JPH07118704A - Hydrogen storage alloy powder, nickel-hydrogen battery having the powder in negative electrode active material and production of the powder - Google Patents
Hydrogen storage alloy powder, nickel-hydrogen battery having the powder in negative electrode active material and production of the powderInfo
- Publication number
- JPH07118704A JPH07118704A JP5265330A JP26533093A JPH07118704A JP H07118704 A JPH07118704 A JP H07118704A JP 5265330 A JP5265330 A JP 5265330A JP 26533093 A JP26533093 A JP 26533093A JP H07118704 A JPH07118704 A JP H07118704A
- Authority
- JP
- Japan
- Prior art keywords
- alloy powder
- cobalt
- hydrogen storage
- storage alloy
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 123
- 239000000956 alloy Substances 0.000 title claims abstract description 123
- 239000000843 powder Substances 0.000 title claims abstract description 94
- 239000001257 hydrogen Substances 0.000 title claims abstract description 76
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 76
- 238000003860 storage Methods 0.000 title claims abstract description 70
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000007773 negative electrode material Substances 0.000 title claims 2
- 229940044175 cobalt sulfate Drugs 0.000 claims abstract description 13
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims abstract description 13
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 150000001869 cobalt compounds Chemical class 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 238000005229 chemical vapour deposition Methods 0.000 claims description 14
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 5
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 5
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 5
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 239000012495 reaction gas Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- AVWLPUQJODERGA-UHFFFAOYSA-L cobalt(2+);diiodide Chemical compound [Co+2].[I-].[I-] AVWLPUQJODERGA-UHFFFAOYSA-L 0.000 claims description 2
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims 3
- 239000011261 inert gas Substances 0.000 claims 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000003518 caustics Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 230000033228 biological regulation Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 229910018007 MmNi Inorganic materials 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は水素を可逆的に吸蔵・放
出し、ニッケル水素蓄電池などに使用される水素吸蔵合
金粉末およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogen storage alloy powder for reversibly storing and releasing hydrogen, which is used in nickel-metal hydride storage batteries and a method for producing the same.
【０００２】[0002]
【従来の技術】近年、可逆的に水素を吸蔵・放出する水
素吸蔵合金粉末を負極に用いたニッケル・水素蓄電池
が、エネルギー密度が高く、充放電サイクル寿命も長い
二次電池として注目されている。2. Description of the Related Art In recent years, a nickel-hydrogen storage battery using a hydrogen storage alloy powder that reversibly stores and releases hydrogen as a negative electrode has attracted attention as a secondary battery having a high energy density and a long charge-discharge cycle life. .
【０００３】水素吸蔵合金には主に希土類元素／ニッケ
ル（Ｎｉ）などからなるＡＢ５タイプと、ジルコン（Ｚ
ｒ）／マンガン（Ｍｎ）などからなるＡＢ２タイプなど
がある。The hydrogen storage alloys are mainly AB5 type consisting of rare earth elements / nickel (Ni) and zircon (Z).
For example, there is an AB2 type composed of r) / manganese (Mn).
【０００４】ＡＢ５タイプ水素吸蔵合金では、従来より
合金中へのコバルト（Ｃｏ）元素添加（Ｃｏ系合金）に
よりニッケル水素蓄電池の充放電サイクル寿命が向上す
ることが知られており、ＡＢ５タイプのニッケル水素蓄
電池用水素吸蔵合金においてはＣｏは必須元素となって
いる。It has been conventionally known that the AB5 type hydrogen storage alloy improves the charge / discharge cycle life of a nickel-hydrogen storage battery by adding a cobalt (Co) element (Co-based alloy) to the alloy. Co is an essential element in the hydrogen storage alloy for hydrogen storage batteries.
【０００５】しかし、Ｃｏは高価なため合金コストのか
なり大きな割合を占める。さらに、Ｃｏは資源量に制約
があるため、大形、中形のニッケル水素蓄電池を量産す
る場合にはＣｏ含有量の削減が必要である。However, since Co is expensive, it accounts for a considerable proportion of the alloy cost. Further, since Co has a limited resource amount, it is necessary to reduce the Co content when mass-producing large-sized or medium-sized nickel-hydrogen storage batteries.
【０００６】そのためＣｏを含有しない合金の使用が考
えられるが、これらの合金では極端に電池の寿命特性が
短い。Therefore, it is considered to use alloys not containing Co, but these alloys have extremely short battery life characteristics.
【０００７】合金表面にＣｏが存在することにより、Ｃ
ｏ系合金においては充放電サイクルでの合金の微粉化が
抑えられるなどの効果があり、電池の長寿命化が達成さ
れるものと考えられている。そのためＣｏ系合金以外に
も水素吸蔵合金に金属ＣｏまたはＣｏ化合物を混合充填
するなどの試みが行われてきた（特開平１−１９７９６
５号公報、特開平５−３６４０５号公報）。Due to the presence of Co on the alloy surface, C
It is considered that the o-based alloy has an effect of suppressing pulverization of the alloy in the charge / discharge cycle, and that the life of the battery can be extended. Therefore, in addition to Co alloys, attempts have been made to mix and fill hydrogen storage alloys with metallic Co or Co compounds (Japanese Patent Laid-Open No. Hei 1-19796).
No. 5, JP-A-5-36405).
【０００８】また、合金のＣｏメッキも試みられてきた
（特開昭５８−１０３２号公報）。Co plating of alloys has also been tried (Japanese Patent Laid-Open No. 58-1032).
