JP2961179B2 - Manufacturing method of hydrogen storage alloy - Google Patents
Manufacturing method of hydrogen storage alloyInfo
- Publication number
- JP2961179B2 JP2961179B2 JP4330028A JP33002892A JP2961179B2 JP 2961179 B2 JP2961179 B2 JP 2961179B2 JP 4330028 A JP4330028 A JP 4330028A JP 33002892 A JP33002892 A JP 33002892A JP 2961179 B2 JP2961179 B2 JP 2961179B2
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- hydrogen storage
- storage alloy
- capacity
- electrode
- Prior art date
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、水素の貯蔵、アルカリ
電池用の負極等に用いられる水素吸蔵合金およびその製
造方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 hydrogen storage alloy used for storage of hydrogen, a negative electrode for an alkaline battery, and a method for producing the same.
【０００２】[0002]
【従来の技術】Ｎｉ−Ｃｄ二次電池に変わる電池とし
て、高容量、高寿命化を目指し、又Ｃｄによる公害の危
険性のない水素吸蔵合金を用いたＮｉ−水素吸蔵合金電
池が実用化されるに到った。この様な水素吸蔵合金とし
て、ＬａＮｉ5 系合金（特開昭５１−１３９３４号公
報）が適していることが判明しているが、ＬａＮｉ系合
金は、容量はＣｄ電池に対して増大するが、長寿命化と
いう点では必ずしも安定したものが得られていない。そ
れ故、最近では、Ｌａに替わるコストの安いＭｍ（ミッ
シュメタル）を使用したＭｍ−Ｎｉ系の水素吸蔵合金電
極が開発され、Ｎｉ−Ｃｄ電池に替わる高容量電池とし
て注目を集めている。2. Description of the Related Art As a battery replacing a Ni-Cd secondary battery, a Ni-hydrogen storage alloy battery using a hydrogen storage alloy which aims at high capacity and long life and has no danger of pollution by Cd has been put into practical use. It has reached. As such a hydrogen storage alloy, a LaNi 5 alloy (JP-A-51-13934) has been found to be suitable. However, the capacity of the LaNi alloy is larger than that of a Cd battery. In terms of prolonging the life, a stable product has not always been obtained. Therefore, recently, an Mm-Ni-based hydrogen storage alloy electrode using Mm (mish metal), which is inexpensive and replaces La, has been developed, and has attracted attention as a high-capacity battery replacing the Ni-Cd battery.
【０００３】例えば、特開昭６２−２０２４５号公報に
は、組成式ＭｍＮｉx （Ｃｏa ・Ｍｎb ・Ａｌc ）y に
おいて、４．３＜ｘ＋ｙ＜５．５であって、Ｍｍ中のＬ
ａの含有量が２５〜７０重量％である水素吸蔵合金が開
示されている。[0003] For example, JP-A-62-20245, in the composition formula MmNi x (Co a · Mn b · Al c) y, a 4.3 <x + y <5.5, in Mm L
A hydrogen storage alloy having a content of 25 to 70% by weight is disclosed.
【０００４】[0004]
【発明が解決しようとする課題】しかし、これら従来の
水素吸蔵合金でも、未だ容量および寿命が十分ではな
く、更に高容量化、長寿命化が要求されている。本発明
者等は、かかる課題を解決すべく鋭意検討した結果、ミ
ッシュメタルの合金にかわって、主として後記組成式
（Ｉ）で表される合金からなり、特殊な処理によって結
晶の短軸方向の長さが１０μｍ以下である微細結晶粒構
造が形成されるまで微細結晶化された水素吸蔵合金が、
従来の合金より格段に高容量、且つ長寿命であることを
見出し、本発明に到達した。即ち本発明の目的は、高容
量且つ長寿命の水素吸蔵合金を提供することに存する。However, even with these conventional hydrogen storage alloys, the capacity and the life are still not sufficient, and further higher capacity and longer life are required. The present inventors have conducted intensive studies to solve such problems, and as a result, instead of the misch metal alloy, the alloy mainly consists of an alloy represented by the following composition formula (I). A hydrogen storage alloy finely crystallized until a fine grain structure having a length of 10 μm or less is formed,
The present inventors have found that the capacity is much higher and the life is longer than conventional alloys, and have reached the present invention. That is, an object of the present invention is to provide a hydrogen storage alloy having a high capacity and a long life.
