogyo Co., Ltd. Alliage de stockage d'hydrogène et électrode pour batterie nickel-hydrogène
JP2008258121A (ja) * 2007-03-30 2008-10-23 Santoku Corp 水素吸蔵合金、ニッケル水素二次電池用負極、ニッケル水素二次電池
JP2010182684A (ja) * 2006-07-25 2010-08-19 Panasonic Corp ニッケル水素電池用負極活物質の処理方法ならびにニッケル水素電池用負極活物質およびニッケル水素電池
JP2011127185A (ja) * 2009-12-18 2011-06-30 Santoku Corp 水素吸蔵合金、その製造方法、ニッケル水素二次電池用負極およびニッケル水素二次電池

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100467168C (zh) * 2007-02-02 2009-03-11 厦门钨业股份有限公司 贮氢合金粉制备方法
CN102181751B (zh) * 2011-01-28 2013-01-09 厦门钨业股份有限公司 一种低自放电贮氢合金及其制备方法
WO2021033582A1 (fr) * 2019-08-19 2021-02-25 株式会社三徳 Matériau de stockage d'hydrogène, récipient de stockage d'hydrogène et dispositif d'alimentation en hydrogène
EP4129534A1 (fr) 2021-08-03 2023-02-08 GRZ Technologies SA Alliages de stockage d'hydrogène de type ab5, leurs procédés de préparation et utilisations
EP4129535A1 (fr) 2021-08-03 2023-02-08 GRZ Technologies SA Alliages de stockage d`hydrogène de type ab2, leurs procédés de préparation et leurs utilisations

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10261413A (ja) * 1997-03-19 1998-09-29 Japan Metals & Chem Co Ltd 二次電池用水素吸蔵合金
JP2000219928A (ja) * 1999-02-01 2000-08-08 Mitsui Mining & Smelting Co Ltd 水素吸蔵合金及びその製造方法
JP2001040442A (ja) * 1999-05-26 2001-02-13 Mitsui Mining & Smelting Co Ltd 水素吸蔵合金
JP2001068101A (ja) * 1999-08-24 2001-03-16 Sanyo Electric Co Ltd 水素吸蔵合金電極及びその製造方法
US6372059B1 (en) * 1998-12-15 2002-04-16 Mitsui Mining & Smelting Co., Ltd. Hydrogen storage alloy and method for preparation thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69727317T2 (de) * 1996-09-06 2004-11-25 Santoku Corp., Kobe Wasserstoffabsorbierende seltene-erden metall/nickel-legierung, herstellungsverfahren und negative elektrode für nickel-wasserstoff-wiederaufladbare-batterie
JPH11191412A (ja) * 1997-06-27 1999-07-13 Hitachi Maxell Ltd アルカリ蓄電池
JP2001126724A (ja) * 1999-10-25 2001-05-11 Shin Etsu Chem Co Ltd 水素吸蔵合金粉末の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10261413A (ja) * 1997-03-19 1998-09-29 Japan Metals & Chem Co Ltd 二次電池用水素吸蔵合金
US6372059B1 (en) * 1998-12-15 2002-04-16 Mitsui Mining & Smelting Co., Ltd. Hydrogen storage alloy and method for preparation thereof
JP2000219928A (ja) * 1999-02-01 2000-08-08 Mitsui Mining & Smelting Co Ltd 水素吸蔵合金及びその製造方法
JP2001040442A (ja) * 1999-05-26 2001-02-13 Mitsui Mining & Smelting Co Ltd 水素吸蔵合金
JP2001068101A (ja) * 1999-08-24 2001-03-16 Sanyo Electric Co Ltd 水素吸蔵合金電極及びその製造方法

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1652947A1 (fr) * 2003-08-08 2006-05-03 Mitsui Mining & Smelting Co., Ltd. Alliage d'occlusion d'hydrogene a faible teneur en co
EP1652947A4 (fr) * 2003-08-08 2008-06-25 Mitsui Mining & Smelting Co Alliage d'occlusion d'hydrogene a faible teneur en co
CN1297021C (zh) * 2005-05-31 2007-01-24 钢铁研究总院 一种高容量镍氢电池用负极材料
WO2007040277A1 (fr) * 2005-10-06 2007-04-12 Mitsui Mining & Smelting Co., Ltd. ALLIAGE À FAIBLE TENEUR EN Co ABSORBANT L'HYDROGÈNE
JP2008053223A (ja) * 2006-07-25 2008-03-06 Matsushita Electric Ind Co Ltd ニッケル水素電池用負極活物質およびニッケル水素電池、およびニッケル水素電池用負極活物質の処理方法
JP2010182684A (ja) * 2006-07-25 2010-08-19 Panasonic Corp ニッケル水素電池用負極活物質の処理方法ならびにニッケル水素電池用負極活物質およびニッケル水素電池
WO2008093437A1 (fr) 2007-01-30 2008-08-07 Chuo Denki Kogyo Co., Ltd. Alliage de stockage d'hydrogène et électrode pour batterie nickel-hydrogène
KR101148806B1 (ko) 2007-01-30 2012-05-24 쥬오 덴끼 고교 가부시키가이샤 수소 흡장 합금, 니켈-수소 전지용 전극, 하이브리드 자동차용 구동 장치 및 하이브리드 자동차
US8377374B2 (en) 2007-01-30 2013-02-19 Chuo Denki Kogyo Co., Ltd. Hydrogen-absorbing alloy and electrode for nickel-metal hydride secondary batteries
TWI395364B (zh) * 2007-01-30 2013-05-01 Chuo Denki Kogyo Co Ltd Adsorption of hydrogen alloy and nickel - hydrogen battery electrode
JP2008258121A (ja) * 2007-03-30 2008-10-23 Santoku Corp 水素吸蔵合金、ニッケル水素二次電池用負極、ニッケル水素二次電池
JP2011127185A (ja) * 2009-12-18 2011-06-30 Santoku Corp 水素吸蔵合金、その製造方法、ニッケル水素二次電池用負極およびニッケル水素二次電池

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