【０００９】[0009]
【発明が解決しようとする課題】しかし、金属Ｃｏまた
はＣｏ化合物を単に充填する方法では、長寿命の効果を
得るために多量（通常１０ｗｔ％以上）のＣｏを必要と
した。However, in the method of simply filling with metallic Co or a Co compound, a large amount (usually 10 wt% or more) of Co is required to obtain the effect of long life.
【００１０】一方、Ｃｏメッキは無電解メッキでは電解
液の寿命が短くコスト的に高価となる。また、電解メッ
キでは極板形成後でしかメッキができず粒子表面全面を
均一にメッキできないため電池寿命特性の改善効果が少
ないという欠点がある。On the other hand, in Co plating, the life of the electrolytic solution is short and the cost is high in electroless plating. In addition, the electrolytic plating has a drawback that the effect of improving the battery life characteristics is small because the plating can be performed only after the electrode plate is formed and the entire surface of the particles cannot be uniformly plated.
【００１１】さらにメッキ工程では粒子表面に均一に薄
く形成することが困難でＣｏ量の削減が困難という課題
も有していた。Further, in the plating process, it is difficult to form a uniform thin film on the particle surface, and it is difficult to reduce the amount of Co.
【００１２】本発明は上記従来の課題を解決するもの
で、Ｃｏ含有量が少なくても、長寿命のニッケル・水素
蓄電池を提供することができる水素吸蔵合金粉末および
その製造方法を提供することを目的とする。The present invention is to solve the above-mentioned conventional problems, and to provide a hydrogen storage alloy powder capable of providing a long-life nickel-hydrogen storage battery even if the Co content is small, and a method for producing the same. To aim.
【００１３】[0013]
【課題を解決するための手段】この目的を達成するため
本発明の水素吸蔵合金粉末およびその製造方法は水素吸
蔵合金粉末の表面に化学気相蒸着法によりＣｏを均一に
付着させるか、または、水素吸蔵合金粉末を硫酸コバル
トの水溶液中に加えて攪拌し、次にこの硫酸コバルト水
溶液中にＫＯＨ水溶液を加えてアルカリ性にし、その後
前記水素吸蔵合金粉末を水洗することにより前記水素吸
蔵合金粉末の表面にコバルト化合物を均一に析出させ、
そのＣｏを均一に付着させた水素吸蔵合金粉末またはそ
のコバルト化合物を均一に析出させた水素吸蔵合金粉末
を熱処理し表面付近にＣｏを拡散させた水素吸蔵合金粉
末を得るものである。In order to achieve this object, the hydrogen storage alloy powder and the method for producing the same according to the present invention are to deposit Co uniformly on the surface of the hydrogen storage alloy powder by a chemical vapor deposition method, or The surface of the hydrogen storage alloy powder is obtained by adding the hydrogen storage alloy powder to an aqueous solution of cobalt sulfate and stirring, and then adding an aqueous KOH solution to the aqueous solution of cobalt sulfate to make it alkaline, and then washing the hydrogen storage alloy powder with water. Uniformly deposit the cobalt compound on the
The hydrogen-absorbing alloy powder having Co uniformly attached thereto or the hydrogen-absorbing alloy powder having the cobalt compound uniformly deposited thereon is heat-treated to obtain hydrogen-absorbing alloy powder having Co diffused near the surface.
【００１４】[0014]
【作用】Ｃｏを含有した水素吸蔵合金粉末はこれをニッ
ケル水素蓄電池に用いた場合、充放電サイクルに伴う合
金の微細化が少なく合金の表面が酸化されにくいことに
より充放電サイクル寿命が長いことが知られている。When the hydrogen-absorbing alloy powder containing Co is used in a nickel-hydrogen storage battery, the alloy may not be finely divided with the charge / discharge cycle and the surface of the alloy may be hardly oxidized, so that the charge / discharge cycle life may be long. Are known.
【００１５】本発明における化学気相蒸着法では極めて
薄いＣｏの層を水素吸蔵合金粉末表面に均一に薄く付着
させることができる。そのため少量のＣｏで効果的に合
金の表面を覆うことができ、その結果ニッケル水素蓄電
池の低コスト化が可能となる。In the chemical vapor deposition method of the present invention, an extremely thin layer of Co can be uniformly and thinly deposited on the surface of the hydrogen storage alloy powder. Therefore, the surface of the alloy can be effectively covered with a small amount of Co, and as a result, the cost of the nickel-hydrogen storage battery can be reduced.
【００１６】一方、水素吸蔵合金粉末を硫酸コバルトの
水溶液中に加えて攪拌し、次にこの硫酸コバルト水溶液
中にＫＯＨ水溶液を加えてアルカリ性にし、その後前記
水素吸蔵合金粉末を水洗することにより水素吸蔵合金粉
末の表面にコバルト化合物を析出させる方法でも、コバ
ルト化合物の層を水素吸蔵合金粉末の表面に均一に薄く
付けることができる。そのため化学気相蒸着法の場合と
同様に、少量のコバルト化合物で効果的に水素吸蔵合金
粉末の表面を覆うことができ、その結果少量のＣｏ量で
これを用いたニッケル水素蓄電池の長寿命化を達成でき
る。On the other hand, the hydrogen storage alloy powder is added to an aqueous solution of cobalt sulfate and stirred, and then a KOH aqueous solution is added to the aqueous solution of cobalt sulfate to make it alkaline, and then the hydrogen storage alloy powder is washed with water to store hydrogen. The method of depositing the cobalt compound on the surface of the alloy powder also makes it possible to uniformly thin the layer of the cobalt compound on the surface of the hydrogen storage alloy powder. Therefore, as in the case of the chemical vapor deposition method, the surface of the hydrogen storage alloy powder can be effectively covered with a small amount of cobalt compound, and as a result, the life of the nickel-hydrogen storage battery using this with a small amount of Co can be extended. Can be achieved.
