JPH0338327B2 - - Google Patents

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Publication number
JPH0338327B2
JPH0338327B2 JP58060075A JP6007583A JPH0338327B2 JP H0338327 B2 JPH0338327 B2 JP H0338327B2 JP 58060075 A JP58060075 A JP 58060075A JP 6007583 A JP6007583 A JP 6007583A JP H0338327 B2 JPH0338327 B2 JP H0338327B2
Authority
JP
Japan
Prior art keywords
hydrogen
cani
alloy
amount
absorption
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.)
Expired - Lifetime
Application number
JP58060075A
Other languages
Japanese (ja)
Other versions
JPS59185755A (en
Inventor
Keizo Oonishi
Takatoshi Ogawa
Kunio Teshirogi
Koji Oowaki
Toshio Takahashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Japan Steel Works Ltd
Original Assignee
Japan Steel Works Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Japan Steel Works Ltd filed Critical Japan Steel Works Ltd
Priority to JP58060075A priority Critical patent/JPS59185755A/en
Publication of JPS59185755A publication Critical patent/JPS59185755A/en
Publication of JPH0338327B2 publication Critical patent/JPH0338327B2/ja
Granted legal-status Critical Current

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Classifications

    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

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  • Hydrogen, Water And Hydrids (AREA)

Description

【発明の詳細な説明】 本発明は所定の温度及び水素ガス圧下で多量の
水素を貯蔵し、しかも若干の加熱又は水素ガスの
減圧或いはその両方の操作により容易に水素を放
出することのできるカルシウム−ニツケル系（一
般式CaNi5）水素貯蔵用材料に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a calcium carbonate which can store a large amount of hydrogen at a predetermined temperature and hydrogen gas pressure, and can easily release hydrogen by slight heating or depressurization of hydrogen gas, or both. - Relating to a nickel-based (general formula: CaNi 5 ) hydrogen storage material.

将来のクリーンエネルギーシステムにおいて水
素は二次エネルギーの中核をなすと思われるが、
その中で水素の貯蔵及び輸送形態として高圧ガ
ス、液体水素、さらに金属水素化物による固形化
が挙げられる。このうち安全性及び取扱い易さか
ら金属水素化物を利用する方法が注目されてい
る。その理由として(1)単位体積当りの水素貯蔵密
度が高く気体水素の1000倍以上を有し、また液体
水素のそれと同程度である、(2)水素の貯蔵に高圧
容器を必要とせず、従つて耐圧や水素脆性の点で
は問題はない、(3)金属水素化物は熱力学的に安定
であるために液体水素のように蒸発による損失は
なく長時間の貯蔵が可能である、(4)金属水素化物
の解離圧はほぼ一定であり、解離温度を決めれば
一定圧の水素ガスが得られる、などが挙げられ
る。従つて、金属水素化物を利用した水素貯蔵容
器をはじめ燃料電池、内燃式エンジン用燃料ボン
ベはもとより、水素精製装置、冷暖房器、コンプ
レツサ、冷凍器に至るまで幅広い用途が考えられ
ており、安全性の向上、装置の簡略化、特性の向
上などの面で従来の水素貯蔵及び輸送形態に比べ
多くの利点を有する。 Hydrogen is expected to form the core of secondary energy in future clean energy systems;
Among these, hydrogen storage and transportation forms include high-pressure gas, liquid hydrogen, and solidification using metal hydrides. Among these methods, methods using metal hydrides are attracting attention because of their safety and ease of handling. The reasons for this are (1) the hydrogen storage density per unit volume is more than 1000 times that of gaseous hydrogen, and is comparable to that of liquid hydrogen; (2) hydrogen storage does not require a high-pressure container; (3) Since metal hydrides are thermodynamically stable, there is no loss due to evaporation like liquid hydrogen, and they can be stored for long periods of time. (4) The dissociation pressure of metal hydrides is almost constant, and if the dissociation temperature is determined, hydrogen gas at a constant pressure can be obtained. Therefore, a wide range of applications are being considered, including hydrogen storage containers using metal hydrides, fuel cells, and fuel cylinders for internal combustion engines, as well as hydrogen purification equipment, air conditioners, compressors, and refrigerators. It has many advantages over conventional hydrogen storage and transportation forms, such as improved hydrogen storage, simplified equipment, and improved characteristics.