【０００５】[0005]
【課題を解決するための手段】しかして、かかる本発明
の目的は、下記組成式（Ｉ）で表される合金を主成分と
し残部は実質的に不純物からなる合金の溶湯を、周速１
０ｍ／ｓｅｃ以上で回転する耐熱性ロール上に、流射す
ることにより薄帯化しつつ急冷凝固させ、ついで３００
〜５００℃で低温焼鈍して結晶の短軸方向の長さが１０
μｍ以下である微細結晶粒組織を形成させることを特徴
とする水素吸蔵合金の製造方法により容易に達成され
る。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a molten alloy comprising an alloy represented by the following composition formula (I) as a main component and the balance substantially consisting of impurities at a peripheral speed of 1: 1.
On a heat-resistant roll rotating at 0 m / sec or more, it is rapidly solidified while being thinned by spraying.
Low temperature annealing at ~ 500 ° C and the length of the crystal in the short axis direction is 10
It is easily achieved by a method for producing a hydrogen storage alloy, which is characterized by forming a fine grain structure of not more than μm.
【０００６】[0006]
【化２】 Ｌａa-y Ｎｉb-x Ａx Ｂy Ｘz … （I） （式中、ＡはＡｌ，Ｚｎ，Ｃｕ，Ｃｏ，Ｃｒ，Ｆｅ，Ｉ
ｎ，Ｍｏ，Ｍｎ，Ｐｂ及びＢｉからなる群から選ばれる
１種以上の元素を表し、１．０≦ａ≦１．３、３．３≦
ｂ≦４．９、０．１＜ｘ＜２．０であり、ＢはＬａ以外
の希土、あるいはＺｒ，Ｔｉを表わし、ＸはＢ，Ｖ，Ｇ
ａ，Ｓｎ，Ａｇ，Ｍｇ，Ｓｂ，Ｓｒからなる群から選ば
れる１種以上の元素を表わし、０≦ｙ≦０．２、０．０
１≦ｚ≦０．０５である）## STR2 ## La ay Ni bx A x B y X z ... (I) ( In the formula, A Al, Zn, Cu, Co, Cr, Fe, I
represents one or more elements selected from the group consisting of n, Mo, Mn, Pb and Bi, and 1.0 ≦ a ≦ 1.3, 3.3 ≦
b ≦ 4.9, 0.1 <x <2.0, B represents a rare earth other than La, or Zr, Ti, and X represents B, V, G
a, Sn, Ag, Mg, Sb, Sr, represents one or more elements selected from the group consisting of 0 ≦ y ≦ 0.2, 0.0
1 ≦ z ≦ 0.05)
【０００７】本発明においては、従来、水素吸蔵合金用
によく用いられてきたミッシュメタルの合金にかわっ
て、Ｌａ以外の希土が２０％以下である、前記組成式
（Ｉ）又は（II）で表される合金を用いることをひとつ
の特徴とする。In the present invention, the composition formula (I) or (II) wherein the rare earth other than La is 20% or less, instead of the misch metal alloy which has been often used for hydrogen storage alloys. One feature is that an alloy represented by
【０００８】かかる合金は、基本合金であるＬａＮｉ5
の結晶において、添加元素としてのＡ（Ａは式（Ｉ）中
と同義、以下同様）は、Ｎｉと置換して含有されている
とみなすことができる。上記のＡとして列挙した元素
は、Ｎｉと電子配列が近似し、原子半径がＮｉよりも大
きい。従ってＮｉと容易に置換し、且つ水素解離圧を下
げる効果がある。また、急冷凝固の際に、結晶を、より
微細化する効果があり、結晶が微細化することにより、
一層水素吸蔵能が向上する。[0008] Such an alloy is LaNi 5 which is a basic alloy.
