JPS599145A - Multicomponent type titanium-cobalt alloy for hydrogen occlusion - Google Patents

Abstract

PURPOSE:To provide a multicomponent type Ti-Co alloy for hydrogen occlusion having a specified composition, very easily activated by hydrogen, capable of occluding a large amount of hydrogen in the form of hydride, and releasing hydrogen easily and rapidly by slight heating. CONSTITUTION:An alloy for hydrogen occlusion represented by the formula TiCo1-xAyBz: is obtd. by blending a three-component type alloy consisting of Ti, Co and a metal A with a metal B by substitution or addition. In the formula A is Al, Cr, Cu, Fe, Mn or Ni; B is Nb, Mo, V, Zr or a rare earth element; 0.01<=x<=0.5, 0.01<=y<=0.5, 0<z<=0.2, and 1.0<=(1-x+y+z)<=1.2. The alloy can be activated very easily, and the activated alloy occludes and releases rapidly a large amount of hydrogen at relatively low temp. and pressure. For example, powder of said alloy is filled into a container, degassed at <=200 deg.C under reduced pressure, and activated. After sealing hydrogen in the container at a temp. above room temp., by applying <=40kg/cm<2> pressure of hydrogen, hydrogen can be occluded up to an almost satd. state within several min. The release of hydrogen is carried out in a short time by heating the powder to a temp. above room temp. and/or by slightly reducing the pressure.

Description

【発明の詳細な説明】 本発明はチタン−コバルト多元系水素吸蔵用冶金に関し
、より詳細には水素による活性化が極めて容易で、水素
化物の彩飾で多量の水素を吸蔵でき、しかも水素の吸蔵
圧と放出圧の岸、即ちヒステリシスが極めて小さく、わ
ずかの加熱で容易且つすみやかに水素を放出するチタン
−コバルト多元系水素吸蔵用合金に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a titanium-cobalt multi-component metallurgy for hydrogen storage, and more specifically, it is extremely easy to activate with hydrogen, can store a large amount of hydrogen by decorating with hydride, and is capable of storing hydrogen. The present invention relates to a titanium-cobalt multi-component hydrogen storage alloy that has extremely small hysteresis between pressure and release pressure, and easily and quickly releases hydrogen with a small amount of heating.

水素←ま資源的な制限がなくクリーンであること、輸送
及び貯蔵が容易であること等の理由から、化石燃料に代
る新しいエイ・ルギーσψとして注目されている。Hydrogen is attracting attention as a new fuel to replace fossil fuels because it is clean, has no resource limitations, and is easy to transport and store.

しかし水素は常温で気体であり、しかも液化温度が極め
て低いから、その貯絶枝術の開発が重要となる。この貯
蔵法としてＣよ、水素を金属に吸蔵させ金鵡水素化物と
して貯蔵する方法が最近注目を集めている。捷た金属に
よる水素の吸蔵・放出反応は可逆的であり、反応に伴っ
て相当楡の反応熱が発生し奴は吸収されること、及び水
素の吸蔵・放出圧力が温度に依存すること、を利用して
、冷暖房装りや熱エネルギー−圧力（機械）エネルギー
変換装置性への応用研４にも進められている。However, since hydrogen is a gas at room temperature and its liquefaction temperature is extremely low, it is important to develop techniques for storing and cutting off hydrogen. As a storage method, a method of storing hydrogen as a gold parapet hydride by absorbing hydrogen into a metal has recently been attracting attention. It is known that the hydrogen storage and desorption reaction by the shredded metal is reversible, that a considerable amount of reaction heat is generated during the reaction, and that hydrogen is absorbed, and that the hydrogen storage and desorption pressures depend on the temperature. Utilizing this technology, it is also being applied to heating and cooling systems and thermal energy to pressure (mechanical) energy conversion devices.