このように水素の貯蔵及び輸送形態として金属
水素化物による水素の固形化が注目を浴びている
が、水素貯蔵用材料として実用化されるために
は、(1)活性化が容易であること、(2)水素の吸収、
放出のくり返しによる合金性能の劣化が少ないこ
と、(3)可逆的に水素を吸収、放出できる量が多い
こと、(4)残留水素量（圧を下げても放出しないで
合金内に残留する水素量）が少ないこと、(5)水素
吸収及び放出平衡圧曲線のヒステリシスが小さい
こと、(6)常温近傍での金属水素化物の生成平衡圧
や水素解離平衡圧が数気圧であること、(7)水素の
吸収及び放出が速いこと、(8)安価であること、な
どが挙げられ、従来より種々の水素貯蔵用材料が
提案されてきた。 As described above, solidification of hydrogen using metal hydrides is attracting attention as a form of hydrogen storage and transportation, but in order to be put to practical use as a hydrogen storage material, (1) it must be easy to activate; (2) absorption of hydrogen;
(3) A large amount of hydrogen can be reversibly absorbed and released; (4) Amount of residual hydrogen (hydrogen that remains in the alloy without being released even when the pressure is lowered). (5) the hysteresis of the hydrogen absorption and desorption equilibrium pressure curves is small; (6) the equilibrium pressure for metal hydride production and equilibrium pressure for hydrogen dissociation near room temperature is several atmospheres; (7) A variety of hydrogen storage materials have been proposed in the past due to the following properties: (1) rapid absorption and release of hydrogen, and (8) low cost.

これらのうち、活性化の容易さや水素貯蔵特性
及び合金コストの面から現在実用化の最短距離に
あるものとして、特公昭49−34315号公報や特開
昭53−14193号公報のCaNi5合金が挙げられるが、
この合金は熱的に比較的不安定である。いま、
CaNi5溶製直後及び水素吸蔵（室温）−脱蔵（250
℃）をくり返した試料のＸ線回折測定を行なつた
ところ、くり返し10回以上からCaNi5のASTM
標準パターン以外にもNiとCaのピークが見られ、
くり返し回数の増加に伴ないそれらのピークは強
くなつた。第１図にCaNi5溶製粉砕直後及びくり
返し20回の試料についてＸ線回折測定した結果を
示す。すなわち、水素吸−脱蔵のくり返しに伴な
いCaNi5から不活性な合金相が不可逆的に析出す
ることによつて水素吸蔵量が減少することとな
る。 Among these, the CaNi 5 alloys disclosed in Japanese Patent Publication No. 49-34315 and Japanese Patent Application Laid-open No. 53-14193 are currently the ones closest to practical application in terms of ease of activation, hydrogen storage properties, and alloy cost. Although it can be mentioned,
This alloy is relatively thermally unstable. now,
Immediately after dissolution of CaNi 5 and hydrogen storage (room temperature) - devolatilization (250
When X-ray diffraction measurements were performed on samples that had been repeatedly exposed to
In addition to the standard pattern, peaks of Ni and Ca can be seen,
Those peaks became stronger as the number of repetitions increased. Figure 1 shows the results of X-ray diffraction measurements of CaNi 5 samples immediately after melting and pulverization and 20 times. That is, as hydrogen absorption and desorption are repeated, an inert alloy phase is irreversibly precipitated from CaNi 5 , resulting in a decrease in the amount of hydrogen storage.

また、実用上常温近傍における水素吸−脱蔵時
の平衡圧が数気圧程度であることが望まれるが、
CaNi5合金では例えば20℃での脱蔵時の平衡圧は
大気圧以下であり、さらに60℃に昇温するとほぼ
大気圧と等しくなる。そのため水素吸蔵した合金
から水素を放出させるためには、大気圧よりも高
い平衡圧を有する温度（例えば３気圧の平衡圧を
得るためには70〜80℃程度）以上に加熱しなけれ
ばならない欠点がある。 Furthermore, for practical purposes, it is desirable that the equilibrium pressure during hydrogen absorption and desorption at around room temperature be approximately several atmospheres;
In CaNi 5 alloy, for example, the equilibrium pressure during devolatilization at 20°C is below atmospheric pressure, and when the temperature is further increased to 60°C, it becomes almost equal to atmospheric pressure. Therefore, in order to release hydrogen from an alloy that has absorbed hydrogen, it must be heated to a temperature at which the equilibrium pressure is higher than atmospheric pressure (for example, about 70 to 80 degrees Celsius to obtain an equilibrium pressure of 3 atmospheres). There is.