In the crystal of A, A as an additive element (A has the same meaning as in the formula (I), and the same applies hereinafter) can be regarded as being contained in place of Ni. The elements listed as A have an electronic arrangement similar to that of Ni, and have an atomic radius larger than that of Ni. Therefore, it has the effect of easily replacing with Ni and lowering the hydrogen dissociation pressure. In addition, at the time of rapid solidification, there is an effect of making the crystal finer, and by making the crystal finer,
The hydrogen storage capacity is further improved.
【０００９】次に式（Ｉ）中のＢはＬａと置換し、Ａと
相まって平衡解離圧を適当ならしむると共に寿命の改善
等の効果がある。添加元素Ａの組成比は、０．１＜ｘ＜
２．０であるが、ｘが２以上となると、ＬａＮｉ5 にみ
られるＣａＣｕ5 型六方晶構造が崩れ、添加元素により
特有な金属間化合物による第２相が生じるためである。
この様な第２相は、一般には水素吸蔵能は少ない。Next, B in the formula (I) is replaced with La, and in combination with A, the equilibrium dissociation pressure can be appropriately adjusted and the life can be improved. The composition ratio of the additive element A is 0.1 <x <
It is 2.0, but when x is 2 or more, the CaCu 5 type hexagonal structure seen in LaNi 5 collapses, and a second phase due to an intermetallic compound peculiar to the added element is generated.
Such a second phase generally has a low hydrogen storage capacity.
【００１０】又Ｂの組成比は０≦ｙ≦０．２であるがｙ
が０．２を超えるとＬａの効果が失なわれてきて容量の
低下をきたす。また、本発明合金は、上記組成式（Ｉ）
で表される合金を主成分とするが、該合金が実質的に水
素吸蔵合金全体の物性を支配する限り、他の金属元素等
を含有していてもよい。この様な不純物としての元素の
うち、例えば、Ｗ，Ｎｂ等は、相当に含有率が大きくて
も、水素吸蔵合金の特性に悪影響を与えない。The composition ratio of B is 0 ≦ y ≦ 0.2.
Exceeds 0.2, the effect of La is lost and the capacity is reduced. Further, the alloy of the present invention has the above composition formula (I)
The main component is an alloy represented by the general formula (1), but may contain other metal elements and the like as long as the alloy substantially controls the physical properties of the entire hydrogen storage alloy. Among such elements as impurities, for example, W, Nb and the like do not adversely affect the characteristics of the hydrogen storage alloy even if the content is considerably large.
【００１１】次にかかる合金に微量添加する元素Ｘにつ
いて述べると、式（I）のＸは、粒界に偏析し易い元素
であり、かかる元素は粒界に偏析して粒界に保護膜を形
成する。本発明合金を電池に使用した場合耐アルカリ保
護膜として電池寿命の改善に役立つ。特に急冷凝固によ
り得られた微細結晶粒の場合粒界の役割は大きく、微量
元素によるかかる効果の出現に好都合である。又適当な
熱処理により偏析は促進され効果は増大する。Next, the element X to be added in a small amount to the alloy will be described. In the formula (I), X is an element which is easily segregated at the grain boundary, and such element segregates at the grain boundary to form a protective film on the grain boundary. Form. When the alloy of the present invention is used for a battery, it is useful as an alkali-resistant protective film for improving the battery life. In particular, in the case of fine crystal grains obtained by rapid solidification, the role of the grain boundary is large, which is advantageous for the appearance of such an effect by the trace element. The segregation is promoted by an appropriate heat treatment, and the effect is increased.
