JPS6227301A - Hydrogen occluding and releasing material having superior resistance to poisoning by impure gas - Google Patents

Abstract

PURPOSE:To improve the resistance to poisoning by impure gas by coating the surfaces of particles of a hydrogen occluding alloy with thin films of Pd, Cu or Ni permeable selectively to only hydrogen. CONSTITUTION:The surfaces of particles of a hydrogen occluding alloy represented by formula I (where A is Nb, a rare earth element or the like, k<=0.3, l<=0.3, m>=0.1 and k>m), formula II (where l<1 and k>m in case of l=0.5-0.99), formula III (where D is Zr or V, 0<n<=0.1 and k>n), formula IV, V or VI (where A is Ti, Nb or Mo, 0.4<=x<=1.0, 0<=y<=0.6, k=l+m and 0.2<=k<=0.3), formula VII (where A is Co, Cu or the like, 0.8<=k<=1.4, 0<l<2, 0<m<2, 0<n<=0.2 and 2<=2-l+m+n<=2.2), formula VIII (where 0.5<x<1.5 and 0<y<1) or formula IX (where 0<z<1 and y+z<=1) are coated with thin films of Pd, Cu or Ni to obtain the titled bydrogen occluding and releasing material.

Description

【発明の詳細な説明】 （産業上の利用分野） 本発明は水素吸蔵および放出用材料に関し、特に本発明
は耐不純ガス被毒性に優れる水素吸蔵および放出用材料
に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a hydrogen storage and release material, and particularly the present invention relates to a hydrogen storage and release material that has excellent resistance to impurity gas poisoning.

（従来の技術） 水素は原料が水で資源的な制約がないこと、クリーンで
あること、輸送・貯蔵が可能であること、自然の循環を
乱さないことから化石燃料に代る新しいエネルギー源と
して注目されている。(Conventional technology) Hydrogen is a new energy source that can replace fossil fuels because it uses water as a raw material and has no resource constraints, is clean, can be transported and stored, and does not disturb natural cycles. Attention has been paid.

しかし、水素は常温圧おいて気体であり、かつ液化温度
が極めて低いので、これを貯蔵する技術の開発が従来大
きな課題になっている。上記課題を解決する一つの方法
として水素を金属水素化物の形で貯蔵する方法が注目さ
れる。この方法は、１５０気圧の市販水素ボンベの２割
以下の容積、あるいは液体水素の８割以下の容積で同ｔ
ｉ′の水素を貯蔵することができるため、容器がコンパ
クトとなり、安全性や取扱い易さの点で極めて優れてい
る。However, since hydrogen is a gas at room temperature and pressure, and its liquefaction temperature is extremely low, the development of technology to store it has been a major challenge. As one method for solving the above problems, a method of storing hydrogen in the form of a metal hydride is attracting attention. This method uses less than 20% of the volume of a commercially available hydrogen cylinder at 150 atm, or 80% or less of liquid hydrogen.
Since hydrogen of i' can be stored, the container can be made compact and is extremely superior in terms of safety and ease of handling.

さて、金属または合金と水素の吸蔵・放出反応は可逆的
であり、水素の貯蔵に利用されるだけでなく、反応に伴
って相当量の反応熱が発生あるいは吸収され、水素の吸
蔵・放出圧力は温度に依存することを利用して水素貯蔵
装置、水素輸送装置。Now, the hydrogen absorption/desorption reaction between metals or alloys is reversible, and not only is it used to store hydrogen, but a considerable amount of reaction heat is generated or absorbed during the reaction, and the hydrogen storage/desorption pressure is Hydrogen storage devices and hydrogen transport devices utilize temperature dependence.

水素精製装置、蓄熱装置、ヒートポンプ、熱−機械エネ
ルギー変換装置などの広範な応用システムの開発が期待
されている。The development of a wide range of applied systems such as hydrogen purification equipment, heat storage equipment, heat pumps, and thermo-mechanical energy conversion equipment is expected.

かかる水素吸蔵および放出材料として要求されろ性質と
しては、安価でかつその資源が豊富であること、活性化
が容易で水素吸蔵量が大きいこと、使用温度において好
適な水素吸蔵・放出平衡圧を有し、吸蔵圧と放出圧との
差であるヒステリシスが小さいこと、水素吸蔵・放出反
応の速度が太きいこと、水分、酸素など不純物に対する
安定性が大きいこと、合金の微粉化が少なく耐久性にす
ぐれていること、有効熱伝導度が大きいことなどがあげ
られろ。The properties required for such a hydrogen storage and release material are that it is inexpensive and has abundant resources, that it is easy to activate and has a large hydrogen storage capacity, and that it has a suitable hydrogen storage and release equilibrium pressure at the operating temperature. However, the hysteresis, which is the difference between storage pressure and release pressure, is small, the speed of the hydrogen storage and release reaction is high, the stability against impurities such as moisture and oxygen is high, and the alloy is less pulverized and has increased durability. Examples include superior properties and high effective thermal conductivity.

代表的な公知の水素吸蔵・放出用材料としてはＭｇ２Ｎ
ｉ、　ＬａＮｉ５．　ＴｉＦｅ　すどが知うレテイル。Mg2N is a typical known hydrogen storage/release material.
i, LaNi5. TiFe Retail that everyone knows.

シカしＭｇ２Ｎｉ　ｉｆ単位重量当りの水素吸蔵量は大
きいが、水素吸蔵・放出温度が高く、この合金を多成分
化しても水素貯蔵材料として十分な性能を有するものは
いまだ得られていない。ＬａＮｉ　５は優れた水素吸蔵
・放出特性を有しているが、ランタンが高価なことが最
大の欠点である。また、ＴｉＦｅは初期の本漬化が困難
であり、活性化処理には高温・高圧（４５０Ｇ、水素圧
力５０気圧）′５ｃ必要とし、ヒステリシスも大きく、
水素吸蔵・放出を繰り返しているうちに水素吸蔵２が減
少するという欠点を有している。ＴｉＦｅにマンガン、
ニオブ、酸素、イオウなどを微量添加することによって
初期活性を改善し元合金が見い出されたが、寸だ水素吸
蔵・放出材料としての十分な性能を有していない。しか
も、ＴｉＦｅ　Ｈ水分、　　０２・Ｇｏ、　ＣＯ２’ｌ
　トが水素中に混入すると合金表面がこれらの不純ガス
によって被毒され、水素吸蔵量が大幅に減少するという
欠点があり実用上大きな問題が残っていた。Although Mg2Ni has a large hydrogen storage capacity per unit weight, its hydrogen storage and release temperatures are high, and even if this alloy is made into a multi-component alloy, no material with sufficient performance as a hydrogen storage material has yet been obtained. Although LaNi 5 has excellent hydrogen storage and desorption properties, its biggest drawback is that lanthanum is expensive. In addition, initial dipping of TiFe is difficult, and activation treatment requires high temperature and pressure (450G, hydrogen pressure 50 atm)'5c, and has large hysteresis.
It has the disadvantage that hydrogen storage 2 decreases while hydrogen storage and release are repeated. Manganese in TiFe,
The initial activity was improved by adding small amounts of niobium, oxygen, sulfur, etc., and a base alloy was found, but it does not have sufficient performance as a hydrogen storage/release material. Moreover, TiFe H moisture, 02・Go, CO2'l
When these impurity gases are mixed into hydrogen, the surface of the alloy is poisoned by these impure gases, resulting in a significant reduction in the amount of hydrogen storage, which remains a major practical problem.

上記の問題点を解決するため、特開昭５８−１０３２号
により水素吸蔵金属材料の製造方法が提案されている。In order to solve the above-mentioned problems, a method for manufacturing a hydrogen storage metal material has been proposed in Japanese Patent Application Laid-Open No. 58-1032.

この方法は、水素を吸蔵する金槌表面にメッキにより異
種金！Ａをコーティングすることを特徴とする水素吸蔵
金属材料のｌｉ！ｉ造方法である。This method uses dissimilar gold plating on the surface of the hammer that absorbs hydrogen! li!, a hydrogen-absorbing metal material characterized by being coated with A! This is an i-building method.

すなわち、活性化の困難なＴｉＦｅ　＠全表面にＮｉ。That is, TiFe, which is difficult to activate, @Ni on the entire surface.