【００１７】さらには、６００℃〜１０００℃で５分間
〜１２０分間と比較的低温、短時間の熱処理により表面
に付着したＣｏを合金中の表面付近に拡散させることに
より、アルカリ中へのＣｏ溶出を最小限にすることがで
きる。また傾斜的にＣｏの含有率を表面付近で高めるこ
とにより、予めＣｏを組成中に含む合金に比べて、少な
いＣｏ量で充放電サイクル時における水素吸蔵合金粉末
の微細化を防ぐことができる。Further, Co adhered to the surface is diffused near the surface in the alloy by heat treatment at 600 ° C. to 1000 ° C. for 5 minutes to 120 minutes at a relatively low temperature for a short time, so that Co is dissolved in the alkali. Can be minimized. Further, by gradually increasing the Co content near the surface, it is possible to prevent the hydrogen storage alloy powder from becoming finer during charge / discharge cycles with a smaller amount of Co than in an alloy containing Co in advance in the composition.
【００１８】なお、Ｃｏ層およびコバルト化合物層の厚
さとしては、０．０５μｍから０．２μｍ程度であれば
十分微細化を防げることが分かった。It has been found that the Co layer and the cobalt compound layer having a thickness of about 0.05 μm to 0.2 μm can sufficiently prevent miniaturization.
【００１９】[0019]
（実施例１）以下に本発明の実施例１を図面を用いて説
明する。(Embodiment 1) Embodiment 1 of the present invention will be described below with reference to the drawings.
【００２０】水素吸蔵合金の母合金としてランタン（Ｌ
ａ）を２０重量％含むミッシュメタル（Ｍｍ）、ニッケ
ル（Ｎｉ）、マンガン（Ｍｎ）、アルミニウム（Ａ
ｌ）、銅（Ｃｕ）を所定の割合で混合し、高周波溶解炉
でＭｍＮｉ3.7 Ｍｎ0.4 Ａｌ0.3Ｃｕ0.6 の組成の水素
吸蔵合金のインゴットを作製した。このインゴットを粉
砕して平均粒径３０μｍの水素吸蔵合金粉末（以下合金
粉末という）を得た。Lanthanum (L) was used as the mother alloy of the hydrogen storage alloy.
a) 20% by weight of misch metal (Mm), nickel (Ni), manganese (Mn), aluminum (A)
1) and copper (Cu) were mixed at a predetermined ratio, and an ingot of a hydrogen storage alloy having a composition of MmNi 3.7 Mn 0.4 Al 0.3 Cu 0.6 was prepared in a high frequency melting furnace. This ingot was crushed to obtain hydrogen storage alloy powder (hereinafter referred to as alloy powder) having an average particle diameter of 30 μm.
【００２１】次に、図１に示すＣＶＤ装置を用いてプラ
ズマ式の化学気相蒸着法（ＣＶＤ）でこの合金粉末表面
にＣｏ膜の付着を行った。反応ガスの出発物質には酢酸
コバルト１を用いて加熱装置２でこれを３００℃に加熱
し、キャリアガスとして窒素ボンベ３からの窒素と、水
素ボンベ４からの水素の混合ガスを流量計５を用いて流
量６００ｃｍ3 ／分で石英管６に流した。ＣＶＤ装置に
は合金粉末７へのＣｏの均一蒸着を行うために改造を施
した。すなわち、高周波電源８に接続された高周波コイ
ル９内の合金粉末７を載せる試料台１０が上下に振動す
るような機構を設け、振動により合金粉末７が気流中に
舞うような仕組みにした。また、気流中に舞っている合
金粉末７の温度を上げるため、赤外線ランプ１１で約３
００℃程度の加熱を行った。なお、石英管６内の圧力は
トラップ１２を経由したロータリーポンプ１３を用いて
５×１０-1ｔｏｒｒに設定した。Next, a Co film was deposited on the surface of the alloy powder by plasma-type chemical vapor deposition (CVD) using the CVD apparatus shown in FIG. Cobalt acetate 1 was used as a starting material of the reaction gas, and this was heated to 300 ° C. by a heating device 2, and a mixed gas of nitrogen from a nitrogen cylinder 3 and hydrogen from a hydrogen cylinder 4 was used as a carrier gas in a flow meter 5. It was used to flow through the quartz tube 6 at a flow rate of 600 cm 3 / min. The CVD apparatus was modified in order to uniformly deposit Co on the alloy powder 7. That is, a mechanism was provided in which the sample table 10 on which the alloy powder 7 in the high-frequency coil 9 connected to the high-frequency power source 8 is placed vibrates up and down, and the alloy powder 7 flies in the airflow due to the vibration. In addition, in order to raise the temperature of the alloy powder 7 that is flying in the air flow, the infrared lamp 11 is used to
Heating was performed at about 00 ° C. The pressure in the quartz tube 6 was set to 5 × 10 -1 torr using the rotary pump 13 via the trap 12.
【００２２】このＣＶＤ装置により作製した合金粉末７
はＣｏ層で連続的に均一に被われていることを、走査型
電子顕微鏡（ＳＥＭ）で合金粉末７を観察することによ
り確認した。またオージェ分析により、Ｃｏ層の厚さは
約０．１μｍであることが分かった。これはＣｏの重量
分率としては２．０％であった。Alloy powder 7 produced by this CVD apparatus
It was confirmed by observing the alloy powder 7 with a scanning electron microscope (SEM) that the Co layer was continuously and uniformly covered. Also, Auger analysis revealed that the thickness of the Co layer was about 0.1 μm. This was 2.0% as a weight fraction of Co.
