WO2001069700A1 - Alliage absorbant l'hydrogene et electrode negative pour cellule auxiliaire au nickel-hydrure metallique - Google Patents

Alliage absorbant l'hydrogene et electrode negative pour cellule auxiliaire au nickel-hydrure metallique Download PDF

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Publication number
WO2001069700A1
WO2001069700A1 PCT/JP2001/001719 JP0101719W WO0169700A1 WO 2001069700 A1 WO2001069700 A1 WO 2001069700A1 JP 0101719 W JP0101719 W JP 0101719W WO 0169700 A1 WO0169700 A1 WO 0169700A1
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WIPO (PCT)
Prior art keywords
alloy
negative electrode
nickel
hydrogen storage
secondary battery
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PCT/JP2001/001719
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English (en)
Japanese (ja)
Inventor
Yuji Tanibuchi
Yasushi Asahi
Toshimi Tokui
Kiyofumi Takamaru
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Santoku Corp
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Santoku Corp
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    • 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
    • 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

Definitions

  • the present invention relates to a hydrogen storage alloy which has excellent corrosion resistance and can be used for a negative electrode material of a nickel hydrogen secondary battery to improve the battery life, and a nickel hydrogen secondary battery using the alloy. For negative electrodes.
  • Mm- N i- C o-A l- Mn -based AB 5 alloys are mainly used.
  • This alloy has a feature that it has a large hydrogen storage capacity compared to other alloys, and has a hydrogen absorption and release pressure at room temperature of 1 to 5 atm, making it easy to use. And then force, rare earth twelve Tsu Kell-based alloy of a conventional AB 5 type structure, the alloy contains the expansion and shrinkage crack by hydrogen absorption and release, there is a drawback of deteriorating the battery characteristics micronized.
  • the transition metal is composed of 4.5 to 5 transition metals in comparison with the rare-earth element 1 in atomic ratio. Alloys with increased La content in rare earth metals and Mn content in transition metals have been developed. However, there is a problem in that, as the electric capacity increases, pulverization and deterioration of corrosion resistance occur, and the battery life characteristics decrease.
  • Japanese Patent Application Laid-Open No. Hei 6-215765 in which at least one additive of an indium and a lithium compound is coated on the negative electrode surface, or A method of adding the compound to the inside of the negative electrode has been proposed.
  • Japanese Patent Publication No. 2713881 proposes that rare earths contain yttrium as an alloying element.
  • Japanese Patent Application Laid-Open No. H10-255529 proposes a hydrogen storage alloy excellent in initial activity, low-temperature characteristics, and high-rate discharge characteristics and containing 100 ppm or less of alkaline earth metal as an impurity. Those having a Vickers hardness of 600 kg mm 2 or more have been proposed.
  • the secondary battery negative electrode alloy has higher corrosion resistance during use and longer battery life as the hardness of the alloy is higher. Therefore, such alloys are being developed, but no alloys with a Vickers hardness of 900 kg Zinni 2 or more have been obtained. Disclosure of the invention
  • An object of the present invention is to provide a hydrogen storage alloy which has excellent alloy strength, suppresses fine powdering when used as a negative electrode material of a nickel-metal hydride secondary battery, and exhibits high corrosion resistance and high capacity. To provide a negative electrode for a nickel-metal hydride secondary battery.
  • the present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, by appropriately selecting cooling conditions, heat treatment conditions, and the like with respect to a molten alloy having a specific composition, a Vickers hardness of 900 kgZmm
  • the present inventors have found that two or more hydrogen storage alloys can be obtained and that such an alloy can be used as a negative electrode material of a nickel hydrogen secondary battery to obtain a nickel hydrogen secondary battery that exhibits excellent performance.