Ｃｕ、Ｇｏなどの水素雰囲気でその酸化物が比較的容易
に還元され易い元素をメッキによりコーティングするも
のである。この方法によれば、従来活性化に４５０〜５
００Ｃの高温で、水素圧３０〜６０ＫＰ／α２で加圧、
あるいは真空排気の繰り返しの操作ｆ、１週間程度行な
う必要があったものが、２００Ｃ以下。Elements such as Cu and Go whose oxides are relatively easily reduced in a hydrogen atmosphere are coated by plating. According to this method, conventional activation requires 450 to 5
At a high temperature of 00C, pressurize with hydrogen pressure of 30 to 60KP/α2,
Or, the repeated evacuation operation f, which had to be carried out for about a week, was below 200C.

水素圧２０〜３０Ｋｇ／ｃＩＬ２で１　日以内ト、処ｆ
ＪＪＡｍＦｌ。Within 1 day at hydrogen pressure of 20-30Kg/cIL2.
JJAmFl.

水素圧力、所要時間等の面で性能が向上した水素吸蔵金
回材料の製造方法が提案されている。A method for producing a hydrogen storage material with improved performance in terms of hydrogen pressure, required time, etc. has been proposed.

（発明が解決しようとする問題点） 前記の製造方法で得られ念水素吸蔵金属材料は活性化が
容易で、水ｆ＠蔵・放出用材料として好適な平衡水素圧
を有しているが、水素吸蔵・放出用材料として要求され
る性質の中で、比較的重要な水分、酸素などにより合金
が被毒されて水素吸蔵量が減少することおよびヒステリ
シスが大キい点で、実用上問題が残されている。(Problems to be Solved by the Invention) The hydrogen storage metal material obtained by the above production method is easy to activate and has an equilibrium hydrogen pressure suitable as a material for storing and releasing water. Among the properties required for hydrogen storage/release materials, there are practical problems in that the alloy is poisoned by moisture, oxygen, etc., which is relatively important, and the hydrogen storage capacity decreases, and hysteresis is large. left behind.

ｃ問題点を解決する九めの手段） 本発明は、従来の水素吸蔵・放出用材料が有する前記諸
欠点ならびに問題点を除去、解決した材料を提供するこ
とを目的とし、特許請求の範囲記載の材料を提供するこ
と罠よって前記目的を達成することができる。c) Ninth Means for Solving Problems) The present invention aims to provide a material that eliminates and solves the above-mentioned drawbacks and problems that conventional hydrogen storage/release materials have, and the scope of the present invention is as follows: The above objective can be achieved by providing a material for the trap.

すなわち本発明は、下記ば）〜（１７）の示性式にょっ
て示す水素吸蔵用合金のいずれか１種の合金の粒子の表
面がＰｄ、　Ｃｕ、　Ｎｉのうちから選ばれるいずれか
１種の薄膜によＶ被覆されてなる耐不純ガス被毒性に優
れる水素吸蔵および放出用材料：（イ）原子数組成で示
性式がＴｉｌ＋ｋＦｅ１−２Ｎｊ４Ａｍ　　で示される
こと’に特徴とするチタン系水翼吸蔵用合金〔但し、式
中Ａ　Ｉｒｉ　Ｚｒ、　Ｎｂ、　Ｖ、希土類元素のなか
から選ばれるいずれか少なくとも１種の元素を示し、ｋ
≦０．３．ｔ≦０．３＋　　ｍ≦０．１でｋ）ｍである
〕。That is, in the present invention, the surface of the particles of any one of the hydrogen storage alloys represented by the following formulas (1) to (17) is one selected from Pd, Cu, and Ni. Hydrogen storage and release material with excellent impurity gas poisoning resistance coated with a thin film of: (a) A titanium-based water blade characterized in that its atomic composition has the characteristic formula Til+kFe1-2Nj4Am. Storage alloy [However, in the formula, A represents at least one element selected from among Zr, Nb, V, and rare earth elements, and k
≦0.3. t≦0.3+ m≦0.1 and k)m].

仲）原子数ｍｃで示性式がＴｉｔ＋ｋ　Ｆｅ１−７ｃＯ
７Ａｍで示されることを特徴とするチタン系水素吸蔵用
合金〔但し、式ｃｐＡＶｉｚｒ、　Ｎｂ、　Ｖ、希土類
元素のなかから選ばれるいずれか少なくとも１種の元素
を示し、ｋ≦０．３．　ｔ＜１．０．　ｍ≦ｏ、ｌであ
り、ｔ＝０．５〜０．９９なるときｋ＞ｍで６る）。Middle) The specific formula is Tit+k Fe1-7cO with the number of atoms mc
A titanium-based hydrogen storage alloy characterized by having the formula cpAVizr, containing at least one element selected from Nb, V, and rare earth elements, and k≦0.3. t<1.0. When m≦o, l, and t=0.5 to 0.99, k>m (6).

ＨＤＫ子数子機ｉｉテ示性式がＴｉｘ＋ｋＦ８１−７Ｍ
ｎｚ　Ｄｎ　で示されるチタン系水素１汲蔵用合合〔但
し、ＤはＺｒ、　　ｖの少なくとも１種からなる元素を
示し、０＜ｋ≦０．３　　、　　Ｏ＜ｌ≦０．３．　０
＜ｎ≦０．１ｋ＞ｎである〕。HDK child number machine II Te indication formula is Tix+kF81-7M
A combination of titanium-based hydrogen 1 and storage represented by nzDn, where D represents an element consisting of at least one of Zr and v, and 0<k≦0.3, O<l≦0.3. 0
<n≦0.1k>n].

に）原子数組成で示性式がＴｉ　１　＋ｋＦｅ　１−１
　Ｍｎｚ　Ａ＠で示されるチタン系水素吸蔵用合金〔但
し、ＡはＮｂ、希土類元素の少なくとも１種からなる元
素ヲ示シ、Ｏ：！；　ｋ　≦０．３　、　　Ｏ＜　ｔ　
≦０．３　、　　Ｏ＜　ｍ≦０．１である。〕。) The specific formula in terms of atomic composition is Ti 1 +kFe 1-1
Mnz A titanium-based hydrogen storage alloy represented by A@ [However, A represents an element consisting of at least one of Nb and rare earth elements, O:! ; k≦0.3, O<t
≦0.3, O<m≦0.1. ].

（ホ）原子数組成で示性式がＴｉ１＋ｋＦｅ１　−１Ｍ
ｎｚＡＢＤｌで示されるチタン系水！８吸蔵用合金〔但
し、ＡはＮｂ、希土類元素の少なくとも１種からなる元
素であり、ＤはＺｒ、Ｖの少なくとも１種からなる元素
を示し、０≦ｋ≦０．３．０＜ｌ≦０．３、０＜ｍ≦０
．１である〕。(e) The specific formula in terms of atomic composition is Ti1+kFe1 -1M
Titanium water indicated by nzABDl! 8 Storage alloy [However, A is an element consisting of at least one of Nb and rare earth elements, D is an element consisting of at least one of Zr and V, and 0≦k≦0.3.0<l≦ 0.3, 0<m≦0
．． 1].

（へ）原子数組成で示性式がＺｒｙＡｙ　（Ｆａｔ−ｋ
Ｖｚ　ｃｒｍ）２で示されること？、特徴とするジルコ
ニウム系水素吸蔵用合金〔但し、式中人はＴｉｔ　Ｎｂ
ｅ　Ｍｏ　のなかから遷ばれるいずれか少なくとも１種
の元素を示し、０．４≦ｘ≦１．０、０．６．に＝Ｌ十
ｍ　ｒ　　０．２　≦ｋ　≦０．３　テあり、且つｙ＝
００ときはｍ＞ｏである〕。(f) The specific formula is ZryAy (Fat-k
What is indicated by Vz crm)2? , a zirconium-based hydrogen storage alloy characterized by TitNb
e represents at least one element selected from Mo, 0.4≦x≦1.0, 0.6. = L0m r 0.2 ≦k ≦0.3 Te exists, and y=
00, m>o].

（ト）原子数組成で示性式力”ｙ　ＴｉｋＣｒ２−７Ｖ
ｍＡｎで示される水素吸蔵用合金〔但し、式中人はｃｏ
、　Ｃｕ・Ｎｂ、希土類元素、Ｚｒのなかから選ばれる
いずれか少なくとも１種の元素を示し、０．８≦ｋ≦１
．４゜０＜ｌ＜２．０＜ｍ＜２．０＜ｎ≦０．２゜２．
０≦２−ｔ＋ｍ＋ｎ　≦２．２である〕。(G) Expressive force "y TikCr2-7V with atomic number composition"
Hydrogen storage alloy shown in mAn [however, the formula middle person is co
, indicates at least one element selected from Cu/Nb, rare earth elements, and Zr, and 0.8≦k≦1
．． 4゜0<l<2.0<m<2.0<n≦0.2゜2.
0≦2−t+m+n≦2.2].

