JPH06228613A - Production of granular hydrogen storage alloy - Google Patents
Production of granular hydrogen storage alloyInfo
- Publication number
- JPH06228613A JPH06228613A JP5014207A JP1420793A JPH06228613A JP H06228613 A JPH06228613 A JP H06228613A JP 5014207 A JP5014207 A JP 5014207A JP 1420793 A JP1420793 A JP 1420793A JP H06228613 A JPH06228613 A JP H06228613A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- alloy
- storage alloy
- crucible
- 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
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】この発明は粒状水素吸蔵合金の製
造法に関するものである。さらに詳しくは、電池用電極
材料等として有用な微細組織を有する粒状水素吸蔵合金
の製造法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a granular hydrogen storage alloy. More specifically, it relates to a method for producing a granular hydrogen storage alloy having a fine structure, which is useful as an electrode material for batteries and the like.
【０００２】[0002]
【従来の技術とその課題】従来より、水素を可逆的に吸
蔵・放出する水素吸蔵合金が知られており、電気、電
子、化学工業等の諸分野においてその応用のための検討
が進められている。この水素吸蔵合金については、その
粉末を電子・電気機器の小型電源としての電池に用いる
ことが提案され、注目を集めている。水素吸蔵合金の粉
末から電池電極を製造し、電池の容量増加を図り、新し
い高容量小型電源として活用しようとするものである。
その使用態様はアルカリ二次電池の電極（負極）であ
る。2. Description of the Related Art Hydrogen storage alloys capable of reversibly storing and releasing hydrogen have been known, and their applications have been studied in various fields such as electric, electronic and chemical industries. There is. With regard to this hydrogen storage alloy, it has been proposed to use the powder for a battery as a small power source for electronic and electric devices, and has been attracting attention. It is intended to manufacture battery electrodes from powder of hydrogen storage alloy to increase the capacity of the battery and utilize it as a new high-capacity small power source.
The usage mode is an electrode (negative electrode) of an alkaline secondary battery.
【０００３】そして、この水素吸蔵合金を用いて電池電
極を製造するためには、水素吸蔵合金を所定の粒度に揃
えるための粉砕が必要であることから、従来は、水素吸
蔵合金のインゴットへ水素を吸収させ、放出させること
により粉砕することや、ボールミル、カッターミル等に
よって機械的に粉砕する方法が採用されてきている。し
かしながら、水素吸蔵合金に水素を吸脱着する粉砕方法
では粉砕後の水素引抜きが不完全だと水素吸蔵合金粉末
が発火する危険性がある他、合金組成の僅かな偏在によ
り粉砕される粒径が部位により異なり、分級時の歩留り
が悪くなるという問題点がある。また、機械的な粉砕法
では粉砕された粉末の粒度分布が非常に広くなりやす
く、分級した際の歩留りが悪い他、直径１μｍ以下の微
粉末が生成し易く、電極を作製した場合に電池特性に悪
影響を及ぼす恐れがある。さらに、いずれの方法におい
ても出発原料は鋳造したインゴットであり、鋳造時の偏
析を減らすため均質化熱処理を施すもののミクロ偏析は
容易には消滅しにくく、これに起因する局部電池の形成
による腐食の進行、粒界偏析による粒界強度の低さに起
因する微粉化が進行して電池特性の経時劣化が進行する
という欠点がある。In order to manufacture a battery electrode using this hydrogen storage alloy, it is necessary to pulverize the hydrogen storage alloy so as to have a predetermined particle size. The method of crushing by absorbing and releasing is used, and the method of mechanically crushing by a ball mill, a cutter mill or the like has been adopted. However, in the crushing method of adsorbing and desorbing hydrogen in the hydrogen storage alloy, there is a risk that the hydrogen storage alloy powder may ignite if the hydrogen abstraction after the crushing is incomplete, and the particle size to be crushed due to slight uneven distribution of the alloy composition. There is a problem that the yield at the time of classification becomes poor depending on the part. In addition, the mechanical pulverization method has a very wide particle size distribution of the pulverized powder, which results in poor yield when classified, and easily produces fine powder with a diameter of 1 μm or less. May be adversely affected. Further, in any method, the starting material is a cast ingot, and although microsegregation is not easily eliminated although homogenization heat treatment is performed to reduce segregation during casting, corrosion due to formation of local cells due to this However, there is a drawback in that pulverization progresses due to progress of the grain boundary segregation and low grain boundary strength, and deterioration of battery characteristics with time progresses.