【００２３】また、反応ガスの出発材料にコバルトジク
ロペンタジエニル、沃化コバルト、塩化コバルト、コバ
ルトニトロシルトリカルボニル、コバルトアセチルアセ
トネートを用いた場合にも同様な粉末が得られた。Similar powders were also obtained when cobalt diclopentadienyl, cobalt iodide, cobalt chloride, cobalt nitrosyltricarbonyl and cobalt acetylacetonate were used as starting materials for the reaction gas.
【００２４】このようにして得られた水素吸蔵合金粉末
１００重量部に水を１６重量部加えて負極用ペーストを
作製した。このペーストをリードを取り付けた縦７ｃｍ
横４ｃｍの発泡ニッケル製の基板に充填、乾燥後、プレ
スして厚さを０．５ｍｍとし、カルボキシメチルセルロ
ース（ＣＭＣ）を塗布して負極板とした。このとき負極
板に充填された合金は約６．３ｇである。16 parts by weight of water was added to 100 parts by weight of the hydrogen storage alloy powder thus obtained to prepare a negative electrode paste. This paste is 7 cm in length with leads attached
The substrate was filled with a foamed nickel substrate having a width of 4 cm, dried, and pressed to have a thickness of 0.5 mm, and carboxymethyl cellulose (CMC) was applied to form a negative electrode plate. At this time, the alloy filled in the negative electrode plate was about 6.3 g.
【００２５】上記のようにして作製した負極板１枚、焼
結式水酸化ニッケル正極板４枚を厚さ０．１５ｍｍのス
ルホン化したポリプロピレン（ＰＰ）製のセパレータで
袋状に包み、負極板を各２枚の正極板で挟んでアクリル
板で固定した。これを円筒形アクリル製の電槽に入れ、
リード部を極柱に溶接した後、水酸化カリウム水溶液
（比重１．３０ｇ／ｃｍ3 ）を主成分とする電解液を多
量に（３００ｇ）注液し、細孔を有するＰＰ製の蓋をし
た後、一旦真空にして脱泡を行い、液リッチの負極規制
の評価電池を作製した。この電池に参照電極として、水
銀電極（Ｈｇ／ＨｇＯ）を組み込んだ。One negative electrode plate and four sintered nickel hydroxide positive electrode plates produced as described above were wrapped in a bag shape with a sulfonated polypropylene (PP) separator having a thickness of 0.15 mm to form a negative electrode plate. Was sandwiched between two positive electrode plates and fixed with an acrylic plate. Put this in a cylindrical acrylic battery case,
After welding the lead portion to the pole, a large amount (300 g) of an electrolytic solution containing a potassium hydroxide aqueous solution (specific gravity: 1.30 g / cm 3 ) as a main component was injected, and a PP lid having pores was put on. Then, it was evacuated once to perform defoaming to prepare a liquid-rich negative electrode regulation evaluation battery. A mercury electrode (Hg / HgO) was incorporated into this battery as a reference electrode.
【００２６】図２に上記液リッチ負極規制の評価電池で
充放電サイクル試験を行った時の負極放電容量の変化を
示す。充放電サイクル試験時は充電は１２５０ｍＡで１
時間行い、放電も１２５０ｍＡで１時間または電位が−
０．６Ｖ（ｖｓ．Ｈｇ／ＨｇＯ）になるまで行った。容
量確認は１００サイクルごとに行った。容量確認時の充
電は１９０ｍＡで１２時間行い、放電は３８０ｍＡで−
０．６Ｖ（ｖｓ．Ｈｇ／ＨｇＯ）まで行った。FIG. 2 shows changes in the negative electrode discharge capacity when a charge / discharge cycle test was conducted on the above-mentioned liquid-rich negative electrode regulation evaluation battery. At the time of charge / discharge cycle test, charging is 1250mA, 1
Discharge for 1 hour at 1250 mA or potential-
It carried out until it became 0.6V (vs.Hg / HgO). The capacity was confirmed every 100 cycles. When checking the capacity, the battery is charged at 190 mA for 12 hours and discharged at 380 mA-
It went to 0.6 V (vs. Hg / HgO).
【００２７】（実施例２）次に本発明の実施例２を図面
を用いて説明する。Second Embodiment Next, a second embodiment of the present invention will be described with reference to the drawings.
【００２８】まず、実施例１と同じように作製した組成
ＭｍＮｉ3.7 Ｍｎ0.4 Ａｌ0.3 Ｃｕ 0.6 の母合金の粉末
（粒径２０μｍ）１００重量部とＣｏＳＯ4 ・７Ｈ2 Ｏ
３重量部に水を加えて攪拌した。この時ｐＨは６〜８に
なる。ここに濃度３１ｗｔ％のＫＯＨ水溶液を徐々に注
ぎこみ攪拌した。ｐＨが１２〜１３になるまでＫＯＨを
加えて、合金粉末表面にコバルト化合物を析出させた。
その後アルカリがぬけるまで前記合金粉末を水洗し、脱
水、乾燥してコバルト化合物析出合金粉末を得た。First, the composition prepared in the same manner as in Example 1
MmNi3.7Mn0.4Al0.3Cu 0.6Mother alloy powder
(Particle size 20 μm) 100 parts by weight and CoSOFour・ 7H2O
Water was added to 3 parts by weight and stirred. At this time the pH is 6-8
Become. A KOH aqueous solution with a concentration of 31 wt% is gradually poured here.
Stirred and stirred. KOH until the pH is 12-13
In addition, a cobalt compound was deposited on the surface of the alloy powder.
After that, wash the alloy powder with water until the alkali is removed and remove it.