（１）原子数組成で示性式がＺｒ）（（Ｍｎｌ　−ｙ　
”ｙ　）２で示されるジルコニウム系水素吸蔵用合金〔
但し１式％式％ （男　原子数組成で示性式がＺｒ）（（）ａｎ　ｔ　−
ｙ−ｚ　ＶｙＦｅｚ　）　２で示されるジルコニウム系
水素吸蔵用合金〔但し、式中ｘ、　ｙ、　ｚはそれぞれ
０．５＜ｘ＜１．５ＩＯ＜Ｙ＜１．０＜Ｚ＜ｌ、ｙ＋ｚ
≦１である〕。(1) The specific formula in terms of atomic composition is Zr)((Mnl -y
Zirconium-based hydrogen storage alloy represented by ``y)2 [
However, 1 formula % formula % (male atomic number composition, the characteristic formula is Zr) (() an t −
Zirconium-based hydrogen storage alloy represented by y-z VyFez ) 2 [where x, y, and z are each 0.5<x<1.5IO<Y<1.0<Z<l, y+z
≦1].

本発明者らは、前記特開昭５８−１０３２号記載の製造
方法てよって得られた水素吸蔵・放出用材料の問題点を
解消すべく研究し念結果、本発明の水素吸蔵・放出用材
料は、全く予期に反して水分。The present inventors conducted research to solve the problems of the hydrogen storage/release material obtained by the manufacturing method described in JP-A-58-1032, and as a result, the hydrogen storage/release material of the present invention was found. It's completely unexpectedly moist.

酸素などによる合金被毒によって水素１汲蔵黛が減少す
ることなく、シかもヒステリシスが小さくなるとともに
、上記の水素吸蔵・放出用材料とじて要求さノｔろ性′
ｊ／をすべて具備しており、水素吸蔵・放出用材ｒ）と
して新規にして極めて有用なものであることを見出し、
ここに本発明を完成するに至り几。The hydrogen storage capacity is not reduced due to alloy poisoning by oxygen, etc., the hysteresis is reduced, and the above-mentioned hydrogen storage/release material has the required low-temperature properties.
We discovered that it is a new and extremely useful material for hydrogen storage and release, as it has all of the following:
We have now completed the present invention.

本発明の水素吸蔵・放出用材料は、上記（イ）〜（１ハ
の示性式によって示す水素吸１＠用合金のいずれか１種
の合金粒子の表面に、水素のみを選択的に透過しゃすい
Ｐｄ、　Ｃｕ、　Ｎ工などのうちから選ばれたいずれか
１種の薄膜によりＶ１覆するものである。The hydrogen absorbing/desorbing material of the present invention selectively permeates only hydrogen onto the surface of the alloy particles of any one of the hydrogen absorbing 1@ alloys shown by the equations (a) to (1c) above. The V1 is covered with a thin film of any one selected from transparent Pd, Cu, N, etc.

水分、ｌ！２素などによる合金被毒を少なくし、ヒステ
リシスが小さくなる理由は、薄膜を形成する金＠　Ｐｄ
、　０１１．　Ｎｉなどが水素分子のみを原子状態に解
離して全日内部に侵入させ、水素のみを内部の（イ）〜
Ｑハの示性式に示す水素吸蔵用合金に吸蔵されることに
よるものと考えられろ。従来の水素吸蔵用合金２例えば
ＴｉＦｅ表面がＮｉによりメッキされた材料では、水分
ｔｏｏｏ　ｐ＞ｍ　＝２含有する水素を用いると０．７
重量％の水素を吸蔵し、４０Ｃにおいて水素吸蔵量が約
１５気圧、水素放出圧は約７気圧であり、ヒステリシス
は約８気圧と極めて大きく、このＴｉＦｅ材料の本来の
水素吸蔵量１．０　ｆｆ１ｆ！　％より大幅に減少する
ばかりでなく、ヒステリシスも大きくなる。ヒステリシ
スが大きいと、水素吸蔵。Moisture, l! The reason why the alloy is poisoned by elements such as 2 and the hysteresis is reduced is because gold@Pd forms a thin film.
, 011. Ni etc. dissociate only hydrogen molecules into atomic state and allow them to enter the interior all day long, leaving only hydrogen inside (a) ~
This is thought to be due to the fact that hydrogen is stored in the hydrogen storage alloy shown in the characteristic equation of Qc. Conventional hydrogen storage alloy 2 For example, in a TiFe material whose surface is plated with Ni, when hydrogen containing water too p>m = 2 is used, 0.7
% by weight of hydrogen, and at 40C, the hydrogen storage capacity is about 15 atm, the hydrogen release pressure is about 7 atm, and the hysteresis is extremely large at about 8 atm, and the original hydrogen storage capacity of this TiFe material is 1.0 ff1f. ! %, and the hysteresis also increases. If the hysteresis is large, hydrogen will be absorbed.

放出の操作をする九めに、水素吸蔵用合金もしくはその
金属水酸化物をより大きな温度差で加熱・冷却しなけれ
ばならず、あるいはより大きな圧力差で水欝加圧・減圧
しなければならないため、水素貯蔵能力、水素化反応熱
を有効に利用することができなくなる。To carry out the release operation, the hydrogen storage alloy or its metal hydroxide must be heated and cooled with a larger temperature difference, or the water must be pressurized and depressurized with a larger pressure difference. Therefore, hydrogen storage capacity and hydrogenation reaction heat cannot be used effectively.

本発明の材料において、原子数組成で（イ）〜（’Ｊ）
の示性式を特許請求の範囲のように定め之理由は下記の
通りである。In the material of the present invention, the atomic composition is (a) to ('J)
The reason for defining the demonstrative formula as in the claims is as follows.

（イ）　ＴＬｔ＋ｋＦｅｘ−ｚＮｉｚＡｍにおいて、ｋ
が０．３より大きいと熱力学的に不均化を生起し易く、
高温にならないと解離しないＴｉＨ２が生成する之め水
素吸蔵・放出だが少なくなり、プラトーの傾斜が大きく
なるので、ｋは０．３以下にする必要がある。まｆｃｔ
が０．３より大きいと吸蔵された水素の放出が困難とな
り、高温にするか、もしくは減圧あるいは真空下での加
ｙＡＸＫ、よらなけれは円滑な水素放出を達成できなく
なるので、ｔは０．３以下にする必要がある。ｍが０．
１より大きいと水素吸蔵量が減少し、さらに水素吸蔵・
放出曲線におけるプラトー域が２段状になり、ヒステリ
シスも大きくなる傾向が現われるので、ｍは０．１以下
にする必要がある。(b) In TLt+kFex-zNizAm, k
is larger than 0.3, thermodynamic disproportionation tends to occur,
Since TiH2, which does not dissociate unless the temperature is high, is produced, hydrogen absorption and release are reduced, and the slope of the plateau becomes large, so k needs to be set to 0.3 or less. fct
If t is larger than 0.3, it becomes difficult to release the occluded hydrogen, and smooth hydrogen release cannot be achieved unless the temperature is raised or pressure is reduced or vacuum is applied. Therefore, t is 0.3. It is necessary to do the following. m is 0.
If it is larger than 1, the amount of hydrogen storage decreases, and even more
Since the plateau region in the release curve becomes two-stepped and the hysteresis tends to increase, m needs to be 0.1 or less.

（ロ）Ｔｉｔ＋ｋＦ６１−ｚｃＯｚＡｍにおいて、ｋが
０．３より大きいと熱力学的に不均化を生起し易く、高
温にならないと解離しないＴｉＨ２が生成するため水素
吸蔵・放出量が少なくなり、プラトーの傾斜が大きくな
るのでｋは０．３以下にする必要がある。また、ｍは０
．１エリ大きいと水素吸椴凰が減少し、プラトー域が２
段状になり、ヒステリシスも大きくなる傾向が現われる
のでｍは０．１以下にする必要がある。(b) In Tit+kF61-zcOzAm, if k is larger than 0.3, disproportionation tends to occur thermodynamically, and TiH2, which does not dissociate unless it becomes high temperature, is generated, so the amount of hydrogen absorption and release decreases, and the plateau occurs. Since the slope becomes large, k needs to be 0.3 or less. Also, m is 0
．． If the area is larger by 1 area, the hydrogen absorption capacity will decrease and the plateau area will increase by 2.
There is a tendency for the layer to become step-like and the hysteresis to increase, so m needs to be set to 0.1 or less.