このような水素吸蔵特性に要求される性りとしては、（
り安価で資許的に褌富であること、（２）活性化が容部
で水素＠献匍が大きいこと、（３）室幅付近で手当な水
素吸蔵・放出平泗圧を山し、＋１４ｉ　４ｉ・放出のヒ
ステリシスが小さいこと、（４）水素吸緘・放出反応、
が可逆的でありその神度が大へいこと、等がノ１−けら
れる。The properties required for such hydrogen storage properties are (
(2) the activation is large and the hydrogen supply is large; (3) the hydrogen storage and release pressure is moderately high near the chamber width; +14i 4i・release hysteresis is small; (4) hydrogen absorption/release reaction;
It is noted that it is reversible and its divine degree is great.

ところで、この抑の水素吸蔵特性月料とし、又は例えば
ＬａＮｉ、　、　Ｍｇ、ＮｉやＦｅＴｉ等が知られテオ
リ、これらの合金は水素の吸蔵・放出ノ又応がｉ’ｉＪ
迎的であり水素吸蔵鋼も太きいが、氷点吸蔵・放出反応
の速度が遅く珪つ活性化が容易とはぎえず、しかもヒス
プリシスが大きく実用上大きな問題があった。By the way, the hydrogen storage properties of these alloys are known, such as LaNi, Mg, Ni, and FeTi, and these alloys have excellent hydrogen storage and release properties.
Although hydrogen storage steel is relatively thick, the freezing point storage and desorption reaction is slow, activation of silica is not easy, and hysteresis is large, which poses a major problem in practical use.

本弁明名は上記のような事情に漸目し、従来の木素吸賦
用＠金の有する特長を保留しつつ１１１）７１Ｓのよう
な欠点を解消すべく佃究を雌めてきた。The title of this defense has been developed in light of the above-mentioned circumstances, and has focused on research to eliminate the drawbacks of 111) 71S while retaining the features of conventional wood adsorption @gold.

その結果、Ｔ１及びｃｏ１ベース合金としこれに特定の
金属元素を適量配合すれば、上記の目的Ｋかなう優れた
水素吸蔵特性の合金が得られることを知り、舷に本発明
を完成した。すなわち本本発明のチタン−コバルト多元
系水素吸蔵用合金は一般式Ｔ１Ｃｏ、、ＡｙＢｚで示さ
れることを特徴とするものである。ただし式中Ａはアル
ミニウム。As a result, it was discovered that an alloy with excellent hydrogen storage properties that satisfies the above-mentioned objective K can be obtained by creating a T1 and CO1 base alloy and blending an appropriate amount of a specific metal element therewith, thereby completing the present invention. That is, the titanium-cobalt multi-component hydrogen storage alloy of the present invention is characterized by being represented by the general formula T1Co, AyBz. However, A in the formula is aluminum.

クロム、銅、鉄、マンガン、またはニッケルであり、Ｂ
はニオブ、モリブデン、バナジウム、ジルコニウムまた
は希土類元素であり、ｘ＝ｏ、０１〜０．５　、　Ｙ　
＝　０．０１〜０．５　、　ｚ≦０．２で、かつ１．Ｏ
≦１−　ｘ　＋　ｙ　＋　ｚ≦１．２である。ただし、
ｚ＝Ｏｉ除く。Chromium, copper, iron, manganese, or nickel; B
is niobium, molybdenum, vanadium, zirconium or a rare earth element, x=o, 01-0.5, Y
= 0.01 to 0.5, z≦0.2, and 1. O
≦1−x+y+z≦1.2. however,
z=Oi excluded.

一般にＴＩとＣＯはｃｓｃｚ型の立方晶を形成して’ｌ
’ｉ　（：’ｏとなり、またＣｏの一部を金栖Ａ即ちＡ
Ｉ！。Generally, TI and CO form a cscz-type cubic crystal.
'i (: 'o, and part of Co is Kanasu A, that is A
I! .