【００１２】微量元素Ｘの組成比は０．０１≦ｚ≦０．
０５であり、ｚが０．０５を超えると微量元素でなくな
り、容量の低下をきたし活性化等に悪影響を与える。
０．０１未満では少なすぎて効果が期待できない。本発
明合金は、粒径１０μｍ以下の微細結晶粒組織、即ち、
粒状またはコラム状の微細結晶粒組織から主として構成
されることをもうひとつの特徴とし、かかる微細な結晶
組織は、上述した原料としての合金の溶湯を、周速１０
ｍ／ｓｅｃ以上で回転する耐熱性ロール上に、前記合金
の溶湯を流射することにより薄帯化しつつ急冷凝固させ
て、ついで３００〜５００℃で低温焼鈍して粒径１０μ
ｍ以下の微細結晶粒組織を形成させることにより製造す
ることができる。The composition ratio of the trace element X is 0.01 ≦ z ≦ 0.
05, and when z exceeds 0.05, it is no longer a trace element, resulting in a reduction in capacity and adversely affecting activation and the like.
If it is less than 0.01, the effect is too small to expect an effect. The alloy of the present invention has a fine grain structure having a particle size of 10 μm or less, that is,
Another feature is that it is mainly composed of a granular or columnar fine crystal grain structure.
A melt of the alloy is sprayed onto a heat-resistant roll rotating at a speed of at least m / sec to rapidly solidify while thinning, and then annealed at 300 to 500 ° C. at a low temperature to obtain a particle size of 10 μm.
It can be produced by forming a fine grain structure of m or less.
【００１３】この方法によれば、ロールの回転数が大き
くなる程、また、押し出しノズルの口径が小さくなる程
冷却速度が大きく、結晶粒組織がより微細になるので、
ロールの回転の周速は、１０ｍ／ｓｅｃ以上とする。一
方、押し出しノズルの口径は、通常用いられる１００μ
ｍ以下程度のもので十分である。合金の溶湯をこの様に
比較的細い流出孔のノズルから加圧下に流出させ、この
流出流を上記ロールに当射すれば、溶湯流はロール上で
拡がり薄帯化して固化する。従って本発明の流射におい
ては、溶湯流が合金上で薄帯化する限り、溶湯を種々の
態様でロール上に流出せしめることができるが、上述し
た通り加圧下で又、連続流で流出させれば操作が簡便と
なり好ましい。According to this method, the cooling rate increases as the rotation speed of the roll increases, and as the diameter of the extrusion nozzle decreases, the crystal grain structure becomes finer.
The peripheral speed of the rotation of the roll is 10 m / sec or more. On the other hand, the diameter of the extrusion nozzle is usually 100 μm.
m or less is sufficient. When the melt of the alloy is caused to flow out from the nozzle having such a relatively small outflow hole under pressure, and this outflow is applied to the roll, the flow of the melt spreads on the roll, becomes thin and solidifies. Therefore, in the spraying of the present invention, as long as the molten metal flow is thinned on the alloy, the molten metal can be discharged onto the roll in various modes. This is preferable because the operation is simplified.
【００１４】かかる方法により製造される合金は、安定
なＣａＣｕ5 型六方晶構造を有するストイキオメトリッ
クな金属間化合物であり、液体からの急冷によってアモ
ルファス化することなく、得られる効果は微細結晶粒組
織による効果である。本発明方法は、超急冷により、結
晶微細組織を得る方法だが、急冷凝固の際に、大きな内
部歪が導入される。この歪は、水素の侵入を妨げるとと
もに、水素の吸蔵・放出時の膨張、収縮に伴い、素材の
劣化、微粉化を招く場合がある。The alloy produced by such a method is a stoichiometric intermetallic compound having a stable CaCu 5 type hexagonal structure, and the effect obtained without being amorphous by rapid cooling from a liquid is fine crystal grains. It is the effect of the organization. In the method of the present invention, a crystal microstructure is obtained by ultra-quenching, but a large internal strain is introduced during rapid solidification. This strain may hinder the intrusion of hydrogen, and may cause deterioration and pulverization of the material due to expansion and contraction at the time of absorbing and releasing hydrogen.