（ハ）　Ｔ１１＋ｋＦｅ’！−４ＭｎｔＤｎ　＋　に）
Ｔ１１＋ｋＦｅｔ　、ｚｊＪｎｚＡＢ　＋（ｆ９　Ｔ１
１＋ｋＦｅｔ−ｌＭｎｌＡｍＤｎ　　において、ｋが０
．３より大きいと熱力学的に不均化が生起し易く、高温
圧ならないと解離しないＴｉＨ２が生起する之め水素吸
蔵・放出量が少なくなる。またｔが０．３より大きいと
水′９吸蔵潰が低下し、しか本吸蔵され念水素の放出が
困難となり、高調にするか、もしくは減圧あるいは真空
下での加熱によらなければ円滑な水素の放出が達成でき
なくなる。ｎ、ｍがそれぞれ０．１より大きいと水素吸
蔵量が減少し之り、吸蔵水素の放出が困難になったりす
る。ｋが０．３以下のＴ１とｎ、　ｍがそれぞれ０．１
以下のり、Ａは水素吸蔵用として適した特性を株持しつ
つ水素吸蔵量を増大する念めに不可欠の成分である。(c) T11+kFe'! −4MntDn + )
T11+kFet, zzJnzAB+(f9 T1
1+kFet-lMnlAmDn, k is 0
．． When it is larger than 3, disproportionation tends to occur thermodynamically, and TiH2, which does not dissociate unless it is at high temperature and pressure, is generated, resulting in a decrease in the amount of hydrogen storage and release. Furthermore, if t is larger than 0.3, the absorption and depletion of water will be reduced, and it will be difficult to release hydrogen due to the main occlusion, and it will be difficult to release hydrogen smoothly unless the temperature is increased or by heating under reduced pressure or vacuum. release becomes impossible to achieve. If n and m are each larger than 0.1, the amount of hydrogen storage decreases, making it difficult to release the stored hydrogen. T1 where k is 0.3 or less, n and m are each 0.1
In the following, A is an essential component for increasing the amount of hydrogen storage while maintaining properties suitable for hydrogen storage.

（へ）　ＺｒｘＡｙ（Ｆｅ、−ｋＶｚＣｒｍ）２におい
て、Ｘが０．４より小さいか、ｙが０．６より大きいと
、水濡吸蔵量が低下し、プラトー域が消失し又ヒステリ
シスが大きくなるので、又は０．４以上、ｙは０．６以
下とする必要がある。ｋが０．２より小さくな、５に従
い水蕾吸蔵量が極度に減少してゆき、ｋが０．３より大
きくなるに従いプラトー域が消失し、平衡水素解離圧が
極度に低下するので、０．２≦ｋ≦０．３とする必要が
ある。(f) In ZrxAy(Fe, -kVzCrm)2, if X is smaller than 0.4 or y is larger than 0.6, the water absorption capacity decreases, the plateau region disappears, and hysteresis increases. , or 0.4 or more, and y needs to be 0.6 or less. As k is smaller than 0.2, the amount of water bud storage decreases extremely, and as k becomes larger than 0.3, the plateau region disappears and the equilibrium hydrogen dissociation pressure drops extremely, so 0. It is necessary to satisfy .2≦k≦0.3.

（ト）　　ＴｉｋＣｒ２−２ＶｍＡｎにおいて、ｋが１
．４より太きいと熱力学的に不均化が生起し易く、高温
にならないと解離しないＴｉＨ２が生成する念め吸セ水
素の放出が困難となり、高温にするか、もしくは減圧あ
るいは真空下での加熱によらなければ円滑な水素放出が
達成できなくなり、ｋが０．８より小さいと活性化が極
めて困難となるので、０．８≦ｋ≦１．４の範囲内にす
る必要がある。(G) In TikCr2-2VmAn, k is 1
．． If it is thicker than 4, disproportionation tends to occur thermodynamically, and it becomes difficult to release the absorbed hydrogen produced by TiH2, which does not dissociate unless the temperature is high. Smooth hydrogen release cannot be achieved without heating, and if k is less than 0.8, activation becomes extremely difficult, so it is necessary to keep it within the range of 0.8≦k≦1.4.

！念、ｍが２以上のときは吸蔵した水素が殆んど放出さ
れなくなるので、０＜ｍ＜２にする必要がある。ｎが０
．２より大きいと、水素吸稙丞が減少し、さらにプラト
ー域が２段状になつ之り、ヒステリシスが大きくなる傾
向が現われるので、０くｎ≦０．２にする必要がある。! Note that when m is 2 or more, almost no occluded hydrogen is released, so it is necessary to set 0<m<2. n is 0
．． If it is larger than 2, the hydrogen absorption rate will decrease, and the plateau region will become two-staged, and the hysteresis will tend to increase. Therefore, it is necessary to set n≦0.2.

υう　　　Ｚｒ）（（Ｍｎｌ−ｙＶｙ）２　　、　　（
’Ｊ）　　　Ｚｒ）（＋１．（ｎｌ−ｙ−ｚＶｙＦ８ｚ
）２において、Ｘが１．５より大きいと熱力学的に不均
化が生起し易く、高温にならないと解離しないＺｒＨ２
が生成するため水素吸蔵・放出量が少なくなる。ま几、
ｘが０．５より小さいと初期活性が困難となり、水素吸
蔵量が低下し、しかも吸蔵された水素の放出が困難とな
り、高温にするか、もしくは減圧あるいは真空下での加
熱によらなければ円滑な水素の放出が達成できなくなる
。ｙ＝１のときは、水素放出条件が室温付近で約１０−
８気圧となり、水素吸蔵用材料として取り扱１ハが困難
となる。ｙ＝ＯのときはそれぞれＺｒＭｎ２　、　Ｚｒ
）（（Ｍｎｌ−２Ｆｅｚ　）ｚ　、！：すり　、イスレ
４１．　ヒステリシスが大きくなる。Ｚ＝１のときは、
水素吸蔵量が低下し、しかも水素放出条件が室温付近で
１０−８気圧に近づくため水素吸蔵材料として取り扱い
が困難となる。２＝０のときはＺｒＸ（Ｍｎｌ−ｙＶｙ
）２　トナ’）、水ｆｆ１ａ？用材料として利用可能な
特性を有するものとなる。υU Zr) ((Mnl-yVy)2, (
'J) Zr) (+1. (nl-y-zVyF8z
)2, if X is larger than 1.5, disproportionation tends to occur thermodynamically, and ZrH2 does not dissociate unless it becomes high temperature.
is generated, reducing the amount of hydrogen absorbed and released. Well,
If x is smaller than 0.5, initial activation becomes difficult, the amount of hydrogen storage decreases, and it becomes difficult to release the stored hydrogen. hydrogen release cannot be achieved. When y=1, the hydrogen release conditions are approximately 10-
The pressure is 8 atm, making it difficult to handle as a hydrogen storage material. When y=O, ZrMn2 and Zr respectively
)((Mnl-2Fez)z,!: Slip, Issle 41. Hysteresis increases. When Z=1,
The hydrogen storage capacity decreases, and the hydrogen release conditions approach 10 −8 atm near room temperature, making it difficult to handle as a hydrogen storage material. When 2=0, ZrX(Mnl-yVy
)2 Tona'), water ff1a? It has properties that can be used as a material for industrial use.

上記の（イ）〜（す）に示性式によって示される本発明
の特許請求の範囲にある合金、かｊえばＺｒ　（Ｍｎ□
　、　ＢＶｏｌＦｅ□、　ｔ　）２合金の粒子表面にｐ
ｄの’＋５．Ｙ　！％　（約１００Ｘ）により皺覆した
材料では、水分１ｏｏｏ　ｐ＞ｍ含有する水素を用・ハ
ろと１．４重力を俤の水素を吸蔵し、水素友、改圧が１
００　Ｃで約０．０７気圧、水素放出圧が約０．０５気
圧であり、ヒステリシスは極めて小さい。Alloys within the scope of claims of the present invention represented by the formulas (a) to (s) above, such as Zr (Mn□
, BVolFe□, t) on the particle surface of the 2 alloy.
d'+5. Y! % (approximately 100X), the material absorbs hydrogen containing 100 p>m of moisture and absorbs 1.4 gravity of hydrogen, and the hydrogen concentration and pressure change are 1.
At 0.00 C, the pressure is about 0.07 atm, and the hydrogen release pressure is about 0.05 atm, so the hysteresis is extremely small.