  • a hydrogen storage alloy having a composition represented by the formula (1) and a Vickers hardness of 90 Ok gZmm 2 or more.
  • A is Y, Gd, Tb, Dy or a mixture thereof
  • R is La, Ce, Pr, Nd or a mixture thereof
  • M is Co, A1, Mn, Fe, Cu, Z r, T i, Mo, W, B or a mixed element thereof
  • x, y and n are 0.011 ⁇ x ⁇ 0.1, 0.011y ⁇ 0.5, 4. 9 ⁇ n ⁇ 5.4
  • a negative electrode for a nickel-metal hydride secondary battery including the hydrogen storage alloy and a conductive material.
  • the hydrogen storage alloy for manufacturing a negative electrode for a nickel-metal hydride secondary battery.
  • the hydrogen storage alloy of the present invention has a composition represented by the above formula (1), and has a Vickers hardness (hereinafter, referred to as Hv) of 900 kg / mm 2 or more, preferably 900 to 1500 kgZmm 2 , particularly preferably. is of 900 ⁇ 1200 k gZmm 2 alloy.
  • Hv Vickers hardness
  • A is Y (ittrium), Gd (gadmium), Tb (terbium), Dy (dysprosium) or a mixture thereof
  • R is La (lantern), Ce (cellium), P ⁇ ( (Praseodymium), Nd (neodymium) or a mixture thereof
  • M is Co (cobalt), A1 (anorenium), Mn (manganese), Fe (iron), Cu (copper), Zr (zirconium), Tr i Tan), Mo (molybdenum), W (tandasten), B (boron) or a mixture thereof.
  • xy and n are each such that X is 0.011 ⁇ x ⁇ 0.1, preferably 0.03 ⁇ x ⁇ 0.08, more preferably 0.03 ⁇ x ⁇ 0.05 y force 0.011 ⁇ y ⁇ 0.5 n is 4.9 ⁇ n ⁇ 5.4.
  • X is less than 0.01, the mechanical strength and corrosion resistance of the obtained alloy will be reduced, and the battery life will be significantly reduced when used as a negative electrode material for a secondary battery.
  • X exceeds 0.1, no improvement in mechanical strength and corrosion resistance of the obtained alloy is observed.
  • n is outside the above range, the second phase will precipitate and the corrosion resistance will be significantly reduced.
  • composition of the hydrogen storage alloy of the present invention is not particularly limited as long as the above formula is satisfied, and the following composition is preferably used.
  • the hydrogen-absorbing alloy of the present invention when producing a secondary battery using the alloy as a negative electrode material for a nickel-metal hydride secondary battery, has a constant temperature of 1.0 mAcm- 2 at a constant temperature of 25 ° C. It is preferable that the oxidation rate ((oxygen value after 200 cycles) Z (initial oxygen value)) after repeating charge / discharge for 200 cycles by electric current is 10.0% or less.
  • the average particle size is usually 60 m or less, preferably 10 to 50 im.
  • the method for producing the hydrogen storage alloy of the present invention is not particularly limited as long as an alloy having the composition represented by the above formula (1) and having an Hv of 900 kg / mm 2 or more can be obtained. Not done. For example, it can be obtained by appropriately selecting conditions from the conditions shown below with reference to the conditions of the examples described later. At this time, the important point is the value of X in the composition represented by the above formula (1). In short, the composition in which R is replaced with A is important, and the hydrogen storage alloy of the present invention can be obtained by adopting this composition and appropriately selecting cooling conditions and the like.
  • the molten alloy having the above composition is supplied to a single-roll cooling device or the like via a tundish, and a supercooling degree of 50 to 500 ° C and a cooling rate of 100 to L0000 ° C / sec are particularly preferable. Is solidified uniformly to a thickness of about 0.1 to 0.5 mm under cooling conditions of SOOO lOOOOtTC / sec.
  • the obtained alloy ribbon is subjected to a vacuum or an inert atmosphere at 600 to 1100.
  • C preferably 800-150.
  • C more preferably 850-1000.
  • the hydrogen storage alloy of the present invention is ground to a desired particle size by a pole mill, a disc mill, a hammer mill, or the like. It can be done by doing. This pulverization can be performed in an inert atmosphere, a hydrogen atmosphere, a vacuum, or the like.
  • a negative electrode for a nickel-metal hydride secondary battery of the present invention includes the hydrogen storage alloy and a conductive material.