本発明の目的は上述したCaNi5合金の欠点であ
る水素吸−脱蔵のくり返し使用に伴なう水素吸蔵
量の低下を防止し、合金寿命を延長させると共
に、水素吸−脱蔵時の平衡圧を常温付近で数気圧
程度とすることによつて、水素の吸蔵及び脱蔵が
容易なより実用的な水素貯蔵用材料を提供するこ
とにある。 The purpose of the present invention is to prevent the decrease in hydrogen storage capacity due to repeated use of hydrogen absorption and desorption, which is the drawback of the CaNi 5 alloy mentioned above, to extend the life of the alloy, and to improve the equilibrium during hydrogen absorption and desorption. The object of the present invention is to provide a more practical hydrogen storage material that can easily absorb and desorb hydrogen by controlling the pressure to about several atmospheres at room temperature.

本発明は、水素と反応して金属水素化物を形成
する水素貯蔵用材料において、該水素貯蔵用材料
が一般式 CaNi5-(x+y)MmxAly （ただしMmはミツシユメタルを表わし、ｘ及び
ｙはそれぞれCaを１とした場合のMm及びAlの
原子比であり、０＜ｘ≦0.4，０＜ｙ≦0.6，0.2≦
ｙ／ｘ≦2.4の範囲） で表わされる組成を有することを特徴とするカル
シウム−ニツケル−ミツシユメタル−アルミニウ
ム四元系水素貯蔵用材料に存する。 The present invention provides a hydrogen storage material that reacts with hydrogen to form a metal hydride, wherein the hydrogen storage material has the general formula CaNi 5-(x+y) Mm x Al y (where Mm represents Mitsushimetal and x and y are the atomic ratios of Mm and Al when Ca is 1, respectively, 0<x≦0.4, 0<y≦0.6, 0.2≦
The present invention relates to a calcium-nickel-mitsumetal-aluminum quaternary hydrogen storage material characterized by having a composition represented by the following formula (y/x≦2.4).

本発明で使用するミツシユメタルの組成はCe
約50％、La約30％、Nd約15％、残部その他の希
土類元素及び不純物元素（Fe0.86％、その他）か
らなる（三徳金属社製）。 The composition of Mitsushi metal used in the present invention is Ce
approximately 50%, La approximately 30%, Nd approximately 15%, and the remainder other rare earth elements and impurity elements (Fe 0.86%, others) (manufactured by Santoku Metals Co., Ltd.).

本発明者らは前述した一般式CaNi5で表わされ
る合金の欠点を改善し、より実用化を促進すべく
数々の研究を重ねた結果、CaNi5合金のNiの一
部をMm及びAlで置換したカルシウム−ニツケ
ル−ミツシユメタル−アルミニウム四元系合金
（CaNi5-(x+y)MmxAly）がCaNi5合金の欠点を著
しく改善し、水素貯蔵用材料として極めて実用性
に優れていることを見出した。Niの一部を置換
したMm及びAlの割合（ｘ及びｙ）は以下の知
見に基いた。 The inventors of the present invention have conducted a number of studies to improve the shortcomings of the alloy represented by the general formula CaNi 5 and promote its practical use. The calcium-nickel-mitsushimetal-aluminum quaternary alloy (CaNi 5-(x+y) Mm x Al y ) has significantly improved the drawbacks of the CaNi 5 alloy and is extremely practical as a hydrogen storage material. I found out. The proportions (x and y) of Mm and Al that replaced part of Ni were based on the following findings.