このように本発明の水素吸蔵および放出用材料は、初め
て開発された新規な材料にして、水素吸蔵および放出用
材料として要求される緒特性をすべて具備するものであ
り、とくに水素吸蔵量は従来の水素吸蔵・放出用材料よ
り大きく、しかも水素吸蔵・放出圧のヒステリシスは従
来の水素吸蔵・放出用材料に比べて大幅に改善され、水
素吸蔵・放出用材料としての水素貯蔵能力、水素吸蔵・
放出に伴う反応熱を有効に利用することができる。As described above, the hydrogen storage and desorption material of the present invention is a new material developed for the first time and has all the characteristics required as a hydrogen storage and desorption material, especially in terms of hydrogen storage capacity compared to conventional materials. Moreover, the hysteresis of hydrogen storage and release pressure is significantly improved compared to conventional hydrogen storage and release materials, and the hydrogen storage capacity and hydrogen storage and release pressure as hydrogen storage and release materials are significantly improved.
The reaction heat accompanying the release can be effectively utilized.

しかも、水素吸蔵・放出反応の活性化が容易であり、反
応速度も極めて速く、水分、酸素などの不純ガスを含有
する水素の吸蔵・放出を繰り返しても材料の劣化はなく
、熱伝導性も向上するなど、実用上玉めで有用な水素吸
蔵・放出用材料である。Furthermore, activation of the hydrogen absorption/desorption reaction is easy, the reaction rate is extremely fast, the material does not deteriorate even after repeated absorption/desorption of hydrogen containing impure gases such as moisture and oxygen, and its thermal conductivity is low. It is a material for hydrogen storage and release that is useful in practical terms.

次に本発明材料の製造方法を説明する。Next, a method for producing the material of the present invention will be explained.

本発明材料のけ）〜（す）の示性式によって示てれろ水
素吸蔵用合金を製造するには、従来知られている水素吸
蔵用合金の製造方法によることができるが、アーク溶融
法ＶＣよることが最も好適である。In order to produce the hydrogen storage alloy shown by the equations (1) to (3) of the material of the present invention, conventionally known methods for producing hydrogen storage alloys can be used, but the arc melting method VC It is most preferable to

次にアーク溶融法による本発明材料に用・ハろ合金の製
造方法について述べろ。（イ）〜（リフの示性式に示さ
れる成分金属をそれぞれ秤取して混合した後、任意の形
状にプレス成形し、この成形体をアーク俗融炉に装入し
て不活性雰囲気下で加熱ｆＢ融し、炉内で凝固筋せて室
温１で冷却し丸後炉外に取出す。この合金を均’Ｆ（Ｋ
するため、Ｋ空容器内に装入し１Ｏ−２Ｔｏｒｒ以下の
高真空雰囲気中で１０００〜］１００Ｃ，８時間以上炉
中に保持した後、真空容器を炉外に取り出し放冷するか
、またけ真空容器を水中に投入して冷却する。その後、
合金の表面種を拡大して水２ｒｙ！！、蔵能力を高める
ため、粒径１００μｍ前後に破砕する。Next, the method for producing the halo alloy used as the material of the present invention using the arc melting method will be described. (b) ~ (After weighing and mixing the component metals shown in Riff's formula, press-form them into an arbitrary shape, and charge this molded body into an arc melting furnace under an inert atmosphere. The alloy is melted by heating at fB, solidified in the furnace, cooled to room temperature 1, and then taken out of the furnace.
In order to Place the vacuum container into water and cool. after that,
Enlarge the surface species of the alloy and use water 2ry! ! In order to increase the storage capacity, the grains are crushed to a particle size of around 100 μm.

合金の表面をＰｄ、　Ｇｕ、　Ｎｉのうち１種の金属の
薄膜により被覆するには、従来知られている無電解メッ
キ法、Ｘ空蒸Ｎ法、電解メッキ法のいずれかによること
が好適である。あらかじめ粒径１００μｍ前後のＡｉＪ
記（イ）〜（す）の示性式によって示てれる水素吸蔵用
合金粒子の表面に無電解メッキ、真空蒸着あるいは電解
メッキにより厚さ１００〜１０００　Ａ前後のＰｄ、　
ＣｕあるいはＮ１のうち一種の金属の薄膜全形成させた
ものである・こ０薄膜０形成１２つて合金自体の水素吸
蔵能が損われ６　コトｔ−ｘ　、ｔ　＜ゝ最初に水素を
吸蔵させるための活性能処理も金属の薄膜により被覆さ
れていないものと同程度あるいはより緩やかな条件で行
うことができろｏまたＮ形成１れたＰｄ、　Ｃｕ、　Ｎ
ｉのうち一種の金属のね重膜は水素ガスの透過に十分な
大きさの原子間間隙を有しておシ、水素吸蔵速度の低下
はほとんど認められない。In order to coat the surface of the alloy with a thin film of one of the metals selected from Pd, Gu, and Ni, it is preferable to use any of the conventionally known electroless plating method, X-evaporation N method, or electrolytic plating method. be. AiJ with a particle size of around 100 μm in advance
Pd with a thickness of about 100 to 1000 A is applied to the surface of the hydrogen storage alloy particles shown by the formulas (a) to (s) by electroless plating, vacuum evaporation, or electrolytic plating.
A thin film of one type of metal, Cu or N1, is formed entirely.The formation of this thin film damages the hydrogen storage capacity of the alloy itself. The activity treatment for Pd, Cu, N with N formation can also be carried out under the same or milder conditions than those not covered with a metal thin film.
The layered film made of one of the metals (i) has interatomic gaps large enough for permeation of hydrogen gas, and there is hardly any decrease in the hydrogen absorption rate.

次に本発明を実施例について説明する。Next, the present invention will be explained with reference to examples.

実施例１ 市販の各成分金属を適量秤取し、これを真空アーク溶解
炉の銅製ルツボ内に装入し、炉内を９９．９９％アルゴ
ン雰囲気とした後、約２０００　ＣＫ加熱溶融して約４
０）の次のような原子数組成のボタン状合金塊１０種類
をそれぞれ製造した。即ち、ＴｉＬＩ　Ｆｅ□、ａ　Ｎ
１ａ２　Ｚｒ（１０５Ｔｉ　ＬＩＦｅＯ，５Ｇｏ（、，
５Ｚｒ□、０５ＴＩＬＩＦｅ０．８ＭｎＱ、２ｖＱ、０
５Ｔｉｔ、ｔ　Ｆｅａ、ｓＭｎｈｚＬａａ、ｏｓＴｉ　
１．１ＦｅＯ，ｓ　ＭｎＯ，２Ｖｏ、　０２５　Ｌａｏ
、　０２５Ｚｒ　Ｏ，８Ｔｉｏ、　ｚ　（Ｆ’ｅ０．７
５ｖ０．１５ｃｒＧ、　ｔ　）　２Ｔ’１Ｌ２ｃｒ１．
２ｖＱ、８Ｌ＋ａ０．０５Ｚｒ（Ｍｎ０．７ＶＱ、３）
２ Ｚｒ　（Ｍｎｃｓ　ＶＯ，ｌ　Ｆ２Ｏ，１）２ｉＦｅ 各ボタン状試料をそれぞれ石英管に挿入し、ロータリー
ポンプを用いて１０　　Ｔｏｒｒの真空下の加熱炉内で
ｌ１００ｒ、　８時間保持した後、試料を石英管に入れ
たまま水中に取出して急冷する均質化熱処理を施した。Example 1 Appropriate amounts of commercially available component metals were weighed out, charged into a copper crucible of a vacuum arc melting furnace, the furnace was made into a 99.99% argon atmosphere, and then heated and melted to approximately 2000 CK. 4
Ten types of button-shaped alloy ingots having the following atomic compositions of 0) were manufactured. That is, TiLI Fe□, a N
1a2 Zr(105Ti LIFeO,5Go(,,
5Zr□, 05TILIFe0.8MnQ, 2vQ, 0
5Tit, t Fea, sMnhzLaa, osTi
1.1FeO,s MnO,2Vo, 025 Lao
, 025Zr O,8Tio, z (F'e0.7
5v0.15crG, t) 2T'1L2cr1.
2vQ, 8L+a0.05Zr (Mn0.7VQ, 3)
2 Zr (Mncs VO,l F2O,1)2iFe Each button-shaped sample was inserted into a quartz tube and held in a heating furnace under a vacuum of 10 Torr for 8 hours using a rotary pump. Homogenization heat treatment was carried out by taking out the tube and quenching it in water.

