JPH02107740A - Hydrogen storage alloy - Google Patents
Hydrogen storage alloyInfo
- Publication number
- JPH02107740A JPH02107740A JP26046688A JP26046688A JPH02107740A JP H02107740 A JPH02107740 A JP H02107740A JP 26046688 A JP26046688 A JP 26046688A JP 26046688 A JP26046688 A JP 26046688A JP H02107740 A JPH02107740 A JP H02107740A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- hydrogen storage
- hydrogen
- pressure
- release
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 105
- 239000001257 hydrogen Substances 0.000 title claims abstract description 105
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000000956 alloy Substances 0.000 title claims abstract description 80
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 78
- 229910001068 laves phase Inorganic materials 0.000 claims abstract description 9
- 238000006467 substitution reaction Methods 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 230000004913 activation Effects 0.000 abstract description 9
- 229910008357 ZrMn2 Inorganic materials 0.000 abstract description 8
- 150000002431 hydrogen Chemical class 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 4
- 229910003165 Mn1–xCox Inorganic materials 0.000 abstract 1
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910000914 Mn alloy Inorganic materials 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 210000001015 abdomen Anatomy 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005338 heat storage Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 229910019083 Mg-Ni Inorganic materials 0.000 description 1
- 229910017706 MgZn Inorganic materials 0.000 description 1
- 229910017708 MgZn2 Inorganic materials 0.000 description 1
- 229910019403 Mg—Ni Inorganic materials 0.000 description 1
- 229910001295 No alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Hydrogen, Water And Hydrids (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
本発明は水素を可逆的に吸蔵、放出する水素吸蔵合金に
関する。DETAILED DESCRIPTION OF THE INVENTION (a) Industrial Application Field The present invention relates to a hydrogen storage alloy that reversibly stores and releases hydrogen.
（ロ）従来の技術
近年、可逆的に水素を吸蔵、放出する能力を有する水素
吸蔵合金を用いた様々な応用シテスムの開発が盛んに行
われている。例えば、水素吸蔵合金が水素を吸蔵、放出
する際に発生する反応熱を利用した菩熱、ヒートポンプ
などの熱利用システムあるいは大量の水素を吸蔵する能
力に着目した水素貯蔵システムなどが挙げられる。(B) Prior Art In recent years, various application systems using hydrogen storage alloys that have the ability to reversibly absorb and release hydrogen have been actively developed. Examples include heat utilization systems such as heat pumps and heat pumps that utilize the reaction heat generated when hydrogen storage alloys store and release hydrogen, and hydrogen storage systems that focus on their ability to store large amounts of hydrogen.
これらの応用システムに使用する水素吸蔵合金に要求さ
れる主な条件としては、
■ 水素化反応初期の活性化が容易であること、■ 使
用温度条件下で操作し易い水素吸蔵圧力および放出圧力
を有すること、
■ 可逆的な水素吸蔵および放出に必要な水素吸蔵圧力
と放出圧力との差が小さいこと。The main requirements for hydrogen storage alloys used in these application systems are: ■ Easy activation at the initial stage of the hydrogenation reaction; ■ Easy-to-operate hydrogen storage and release pressures under the operating temperature conditions. ■ The difference between the hydrogen storage pressure and release pressure required for reversible hydrogen storage and release is small.
■ 使用温度条件下で水素吸蔵量が大きいこと、■ 原
料が安価に入手できること、
等が重要である。It is important that the hydrogen storage capacity is large under the operating temperature conditions, and that the raw materials are available at low cost.
従来より、前記応用システムに使用する水素吸蔵合金と
してその使用条件および用途に応じて、希土類−Ｎｉ系
合金やＺｎ−Ｍｎ系合金及びＭｇ系合金などの水素吸蔵
合金の開発が進められている。BACKGROUND ART Conventionally, hydrogen storage alloys such as rare earth-Ni alloys, Zn-Mn alloys, and Mg-based alloys have been developed as hydrogen storage alloys for use in the application systems, depending on the usage conditions and applications.