CaNi5-(x+y)MmxAlyにおいてｘの増加に伴ない
その熱的安定性は増大し、水素の吸−脱蔵のくり
返しに伴なう水素吸蔵量の低下は次第に小さくな
るとともに、平衡圧は著しく上昇する。しかし、
ｘが0.4を超えても前者の効果はほとんど変わら
ないばかりか逆に平衡圧が高すぎること（そのた
め合金に水素を吸蔵させる場合は高圧に加圧しな
ければならない）、またプラト一部が不明瞭にな
ること、さらにMmが比較的高価であることなど
から０＜ｘ≦0.4の範囲（好ましくは0.20≦ｘ≦
0.40）における改善が最も効果がある。 CaNi 5-( x +y) Mm , the equilibrium pressure increases significantly. but,
Even if x exceeds 0.4, not only does the former effect hardly change, but on the contrary, the equilibrium pressure is too high (therefore, if the alloy is to absorb hydrogen, it must be pressurized to a high pressure), and part of the plateau is unclear. 0<x≦0.4 (preferably 0.20≦x≦
0.40) is the most effective.

また、AlはMmの０＜ｘ≦0.4の添加に伴なう
平衡圧の著しい上昇を緩和し、平衡圧を常温付近
で数気圧程度に調節する目的で添加した。ｙの増
加に伴ない平衡圧は次第に低下し、室温近傍での
水素吸蔵または脱蔵が容易となるが、ｙが0.6を
越えると残留水素量が急激に多くなること、また
可逆的に水素を吸収−放出できる量が著しく減少
すること、さらにプラト一部が不明瞭になること
から０＜ｙ≦0.6の範囲における改善が最も効果
がある。 Further, Al was added for the purpose of alleviating the significant increase in equilibrium pressure caused by the addition of Mm in the range of 0<x≦0.4, and adjusting the equilibrium pressure to about several atmospheres near room temperature. As y increases, the equilibrium pressure gradually decreases, making it easier to absorb or desorb hydrogen near room temperature. However, when y exceeds 0.6, the amount of residual hydrogen increases rapidly, and hydrogen cannot be reversibly absorbed. Improvement in the range of 0<y≦0.6 is most effective since the amount that can be absorbed and released is significantly reduced and a part of the plateau becomes unclear.

以下に実施例に基づき本発明をさらに具体的に
説明する。 The present invention will be explained in more detail below based on Examples.