【０００４】そこでこのような問題を解決するための方
法として、高速回転体の走行面に水素吸蔵合金の溶湯を
供給し、この回転体の運動力によって水素吸蔵合金を微
細分散させ、急速凝固させる方法が提案されている（特
開昭平３−１１６６５５号公報）。この方法は、均一微
細粉末を形成する方法として有利なものであるが、一
方、このすでに提案されている方法の場合には、水素吸
蔵合金の水素吸蔵特性が失われる場合や、電池容量の増
加が期待できないもの、さらには経時劣化が大きなもの
等の不都合の著しい合金粉末が生成するという欠点があ
った。Therefore, as a method for solving such a problem, a molten metal of a hydrogen storage alloy is supplied to the running surface of a high-speed rotating body, and the hydrogen storage alloy is finely dispersed and rapidly solidified by the kinetic force of the rotating body. A method has been proposed (Japanese Patent Laid-Open No. 3-116655). This method is advantageous as a method for forming a uniform fine powder, but on the other hand, in the case of this already proposed method, the hydrogen storage characteristics of the hydrogen storage alloy are lost or the battery capacity is increased. However, there is a drawback in that alloy powders that are extremely inconvenient, such as those that cannot be expected, and those that are greatly deteriorated with time, are generated.
【０００５】そこで、この発明は、この高速回転体によ
る粉末形成方法の特徴を生かしつつ、従来技術では実現
することのできなかった優れた特性を有し、微細均一組
織を有する、新しい粒状水素吸蔵合金の製造方法を提供
することを目的としている。Therefore, the present invention makes use of the characteristics of the powder forming method using the high-speed rotating body, and has a new granular hydrogen storage having excellent characteristics which cannot be realized by the conventional technique and having a fine uniform structure. It is an object to provide a method for producing an alloy.
【０００６】[0006]
【課題を解決するための手段】この発明は、上記の課題
を解決するものとして、水素を可逆的に吸蔵・放出する
合金をＭｇＯるつぼにおいて溶解し、この合金の融点の
５０℃以上で２００℃以下の温度において高速回転して
いる黒鉛または黒鉛と炭素繊維複合材からなる円板上に
溶湯を注ぎ、遠心噴霧して急冷凝固することを特徴とす
る粒状水素吸蔵合金の製造法を提供する。In order to solve the above-mentioned problems, the present invention melts an alloy capable of reversibly occluding and releasing hydrogen in a MgO crucible, and melts it at a temperature of 50 ° C or higher to 200 ° C. Provided is a method for producing a granular hydrogen storage alloy, which comprises pouring a molten metal on a graphite or a disk made of a graphite and carbon fiber composite material which is rotating at a high speed at the following temperature, centrifugally spraying and rapidly solidifying.
【０００７】またこの発明は、前記の急冷凝固により得
られる粒子をさらに機械的に粉砕し、もしくは水素化・
脱水素処理して粉砕し、粒径１００μｍ以下の粒子とす
ることを特徴とする水素吸蔵合金の製造法をも提供す
る。すなわち、この発明においては、高速回転している
円板上に水素吸蔵合金の溶湯を注ぎ、遠心噴霧させ、急
冷凝固させることをその構成としているが、その際に、
水素吸蔵合金の溶解をＭｇＯるつぼにおいて溶解するこ
とと、回転円板上への注湯を、合金の融点より５０℃以
上で２００℃以下の特定の温度範囲にあるように温度制
御し、しかも、黒鉛または黒鉛と炭素繊維との複合材と
いう特定の材料によって形成された円板を使用すること
を必須としている。Further, according to the present invention, the particles obtained by the above-mentioned rapid solidification are further mechanically pulverized, or hydrogenated.