Ｃｒ　ｌ　Ｃｕ　ｌ　Ｆｅ　、　Ｍｎ及びＮｉなどとｔ
ｆｔ［して一般式ＴｉＣ０＋−ａＡａの金属間化合物と
なり、水素吸蔵能を発揮することが確認されている。Cr l Cu l Fe, Mn and Ni etc.
ft[ to form an intermetallic compound with the general formula TiC0+-aAa, and it has been confirmed that it exhibits hydrogen storage ability.

しかしながら、これらの＠？ｔは、（”Ｊれも活性化の
ために高温、高庄を要すると共に水累紳晟の影智を受は
易く、しかも水素吸蔵圧と水素ｂ（高圧の差、即ちヒス
テリシスが大きい、例えは、ＴｉＣｏｏ、ｓ　Ｍｎｏ、
ｓの合金では、水素吸蔵圧が１５０°Ｃで約１０気圧で
あるの°に対し水素放出圧は約３気圧であり、ヒステリ
シスは約７気圧もある。そのため水素吸蔵、放出を行う
に当っては、水素吸蔵合金又りその金属水素化物を大き
な温度差でθ１１熱又は冷却するか、或いは大きな圧力
差で水素加圧又は減圧を行なわなければならず、せっか
くの水素貯蔵能力や水素化反応熱も有効に活用すること
ができない。However, these @? t requires high temperature and high pressure for activation, and is easily affected by the influence of Mizuki Shinsei, and the difference between hydrogen storage pressure and hydrogen b (high pressure, that is, hysteresis is large, e.g. , TiCoo, s Mno,
In the alloy No. s, the hydrogen storage pressure is about 10 atm at 150°C, whereas the hydrogen release pressure is about 3 atm, and the hysteresis is about 7 atm. Therefore, in order to absorb and release hydrogen, it is necessary to heat or cool the hydrogen storage alloy or its metal hydride with a large temperature difference, or to pressurize or depressurize hydrogen with a large pressure difference. The precious hydrogen storage capacity and hydrogenation reaction heat cannot be used effectively.

ところが上記Ｔ１Ｃｏ＋−，＋Ａａの一部を前記金属Ｂ
１即ちＮｂ　＋　Ｍｏ　、　Ｖ　＋　Ｚｒ及び希土類元
素で１〜．押したり、或いは金ｍＢを追加すると、ヒス
テリシスを大幅に減少させることができることが分った
。However, part of the above T1Co+-, +Aa is replaced with the metal B.
1, that is, 1 to .1 for Nb + Mo, V + Zr and rare earth elements. It has been found that pressing or adding mB gold can significantly reduce the hysteresis.

即ち、本発明の水素吸蔵特性＠はＴｆ　＋　Ｃｏ及び金
−Ａよりなる三元糸合金罠前記Ｂを置換的若しくは追加
的に配合したものでＴ１Ｃｏ＋−ｘＡｙＢｚの一般式で
表わすことができる。That is, the hydrogen storage properties of the present invention can be expressed by the general formula T1Co+-xAyBz, which is a ternary thread alloy trap consisting of Tf + Co and gold-A, with the above-mentioned B being substituted or additionally blended.

たたし、ｉ（７中Ｘは０．０１〜０．５．ｙは０．０１
　’−０，５。Tatami, i (X in 7 is 0.01 to 0.5, y is 0.01
'-0,5.

２は０．２以ト（θヶ除く）であり、これらは１．０６
（１−ｘ＋３／＋ｚ）５１．２の関係を満足するものと
する。2 is 0.2 or more (excluding θ), and these are 1.06
It is assumed that the relationship (1-x+3/+z)51.2 is satisfied.