Water and drying were performed to obtain a cobalt compound precipitation alloy powder.
【００２９】この合金粉末をＳＥＭで観察したところ直
径約０．２μｍの細かい粒が合金表面に均一に付着して
いた。Ｘ線回折の結果からこの細かい粒子は水酸化コバ
ルトと酸化コバルトの混合物と考えられる。この時のＣ
ｏの重量分率は約５．５％であった。When the alloy powder was observed by SEM, fine particles having a diameter of about 0.2 μm were uniformly attached to the surface of the alloy. From the results of X-ray diffraction, these fine particles are considered to be a mixture of cobalt hydroxide and cobalt oxide. C at this time
The weight fraction of o was about 5.5%.
【００３０】この合金粉末を用いて実施例１と同じよう
に液リッチ負極規制の評価電池を作製した。この評価電
池の充放電サイクル試験の結果を図２に示す。 （実施例３）次に、本発明の実施例３を図面を用いて説
明する。Using this alloy powder, an evaluation battery under liquid-rich negative electrode regulation was prepared in the same manner as in Example 1. The results of the charge / discharge cycle test of this evaluation battery are shown in FIG. (Third Embodiment) Next, a third embodiment of the present invention will be described with reference to the drawings.
【００３１】実施例１で得られた均一にＣｏで被覆され
た合金粉末に対し、真空雰囲気で熱処理を行った。熱処
理の条件は４００℃から１１００℃の範囲で５分から６
時間行った。しかし、１１００℃以上の温度で熱処理を
行うと粉末試料が溶解し焼結状態となってしまうことが
分かった。また実施例２から得られたＣｏ化合物析出合
金粉末でも同様の熱処理を行ったが、やはり１１００℃
以上の温度で溶解した。The alloy powder uniformly coated with Co obtained in Example 1 was heat-treated in a vacuum atmosphere. The heat treatment conditions are from 400 ° C to 1100 ° C for 5 minutes to 6 minutes.
I went on time. However, it was found that when the heat treatment was performed at a temperature of 1100 ° C. or higher, the powder sample was melted into a sintered state. The same heat treatment was performed on the Co compound precipitation alloy powder obtained from Example 2, but it was still 1100 ° C.
It melted at the above temperature.
【００３２】１０００℃以下の温度で熱処理した合金粉
末を用いて実施例１と同様の方法で液リッチ負極規制の
評価電池を作製した。このうち、８００℃で６０分間熱
処理した合金を用いた評価電池の充放電サイクル試験の
結果を図２に示す。ＥＰＭＡ分析で合金粉末の断面組織
を調べた所、粉末の表面にＣｏが偏在していることが分
かった。Using the alloy powder heat-treated at a temperature of 1000 ° C. or lower, a liquid-rich negative electrode regulation evaluation battery was prepared in the same manner as in Example 1. Of these, the results of the charge / discharge cycle test of the evaluation battery using the alloy heat-treated at 800 ° C. for 60 minutes are shown in FIG. When the cross-sectional structure of the alloy powder was examined by EPMA analysis, it was found that Co was unevenly distributed on the surface of the powder.
【００３３】また比較例１としてＣｏを付着させていな
い組成ＭｍＮｉ3.7 Ｍｎ0.4 Ａｌ0. 3 Ｃｕ0.6 の母合金
の粉末を負極に用い、同一構成の評価電池を作製した。Further using powder of mother alloy of Comparative Example 1 as not to adhere the Co composition MmNi 3.7 Mn 0.4 Al 0. 3 Cu 0.6 the negative electrode, to produce a rated battery of the same configuration.
【００３４】さらに比較例２としてＣｏを合金組成中に
含むＭｍＮｉ3.55Ｍｎ0.4 Ａｌ0.3Ｃｏ0.75の合金粉末
（Ｃｏ含有率１１％）を作製して負極に用い、同一構成
の評価電池を作製した。Furthermore Co was used to MmNi 3.55 Mn 0.4 Al 0.3 Co 0.75 alloy powder (Co content 11%) negative electrode was prepared, including in the alloy composition as Comparative Example 2 was produced to evaluate batteries with the same configuration.
【００３５】実施例１〜３と比較例１，２の合金粉末を
用いた評価電池の寿命特性を示す図２において、実施例
１〜３と比較例１，２の負極の初期放電容量はいずれも
２９０ｍＡｈ／ｇ程度であった。充放電サイクル試験の
結果は比較例１の場合は２００サイクル時にピーク時の
容量の８０％より少くなった。しかし本発明の実施例の
場合は５００サイクル経過時でもピーク時の容量の８０
％以上を確保した。そして実施例１では５００サイクル
後の放電容量は２３０ｍＡｈ／ｇで、ピーク時の容量に
対する５００サイクル経過後の容量の割合（容量維持
率）は８９％であった。また実施例２では容量維持率９
１％、実施例３では９２％であった。これに対して比較
例１の５００サイクル経過時の容量維持率は６３％であ
り、比較例２では９１％であった。本実施例では全合金
重量に対するＣｏの比率が２〜５．５ｗｔ％であるにも
かかわらず、Ｃｏ１１ｗｔ％を合金組成内に含む比較例
２の合金と比べて電池の寿命特性に遜色のない合金を提
供することができる。In FIG. 2, which shows the life characteristics of the evaluation batteries using the alloy powders of Examples 1 to 3 and Comparative Examples 1 and 2, the initial discharge capacities of the negative electrodes of Examples 1 to 3 and Comparative Examples 1 and 2 are Was about 290 mAh / g. In the case of Comparative Example 1, the result of the charge-discharge cycle test was less than 80% of the peak capacity at 200 cycles. However, in the case of the embodiment of the present invention, the peak capacity of
Secured more than%. In Example 1, the discharge capacity after 500 cycles was 230 mAh / g, and the ratio of the capacity after 500 cycles to the peak capacity (capacity retention rate) was 89%. Further, in Example 2, the capacity retention rate is 9
1%, and in Example 3 it was 92%. On the other hand, the capacity retention rate after 500 cycles of Comparative Example 1 was 63%, and that of Comparative Example 2 was 91%. In the present example, although the ratio of Co to the total alloy weight was 2 to 5.5 wt%, the alloy had the same battery life characteristics as the alloy of Comparative Example 2 containing 11 wt% of Co in the alloy composition. Can be provided.