【００１５】そこで、本発明方法においては、この様な
内部歪を除去すべく、合金の溶湯を、耐熱性ロール上
に、流射して薄帯化しつつ急冷凝固させた後、追加の工
程として、３００〜５００℃で低温焼鈍する。３００℃
以下では、焼鈍の効果が少なく歪を十分除去できず、５
００℃以上では、結晶粒の粗大化を招き微細結晶粒組織
の効果が失われる怖れがある。焼鈍の時間は、温度が高
いときは短く、温度が低いときは長くてよいのは、通常
の熱処理と同様である。かかる範囲の熱処理は微量元素
の粒界偏析を促し、粒界保護膜の形成に効果があること
は十分推察できる。Therefore, in the method of the present invention, in order to remove such internal strains, the molten alloy is rapidly cooled and solidified while being sprayed and thinned on a heat-resistant roll. And low temperature annealing at 300 to 500 ° C. 300 ℃
In the following, the effect of annealing is so small that the strain cannot be sufficiently removed.
If the temperature is higher than 00 ° C., the crystal grains may be coarsened and the effect of the fine crystal grain structure may be lost. The annealing time may be short when the temperature is high and long when the temperature is low, as in the case of ordinary heat treatment. It can be sufficiently inferred that heat treatment in such a range promotes grain boundary segregation of trace elements and is effective in forming a grain boundary protective film.
【００１６】[0016]
【発明の効果】本発明の水素吸蔵合金は、水素の吸蔵容
量が従来の合金より大きく、繰り返し使用してもさほど
吸蔵容量が減少しない。また、水素の吸蔵に伴い生ずる
歪（体積で約１．２〜１．３倍の膨張）を結晶粒界で吸
収、緩和し、水素の吸蔵、放出がより容易となる。従っ
て、各種用途に好適で、特に、電池の電極として使用し
た場合、Ｐ．Ｃ．Ｔ．曲線での平坦なプラトーが得られ
るだけでなく、電極の膨張、収縮に伴う劣化、微粉化を
防ぎ、又、強固な粒界被膜の形成等により高容量、長寿
命を実現するものである。本発明方法は、超急冷によ
り、結晶粒組織を非常に微細とすることができ、高性能
の水素吸蔵合金を容易に製造できる。As described above, the hydrogen storage alloy of the present invention has a larger hydrogen storage capacity than conventional alloys, and the storage capacity does not decrease so much even when used repeatedly. Further, the strain (expansion of about 1.2 to 1.3 times in volume) caused by the occlusion of hydrogen is absorbed and relaxed at the crystal grain boundaries, and the occlusion and release of hydrogen become easier. Therefore, it is suitable for various uses. C. T. Not only can a flat plateau in a curve be obtained, but also deterioration and pulverization due to expansion and contraction of the electrode can be prevented, and high capacity and long life can be realized by forming a firm grain boundary film. According to the method of the present invention, the crystal grain structure can be made very fine by ultra-quenching, and a high-performance hydrogen storage alloy can be easily produced.
【００１７】[0017]
【実施例】以下、実施例により本発明を更に詳細に説明
するが、本発明は、その要旨を越えない限り下記実施例
により限定されるものではない。各実施例及び比較例に
おいては、水素吸蔵合金及びそれを用いた電極を製造
し、次の通り、電極の充放電サイクル試験を行なった。EXAMPLES The present invention will be described in more detail with reference to the following Examples, which, however, are not intended to limit the scope of the present invention unless it exceeds the gist thereof. In each of Examples and Comparative Examples, a hydrogen storage alloy and an electrode using the same were manufactured, and a charge / discharge cycle test of the electrode was performed as follows.