ここでＸ、又けｙが０．５を越えると吸蔵水素の放出が
困雌になり、高温加Ｍ或いは真空加熱（又は若干の減圧
加熱）の条件下でなければスムーズな放出が行われなく
なる。また、２が０．２を越えると合金の水素吸蔵鋼・
が減少したり、水素吸蔵、放出圧曲線のプラトー城が２
段状になる傾向が現われる。また２はｙより小さいこと
が好ましく、ｘ＝ｙであるときの２の好ましい範囲ｈｏ
〜０．１（但し０は除く）のゆ１」、囲である。Here, if X and y exceed 0.5, it becomes difficult to release the stored hydrogen, and smooth release will not occur unless under high temperature M or vacuum heating (or slightly reduced pressure heating) conditions. . In addition, if 2 exceeds 0.2, the hydrogen storage steel of the alloy
decreases, and the plateau castle of the hydrogen absorption and release pressure curves increases.
A step-like tendency appears. Also, 2 is preferably smaller than y, and the preferable range of 2 when x=y is ho
~0.1 (excluding 0).

上記ｘｌ）’ｌｚの好適範囲から、Ｔ１Ｃｏ＋−ａＡａ
合金の一部を金ｊＪｍＢで置換する場合番コ、Ｔ１Ｃｏ
＋−ｘＡｙＢｚにおいてｘ＝（ｙ＋ｚ）、ｙ≧２の関係
が成立し、（１−ｘ　＋　Ｙ　＋　ｚ　）　＝　１とな
る。また’１”ｉＣｏ＋−＊Ａａ合金に金属Ｂを添加す
る場合をよ、Ｔｉ　Ｃｏ＋−ｘＡｙＢｚにおいてＸ＝）
’ｌ　）’≧２の関係が成立し、２はＯ〜０．１（Ｏを
除く）であるから、これらの関係は１．０＜（１−ｘ十
ｙ＋ｚ）≦１，１となる。From the preferred range of xl)'lz above, T1Co+-aAa
When part of the alloy is replaced with gold jJmB, T1Co
In +-xAyBz, the relationship x=(y+z) and y≧2 holds true, and (1-x + Y + z) = 1. Also, when adding metal B to '1'' iCo+-*Aa alloy, X=) in TiCo+-xAyBz
Since the relationship 'l)'≧2 is established, and 2 is O to 0.1 (excluding O), these relationships are 1.0<(1-xy+z)≦1,1.

同、上記では金属Ｂを置換的に加える場合と追加的に加
える場合の典型的な例を示したが、これらの両名にまた
がる範１ｔ、ｆ＋で金ｍＢを加えることも勿論可ｈヒで
ある。Similarly, the above shows typical examples of adding metal B substitutively and adding it additionally, but of course it is also possible to add gold mB in the range 1t, f+ that spans both of these. be.

このように、Ｔ１Ｃｏ＋−ａＡａ合金に適蟻の金帆Ｂを
カロえることによって、例えばＴｉＣｏｏ、ｓ　Ｍｎｏ
、ｓ合金のヒステリシスが前述の如＜１５０°Ｃで約７
気圧であるものが、ＴｊＣｏｏ、ｓ　Ｍｎｏ、ｓ　Ｚｒ
ｏ、ｏｓ金合金約２気圧、Ｔｉｅｏｏ、ｓＭｎｏ４ｓＶ
ｏ、ｏｓ金合金約３気圧となり、ヒステリシスはベース
合金の捧以下に低減する。In this way, by adding a suitable ant, Kinho B, to the T1Co+-aAa alloy, for example, TiCoo, s Mno
, the hysteresis of the s-alloy is about 7 at <150°C as mentioned above.
The atmospheric pressure is TjCoo, s Mno, s Zr
o, os gold alloy approximately 2 atm, Tieoo, sMno4sV
The o, os gold alloy has a pressure of about 3 atmospheres, and the hysteresis is reduced to less than that of the base alloy.

本発明合金の製造法は何ら制御Ｎｉ場されず公知の方法
をすべて適用できるが、最も好ましいのは一アーク溶融
法である。即ち、Ｔｉ、Ｃｏ＋金川Ａ用び金属Ｂの各元
素を朽゛Ｊ↓ｙして混合した後、任慧の作ｋ　￥Ｋ　Ｉ
ｔＣ７レス成形し、次いでこれトアーク溶融炉ＶＬ段大
して不活性雰囲気で力１１熱溶障駿することにより容易
に夷造することができる。The method for producing the alloy of the present invention is not controlled in any way and all known methods can be applied, but the most preferred method is the one-arc melting method. That is, after mixing each element of Ti, Co + Kanagawa A and metal B, Renhui's production k ￥K I
It can be easily fabricated by forming a tC7 resin and then melting it in a high-temperature arc melting furnace VL stage in an inert atmosphere.