【００３６】表１は実施例３における各種熱処理条件に
対する充放電サイクル試験における５００サイクル経過
時の容量維持率の値を示したものである。Table 1 shows the value of the capacity retention rate after 500 cycles in the charge / discharge cycle test under various heat treatment conditions in Example 3.
【００３７】[0037]
【表１】 [Table 1]
【００３８】１１００℃以上で熱処理したものは先に記
述したように溶解した。５００℃以下で熱処理した合金
粉末は熱処理していない合金と差がなく温度が低すぎて
Ｃｏの拡散が起こっていないと考えられる。また６時間
以上熱処理した合金は比較的容量維持率が小さいので、
Ｃｏの拡散が進行しすぎて表面と内部のＣｏ含有率が等
しくなった結果、他の条件で熱処理した合金に比べて表
面付近のＣｏ含有率が希薄になったものと考えられる。
したがって本発明における熱処理条件は６００℃〜１０
００℃の温度範囲で５分間〜１２０分間処理が適当と考
えられる。Those heat-treated at 1100 ° C. or higher melted as described above. It is considered that the alloy powder heat-treated at 500 ° C. or lower has no difference from the alloy not heat-treated and the temperature is too low to cause Co diffusion. Also, the alloy that has been heat treated for 6 hours or more has a relatively small capacity retention rate,
It is considered that the Co content near the surface was diluted as compared with the alloy heat-treated under other conditions, as a result of the excessive diffusion of Co and the equalization of the Co content on the surface with that in the interior.
Therefore, the heat treatment condition in the present invention is 600 ° C to 10 ° C.
Treatment in the temperature range of 00 ° C. for 5 minutes to 120 minutes is considered appropriate.
【００３９】また、本実施例においてＣｏ層またはコバ
ルト化合物層の厚さが０．０５μｍ〜０．２μｍで合金
粉末の微粉化が妨げた。０．２μｍ以上ではＣｏ含有量
が大きくなり低コスト化および資源的にも課題を有する
ことになる。Further, in the present embodiment, when the thickness of the Co layer or the cobalt compound layer was 0.05 μm to 0.2 μm, the pulverization of the alloy powder was hindered. If it is 0.2 μm or more, the Co content becomes large, which causes problems in cost reduction and resources.
【００４０】[0040]
【発明の効果】以上の説明により明らかなように本発明
の水素吸蔵合金粉末およびその製造方法によれば、極め
て薄いＣｏまたはコバルト化合物の層を水素吸蔵合金粉
末表面に均一に付けることができる。そのため少量のＣ
ｏで効果的に合金粉末の表面を覆うことができ、その結
果Ｃｏ量を抑制でき、これを用いたニッケル水素蓄電池
の長寿命を達成できる。高価で資源量の乏しいＣｏを減
らせるため、合金コストが安くなりＣｏの資源量につい
ての不安が解消される。As is clear from the above description, according to the hydrogen storage alloy powder and the method for producing the same of the present invention, an extremely thin layer of Co or cobalt compound can be uniformly applied to the surface of the hydrogen storage alloy powder. Therefore, a small amount of C
The surface of the alloy powder can be effectively covered with o, and as a result, the amount of Co can be suppressed, and the long life of the nickel-hydrogen storage battery using this can be achieved. Since expensive and resource-poor Co can be reduced, alloy cost is reduced and anxiety about Co resource is eliminated.
【００４１】さらに、比較的低温、短時間の熱処理によ
り表面に付着したＣｏを合金中の表面付近に拡散させる
ことにより傾斜的にＣｏの含有率を表面付近で高め、ア
ルカリ中へのＣｏ溶出を最小限に抑えることができ、予
めＣｏを組成中に含む合金に比べて、少ないＣｏ量で充
放電サイクル数の経過による負極合金粉末の微細化を防
ぐことができる。Further, the Co content adhering to the surface is diffused near the surface in the alloy by heat treatment at a relatively low temperature for a short time, so that the content ratio of Co is gradually increased near the surface to elute Co into the alkali. It can be minimized, and the negative electrode alloy powder can be prevented from becoming finer due to the passage of the number of charge / discharge cycles with a smaller amount of Co as compared with an alloy containing Co in the composition in advance.
【００４２】以上のように本発明の水素吸蔵合金粉末お
よびその製造方法によって低コストで長寿命のニッケル
水素蓄電池を提供することができる。As described above, the hydrogen storage alloy powder and the method for producing the same according to the present invention can provide a low cost, long life nickel-metal hydride storage battery.
【図１】本発明の実施例１の水素吸蔵合金粉末の製造法
における化学気相蒸着法の装置の略図FIG. 1 is a schematic diagram of an apparatus for chemical vapor deposition in a method for producing hydrogen storage alloy powder according to Example 1 of the present invention.