【００１８】充放電サイクル試験 ４０ｍＡ×３時間充電し、レストタイム３０分の後、２
０ｍＡで電圧０．６Ｖとなるまで放電するサイクルを繰
り返し、各サイクルの放電時における放電時間から総放
出電気量を算出した。 Charge / discharge cycle test: Charged at 40 mA × 3 hours, and after a rest time of 30 minutes,
The cycle of discharging at 0 mA until the voltage reached 0.6 V was repeated, and the total amount of discharged electricity was calculated from the discharge time at the time of discharging in each cycle.
【００１９】（比較例１） ＬａＮｉ4.6 Ａｌ0.4 の組成になる様に金属元素を配合
し、約５０ｇをアークメルト溶解した。アークメルト溶
解は、約５×１０-5Torrまで真空引後、アルゴン置換を
行い、裏表合計４回行なって均一な合金とした。Comparative Example 1 A metal element was blended so as to have a composition of LaNi 4.6 Al 0.4 , and about 50 g was melted by arc melt. The arc melt was evacuated to about 5 × 10 −5 Torr, and then replaced with argon.
【００２０】次に、その合金から約１０ｇを取り、石英
管に封入し、同じく真空引き後、アルゴン置換したチャ
ンバー中で、高周波誘導加熱により瞬時に溶解し、アル
ゴン気流（０．６気圧）とともに石英管底に設けた約
０．７ｍｍの孔から流射し、回転ロール（約３０００r.
p.m.、２０ｃｍφ銅ロール）上、約０．２ｍｍ隙間で５
０μ前後の厚さの合金薄帯となした。Next, about 10 g of the alloy was taken, sealed in a quartz tube, evacuated, melted instantaneously by high-frequency induction heating in a chamber replaced with argon, and heated with an argon gas flow (0.6 atm). Spray from a hole of about 0.7 mm provided on the bottom of the quartz tube, and rotate it (about 3000 r.
pm, 20cmφ copper roll)
An alloy ribbon having a thickness of about 0 μm was formed.
【００２１】上記の様に作製した合金薄帯を、大気中で
粉砕し、１００メッシュ以下の粉とした。この粉を、銅
２０％になる様に無電解銅メッキを施し、ＦＥＰ（フッ
ソ樹脂）粉１０％と混合し、約０．３ｇを採り、１３ｍ
ｍφの金型にてゴールドプレスし、薄い円板状タブレッ
トを作り、更に、ホットプレス（３００℃、２００ｋｇ
／ｃｍ2 、３分）し、バインダーを硬化させ、電極を作
製した。The alloy ribbon produced as described above was pulverized in the air to obtain a powder having a size of 100 mesh or less. This powder is subjected to electroless copper plating so as to have a copper content of 20%, mixed with FEP (fluororesin) powder 10%, and about 0.3 g is taken.
Gold press with a mφ mold to make a thin disk-shaped tablet, and then hot press (300 ℃, 200kg
/ Cm 2 , 3 minutes) to cure the binder, thereby producing an electrode.
【００２２】この合金電極を、負極として、Ｎｉ正極と
ともに６規定ＫＯＨ水溶液で満たしたガラスのセルに組
み込み、充放電サイクル試験を行い、容量及び容量低下
（寿命）を測定した。結果を図１に示す。This alloy electrode was mounted as a negative electrode together with a Ni positive electrode in a glass cell filled with a 6N KOH aqueous solution, and a charge / discharge cycle test was performed to measure the capacity and capacity reduction (life). The results are shown in FIG.
【００２３】（比較例２） アークメルト溶解して製造したＬａＮｉ4.6 Ａｌ0.4 な
る組成の合金を、薄帯化することなく、粉砕し或いは電
極として充放電サイクル試験を行なった以外、前記比較
例１と全く同様にした結果を図１に示す。Comparative Example 2 Comparative Example 1 was performed except that an alloy having a composition of LaNi 4.6 Al 0.4 produced by melting an arc melt was pulverized without thinning or subjected to a charge / discharge cycle test as an electrode. FIG. 1 shows the result obtained in the same manner as in FIG.