このようにしてＭたチタン−コノ＜ノしト多元系水素吸
ｉｔ用住金１１表面積を拡大し７水素１教蔵自ヒ力を’
ｈｙめる為に粉末状にして使用するＣ）力（よい。In this way, we expanded the surface area of the multi-component hydrogen absorbing metal 11 and increased the hydrogen absorption capacity of the multi-component titanium alloy.
C) Force (good) used in powder form for hydration.

このようにして旬た粉末状の水素１＆　＃、　７月合金
後は大量の水素を比較的低い温度及び圧力で負速に吸蔵
し且つ放出する。例えば上記合金粉末を適当な容器に充
填し、桔圧下２００°Ｃ以下の温度で脱ガス処理して活
性化を行なった後、室温以上の温場二で水素を封入し、
例えば４０”／ｄ以下の水素圧を印加することにより、
数分以内でほぼ飽和状態まで水素を吸蔵させることがで
きる。In this way, after the powdered hydrogen is mixed, a large amount of hydrogen is absorbed and released at a negative speed at a relatively low temperature and pressure. For example, the above-mentioned alloy powder is filled into a suitable container, degassed and activated at a temperature of 200° C. or less under pressure in a container, and then hydrogen is enclosed in a temperature field above room temperature.
For example, by applying a hydrogen pressure of 40"/d or less,
Hydrogen can be absorbed to almost saturation within a few minutes.

また、この金属水素化物からの水素の放出は、該水素化
物を室温以上に加熱するか、わずかに減圧し或いは双方
を組み合わせ゛Ｃ実施することにより、短時間で効率良
く行なうことができる。Further, hydrogen can be released efficiently from the metal hydride in a short time by heating the hydride to a temperature above room temperature, slightly reducing the pressure, or a combination of both.

本発明のチタン−コバルト多元糸水素吸賦用合金は概略
以上のように構成されており、後述する実施例でも明ら
かにする如く水素吸ａｎ料として襞求される諸性能を全
て具備するものであり、特に水素吸蔵・放出圧のヒステ
リシスは佐来の水素吸蔵用合金に比べて大幅に改善され
ている。The titanium-cobalt multi-fiber hydrogen absorbing alloy of the present invention is roughly constructed as described above, and as will be clear from the examples described below, it has all the performances required as a hydrogen absorber. In particular, the hysteresis of hydrogen storage and release pressure is significantly improved compared to Sarai's hydrogen storage alloy.

しかもこの合金は活性化が極めて容易であり、太細の水
素を密ｊ８−高く吸蔵し得ると共に水素の吸相・放出反
応が完全に可逆的に行なわれ、吸藤、と放出を（”Ｉ　
ｌ！！Ｉ紗り返１−ても合金自体の劣化は実Ｔ（的に認
められず、史には酸素、窒素、アルゴン、炭晒カスのよ
うな小細ぜカスによる影響が殆んどない等の諸物件を有
しており、理想的な水素吸蔵用合金と河うことができる
。従って本来の水素貯蔵Ｈ料としての用途はもとより、
水素吸蔵・放出反応に伴う反１ｂ熱を利用する他の用途
に７１しても卓越した引］嚇を発弾−する。In addition, this alloy is extremely easy to activate and can absorb hydrogen in thick and thin particles with a high degree of density, and the hydrogen phase absorption and release reactions are completely reversible.
l! ! Even if the alloy itself is recycled, no deterioration of the alloy itself is observed in reality. It has various properties and can be used as an ideal hydrogen storage alloy.Therefore, it can be used not only as a hydrogen storage material, but also as a hydrogen storage material.
It also provides an outstanding threat to other applications that utilize the anti-1b heat associated with hydrogen absorption and desorption reactions.