Also provided is a method for producing a hydrogen storage alloy, which comprises dehydrogenation treatment and pulverization to obtain particles having a particle size of 100 μm or less. That is, in the present invention, the molten metal of the hydrogen storage alloy is poured onto a disc that is rotating at high speed, centrifugally sprayed, and rapidly solidified, but at that time,
Melting the hydrogen-absorbing alloy in a MgO crucible, and pouring the molten metal on the rotating disk so that the temperature is controlled to be within a specific temperature range of 50 ° C. or higher and 200 ° C. or lower than the melting point of the alloy It is essential to use a disk made of a specific material such as graphite or a composite material of graphite and carbon fiber.
【０００８】るつぼにＭｇＯを用いることは、水素吸蔵
合金の組成を所定のものとするために必須であり、この
るつぼとして、カーボンるつぼや、Ａｌ2 Ｏ3 等の他種
酸化物、あるいは銅等の金属を用いる場合には、水素吸
蔵合金成分との反応や酸化が生じ、所定の組成の水素吸
蔵合金が得られないことになる。ＣａＯの高純度品から
なるるつぼも有用であって、このＣａＯるつぼを用いる
方法を、発明者はすでに提案している。水素吸蔵合金
は、Ｔｉ，Ｚｒ，Ｍｎなどの活性元素を多く含有し、る
つぼ材質との反応性が問題となり、特に、酸素は容易に
合金中に侵入し、水素吸蔵合金の吸蔵特性を劣化させる
ことになる。酸化物として安定なＣａＯるつぼはこの劣
化を抑止する上で有効である。The use of MgO for the crucible is indispensable for making the composition of the hydrogen storage alloy to be a predetermined one. As this crucible, there are a carbon crucible, other oxides such as Al 2 O 3 and copper. When such a metal is used, reaction with a hydrogen storage alloy component or oxidation occurs, and a hydrogen storage alloy having a predetermined composition cannot be obtained. A crucible made of a highly pure CaO is also useful, and the inventor has already proposed a method of using this CaO crucible. The hydrogen storage alloy contains many active elements such as Ti, Zr and Mn, and its reactivity with the crucible material becomes a problem. Especially, oxygen easily penetrates into the alloy and deteriorates the storage characteristics of the hydrogen storage alloy. It will be. A CaO crucible that is stable as an oxide is effective in suppressing this deterioration.
【０００９】だが、ＣａＯるつぼは高価であって、吸湿
性があり、かつ粉塵が有害である等の弱点もあった。ま
た、従来一般的にはＡｌ2 Ｏ3 るつぼが使用されてきた
が、Ａｌ2 Ｏ3 るつぼはヒートショックに弱いという欠
点がある。これらに対して、この発明のＭｇＯるつぼは
不純物による別管を排除して汚染のない高純度、高特性
粉末の製造を可能とするものである。However, CaO crucibles are also expensive, they are hygroscopic, and they have the disadvantages that dust is harmful. Further, conventionally, an Al 2 O 3 crucible has been generally used, but the Al 2 O 3 crucible has a drawback that it is weak against heat shock. On the other hand, the MgO crucible of the present invention eliminates a separate tube due to impurities and enables the production of high-purity, high-characteristic powder without contamination.
【００１０】水素吸蔵合金の溶解後の回転円板上への注
湯については、前記の通りの温度範囲にあるものとする
が、合金の融点より５０℃未満、もしくは２００℃を超
えた温度とする場合には、円板体による分散によって生
成される合金微粒子の粒径が均一になりにくく、しか
も、微細組織の均一性が失われるという問題が生じる。
そして、高速回転の円板体は、そのぬれ性および強度、
さらには溶湯との反応を抑制する等の点から、前記の通
り、黒鉛もしくは黒鉛と炭素繊維複合体によって製造さ
れたものとする。Regarding the pouring of the hydrogen-absorbing alloy onto the rotating disk after melting, it is assumed that the temperature is within the above-mentioned temperature range, but the temperature is lower than 50 ° C. or higher than 200 ° C. from the melting point of the alloy. In such a case, there arises a problem that the particle diameter of the alloy fine particles generated by the dispersion by the disc body is hard to be uniform and the uniformity of the fine structure is lost.