【００２４】（実施例１〜９、比較例３） 表−１に記載するＸ成分を含み、合金組成がＬａ1.02Ｎ
ｉ4.0 Ｃｏ0.6 Ａｌ0.4 Ｘ0.05となる様に金属元素を配
合した以外前記比較例１と全く同様にした後、合金薄帯
を、３８０℃で３０分低温焼鈍し、結晶の短軸方向の長
さが１０μｍ以下である微細結晶粒組織状の合金を得
た。これより比較例１と同様に電極を作製し、充放電サ
イクル試験を行なった。１００サイクル後の容量低下
（寿命）を表−１に示す。(Examples 1 to 9, Comparative Example 3) An alloy composition containing the X component shown in Table 1 and having an alloy composition of La 1.02 N
After exactly the same as in Comparative Example 1 except that the metal element was blended to obtain i 4.0 Co 0.6 Al 0.4 X 0.05 , the alloy ribbon was annealed at 380 ° C. for 30 minutes at a low temperature, and the length of the crystal in the minor axis direction was measured. An alloy having a fine grain structure with a grain size of 10 μm or less was obtained. From this, an electrode was produced in the same manner as in Comparative Example 1, and a charge / discharge cycle test was performed. Table 1 shows the capacity decrease (lifetime) after 100 cycles.
【００２５】[0025]
【表１】 [Table 1]
【図１】水素吸蔵合金からなる電極の充放電サイクル試
験の結果を示すグラフであって、横軸は、充放電サイク
ル数、縦軸は、電極単位重量あたりの総放出電気量を示
す（単位ｍＡｈｒ／ｇ）。図中、実線が比較例１、破線
が比較例２の電極の試験結果を表す。FIG. 1 is a graph showing the results of a charge / discharge cycle test of an electrode made of a hydrogen storage alloy, in which the horizontal axis represents the number of charge / discharge cycles, and the vertical axis represents the total amount of discharged electricity per unit weight of the electrode (unit). mAhr / g). In the figure, the solid line represents the test result of the electrode of Comparative Example 1, and the broken line represents the test result of the electrode of Comparative Example 2.
フロントページの続き (72)発明者 石川 博 大阪府池田市五月丘１−10−16 (72)発明者 宮村 弘 大阪府豊中市新千里西町３−20−10 (72)発明者 上原 斎 大阪府池田市伏尾台２−３−12 審査官 城所 宏 (56)参考文献 特開 平２−291665（ＪＰ，Ａ) 特開 平３−188236（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C22C 1/00 - 28/00 Continued on the front page (72) Inventor Hiroshi Ishikawa 1-10-16, Satsukioka, Ikeda-shi, Osaka (72) Inventor Hiroshi Miyamura 3-20-10, Shinsenri-nishimachi, Toyonaka-shi, Osaka (72) Inventor Sei Uehara Osaka 2-3-12 Fushiodai, Ikeda-shi Examiner Hiroshi Shirosho (56) References JP-A-2-291665 (JP, A) JP-A-3-188236 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C22C 1/00-28/00
Claims (1)
分とし残部は実質的に不純物からなる合金の溶湯を、周
速１０ｍ／ｓｅｃ以上で回転する耐熱性ロール上に、流
射することにより薄帯化しつつ急冷凝固させ、ついで３
００〜５００℃で低温焼鈍して結晶の短軸方向の長さが
１０μｍ以下である微細結晶粒組織を形成させることを
特徴とする水素吸蔵合金の製造方法。 【化１】 Ｌａa-y Ｎｉb-x Ａx Ｂy Ｘz … （I） （式中、ＡはＡｌ，Ｚｎ，Ｃｕ，Ｃｏ，Ｃｒ，Ｆｅ，Ｉ
ｎ，Ｍｏ，Ｍｎ，Ｐｂ及びＢｉからなる群から選ばれる
１種以上の元素を表し、１．０≦ａ≦１．３、３．３≦
ｂ≦４．９、０．１＜ｘ＜２．０であり、ＢはＬａ以外
の希土、あるいはＺｒ，Ｔｉを表わし、ＸはＢ，Ｖ，Ｇ
ａ，Ｓｎ，Ａｇ，Ｍｇ，Ｓｂ，Ｓｒからなる群から選ば
れる１種以上の元素を表わし、０≦ｙ≦０．２、０．０
１≦ｚ≦０．０５である）1. A spray of a molten alloy of an alloy represented by the following composition formula (I) as a main component and the balance substantially consisting of impurities onto a heat-resistant roll rotating at a peripheral speed of 10 m / sec or more. Quenching and solidification while thinning, and then 3