実施例 CaNi5合金及び本発明による合金CaNi4.8
Mm0.1Al0.1、CaNi4.65Mm0.25Al0.1、CaNi4.5
Mm0.25Al0.25及びCaNi4.35Mm0.25Al0.4をそれぞれ
Ar中でアーク溶解にて溶製し、大気中で50〜100
メツシユに粉砕した。各合金を高圧水素ガス雰囲
気中で温度、圧力制御可能な熱天秤装置にセツト
し、合金の水素吸収及び放出反応に伴なう重量変
化により合金が吸収又は放出する水素量を求め
た。第１図、第２図及び第３図はそれぞれ
CaNi5、CaNi4.8Mm0.1Al0.1及びCaNi4.65Mm0.25
Al0.1の合金試料について、溶製粉砕直後及び20
℃で60分間水素を吸収させ250℃で15分間放出さ
せる操作を20回くり返した後の試料についてＸ線
回折を行なつた結果である。第１図のCaNi5合金
では溶製粉砕直後の試料ではみられなかつたNi
やCaのピークが、水素吸収−放出20回くり返し
後にはみられたのに対して、第２図及び第３図の
本発明合金では合金粉砕直後と水素吸収−放出20
回くり返し後との試料の回折パターンはほぼ同様
であり、第１図のNiやCa相の析出はなかつた。
このことは第４図に示すように水素吸収−放出の
くり返し操作に伴う水素吸収量（水素吸蔵時と水
素脱蔵時との試料の重量差より換算）の変化にも
反映しており、CaNi5合金の場合にはくり返し回
数の増加に伴ない水素吸収量の低下が著しいのに
対して、本発明による合金ではMmが増加するに
つれて水素吸収量低下の傾向は減少し、例えば
Mmをｘ＝0.25添加すると水素吸収量の低下はほ
とんどなかつた（CaNi4.65Mm0.25Al0.1及び
CaNi4.5Mm0.25Al0.25合金）。また第５図は本発明
による合金を上記のように20回水素吸収−放出を
くり返した後の60℃における平衡圧曲線である。
平衡圧はMm添加量の増加に伴ない著しく上昇
し、例えば水素量（水素原子／金属原子）が2.5
においてMmを0.25添加したCaNi4.65Mm0.25Al0.1
合金では平衡圧は10気圧以上になる。一方Al添
加量の増加な伴なわない平衡圧は次第に減少し、
例えばAlを0.4添加したCaNi4.35Mm0.25Al0.4合金
では水素吸蔵時の平衡圧は3.8気圧、脱蔵時の平
衡圧は3.4気圧であり、水素吸−脱蔵が著しく容
易となつた。Examples CaNi 5 alloy and alloy CaNi 4.8 according to the invention
Mm 0.1 Al 0.1 , CaNi 4.65 Mm 0.25 Al 0.1 , CaNi 4.5
Mm 0.25 Al 0.25 and CaNi 4.35 Mm 0.25 Al 0.4 respectively
Melted by arc melting in Ar, 50 to 100 in the atmosphere
Shattered into pieces. Each alloy was placed in a thermobalance device capable of controlling temperature and pressure in a high-pressure hydrogen gas atmosphere, and the amount of hydrogen absorbed or released by the alloy was determined from weight changes accompanying the hydrogen absorption and release reactions of the alloy. Figures 1, 2 and 3 are respectively
CaNi 5 , CaNi 4.8 Mm 0.1 Al 0.1 and CaNi 4.65 Mm 0.25
For alloy samples of Al 0.1 , immediately after melting and crushing and 20
These are the results of X-ray diffraction on a sample after repeating 20 times an operation of absorbing hydrogen at ℃ for 60 minutes and releasing it at 250℃ for 15 minutes. In the CaNi 5 alloy shown in Figure 1, Ni was not observed in the sample immediately after melting and crushing.
In contrast, peaks for hydrogen absorption and desorption were observed after 20 cycles of hydrogen absorption and desorption in the alloys of the present invention shown in Figures 2 and 3, immediately after alloy crushing and after 20 cycles of hydrogen absorption and desorption.
The diffraction patterns of the samples after repeating the test were almost the same, and there was no precipitation of the Ni and Ca phases shown in Figure 1.
As shown in Figure 4, this is reflected in the change in the amount of hydrogen absorbed (calculated from the difference in weight of the sample between hydrogen absorption and hydrogen desorption) due to repeated hydrogen absorption and desorption operations, and CaNi In the case of the 5 alloy, the amount of hydrogen absorption decreases significantly as the number of repetitions increases, whereas in the alloy according to the present invention, the tendency for the amount of hydrogen absorption to decrease decreases as Mm increases.
When Mm was added at x=0.25, there was almost no decrease in hydrogen absorption (CaNi 4.65 Mm 0.25 Al 0.1 and
CaNi 4.5 Mm 0.25 Al 0.25 alloy). FIG. 5 shows an equilibrium pressure curve at 60 DEG C. after the alloy according to the present invention was subjected to hydrogen absorption and desorption 20 times as described above.
The equilibrium pressure increases significantly as the amount of Mm added increases, for example, when the amount of hydrogen (hydrogen atoms/metal atoms) is 2.5
CaNi with 0.25 Mm added in 4.65 Mm 0.25 Al 0.1
For alloys, the equilibrium pressure is greater than 10 atmospheres. On the other hand, the equilibrium pressure gradually decreases without accompanying increase in the amount of Al added.
For example, in a CaNi 4.35 Mm 0.25 Al 0.4 alloy to which 0.4 Al was added, the equilibrium pressure during hydrogen absorption was 3.8 atm, and the equilibrium pressure during devolatilization was 3.4 atm, making hydrogen absorption and desorption significantly easier.

第６図はMmの原子比ｘを0.25または0.10とし
てAlの原子比ｙを変えた供試材にて20回の水素
吸・放出を行いｙ／ｘと20回くり返し後の水素吸
収量との関係を求めた図である。なお、測定条件
は下記のとおりである： 活性化 各供試材を粉砕後、オートクレーブ内に挿入
し、次に示す水素吸収・放出サイクルを20回く
り返した。 Figure 6 shows the relationship between y/x and the hydrogen absorption amount after 20 cycles of hydrogen absorption and desorption using test materials with Mm atomic ratio x of 0.25 or 0.10 and Al atomic ratio y changed. This is a diagram showing the relationship. The measurement conditions are as follows: Activation After each sample material was crushed, it was inserted into an autoclave, and the following hydrogen absorption/release cycle was repeated 20 times.