その後、合金を１００μｍ＠後に粉破した。このように
して製造したそれぞれの合金の表面を塩酸で活性化した
後、Ｐｄ塩による無電解メッキを施し、１００〜１００
０　Ａ程度のＰｄ薄膜により被覆させ、これを水洗、ア
ルコール洗浄を行なった後、乾燥した。Thereafter, the alloy was pulverized after 100 μm. After activating the surface of each alloy produced in this way with hydrochloric acid, electroless plating with Pd salt was applied to
It was coated with a Pd thin film of about 0 A, washed with water and alcohol, and then dried.

この材料１５９を秤取してステンレス辺水素吸だ・放出
反応器に封入した。密閉反応器を室温〜１７０Ｃの温度
で真空吸引して脱ガスを行なった後、密閉反応容器に純
度９９．９９９％の水素な２導入して３０ｋｖ／ｃｒｎ
２に加圧したところ、室温で直ちに水素吸蔵反応を開始
した。充分に水素を吸蔵した後、再び真空吸引した。材
料の活性化は１回の水素吸蔵・放出処理によりほぼ完全
に行なうことができた。This material 159 was weighed and sealed in a stainless steel-lined hydrogen absorption/release reactor. After degassing the sealed reactor by vacuum suction at a temperature of room temperature to 170C, hydrogen 2 with a purity of 99.999% was introduced into the sealed reaction vessel at 30 kv/crn.
When the pressure was increased to 2, the hydrogen storage reaction immediately started at room temperature. After sufficiently absorbing hydrogen, vacuum suction was performed again. The material could be almost completely activated by one hydrogen storage/release treatment.

この密閉反応容器を一定温度に維持した恒温槽に浸漬し
、水分１０００　Ｍｉｎを含有する水素を導入して１〜
３０ｋＩＶ／Ｃｒｎ２に加圧し、導入水素量と圧力変化
を測定し、この測定により作成した王カー組成等温線図
から水素吸Ｍ貸および吸蔵圧と放出圧との差すなわちヒ
ステリシスを求めた。その結果を第１表に示す。This sealed reaction container was immersed in a constant temperature bath maintained at a constant temperature, hydrogen containing 1000 min of water was introduced, and
The pressure was increased to 30 kIV/Crn2, the amount of hydrogen introduced and the change in pressure were measured, and the difference between hydrogen adsorption and storage pressure and release pressure, that is, hysteresis, was determined from the Kerr composition isotherm diagram created by these measurements. The results are shown in Table 1.

第１表から明らかなように、本発明材料は、従来の材料
（試料＆１０）に比べて水素吸蔵量は大きく、シかもヒ
ステリシスは大幅に改善されている。As is clear from Table 1, the material of the present invention has a larger hydrogen storage capacity and significantly improved hysteresis than the conventional material (Sample & 10).

実施例２ 次のような原子数組成のボタン状水素吸蔵用合金塊１０
種頌をそれぞれ実施９ＩＩｌと同様に製造し、均質化熱
処理を砲した。ν１ノち、 Ｔｉ１．Ｉ　Ｆｅ０．８　Ｎｉ０．２　Ｚｒ（、、０５
Ｔｉｔｔ　Ｆｅｏ、ｓ　ＣＯｏ、５　Ｚｒ０．０５Ｔｈ
　１４　Ｆ’ｅ０．８　Ｍｎ□、２　Ｖ００５Ｔｉ１．
Ｉ　Ｆｅｏ、ＢｋＡｎ′０，２　ＬａＯ，０５Ｔｉ　１
．Ｉ　Ｆ”３０．８　Ｍｎ□、２　ＶＱ、０２Ｓ　Ｌ＋
ａ０．０２５ｚｒＱ、８　Ｔｉ０．２　（Ｆ’ｅ０．７
Ｓ　■０．ｔ５　Ｃｒｏ、ｔ　）２Ｔｉ１．２　Ｃｒ１
．ｚ　Ｖｏ、ｇ　Ｌａｏ、ｏｓＺｒ　（Ｍｎ０．７’Ｖ
０．３　）　２ｚｒ（ＭＴｌｏ、ｓ　ＶＯ，ｌ　ＦｆＢ
ｏ、１．）　２ｉ　Ｆｅ その後、合金を１００μｍ前後に粉砕した。このように
して製造した合金粒子表面をＡ２下（ＩＦ’Ｔｏｒｒ　
）でＰｄ蒸着を施し、Ｐｄ？ｉｔ膜により被覆させた。Example 2 Button-shaped hydrogen storage alloy ingot 10 having the following atomic composition
Seeds were each prepared as in Run 9III and subjected to a homogenization heat treatment. ν1 nochi, Ti1. I Fe0.8 Ni0.2 Zr(,,05
Titt Feo, s COo, 5 Zr0.05Th
14 F'e0.8 Mn□, 2 V005Ti1.
I Feo, BkAn'0,2 LaO,05Ti 1
．． I F”30.8 Mn□, 2 VQ, 02S L+
a0.025zrQ, 8 Ti0.2 (F'e0.7
S ■0. t5 Cro, t )2Ti1.2 Cr1
．． z Vo, g Lao, osZr (Mn0.7'V
0.3) 2zr(MTlo, s VO, l FfB
o, 1. ) 2i Fe Thereafter, the alloy was ground to around 100 μm. The surface of the alloy particles produced in this way was placed under A2 (IF' Torr
) to perform Pd evaporation and Pd? It was covered with an IT film.

この合金粉末をその都度攪拌を行なって蒸清を約１０回
程度繰り返して１００〜１０００　Ｘ程度のＰｄ薄膜に
より被覆させた。This alloy powder was stirred each time and distilled about 10 times to coat it with a Pd thin film of about 100 to 1000×.

この材料１５？を秤取してステンレス製水素吸鷺・放出
反応器に封入した。密閉反応器を実施例１と同様に操作
して材料の活性化を行なった。材料の活性化は１回の水
素吸蔵・放出処理によりほぼ完全に行なうことができた
。この密閉反応器を一定温度に維持した恒温槽に浸漬し
、水分１０００　ｐＩ）１１１１１゜０２１１０００ｐ
ｐ、　ＧＯ２１％　ｋ含有Ｔル水索ｔ４人（、テ１〜３
０ｋｐ／稀２に加圧し、導入水素賃と圧力変化を測定し
、この世゛ｊ定により作成した王カー組成等色線図から
水素吸Ｒｆおよび吸蔵圧と放出圧との差すなわちヒステ
リシスを求めた。その結果を第２表に示す。This material is 15? was weighed and sealed in a stainless steel hydrogen absorption/release reactor. A closed reactor was operated in the same manner as in Example 1 to effect activation of the material. The material could be almost completely activated by one hydrogen storage/release treatment. This sealed reactor was immersed in a constant temperature bath maintained at a constant temperature, and the moisture content was 1000 pI) 11111°0211000p.
p, GO 21%
Pressurized to 0 kp/2, measured the introduced hydrogen rate and pressure change, and determined the hydrogen adsorption Rf and the difference between the storage pressure and the release pressure, that is, hysteresis, from the Kerr composition isochromic diagram created based on this specification. . The results are shown in Table 2.

第２表から明らかなように、本発明材料は従来の材料（
試料７ぢ２０）ＶＣ比べて水素吸ｗ、量は大きく、しか
もヒステリシスは大幅に改善てれている。As is clear from Table 2, the material of the present invention is similar to the conventional material (
Sample 7-20) Compared to VC, the amount of hydrogen absorbed is large, and the hysteresis is greatly improved.