A method for producing a hydrogen storage alloy, wherein low-temperature annealing is performed at 00 to 500 ° C. to form a fine grain structure in which the length of a crystal in a minor axis direction is 10 μm or less. Embedded image Laay Ni bx A x B y X z (I) (where A is Al, Zn, Cu, Co, Cr, Fe, I
represents one or more elements selected from the group consisting of n, Mo, Mn, Pb and Bi, and 1.0 ≦ a ≦ 1.3, 3.3 ≦
b ≦ 4.9, 0.1 <x <2.0, B represents a rare earth other than La, or Zr, Ti, and X represents B, V, G
a, Sn, Ag, Mg, Sb, Sr, represents one or more elements selected from the group consisting of 0 ≦ y ≦ 0.2, 0.0
1 ≦ z ≦ 0.05)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4330028A JP2961179B2 (en) | 1991-11-18 | 1992-11-16 | Manufacturing method of hydrogen storage alloy |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32955991 | 1991-11-18 | ||
| JP3-329559 | 1991-11-18 | ||
| JP4330028A JP2961179B2 (en) | 1991-11-18 | 1992-11-16 | Manufacturing method of hydrogen storage alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06145851A JPH06145851A (en) | 1994-05-27 |
| JP2961179B2 true JP2961179B2 (en) | 1999-10-12 |
Family
ID=26573251
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4330028A Expired - Lifetime JP2961179B2 (en) | 1991-11-18 | 1992-11-16 | Manufacturing method of hydrogen storage alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2961179B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100239742B1 (en) * | 1995-07-10 | 2000-01-15 | 이노우에 유스케 | Rare earth metal nickel base hydrogen absorbing alloy process for preparing the same and negative electrode for nickel hydrogen secondary battery |
| DE69616741T2 (en) * | 1995-08-31 | 2002-05-08 | Santoku Metal Ind | HYDROGEN ABSORBING RARE EARTH METAL / NICKEL BASED ALLOY, PRODUCTION PROCESS AND NEGATIVE ELECTRODE FOR NICKEL HYDROGEN SECONDARY BATTERY |
| TW488106B (en) * | 1999-08-05 | 2002-05-21 | Shinetsu Chemical Co | Hydrogen absorbing alloy and nickel-metal hydride rechargeable battery |
| JP4503915B2 (en) * | 2002-09-26 | 2010-07-14 | 株式会社三徳 | Hydrogen storage alloy and method for producing the same |
| CN1313632C (en) * | 2004-06-23 | 2007-05-02 | 中国科学院金属研究所 | Hydrogen-storage alloy of metal oxide for air-conditioner |
| CN102152528B (en) * | 2010-10-21 | 2015-03-11 | 江西理工大学 | Carrier ultrathin copper foil with rare earth modified peel strength and preparation method thereof |
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| JP3345889B2 (en) * | 1989-02-23 | 2002-11-18 | 松下電器産業株式会社 | Manufacturing method of alkaline storage battery and its negative electrode |
| JP2771592B2 (en) * | 1989-04-18 | 1998-07-02 | 三洋電機株式会社 | Hydrogen storage alloy electrode for alkaline storage batteries |
-
1992
- 1992-11-16 JP JP4330028A patent/JP2961179B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JPH06145851A (en) | 1994-05-27 |
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