【図２】本発明の実施例１〜３と比較例１，２の水素吸
蔵合金粉末を負極に用いた評価電池の充放電サイクル試
験における負極放電容量の変化を示したグラフFIG. 2 is a graph showing changes in the negative electrode discharge capacity in a charge / discharge cycle test of an evaluation battery using the hydrogen storage alloy powders of Examples 1 to 3 of the present invention and Comparative Examples 1 and 2 as a negative electrode.
１ 醋酸コバルト ２ 加熱装置 ３ 窒素ボンベ ４ 水素ボンベ ５ 流量計 ６ 石英管 ７ 水素吸蔵合金粉末 ８ 高周波電源 ９ 高周波コイル １０ 試料台 １１ 赤外線ランプ １２ トラップ １３ ロータリーポンプ 1 Cobalt Acetate 2 Heating Device 3 Nitrogen Cylinder 4 Hydrogen Cylinder 5 Flow Meter 6 Quartz Tube 7 Hydrogen Storage Alloy Powder 8 High Frequency Power Supply 9 High Frequency Coil 10 Sample Stage 11 Infrared Lamp 12 Trap 13 Rotary Pump
───────────────────────────────────────────────────── フロントページの続き (72)発明者 豊口 吉徳 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 鈴木 剛平 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 山口 誠二 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 生駒 宗久 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshinori Toyokuchi 1006 Kadoma, Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Gohei Suzuki, 1006 Kadoma, Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd. 72) Inventor Seiji Yamaguchi 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.
Claims (13)
着させた表面を備えた水素吸蔵合金粉末。1. A hydrogen storage alloy powder having a surface on which cobalt is uniformly deposited by a chemical vapor deposition method.
ｍの範囲である請求項１記載の水素吸蔵合金粉末。2. The cobalt layer has a thickness of 0.05 to 0.2 μm.
The hydrogen storage alloy powder according to claim 1, which is in a range of m.
中に加えて攪拌し、次にこの硫酸コバルトの水溶液中に
苛性カリ水溶液を加えてアルカリ性にし、その後前記水
素吸蔵合金粉末を水洗することにより、コバルト化合物
を均一に析出させた表面を備えた水素吸蔵合金粉末。3. A hydrogen storage alloy powder is added to an aqueous solution of cobalt sulfate and stirred, and then an aqueous caustic potash solution is added to the aqueous solution of cobalt sulfate to make it alkaline, and then the hydrogen storage alloy powder is washed with water. A hydrogen storage alloy powder having a surface on which a cobalt compound is uniformly deposited.
０．２μｍの範囲である請求項３記載の水素吸蔵合金粉
末。4. The hydrogen storage alloy powder according to claim 3, wherein the thickness of the cobalt compound layer is in the range of 0.05 to 0.2 μm.
コバルト水酸化物または、コバルト酸化物またはコバル
ト水酸化物の少なくとも一方である請求項３または４記
載の水素吸蔵合金粉末。5. The hydrogen storage alloy powder according to claim 3, wherein the cobalt compound is at least one of cobalt oxide and cobalt hydroxide, or cobalt oxide or cobalt hydroxide.
一に付着させた水素吸蔵合金粉末、または、水素吸蔵合
金粉末を硫酸コバルトの水溶液中に加えて攪拌し、次に
この硫酸コバルトの水溶液中に苛性カリ水溶液を加えて
アルカリ性にし、その後前記水素吸蔵合金粉末を水洗す
ることにより、コバルト化合物を均一に析出させた前記
水素吸蔵合金粉末を、真空中または不活性ガス雰囲気中
で熱処理することにより、前記水素吸蔵合金粉末の表面
付近で傾斜的にコバルト含有率を高くした水素吸蔵合金
粉末。6. A hydrogen storage alloy powder having cobalt uniformly deposited on its surface by a chemical vapor deposition method or a hydrogen storage alloy powder is added to an aqueous solution of cobalt sulfate and stirred, and then this aqueous solution of cobalt sulfate is added. By adding a caustic potash aqueous solution to make it alkaline, and then washing the hydrogen storage alloy powder with water, the hydrogen storage alloy powder on which a cobalt compound is uniformly deposited is heat treated in a vacuum or in an inert gas atmosphere. A hydrogen-absorbing alloy powder in which the cobalt content is gradually increased near the surface of the hydrogen-absorbing alloy powder.
吸蔵合金を負極活物質に有するニッケル・水素蓄電池。7. A nickel-hydrogen storage battery comprising the hydrogen storage alloy according to claim 1 as a negative electrode active material.
によりコバルトを均一に付着させる水素吸蔵合金粉末の
製造方法。8. A method for producing a hydrogen storage alloy powder, wherein cobalt is uniformly deposited on the surface of the hydrogen storage alloy powder by a chemical vapor deposition method.
料が、酢酸コバルト、コバルトニトロシルトリカルボニ
ル、沃化コバルト、塩化コバルト、コバルトアセチルア
セトネート、コバルトジクロペンタジエニルのいずれか
である請求項８記載の水素吸蔵合金粉末の製造方法。9. The starting material of the reaction gas used in the chemical vapor deposition method is any one of cobalt acetate, cobalt nitrosyltricarbonyl, cobalt iodide, cobalt chloride, cobalt acetylacetonate and cobalt diclopentadienyl. Item 9. A method for producing a hydrogen storage alloy powder according to Item 8.
液中に加えて攪拌し、次にこの硫酸コバルト水溶液中に
苛性カリ水溶液を加えてアルカリ性にし、その後前記水
素吸蔵合金粉末を水洗することにより、前記水素吸蔵合
金粉末の表面にコバルト化合物を均一に析出させる水素
吸蔵合金粉末の製造方法。10. The hydrogen-absorbing alloy powder is added to an aqueous solution of cobalt sulfate and stirred, and then an aqueous solution of caustic potassium is added to the aqueous solution of cobalt sulfate to make it alkaline, and then the hydrogen-absorbing alloy powder is washed with water. A method for producing hydrogen storage alloy powder, wherein a cobalt compound is uniformly deposited on the surface of hydrogen storage alloy powder.