And, the disc body of high speed rotation has its wettability and strength,
Further, from the viewpoint of suppressing the reaction with the molten metal, as described above, it is assumed to be manufactured from graphite or a graphite and carbon fiber composite.
【００１１】水素吸蔵合金のこの高速回転円板体への注
湯による噴霧分散は、アルゴン、ヘルウム等の不活性ガ
ス雰囲気において、もしくはこれら不活性ガスに水素を
５〜２０％程度含有された雰囲気とするのが好ましい。
円板体は所要の水素吸蔵合金の粒径によってその回転速
度を変えることができる。たとえば、水素吸蔵合金の注
湯落下速度を３kg／分程度とする場合には、１００００
rpm で３００μｍ〜１mm程度の粒径のものを、また２０
０００rpm で９０μｍ〜１５０μｍ程度のものを製造す
ることができる。もちろんこの場合、円板の大きさによ
っても変ってくる。The hydrogen storage alloy is spray-dispersed into the high-speed rotating disk body by pouring the molten metal in an atmosphere of an inert gas such as argon or helium, or in an atmosphere containing about 5 to 20% of hydrogen in the inert gas. Is preferred.
The rotation speed of the disk can be changed according to the required particle size of the hydrogen storage alloy. For example, if the pouring speed of the hydrogen storage alloy is about 3 kg / min, 10,000
If the particle size is about 300 μm to 1 mm at rpm,
It is possible to manufacture a product having a size of 90 μm to 150 μm at 000 rpm. Of course, in this case, it also depends on the size of the disc.
【００１２】噴霧分散させた粉末は、回転円板体の周辺
部に配置した壁体あるいは捕集容器部において冷却回収
する。この場合の冷却は、水冷、冷媒冷却等によって行
ない、常温近郊にまで急速に冷却する。粒径１００μｍ
以下にするためには、この発明の方法においては、前記
の噴霧分散により得られた水素吸蔵合金粉末をさらに機
械的に、あるいは水素化・脱水変化によって粉砕するこ
とができる。真空、加熱等の条件が適宜に採用される。The spray-dispersed powder is cooled and recovered in the wall body or the collecting container portion arranged around the rotating disk body. In this case, cooling is performed by water cooling, refrigerant cooling, or the like, and is rapidly cooled to the vicinity of room temperature. Particle size 100μm
In order to make the following, in the method of the present invention, the hydrogen storage alloy powder obtained by the above-mentioned spray dispersion can be pulverized further mechanically or by hydrogenation / dehydration change. Conditions such as vacuum and heating are appropriately adopted.
【００１３】このような、この発明の製造方法において
は、各種の組成の水素吸蔵合金をその対象とすることが
できる。一般的には、少なくとも希土類元素およびその
混合物、Ｎｉ，Ｔｉ，Ｃｏ，Ｍｎ，Ａｌで構成されるも
の、少なくともＴｉ，Ｚｒ，Ｎｉ，Ｖ，Ｃｏ，Ｍｎ等に
よって構成されるものなどが例示される。In such a manufacturing method of the present invention, hydrogen storage alloys having various compositions can be used. Generally, at least rare earth elements and mixtures thereof, those composed of Ni, Ti, Co, Mn, Al, those composed of at least Ti, Zr, Ni, V, Co, Mn, etc. are exemplified. .
【００１４】[0014]
【作用】以上のこの発明の方法によって、不純物による
悪影響もなく、微細均一粒径の水素吸蔵合金と、その微
細組織の均一性が実現され、しかもこの発明による水素
吸蔵合金の場合には、その組成が安定で、水素吸蔵特性
はもちろんのこと、電池電極として使用する場合には、
高容量を実現し、経時的劣化も抑制されることになる。According to the method of the present invention described above, the hydrogen storage alloy having a fine and uniform grain size and the homogeneity of its fine structure can be realized without adverse effects of impurities, and in the case of the hydrogen storage alloy according to the present invention, The composition is stable, not only hydrogen storage characteristics, but when used as a battery electrode,
A high capacity is realized and deterioration over time is suppressed.