  • it is not particularly limited as long as it contains the hydrogen storage alloy powder of the present invention having the above preferred particle size and a conductive material, and can be produced using a binder or the like according to a conventional method.
  • the negative electrode for a nickel-metal hydride secondary battery of the present invention has an oxidation rate ((2 0 0 0) after repeating charging and discharging 200 cycles at a constant temperature of 25 ° C. and a constant current of 1.0 mA′cm ⁇ 2 . Those having an oxygen value after cycle (initial oxygen value) of 10.0% or less are preferred. Since the hydrogen storage alloy of the present invention has a specific composition and excellent Hv, it has excellent alloy strength, and when used as a negative electrode material of a nickel-metal hydride secondary battery, pulverization is suppressed and high It shows insect resistance and high capacity.
  • the negative electrode for a nickel-hydrogen secondary battery of the present invention uses the above-mentioned hydrogen storage alloy, so that the battery life of the nickel-hydrogen secondary battery can be improved.
  • the obtained molten alloy was subjected to subcooling of 150 ° C. and a cooling rate of 200 to 500 ° C. for 0 seconds using a single roll forming apparatus equipped with a tundish. Strip alloys of 1-0.3 mm were produced. The obtained alloy was heat-treated at 950 ° C. for 6 hours in an argon gas atmosphere. Next, the obtained heat-treated alloy was mirror-polished, and the Hv of the alloy was measured using a micro hardness tester (manufactured by Akashi Seisakusho Co., Ltd.). Table 1 shows the results.
  • a hydrogen storage alloy was prepared in the same manner as in Example 1 except that the raw material composition was changed as shown in Table 1, and ⁇ was measured. Table 1 shows the results.
  • Example 1 the molten alloy was cooled by a single-roll forming apparatus by pouring into a water-cooled copper mold to obtain a 20-mm-thick alloy ingot, and heat-treated and pulverized as in Example 1. A hydrogen storage alloy was prepared and Hv was measured. Table 1 shows the results. Alloy composition ( ⁇ child ratio) AB x
  • Example 1 0.30 0.44 0.04 0.17 0.05 3.55 0.75 0.30 0.40 5.00 Single roll 990
  • Example 2 0.30 0.44 0.04 0. 17 0.05 3.40 0.80 0.30 0.40 4.90 Single roll 990
  • Example 3 0.35 0.42 0.03 0.15 0.05 3.75 0.60 0.30 0 45 5.10 980
  • Example 4 0.38 0.40 0.03 0.14 0.05 3.90 0.50 0.30 0.50 5.20
  • Example 5 0.42 0.40 0.02 0.11 0.05 4.20 0.40 0.30 0.50 5.40 Single roll 956
  • Example 6 0.30 0.45 0.04 0.18 0.03 3.
  • Example 7 0 30 0.45 0.04 0.18 0 03 0 50 0 50 5.20 Single roll 932
  • Example 8 0.28 0.47 0.05 0.19 0.01 3.55 0.75 0.30 0.40 5.00
  • Single roll 912 Example 9 0.28 0.47 0.05 0.19 0.01 3. 65 0.65 0.30 0.40 5.00
  • Single roll 900 Example 10 0.46 0.33 0.02 0.09 0.01 3.55 0.75 0.30 0.40 5.00
  • Example 11 0.30 0.44 0.04 0.17 0.03 3.55 0.7.5 5 0.30 0.40 5.00 Single Roll 940
  • Example 12 0.30 0.44 0. 04 0.17 0.
  • the alloy prepared in Example 1 was pulverized with a hammer mill, and the alloy powder (10 g), copper powder (1 g) as a conductive agent, and FEP (tetrafluoroethylene / tetrafluoropropylene copolymer) powder 0.3 were used. g was mixed to produce a 20 mm diameter pellet electrode.
  • the obtained electrode was immersed in a 6N KOH solution, a battery was constructed using a mercury oxide reference electrode, and the electrode characteristics were measured using a potentiogalvanostat (manufactured by Hokuto Denko). The measurement was conducted at a constant temperature of 25 ° C. and at a constant current of 60 mA / g for 200 cycles of charge / discharge.
  • oxidation rate (oxygen value after 200 cycles) / (initial oxygen value).
  • Example 16 in place of the alloy prepared in Example 1, the alloy prepared in Example 2 (Example 17), the alloy prepared in Example 4 (Example 18), and the alloy prepared in Example 6 were used.
  • the prepared alloy (Example 19), the alloy prepared in Example 7 ( ⁇ Example 20), the alloy prepared in Example 8 (Example 21), the alloy prepared in Comparative Example 1 (Comparative Example 5), the alloy prepared in Comparative Example 2 (Comparative Example 6), or the alloy prepared in Comparative Example 4 (Comparative Example 7), a pellet electrode was prepared in the same manner, and various measurements were performed. . Table 2 shows the results.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Powder Metallurgy (AREA)