実施例３ 次のような原子数組成のボタン状水素吸蔵用合金塊１０
種類をそれぞれ実施例１と同様に製造し、均質化熱処理
を施した。即ち、 Ｔｉｔ、ｔ　Ｆｅ０．８　Ｎｉ０．２　ｚｒｏ、０５Ｔ
ｈ１．ｌ　Ｆ’３０．５　Ｃ００，５ｚｒｏ、ｏｓＴｉ
　１．１　Ｆｅｏ、ｇ　ＭｎＯ４ｖｏ、０５Ｔｉ　１４
　Ｆｅ３０．Ｂ　Ｍｎｏ、２　ＬａＯ，０５Ｔｉ　１．
Ｉ　Ｆｅｏ、ｓ　ＭｎＯ２Ｖｏ、０２５　Ｌａ０．０２
５Ｚｒ０６　ＴｉＯ，２（Ｆｅ０．７５　Ｖｏ、１５０
ｒＯ，１）２Ｔｉ　１．２　ｃｒ　１．２　Ｖｏ、ｓ　
Ｌａｏ、ｏｓＺｒ　（ＭｎＯ，７Ｖｏ、３　）２ Ｚｒ　（Ｍｎｏ、ｓ　Ｖｏ、ｒ　Ｆｅｏ、ｔ　）２ｉ　
Ｆｅ その後、合金を１００師前後に粉砕した。このようにし
て製造した合金粒子表面を塩酸で活性化した後、塩化鋼
による無電解メッキ５！：施し、１００〜１０００　Ａ
程度のＣｕ薄膜により被覆させ、これを水洗、アルコー
ル洗浄を行なった後、乾燥した。Example 3 Button-shaped hydrogen storage alloy ingot 10 having the following atomic composition
Each type was manufactured in the same manner as in Example 1 and subjected to homogenization heat treatment. That is, Tit, t Fe0.8 Ni0.2 zro, 05T
h1. l F'30.5 C00,5zro,osTi
1.1 Feo, g MnO4vo, 05Ti 14
Fe30. B Mno, 2 LaO, 05Ti 1.
I Feo, s MnO2Vo, 025 La0.02
5Zr06 TiO,2(Fe0.75 Vo, 150
rO, 1) 2Ti 1.2 cr 1.2 Vo, s
Lao, osZr (MnO,7Vo, 3 )2 Zr (Mno, s Vo, r Feo, t ) 2i
Fe The alloy was then ground to about 100 grains. After activating the surface of the alloy particles thus produced with hydrochloric acid, electroless plating with chloride steel 5! : Alms, 100-1000 A
After washing with water and alcohol, it was dried.

この材料１５５’を秤取してステンレス製水素吸蔵・放
出反応器に封入した。密閉反応器を実施例１と同様に操
作して材料の活性化を行なった。材料の活性化は１回の
水素吸蔵・放出処理によりほぼ完全に行なうことができ
た。この密閉反応器を重宝温度ＶＣ維持した恒温槽に浸
漬し、水分ｉｏｏｏｐ＞ｍを含有する水素を導入して１
〜３０　ｋｙ／ＣｒＩｒ２に加圧し、導入水素量と圧力
変化を測定し、この測定により作成した圧力−組成等温
線図から水素吸蔵量および吸蔵圧と放出圧との差、すな
わちヒステリ７スを求めた。その結果を第３表に示す。This material 155' was weighed and sealed in a stainless steel hydrogen storage/release reactor. A closed reactor was operated in the same manner as in Example 1 to effect activation of the material. The material could be almost completely activated by one hydrogen storage/release treatment. This sealed reactor was immersed in a constant temperature bath maintained at a useful temperature VC, and hydrogen containing water iooop>m was introduced.
Pressurize to ~30 ky/CrIr2, measure the amount of hydrogen introduced and the change in pressure, and determine the hydrogen storage amount and the difference between the storage pressure and the release pressure, that is, the hysteresis, from the pressure-composition isotherm diagram created by this measurement. Ta. The results are shown in Table 3.

第３表から明らかなように、本発明材料は、従来の材料
（試料ム３０）に比べて水素吸蔵量は大きく、シかもヒ
ステリシスは大幅に改善されている。As is clear from Table 3, the material of the present invention has a larger hydrogen storage capacity and significantly improved hysteresis than the conventional material (sample 30).

実施例４ 次のような原子数組成のボタン状水素吸蔵用合金塊１０
種類をそれぞれ実施例１と同様に製造し、均質化熱処理
を施した。即ち、 Ｔｉｌ、ｌ　Ｆ’ｅ０．８　ＮｉＱ、２　ＺｒＯ，６５
Ｔｉ　１．Ｉ　Ｆｅ□、５　Ｇｏ、）、５　ｚｒｏ、０
５Ｔｉｔｔ　Ｆｅｏ、ｓ　ＭｎＯ，２ｖｏ、０５Ｔｉｕ
　Ｆｅ０４　Ｍｎｏ、２　Ｌａｏ、ｏｓＴｉｌ、ｌ　Ｆ
ｅｏ、ａ　Ｍｎ（１，２Ｖｏ、０２５　Ｌａｏ、ｏｓＺ
ｒＯ，８Ｔｉ０．２　（Ｆｅ１Ｏ，７５Ｖｏ、１５　Ｃ
ｒｒａ、１）２Ｔｉｔｚ　Ｃｒｘ、２Ｖｏ、ｓ　Ｌ＋ａ
０．０５Ｚｒ　（Ｍｎ０１７　Ｖ□、３　）　２Ｚｒ　
（Ｍｎ０．８　ＶＯ，ｌ　Ｆｅ０．１　）２ｉ　Ｆｅ その後、合金を１００μｍ前後に粉砕した。このように
して製造した合金粒子表面を塩酸で活性化した後、塩化
ニッケルによる無電解メッキを施し、１００〜１０００
　Ａ程度のＮ上薄嗅により被覆させ、これを水洗、アル
コール洗浄を行なった後、乾燥した。Example 4 Button-shaped hydrogen storage alloy ingot 10 having the following atomic composition
Each type was manufactured in the same manner as in Example 1 and subjected to homogenization heat treatment. That is, Til,l F'e0.8 NiQ,2 ZrO,65
Ti 1. I Fe□, 5 Go, ), 5 zro, 0
5Titt Feo,s MnO,2vo,05Tiu
Fe04 Mno, 2 Lao, osTil, l F
eo, a Mn(1,2Vo, 025 Lao, osZ
rO,8Ti0.2 (Fe1O,75Vo,15C
rra, 1) 2Titz Crx, 2Vo, s L+a
0.05Zr (Mn017 V□, 3) 2Zr
(Mn0.8 VO,l Fe0.1 )2i Fe Thereafter, the alloy was ground to about 100 μm. After activating the surface of the alloy particles produced in this way with hydrochloric acid, electroless plating with nickel chloride was applied to
It was coated with a light coat of N of grade A, washed with water and alcohol, and then dried.

この材料１５？を秤取してステンレス製水素吸蔵・放出
反応器に封入した。密閉反応器を実施例１と同様に操作
して材料の活性化を行なった。材料の活性化は１回の水
素吸蔵・放出処理によりほぼ完全に行なうことができた
。この密閉反応器を重宝已度ＶＣ，維持した恒温槽に浸
漬し、水分１ｏｏｏｐ＞ｍを含有する水素を導入して１
〜３Ｑ　ｋｐ／ｃｍ２に加圧し、導入水素Ｖと圧力賓化
を測定し、この測定により作成した圧力−組成等の線図
から水素吸蔵量および吸蔵圧と放出圧との差、すなわち
ヒステリシスを求めた。その結果を第４表に示す。This material is 15? was weighed and sealed in a stainless steel hydrogen storage/release reactor. A closed reactor was operated in the same manner as in Example 1 to effect activation of the material. The material could be almost completely activated by one hydrogen storage/release treatment. This sealed reactor was immersed in a constant temperature bath maintained at a temperature of VC, and hydrogen containing 1 ooop>m of moisture was introduced.
Pressurize to ~3Q kp/cm2, measure the introduced hydrogen V and pressure concentration, and calculate the hydrogen storage amount and the difference between the storage pressure and release pressure, that is, hysteresis, from the pressure-composition diagram created by this measurement. Ta. The results are shown in Table 4.

第４表から明らかなように、本発明材料は、従来の材料
（試料）に＝１０）ＶＣ，比べて水素吸蔵能力は大きく
、シかもヒステリシスは大幅に改善されている。As is clear from Table 4, the material of the present invention has a greater hydrogen storage capacity and significantly improved hysteresis than the conventional material (sample) (=10) VC.

（発明の効果） 本発明材料は上記の緒特性を有することがら、下記の効
果をあげることができる。(Effects of the Invention) Since the material of the present invention has the above characteristics, it can bring about the following effects.

■　水分ｔ　　０２１　ｃｏ２などの不純ガスを含有す
る水素の吸蔵・放出を繰り返しても材料の劣化は実質的
に少なく、耐不純ガス被毒性に優れている。(2) Even if hydrogen containing impurity gases such as water t 021 co2 is repeatedly absorbed and released, there is virtually no deterioration of the material, and the material has excellent resistance to impurity gas poisoning.

■　水素吸蔵量は従来の合金より大きい。■Hydrogen storage capacity is greater than conventional alloys.

■　水素の吸蔵量と放出圧の差、即ちヒステリシスが従
来の合金に比べて極めて小さいので、水素吸蔵能力や反
応熱を有効に利用することができる。- Since the difference between the amount of hydrogen storage and the release pressure, that is, hysteresis, is extremely small compared to conventional alloys, the hydrogen storage capacity and reaction heat can be used effectively.

■　活性化は容易で、水素吸蔵・放出速度本大きく、従
来の材料とほぼ同等あるいはそれ以上である。■ Activation is easy, and the hydrogen storage and release rates are high, almost equal to or higher than conventional materials.