【００１５】以下、実施例を示し、さらに詳しくこの発
明の方法について説明する。Examples will be shown below to describe the method of the present invention in more detail.
【００１６】[0016]
【実施例】実施例１ Ｍｍ（Ｌａ＋Ｃｅその他の希土類の混合物）、ペレット
状Ｎｉ、電解Ｍｎ、Ａｌショット、電解Ｃｏを原料とし
て、組成式ＭｍＮｉ3.4 Ｃｏ0.8 Ｍｎ0.5 Ａｌ 0.3 の配
合になるように、全量で３kgを秤量して、内径１１０m
m、深さ２５０mmのＭｇＯるつぼに装入した。真空引き
後、Ａｒガスを0.8 気圧導入して、高周波で溶解を行な
った。全ての原料が解け落ちた後、るつぼを傾動して溶
湯をタンディシュ上に注ぎ、タンダィシュ中心部の３mm
径の孔より、１５０００rpm で回転している黒鉛ディス
ク（９０mm径）の中心部に落下させ、遠心力で飛散させ
粉末を得た（平均粒径１２０μｍ）。注湯温度は、合金
融点より８０℃高い温度とした。このようにして均一微
粒子粉末を得たのでこれを使用して、水素吸蔵特性及び
半電池状態での放電容量を求めた。【Example】Example 1 Mm (La + Ce and other rare earth mixtures), pellets
Ni, electrolytic Mn, Al shot, electrolytic Co as raw materials
The composition formula MmNi3.4Co0.8Mn0.5Al 0.3Distribution of
Weigh 3 kg in total so that the inner diameter is 110 m
It was placed in a MgO crucible having a depth of 250 mm and a depth of 250 mm. Evacuation
After that, introduce Ar gas at 0.8 atm and dissolve at high frequency.
It was. After all the ingredients have melted down, tilt the crucible to melt
Pour hot water onto the tundish, 3 mm in the center of tundish
Graphite disk rotating at 15000 rpm through the diameter hole
(90mm diameter) drop it on the center and scatter it by centrifugal force.
A powder was obtained (average particle size 120 μm). Pouring temperature is alloy
The temperature was 80 ° C. higher than the melting point. In this way uniform
Since the particle powder was obtained, it was used to detect the hydrogen storage characteristics and
The discharge capacity in the half-battery state was determined.
【００１７】その結果を表１に示した。優れた性能の水
素吸蔵合金を得た。The results are shown in Table 1. A hydrogen storage alloy with excellent performance was obtained.
【００１８】[0018]
【表１】 [Table 1]
【００１９】なお、水素吸蔵特性は、内径約５mm、長さ
１５０mmのステンレス製パイプに、合金約６ｇを充填
し、活性化処理後、水素圧力を変化させ、その時の吸蔵
量を求めて得た。また放電容量は、合金１ｇに対して、
Ｎｉ粉末３ｇ、ポリエチレン樹脂0.1 ｇの割で混合して
ペースト状にし、Ｎｉ網に塗り込んで電極とした。充電
は、0.1Ａ×5.5hr 行い、放電は、0.05Ａで、0.7 Ｖカ
ットで容量を測定した。The hydrogen storage characteristics were obtained by filling a stainless steel pipe having an inner diameter of about 5 mm and a length of 150 mm with about 6 g of the alloy, activating and then changing the hydrogen pressure, and determining the storage amount at that time. . The discharge capacity is
3 g of Ni powder and 0.1 g of polyethylene resin were mixed to form a paste, which was applied to a Ni net to form an electrode. Charging was performed at 0.1 A × 5.5 hr, discharging was at 0.05 A, and the capacity was measured at 0.7 V cut.