次に本発明の実ＩＱ例を示す。Next, an actual IQ example of the present invention will be shown.

夾かＩｊ例１ 市販のｉ’ｉ　、　Ｃｏ　、金ＪＲＡ　（Ａ／　ｌ　Ｃ
ｒ　＋　Ｃｕ　ｌ　Ｆｅ　＋Ｍｎ又はＮｉ）及びＱＩＱ
Ｂ　ＣＮｂ、Ｍｏ、Ｖ、Ｚｒ又はＭｍ（ミツシュメタル
）〕をノω、予圧でＴｉ：Ｃｏ：Ａ：Ｂ＝１：Ｏ１５：
　０．５　：　０．０５となるように分取し、これを高
真空アーク溶解炉の銅製るつは内に装入（〜、炉内を畠
糾（匿アルゴン雰囲気とした後、斧’Ｊ　２０００　”
Ｃで加熱溶解し放冷してＴｉ　ＣＯｏ、８　Ａｏ、５　
Ｂｏ、０５（世し、Ａ及びＢは上記金属を夫々１　＋１
１ずつ含翁するもの）よりなる組成の合金を製造した。Ij Example 1 Commercially available i'i, Co, gold JRA (A/l C
r + Cu l Fe + Mn or Ni) and QIQ
B CNb, Mo, V, Zr or Mm (Mitshu Metal)] with preload Ti:Co:A:B=1:O15:
0.5: 0.05, and charged it into a copper crucible of a high vacuum arc melting furnace. 2000”
Ti COo, 8 Ao, 5 was dissolved by heating with C and allowed to cool.
Bo, 05 (Serial, A and B are each of the above metals 1 + 1
An alloy having a composition consisting of (containing 1 manganese) was produced.

ｒ＾Ｊ、　Ｍｍとけ希土類元素混合物にＦｅ　ｒ　Ｍｇ
　＋　Ａ’及び＄１等の不純物の少量含有する混合金属
である。r^J, Fe r Mg in Mm melt rare earth element mixture
+ It is a mixed metal containing small amounts of impurities such as A' and $1.

得られた各合金を１２０メツシュ全通に粉砕し、その５
．０２をステンレス製水素吸幇・放出反応器に採取し、
反応器を排気装置に接続して減圧下の室温にて脱ガスを
行なった。次いで器内に純度９９．９９９チの水素を導
入し水素圧を４０Ｋｇ７′ｃｄ以Ｆに保持し、１００〜
２００℃に加熱すると直ちに水素の吸蔵が起こった。Each of the obtained alloys was ground into 120 mesh pieces, and 5
．． 02 was collected in a stainless steel hydrogen absorption/release reactor,
The reactor was connected to an exhaust system and degassed at room temperature under reduced pressure. Next, hydrogen with a purity of 99.999% was introduced into the vessel, and the hydrogen pressure was maintained at less than 40 kg 7' cd.
Upon heating to 200°C, hydrogen storage occurred immediately.

水素の吸蔵が完了した後、掬び排気して水素の放出を行
ない、活性化処理を完了した。その後膣反応器に純度９
９．９９９％の水素を字部以上の瀞ｍ、４０Ｋｇ／ｃｄ
以下の圧力で導入し、水素の吸蔵を行なった。次いで行
なわれる水素の放出は、反応器の加熱或いは減圧又はこ
れらを組み合わせることによって行なう。After hydrogen storage was completed, it was scooped out and evacuated to release hydrogen, completing the activation process. Then into the vaginal reactor purity 9
9.999% hydrogen above the character part, 40Kg/cd
Hydrogen was absorbed by introducing the gas at the following pressure. The subsequent release of hydrogen is carried out by heating or depressurizing the reactor, or a combination thereof.