びコバルト水酸化物または、コバルト酸化物またはコバ
ルト水酸化物のいづれか一方である請求項１０記載の水
素吸蔵合金粉末の製造方法。11. The method for producing a hydrogen storage alloy powder according to claim 10, wherein the cobalt compound is one of cobalt oxide and cobalt hydroxide, or cobalt oxide or cobalt hydroxide.
トを均一に付着させた水素吸蔵合金粉末、または、水素
吸蔵合金粉末を硫酸コバルトの水溶液中に加えて攪拌
し、次にこの硫酸コバルトの水溶液中に苛性カリ水溶液
を加えてアルカリ性にし、その後前記水素吸蔵合金粉末
を水洗することにより、コバルト化合物を均一に析出さ
せた前記水素吸蔵合金粉末を、真空中または不活性ガス
雰囲気中で熱処理することにより、前記水素吸蔵合金粉
末の表面付近で傾斜的にコバルト含有率を高くする水素
吸蔵合金粉末の製造方法。12. A hydrogen storage alloy powder having cobalt uniformly deposited on its surface by a chemical vapor deposition method, or a hydrogen storage alloy powder is added to an aqueous solution of cobalt sulfate and stirred, and then this cobalt sulfate is added. A caustic potash solution is added to the aqueous solution to make it alkaline, and then the hydrogen storage alloy powder is washed with water to heat-treat the hydrogen storage alloy powder in which a cobalt compound is uniformly deposited, in a vacuum or an inert gas atmosphere. According to the method for producing a hydrogen storage alloy powder, the cobalt content is gradually increased near the surface of the hydrogen storage alloy powder.
℃の温度範囲で、５分間から１２０分間である請求項１
２記載の水素吸蔵合金粉末の製造方法。13. The heat treatment condition is 600 ° C. to 1000 ° C.
The temperature range of ° C is 5 minutes to 120 minutes.
2. The method for producing the hydrogen storage alloy powder according to 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5265330A JPH07118704A (en) | 1993-10-25 | 1993-10-25 | Hydrogen storage alloy powder, nickel-hydrogen battery having the powder in negative electrode active material and production of the powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5265330A JPH07118704A (en) | 1993-10-25 | 1993-10-25 | Hydrogen storage alloy powder, nickel-hydrogen battery having the powder in negative electrode active material and production of the powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07118704A true JPH07118704A (en) | 1995-05-09 |
Family
ID=17415694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5265330A Pending JPH07118704A (en) | 1993-10-25 | 1993-10-25 | Hydrogen storage alloy powder, nickel-hydrogen battery having the powder in negative electrode active material and production of the powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07118704A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0765705A1 (en) * | 1995-09-27 | 1997-04-02 | Furukawa Denchi Kabushiki Kaisha | Manufacturing method for a hydrogen storage alloy powder for batteries |
| CN104043824A (en) * | 2014-06-29 | 2014-09-17 | 桂林理工大学 | Modification method for improving electrochemical performance of AB3 type hydrogen storage alloy |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS581032A (en) * | 1981-06-27 | 1983-01-06 | Nippon Steel Corp | Production of hydrogen absorbing metallic material |
| JPS5927505A (en) * | 1982-08-09 | 1984-02-14 | Hitachi Maxell Ltd | Ferromagnetic metal powder |
| JPS63223104A (en) * | 1987-03-12 | 1988-09-16 | Sekometsukusu Kk | Production of sintered hard alloy product |
| JPS649603A (en) * | 1987-07-01 | 1989-01-12 | Kao Corp | Ferromagnetic metal powder and manufacture thereof |
| JPH059504A (en) * | 1991-07-08 | 1993-01-19 | Agency Of Ind Science & Technol | Material for hydrogen occlusion alloy and production thereof |
| JPH05267029A (en) * | 1992-03-24 | 1993-10-15 | Titan Kogyo Kk | Ferromagnetic iron oxide powder for magnetic recording |
-
1993
- 1993-10-25 JP JP5265330A patent/JPH07118704A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS581032A (en) * | 1981-06-27 | 1983-01-06 | Nippon Steel Corp | Production of hydrogen absorbing metallic material |
| JPS5927505A (en) * | 1982-08-09 | 1984-02-14 | Hitachi Maxell Ltd | Ferromagnetic metal powder |
| JPS63223104A (en) * | 1987-03-12 | 1988-09-16 | Sekometsukusu Kk | Production of sintered hard alloy product |
| JPS649603A (en) * | 1987-07-01 | 1989-01-12 | Kao Corp | Ferromagnetic metal powder and manufacture thereof |
| JPH059504A (en) * | 1991-07-08 | 1993-01-19 | Agency Of Ind Science & Technol | Material for hydrogen occlusion alloy and production thereof |
| JPH05267029A (en) * | 1992-03-24 | 1993-10-15 | Titan Kogyo Kk | Ferromagnetic iron oxide powder for magnetic recording |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0765705A1 (en) * | 1995-09-27 | 1997-04-02 | Furukawa Denchi Kabushiki Kaisha | Manufacturing method for a hydrogen storage alloy powder for batteries |
| CN104043824A (en) * | 2014-06-29 | 2014-09-17 | 桂林理工大学 | Modification method for improving electrochemical performance of AB3 type hydrogen storage alloy |
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