【００２０】実施例２ スポンジＺｒ，スポンジＴｉ，ペレット状Ｎｉ，Ｖメタ
ル，電解Ｍｎ，電解Ｆｅを原料として、組成式Ｚｒ0.5
Ｔｉ0.5 （Ｖ0.5 Ｎｉ1.1 ，Ｍｎ0.2 Ｆｅ0.2) 1.8 にな
るように配合し、全量で２kgを秤り取り、ＭｇＯるつぼ
に装入し溶解した。溶解中の雰囲気はＨｅガス0.8 気圧
とした。注湯温度は、合金融点より約１００℃高い温度
とした。ディスクは、直径１１０mmの黒鉛炭素繊維複合
材料を用いた。ディスクの回転数は30,000rpm である。
均一微粒子粉末（平均粒径５０μｍ) を得た。実施例１
と同様に優れた水素吸蔵特性及び放電容量が得られた。[0020]Example 2 Sponge Zr, Ti sponge, Ni pellet, V meta
Composition of Zr, electrolytic Mn and electrolytic Fe as raw materials0.5
Ti0.5(V0.5Ni1.1, Mn0.2Fe0.2) 1.8In
Mix as follows, weigh 2 kg in total, and place in a MgO crucible.
It was charged and melted. The atmosphere during melting is He gas 0.8 atm.
And The pouring temperature is about 100 ° C higher than the melting point of the alloy.
And The disk is a graphite carbon fiber composite with a diameter of 110 mm.
Material was used. The rotation speed of the disk is 30,000 rpm.
A uniform fine particle powder (average particle size 50 μm) was obtained. Example 1
Excellent hydrogen storage characteristics and discharge capacity were obtained as well.
【００２１】比較例１〜４ 実施例１と同じ組成の合金をＭｇＯるつぼ中で溶解し、
ディスク材等としてＴｉ，Ｔｉ−６Ａｌ−４Ｖ合金、Ｎ
ｉ，ＳＵＳ３０４を用いて、Ｎ2 ガス雰囲気中で噴霧
し、粉末を得た。いずれの材質とも、溶湯との反応が顕
著であり、中心部が大きくえぐられていた。また、一部
では、ディスクが破壊したものもみられた。表１に示し
た通り、粉末には水素吸蔵特性はなかった。 Comparative Examples 1 to 4 An alloy having the same composition as in Example 1 was melted in a MgO crucible,
Ti, Ti-6Al-4V alloy, N as disk material
i, SUS304 was used to spray in an N 2 gas atmosphere to obtain a powder. The reaction with the molten metal was remarkable in all materials, and the central part was largely scooped. In addition, some discs were destroyed. As shown in Table 1, the powder did not have hydrogen storage characteristics.
【００２２】比較例５ 実施例１の合金を黒鉛、およびＡｌ2 Ｏ3 のるつぼの各
々で溶解し、実施例１と同じように噴霧して粉末を得
た。水素吸蔵特性、電池容量ともに、実施例１のものに
はるかに劣っている。実施例３ 合金組成がＺｒ0.5 Ｔｉ0.5 （Ｖ0.5 Ｎｉ1.1 Ｍｎ0.2
Ｆｅ0.2 ）1.8 の合金について表２に示した各種のるつ
ぼを用いて溶解して実施例１と同様にして粉末とした。 Comparative Example 5 The alloy of Example 1 was melted in each of the graphite and the Al 2 O 3 crucible and sprayed in the same manner as in Example 1 to obtain a powder. Both the hydrogen storage characteristics and the battery capacity are far inferior to those of Example 1. Example 3 The alloy composition was Zr 0.5 Ti 0.5 (V 0.5 Ni 1.1 Mn 0.2
The Fe 0.2 ) 1.8 alloy was melted using various crucibles shown in Table 2 and powdered in the same manner as in Example 1.
【００２３】この合金について、炭素、窒素および酸素
の含有量を評価し、表２の結果を得た。Ａｌ2 Ｏ3 るつ
ぼの場合には急速加熱により割れが発生した。この発明
のＭｇＯるつぼにより、不純物（Ｃ，Ｎ，Ｏ）の汚染の
ない溶解ができ、高純度、高特性粉末が製造できること
が確認された。With respect to this alloy, the contents of carbon, nitrogen and oxygen were evaluated, and the results shown in Table 2 were obtained. In the case of the Al 2 O 3 crucible, cracking occurred due to rapid heating. It has been confirmed that the MgO crucible of the present invention can dissolve impurities (C, N, O) without contamination and can produce high-purity, high-characteristic powder.