上記の方法で夫々のチタン−コバルト多元系水素吸蔵合
金の水素吸蔵・放出に及はす圧力一温度の関係を求めた
。Using the method described above, the pressure-temperature relationship affecting hydrogen storage and release of each titanium-cobalt multi-component hydrogen storage alloy was determined.

その−例としてＴＩＣｏｏ、ｓＭｎｏ５Ｚｒｏ、ｏ５−
　）（系について圧力の９ｊＪ数−絶対温域の逆数で表
わしたのが第１図であり、直線Ａが水素吸紙Ｆモ、１ｉ
ｐνＢが水素放出圧である。Examples include TICoo, sMno5Zro, o5-
) (Figure 1 shows the system expressed as the 9jJ number of pressure - the reciprocal of the absolute temperature range, and the straight line A is the hydrogen absorption paper Fmo, 1i
pνB is the hydrogen release pressure.

また点線で不し１ζ比較例は、Ｔｉ　ＣＯｏ、５　Ｍｎ
ｏ５の組成を廟する三元系水素吸紙合金を用いた場合の
圧カー滉度髪図であり、点倒へ′が水＊吸厭庄、点卿Ｂ
′が水素放出圧である８ 與１図からも明らかなように本発明の合金は、比較例に
示した従来の水素吸蔵用合金に比べてヒステリシスが大
幅に改着されている。Comparative examples with 1ζ indicated by the dotted line are Ti COo, 5 Mn
This is a pressure curve diagram when using a ternary hydrogen-absorbing paper alloy with the composition of
8 where ' is the hydrogen release pressure.As is clear from Figure 1, the hysteresis of the alloy of the present invention is significantly improved compared to the conventional hydrogen storage alloy shown in the comparative example.

−また下配第１六目上記で掛た代表的な各合金の水素１
内蔵、―を示したもので、セＪ１来の合金（試料、４６
１６〜〕ぢ２１）と比べて水素吸＃、州もほとんど１ｄ
Ｉ等であった。- Also, the hydrogen 1 of each representative alloy multiplied above in the lower 1st 6th
Built-in, - is shown, alloy from SE J1 (sample, 46
16~] Compared to J21), the hydrogen absorption # is almost 1d.
It was I etc.

夷師例２ 実７７ｉ５　＄１１と同様の方法でＴｉ　ＣＯｏ、３　
Ａｏ、４５　ＢＯ０５（金臓Ａ及び金）ｕ、　Ｒは実施
ｆｌｌ　１と同様の金属を用し）た）を幻】′へして粘
性化し、水素の吸紙・放出実１刊をイエない、名合金に
ついて水素吸紙・放出に及Ｆ９す圧力一温度の関係に求
めた。Yishi Example 2 Ti COo, 3 using the same method as Mi77i5 $11
Ao, 45 BO05 (metal A and gold u, R used metals similar to those used in 1) were made into phantom]' to make them viscous, and hydrogen absorption and release were not possible. The relationship between pressure and temperature at F9 for hydrogen absorption and release was determined for a famous alloy.

その−例としてＴＩＣｏｏ、ｓＭｎｏ４５Ｖｏ、ｏ５Ｈ
系について圧力の対数−絶対温度の逆数で表わしたのが
第２図であり、直＃Ｃが水素吸蔵圧、ｌｉ！を紳りが水
素放出圧である。Examples include TICoo, sMno45Vo, o5H.
Figure 2 shows the system expressed as the logarithm of pressure - the reciprocal of absolute temperature, where direct #C is the hydrogen storage pressure, li! is the hydrogen release pressure.

また点線で示した比較例は、ＴｉＣｏｏ５Ｍｎｏ、ｓの
組成を有する三ツし系水素吸蔵合金を用いた場合の圧カ
一温度線図であり、点線Ｃ′が水素吸献圧、点纏Ｄ′が
水素放出圧である。In addition, the comparative example shown by the dotted line is a pressure-temperature diagram when using a Mitsushi hydrogen storage alloy having the composition of TiCoo5Mno,s, where the dotted line C' is the hydrogen adsorption pressure, and the dotted line D' is the hydrogen release pressure.