水素吸収…20℃において水素圧約50気圧で60
分 水素放出…250℃大気圧で15分間放出 水素吸収量の測定 上記の活性化処理後、再度オートクレーブを
250℃に加熱して真空ポンプを用いて15分間排
気した。その後60℃の試験温度において、初期
圧50atmの水素ガスを導入し、その圧力低下か
ら合金に吸収された水素量を求めた。 Hydrogen absorption...60 at 20℃ and hydrogen pressure of about 50 atm
Minutes Hydrogen release...Release for 15 minutes at 250℃ and atmospheric pressure Measurement of hydrogen absorption amount After the above activation treatment, autoclave again.
It was heated to 250°C and evacuated using a vacuum pump for 15 minutes. Thereafter, at a test temperature of 60°C, hydrogen gas was introduced at an initial pressure of 50 atm, and the amount of hydrogen absorbed by the alloy was determined from the pressure drop.

水素放出量の測定 水素吸収後、60℃において大気中（１気圧）
へ水素を放出させ合金の水素放出量を求めた。 Measurement of hydrogen release amount After hydrogen absorption, in the atmosphere at 60℃ (1 atm)
The amount of hydrogen released from the alloy was determined.

第６図によればｙ／ｘ＝0.4の点（CaNi4.65
Mm0.25Al0.10）で水素吸収量は約5.7であるがｙ／
ｘ＝0.2（CaNi4.70Mm0.25Al0.05）では水素吸収量
は約4.7に低下するが、第４図から得られる
CaNi5の20回くり返し水素吸・放出後の水素吸収
量1.5より大きいことから、ｙ／ｘ＝0.2を下限と
した。一方、CaNi4.15Mm0.25Al0.6の水素吸収量
は約2.0で、このときのｙ／ｘ＝0.6／0.25＝2.4と
なる。この水素吸収量2.0はCaNi5の水素吸収量
1.5よりも大きく、しかもｙ／ｘが2.4を越えても
水素吸収量は変わらないことから、このｙ／ｘ＝
2.4及びこのときのAlの原子比ｙ＝0.6をそれぞれ
上限とした。従つて、MmとAlの原子比ｘ及び
ｙの範囲は第７図の斜線で示す領域となる。 According to Figure 6, the point at y/x = 0.4 (CaNi 4.65
Mm 0.25 Al 0.10 ), the hydrogen absorption amount is about 5.7, but y/
At x = 0.2 (CaNi 4.70 Mm 0.25 Al 0.05 ), the hydrogen absorption amount decreases to about 4.7, which can be obtained from Fig. 4.
Since the hydrogen absorption amount after repeated hydrogen absorption and release of CaNi 5 was greater than 1.5, y/x = 0.2 was set as the lower limit. On the other hand, the hydrogen absorption amount of CaNi 4.15 Mm 0.25 Al 0.6 is about 2.0, and y/x=0.6/0.25=2.4 at this time. This hydrogen absorption amount of 2.0 is the hydrogen absorption amount of CaNi 5
Since the hydrogen absorption amount does not change even if y/x exceeds 2.4, this y/x=
2.4 and the Al atomic ratio y=0.6 at this time were set as upper limits, respectively. Therefore, the range of the atomic ratios x and y of Mm and Al is the area shown by diagonal lines in FIG.