【００２４】[0024]
【表２】 [Table 2]
【００２５】[0025]
【発明の効果】この発明により、以上詳しく説明した通
り、不純物による悪影響もなく、水素吸蔵合金の微細粉
末の取得と、その電池材料への応用における容量増大等
の特性向上が可能となる。As described in detail above, according to the present invention, it is possible to obtain fine powder of a hydrogen storage alloy and to improve the characteristics such as the capacity increase in the application to the battery material without adverse effects of impurities.
Claims (3)
ｇＯるつぼにおいて溶解し、この合金の融点の５０℃以
上で２００℃以下の温度において高速回転している黒鉛
または黒鉛と炭素繊維複合材からなる円板上に溶湯を注
ぎ、遠心噴霧して急冷凝固することを特徴とする粒状水
素吸蔵合金の製造法。1. An alloy which absorbs and releases hydrogen reversibly is M
Melt in a gO crucible and pour the molten metal onto a disk made of graphite or graphite and carbon fiber composite material that is rotating at a high speed at a melting point of this alloy of 50 ° C or higher and 200 ° C or lower, centrifugally spray and solidify rapidly. A method for producing a granular hydrogen storage alloy, comprising:
活性ガスもしくは不活性ガスと水素との混合とする請求
項１の製造法。2. The method according to claim 1, wherein the atmosphere during the rapid solidification by centrifugal spraying is an inert gas or a mixture of an inert gas and hydrogen.
をさらに機械的に粉砕し、もしくは水素化・脱水素処理
して粉砕し、粒径１００μｍ以下の粒子とすることを特
徴とする粒状水素吸蔵合金の製造法。3. Granules obtained by the rapid solidification according to claim 1, which are further mechanically pulverized or hydrotreated and dehydrogenated to be pulverized to obtain particles having a particle diameter of 100 μm or less. Manufacturing method of storage alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5014207A JPH06228613A (en) | 1993-01-29 | 1993-01-29 | Production of granular hydrogen storage alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5014207A JPH06228613A (en) | 1993-01-29 | 1993-01-29 | Production of granular hydrogen storage alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06228613A true JPH06228613A (en) | 1994-08-16 |
Family
ID=11854664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5014207A Pending JPH06228613A (en) | 1993-01-29 | 1993-01-29 | Production of granular hydrogen storage alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06228613A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0756343A1 (en) * | 1995-07-27 | 1997-01-29 | VARTA Batterie Aktiengesellschaft | Alloys for use as active material for the negative electrode of an alkaline,rechargeable, nickel metal-hybride battery and its method of preparation |
| WO1997009144A1 (en) * | 1995-09-07 | 1997-03-13 | Shanghai Shen-Jian Metallurgical & Machinery-Electrical Technology Engineering Corp. | A method and an equipment for producing rapid condensation hydrogen storage alloy powder |
| JP2005520351A (en) * | 2001-02-28 | 2005-07-07 | マグネクエンチ・インコーポレーテッド | Bond magnet manufactured using atomized permanent magnet powder |
-
1993
- 1993-01-29 JP JP5014207A patent/JPH06228613A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0756343A1 (en) * | 1995-07-27 | 1997-01-29 | VARTA Batterie Aktiengesellschaft | Alloys for use as active material for the negative electrode of an alkaline,rechargeable, nickel metal-hybride battery and its method of preparation |
| WO1997009144A1 (en) * | 1995-09-07 | 1997-03-13 | Shanghai Shen-Jian Metallurgical & Machinery-Electrical Technology Engineering Corp. | A method and an equipment for producing rapid condensation hydrogen storage alloy powder |
| US6174345B1 (en) | 1995-09-07 | 2001-01-16 | Yu Chen | Method and an equipment for producing rapid condensation hydrogen storage alloy powder |
| JP2005520351A (en) * | 2001-02-28 | 2005-07-07 | マグネクエンチ・インコーポレーテッド | Bond magnet manufactured using atomized permanent magnet powder |
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