第２図からも明らかなように本発明の合金は、比較例の
従来合金に比べてヒスプリシスが大幅に改善されている
。As is clear from FIG. 2, the alloy of the present invention has significantly improved hysteresis compared to the conventional alloy of the comparative example.

斗た下配第２表は上記で（４だ代表的な各合金の水素吸
＃、州を示したもので、従来の合金（試料／５６３８〜
Ａ４３）に比べて水素吸＃、量もほとんど同等であった
。　　　　　（本Ｉ′！以Ｙ余白）第　　　　１　　　
　表 第　　　　２　　　　表 ４し１而の簡、４Ｌな四明 第１図及び第２図は本発明に係るチタン−コバルト多元
糸水素吸蔵用合金と従来の合金の水素収蔵・放出に及は
すＦ（−力一温度の関係を示す１！−４＋である、 ％打出、！ｉ人　　　二１−螢技休「院Ｊ〉　　　　　
イ１　　サえ　　れ成　−和定代理人　　工業技術院大
阪上業枝山試−所長内バか−υＪTable 2 shows the hydrogen absorption number and state of each representative alloy as shown above (4).
Compared to A43), the number and amount of hydrogen absorption were almost the same. (Book I'! After Y margin) Part 1
Table 2 Table 4 shows the results of hydrogen storage and release in the titanium-cobalt multi-fiber hydrogen storage alloy according to the present invention and the conventional alloy. (1!-4+, which shows the relationship between -force and temperature, % Uchide,!i people 21-Hotaku Gikyu ``In J〉
I1 Sae Renari - Wasada representative Agency of Industrial Science and Technology Osaka Kamigyo Edayama exam - Director Naibaka - υJ

Claims (1)

【特許請求の範囲】 １、一般式がＴ１Ｃｏ、□ＡＶＢｚで示されることを特
色とするチタン−コバルト多元系水素ｌＰＪ、Ｍ用合金
。たたし、式中Ａはアルミニウム、クロム。 銅、鉄、マンガンまたはニッケル、Ｂはニオブ。 モリブデン、バナジウム、ジルコニウムまたけ希土類元
素であり、ｘ＝０．０１〜０．５　、　ｙ＝　０．０１
〜（１，５、ｚ　５０．２で、かつ１．０−？−、ｌ−
ｘ＋ｙ＋ｚト、１２である。たたし、ｚ＝０を除く。 ２、　　ｘ＝ｙ＋ｚのとへ、ｙ　＞　ｚであるｉｆｌ　
Ｍｅ　％ｆＦ　ａｈ求のφ１゛シ曲第１墳記載のチタン
−コバルト多元系水素吸蔵用合金。 ３、ｘ＝ｙのとへｙ≧２で、かつＺ　Ｓ　０．１である
＋ｊｉＪＲα！）ケＷ＋Ｒ１′Ｉ求の甲り間第１項Ｈ己
載のチタン−コバルト多元系水素吸蔵用合金。ただし、
２二〇を除く。[Claims] 1. A titanium-cobalt multi-component hydrogen lPJ, M alloy characterized by having the general formula T1Co, □AVBz. However, A in the formula is aluminum and chromium. Copper, iron, manganese or nickel, B is niobium. It is a rare earth element that spans molybdenum, vanadium, and zirconium, x = 0.01 to 0.5, y = 0.01
~(1,5, z 50.2 and 1.0-?-, l-
x+y+zt, 12. t, excluding z=0. 2. If x = y + z, if y > z
Me%fF ah The titanium-cobalt multi-component alloy for hydrogen storage described in the φ1゛ curve No. 1. 3. Since x=y, y≧2 and Z S 0.1 +jiJRα! ) A titanium-cobalt multi-component hydrogen storage alloy containing W + R1'I. however,
220 is excluded.