このように本発明による合金によつて、水素吸
−脱蔵のくり返しに伴なう水素吸蔵量の低下を防
止し、合金寿命を延長させると共に、水素吸−脱
蔵時の平衡圧を常温付近で数気圧程度とする効果
が得られる。 As described above, the alloy according to the present invention prevents a decrease in the hydrogen storage capacity due to repeated hydrogen absorption and desorption, extends the alloy life, and maintains the equilibrium pressure during hydrogen absorption and desorption near room temperature. The effect of reducing the pressure to several atmospheres can be obtained.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図、第２図、及び第３図はそれぞれCaNi5
合金、本発明によるCaNi4.8Mm0.1Al0.1合金、及
び本発明によるCaNi4.65Mm0.25Al0.1合金につい
て、溶製粉砕直後及び水素吸−脱蔵を20回くり返
した後のＸ線回折の測定結果を示す図、第４図は
CaNi5合金及び本発明による合金について水素吸
−脱蔵のくり返し回数と水素吸収量との関係を示
す図、第５図は本発明による合金の60℃における
水素吸−脱蔵の平衡圧曲線を示す図、第６図は本
発明の合金におけるｙ／ｘと20回くり返し後の水
素吸収量との関係を示す図、第７図は本発明の合
金のｘとｙの範囲（特許請求の範囲）を示す図で
ある。 Figures 1, 2, and 3 are CaNi 5
The results of X-ray diffraction measurements are shown for the alloy, the CaNi 4.8 Mm 0.1 Al 0.1 alloy according to the present invention, and the CaNi 4.65 Mm 0.25 Al 0.1 alloy according to the present invention, immediately after melting and crushing and after repeating hydrogen absorption and desorption 20 times. The diagram shown in Figure 4 is
Figure 5 shows the relationship between the number of repetitions of hydrogen absorption and desorption and the amount of hydrogen absorbed for the CaNi 5 alloy and the alloy according to the present invention. Figure 6 is a diagram showing the relationship between y/x and hydrogen absorption amount after 20 repetitions in the alloy of the present invention, and Figure 7 is a diagram showing the range of x and y of the alloy of the present invention (claims). ).

Claims (1)

【特許請求の範囲】 １ 水素と反応して金属水素化物を形成する水素
貯蔵用材料において、該水素貯蔵用材料が一般式 CaNi5-(x+y)MmxAly （ただしMmはミツシユメタルを表わし、ｘ及び
ｙはそれぞれCaを１とした場合のMm及びAlの
原子比であり、０＜ｘ≦0.4，０＜ｙ≦0.6，0.2≦
ｙ／ｘ≦2.4の範囲） で表わされる組成を有することを特徴とするカル
シウム−ニツケル−ミツシユメタル−アルミニウ
ム四元系水素貯蔵用材料。[Claims] 1. A hydrogen storage material that reacts with hydrogen to form a metal hydride, the hydrogen storage material having the general formula CaNi 5-(x+y) Mm x Al y (where Mm represents Mitsushi Metal). where x and y are the atomic ratios of Mm and Al when Ca is 1, respectively, 0<x≦0.4, 0<y≦0.6, 0.2≦
y/x≦2.4) A quaternary calcium-nickel-mitsumetal-aluminum hydrogen storage material characterized by having a composition represented by the following formula.
JP58060075A 1983-04-07 1983-04-07 Four-element material composed of calcium-nickel- mischmetal-aluminum for hydrogen occlusion Granted JPS59185755A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP58060075A JPS59185755A (en) 1983-04-07 1983-04-07 Four-element material composed of calcium-nickel- mischmetal-aluminum for hydrogen occlusion

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP58060075A JPS59185755A (en) 1983-04-07 1983-04-07 Four-element material composed of calcium-nickel- mischmetal-aluminum for hydrogen occlusion

Publications (2)

Publication Number Publication Date
JPS59185755A JPS59185755A (en) 1984-10-22
JPH0338327B2 true JPH0338327B2 (en) 1991-06-10

Family

ID=13131597

Family Applications (1)

Application Number Title Priority Date Filing Date
JP58060075A Granted JPS59185755A (en) 1983-04-07 1983-04-07 Four-element material composed of calcium-nickel- mischmetal-aluminum for hydrogen occlusion

Country Status (1)

Country Link
JP (1) JPS59185755A (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60135540A (en) * 1983-12-23 1985-07-18 Agency Of Ind Science & Technol Hydrogenatable alloy
CN115948678B (en) * 2022-12-19 2024-06-25 包头稀土研究院 AB5 type hydrogen storage alloy, preparation method and application of Ce and Al

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5314193A (en) * 1976-07-26 1978-02-08 Matsushita Electric Ind Co Ltd Storing and releasing method for hydrogen
JPS5837374B2 (en) * 1980-06-03 1983-08-16 工業技術院長 Mitsushi Metal for Hydrogen Storage - Calcium Alloy

Also Published As

Publication number Publication date
JPS59185755A (en) 1984-10-22

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