Claims (1)

【特許請求の範囲】 １、下記（イ）〜（リ）の示性式によって示す水素吸蔵
用合金のいずれか１種の合金の粒子の表面がＰｄ、Ｃｕ
、Ｎｉのうちから選ばれるいずれか１種の薄膜により被
覆されてなる耐不純ガス被毒性に優れる水素吸蔵および
放出用材料； （イ）原子数組成で示性式がＴｉ＿１＿＋＿ｋＦｅ＿１
＿−＿ｌＮｉ＿ｌＡ＿ｍで示されることを特徴とするチ
タン系水吸吸蔵用合金〔但し、式中ＡはＺｒ、Ｎｂ、Ｖ
、希土類元素のなかから選ばれるいずれか少なくとも１
種の元素を示し、ｋ≦０．３、ｌ≦０．３、ｍ≦０．１
でｋ＞ｍである〕。 （ロ）原子数組成で示性式がＴｉ＿１＿＋＿ｋＦｅ＿１
＿−＿ｌＣｏ＿ｌＡ＿ｍで示されることを特徴とするチ
タン系水素吸蔵用合金〔但し、式中ＡはＺｒ、Ｎｂ、Ｖ
、希土類元素のなかから選ばれるいずれか少なくとも１
種の元素を示し、ｋ≦０．３、ｌ＜１．０、ｍ≦０．１
であり、ｌ＝０．５〜０．９９なるときｋ＞ｍである〕
。 （ハ）原子数組成で示性式がＴｉ＿１＿＋＿ｋＦｅ＿１
＿−＿ｌＭｎ＿ｌＤ＿ｎで示されるチタン系水素吸蔵用
合金〔但し、ＤはＺｒ、Ｖの少なくとも１種からなる元
素を示し、０＜ｋ≦０．３、０＜ｌ≦０．３、０＜ｎ≦
０．１、ｋ＞ｎである〕。 （ニ）原子数組成で示性式がＴｉ＿１＿＋＿ｋＦｅ＿１
＿−＿ｌＭｎ＿ｌＡ＿ｍで示されるチタン系水素吸蔵用
合金〔但し、ＡはＮｂ、希土類元素の少なくとも１種か
らなる元素を示し、０≦ｋ≦０．３、０＜ｌ≦０．３、
０＜ｍ≦０．１である〕。 （ホ）原子数組成で示性式がＴｉ＿１＿＋＿ｋＦｅ＿１
＿−＿ｌＭｎ＿ｌＡ＿ｍＤ＿ｎで示されるチタン系水素
吸蔵用合金〔但し、ＡはＮｂ、希土類元素の少なくとも
１種からなる元素であり、ＤはＺｒ、Ｖの少なくとも１
種からなる元素を示し、０≦ｋ≦０．３、０＜ｌ≦０．
３、０＜ｍ≦０．１、０＜ｎ≦０．１である〕。 （ヘ）原子数組成で示性式がＺｒ＿ｘＡ＿ｙ（Ｆｅ＿１
＿−＿ｋＶ＿ｌＣｒ＿ｍ）＿２で示されることを特徴と
するジルコニウム系水素吸蔵用合金〔但し、式中ＡはＴ
ｉ、Ｎｂ、Ｍｏのなかから選ばれるいずれか少なくとも
１種の元素を示し、０．４≦ｘ≦１．０、０≦ｙ≦０．
６、ｋ＝ｌ＋ｍ、０．２≦ｋ≦０．３であり、且つｙ＝
０のときはｍ＞０である〕。 （ト）原子数組成で示性式がＴｉ＿ｋＣｒ＿２＿−＿ｌ
Ｖ＿ｍＡ＿ｎで示される水素吸蔵用合金〔但し、式中Ａ
はＣｏ、Ｃｕ、Ｎｂ、希土類元素、Ｚｒのなかから選ば
れるいずれか少なくとも１種の元素を示し、０．８≦ｋ
≦１．４、０＜ｌ＜２、０＜ｍ＜２、０＜ｎ≦０．２、
２．０≦２−ｌ＋ｍ＋ｎ≦２．２である〕。 （チ）原子数組成で示性式がＺｒ＿ｘ（Ｍｎ＿１＿−＿
ｙＶ＿ｙ）２で示されるジルコニウム系水素吸蔵用合金
〔但し、式中ｘ、ｙはそれぞれ０．５＜ｘ＜１．５、０
＜ｙ＜１である〕。 （リ）原子数組成で示性式がＺｒ＿ｘ（Ｍｎ＿１＿−＿
ｙ＿−＿ｚＶ＿ｙＦｅ＿ｚ）＿２で示されるジルコニウ
ム系水素吸蔵用合金〔但し、式中ｘ、ｙ、ｚはそれぞれ
０．５＜ｘ＜１．５、０＜ｙ＜１、０＜ｚ＜１、ｙ＋ｚ
≦１である〕。 ２、前記薄膜は無電解メッキ、蒸着、電解メッキのいず
れか１つの方法により形成されてなる薄膜であることを
特徴とする特許請求の範囲第１項記載の材料。 ３、前記薄膜の厚さは１００〜１０００Åである特許請
求の範囲第１あるいは２項記載の材料。[Claims] 1. The surface of the particles of any one of the hydrogen storage alloys represented by the following formulas (a) to (li) is Pd, Cu.
, Ni, and is coated with a thin film of any one kind selected from Ni, and has excellent resistance to impurity gas poisoning.
A titanium-based water storage alloy characterized by being represented by ___lNi_lA_m [However, in the formula, A is Zr, Nb, V
, at least one selected from rare earth elements
Indicates the seed element, k≦0.3, l≦0.3, m≦0.1
and k>m]. (b) The specific formula in terms of atomic composition is Ti_1_+_kFe_1
A titanium-based hydrogen storage alloy characterized by being represented by ___lCo_lA_m [However, in the formula, A is Zr, Nb, V
, at least one selected from rare earth elements
Indicates the seed element, k≦0.3, l<1.0, m≦0.1
and when l=0.5 to 0.99, k>m]
. (c) The specific formula in terms of atomic composition is Ti_1_+_kFe_1
Titanium-based hydrogen storage alloy represented by _-_lMn_lD_n [However, D represents an element consisting of at least one of Zr and V, and 0<k≦0.3, 0<l≦0.3, 0<n≦
0.1, k>n]. (d) The specific formula in terms of atomic composition is Ti_1_+_kFe_1
Titanium-based hydrogen storage alloy represented by ___lMn_lA_m [However, A represents an element consisting of at least one of Nb and rare earth elements, 0≦k≦0.3, 0<l≦0.3,
0<m≦0.1]. (e) The specific formula in terms of atomic composition is Ti_1_+_kFe_1
Titanium-based hydrogen storage alloy represented by ___lMn_lA_mD_n [However, A is an element consisting of at least one of Nb and a rare earth element, and D is an element consisting of at least one of Zr and V.
Indicates an element consisting of seeds, 0≦k≦0.3, 0<l≦0.
3, 0<m≦0.1, 0<n≦0.1]. (F) In terms of atomic composition, the specific formula is Zr_xA_y(Fe_1
_−_kV_lCr_m)_2 [However, in the formula, A is T
It represents at least one element selected from i, Nb, and Mo, and 0.4≦x≦1.0, 0≦y≦0.
6, k=l+m, 0.2≦k≦0.3, and y=
0, m>0]. (g) The specific formula in terms of atomic composition is Ti_kCr_2_-_l
Hydrogen storage alloy represented by V_mA_n [However, in the formula, A
represents at least one element selected from Co, Cu, Nb, rare earth elements, and Zr, and 0.8≦k
≦1.4, 0<l<2, 0<m<2, 0<n≦0.2,
2.0≦2-l+m+n≦2.2]. (H) The specific formula is Zr_x(Mn_1_-_
Zirconium-based hydrogen storage alloy represented by yV_y)2 [where x and y are respectively 0.5<x<1.5, 0
<y<1]. (li) The specific formula for the atomic composition is Zr_x(Mn_1_-_
Zirconium-based hydrogen storage alloy represented by y_-_zV_yFe_z)_2 [wherein x, y, and z are respectively 0.5<x<1.5, 0<y<1, 0<z<1, y+z
≦1]. 2. The material according to claim 1, wherein the thin film is a thin film formed by any one of electroless plating, vapor deposition, and electrolytic plating. 3. The material according to claim 1 or 2, wherein the thin film has a thickness of 100 to 1000 Å.