Abstract

Cette invention concerne un alliage absorbant l'hydrogène dont la composition chimique est représentée par la formule (I) suivante : AxR1-x(MyNi1-y)n. Selon cette formule, A représente Y, Gd, Tb, Dy ou un mélange de ces éléments, R représente La, Ce, Pr, Nd ou un mélange de ces éléments, M représente Co, Al, Mn, Fe, Cu, Zr, Ti, Mo, W, B ou un mélange de ces éléments, x, y et n sont des nombres satisfaisant chacun à la relation 0,01 ≤ x ≤ 0,1, 0,01 ≤ y ≤ 0,5 ou 4,9 ≤ n ≤ 5,4. Cet alliage présente un Hv de 900kg/mm2 ou plus. L'invention concerne également une cellule auxiliaire au nickel-hydrure métallique utilisant l'alliage susmentionné. L'alliage absorbant l'hydrogène présente une remarquable robustesse et, lorsqu'il est utilisé comme matériau pour l'électrode négative d'une cellule auxiliaire au nickel-nitrure métallique, une absence de pulvérisation, une résistance élevée à la corrosion et une grande capacité.
PCT/JP2001/001719 2000-03-15 2001-03-06 Alliage absorbant l'hydrogene et electrode negative pour cellule auxiliaire au nickel-hydrure metallique Ceased WO2001069700A1 (fr)

Applications Claiming Priority (2)

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JP2000072751A JP2001266864A (ja) 2000-03-15 2000-03-15 水素吸蔵合金、ニッケル水素２次電池負極用合金粉末及びニッケル水素２次電池用負極
JP2000-72751 2000-03-15

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111471893A (zh) * 2020-04-14 2020-07-31 包头稀土研究院 掺杂的a5b19型含钆储氢合金、电极、电池及其制备方法

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4979178B2 (ja) * 2003-07-04 2012-07-18 三洋電機株式会社 密閉型アルカリ蓄電池用水素吸蔵合金粉末及びそれを用いた密閉型アルカリ蓄電池
CN1294664C (zh) * 2004-06-03 2007-01-10 刘华福 可用于高温镍氢电池的负极储氢材料
JP5213314B2 (ja) * 2006-05-31 2013-06-19 三洋電機株式会社 アルカリ蓄電池
US10566614B2 (en) * 2014-08-28 2020-02-18 Baotou Research Institute of Rare Earths Rare earth based hydrogen storage alloy and application thereof
CN111893346B (zh) 2019-05-06 2022-10-21 中国石油化工股份有限公司 固溶体型储氢合金及其制备方法和应用以及含有机物氢气提纯方法
EP3967396A4 (fr) 2019-05-06 2023-04-12 China Petroleum & Chemical Corporation Catalyseur pour déshydrogéner un matériau brut de stockage d'hydrogène organique, support pour catalyseur, alliage de stockage d'hydrogène et procédé pour fournir de l'hydrogène de haute pureté

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06124702A (ja) * 1992-10-09 1994-05-06 Sanyo Electric Co Ltd 水素吸蔵合金の評価方法
EP0790323A1 (fr) * 1995-08-31 1997-08-20 Santoku Metal Industry Co., Ltd. Alliage a base de metal du groupe des terres rares/nickel absorbant l'hydrogene, son procede de fabrication et electrode negative pour batterie secondaire au nickel/hydrogene.
JPH10102172A (ja) * 1996-09-30 1998-04-21 Toshiba Corp 水素吸蔵合金，その製造方法およびニッケル水素二次電池

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06124702A (ja) * 1992-10-09 1994-05-06 Sanyo Electric Co Ltd 水素吸蔵合金の評価方法
EP0790323A1 (fr) * 1995-08-31 1997-08-20 Santoku Metal Industry Co., Ltd. Alliage a base de metal du groupe des terres rares/nickel absorbant l'hydrogene, son procede de fabrication et electrode negative pour batterie secondaire au nickel/hydrogene.
JPH10102172A (ja) * 1996-09-30 1998-04-21 Toshiba Corp 水素吸蔵合金，その製造方法およびニッケル水素二次電池

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111471893A (zh) * 2020-04-14 2020-07-31 包头稀土研究院 掺杂的a5b19型含钆储氢合金、电极、电池及其制备方法

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