（ハ）発明が解決しようとする課題
そして、上記熱利用システムにおいては、鉄鋼化学ブラ
ント等よりの排熱の有効利用を図ることができる。特に
１００°Ｃ以。１−ではこれらの排熱が多く、このため
これを有効利用するための水素吸蔵合金材料として本発
明者らは、既に２００℃までの温度レベルで使用可能な
ラベス相構造を有するＺｒ−訃−Ｃｏ−Ａｌ系の水素吸
蔵合金を特願昭６２−２５２３５１号に提示している。(c) Problems to be Solved by the Invention In the heat utilization system described above, it is possible to effectively utilize exhaust heat from a steel chemical blunt or the like. Especially above 100°C. In order to effectively utilize this waste heat, the present inventors have developed a Zr alloy material with a Laves phase structure that can be used at temperatures up to 200°C. A Co--Al type hydrogen storage alloy is proposed in Japanese Patent Application No. 1983-252351.
しかし、２００°Ｃ以−１−の高温域で作動する水素貯
蔵システムや蓄熱システム、゛ヒートポンプなどの熱利
用システムに使用する場合には、現状の合金系では下記
に述べる如く種々の問題点がある。However, when used in heat utilization systems such as hydrogen storage systems, heat storage systems, and heat pumps that operate at high temperatures above 200°C, the current alloy systems have various problems as described below. be.
先ず、希に類−Ｎｉ系合金は前記■〜■の条件を満たす
優れた合金系として活発に研究が行われてきたが、主要
成分である希土類が高価につく。また、２００℃以−１
−の温度条件の下では、その水素吸蔵量が小さくなって
、ｎ訂記■の条件を満足しなくなる。２００°Ｃ以」−
では、水素吸蔵圧力、および放出圧力が高くなり、この
ため、希１．類−Ｎ１系水素吸蔵合金では２００°Ｃ以
上で作動するシステムに応用した場合危険性が高くなる
。これに対し１Ｍｇ２ＮｉをはじめとするＭｇ系合金で
は、希に類−Ｎｉ系合金に比べ原料が安価であり、しか
も前記■および■の条件を２００℃以上でも満たすが、
前記のと■の条件をも満足する合金は得られていない。First, rare-Ni alloys have been actively researched as an excellent alloy system that satisfies the conditions (1) to (3) above, but the rare earth elements, which are the main components, are expensive. In addition, -1
Under the temperature condition -, the amount of hydrogen absorbed becomes small and the condition of n correction ■ is no longer satisfied. 200°C or higher”-
In this case, the hydrogen absorption pressure and the release pressure become high, and therefore the dilution rate of 1. Class-N1 hydrogen storage alloys are highly dangerous when applied to systems that operate at temperatures above 200°C. On the other hand, Mg-based alloys such as 1Mg2Ni have cheaper raw materials than rare-Ni-based alloys, and satisfy the conditions (1) and (2) above even at temperatures above 200°C.
No alloy has been obtained that satisfies the conditions (1) and (2) above.
そして、ラベス構造を有するＺｒ−Ｍｎ系合金では、基
本組成合金であるＺｒＭｎ２合金は２００℃以」−で前
記■、■、■、■の条件を満足するが、一定Ｕ水素吸蔵
時における水素吸蔵圧力と放出圧力の差（ヒステリシス
）が大きく、前記■の条件を満足しない。更に、本発明
者らが先に開示したＺｒ−Ｍｎ−Ｃ。In Zr-Mn alloys having a Laves structure, the ZrMn2 alloy, which is the basic composition alloy, satisfies the conditions of (1), (2), (2), and (3) above at temperatures above 200°C. The difference between the pressure and the discharge pressure (hysteresis) is large, and the condition (2) above is not satisfied. Furthermore, Zr-Mn-C previously disclosed by the present inventors.
Ａｌ系合金では１００〜２００℃の温度域で■〜■の条
件を全て満足する。しかし２００℃以上となると平衡水
素圧力が相当品（（１０ａＬｍ以十）なる恐れがあり、
この場合にも２００℃以上で作動するシステムへの使用
に危険性を伴うこととなる。これはＺｒ−Ｍｎ系の他の
組成多元化合金についても同様である。以ト、の様に現
状の合金系では２００°Ｃ以１−の高温域での使用に難
点がある。Al-based alloys satisfy all conditions (1) to (2) in the temperature range of 100 to 200°C. However, when the temperature exceeds 200℃, the equilibrium hydrogen pressure may become equivalent ((10aLm or more)).
In this case as well, there is a danger in using it in a system that operates at temperatures above 200°C. This also applies to other Zr-Mn-based alloys with multiple compositions. As shown above, the current alloy systems have difficulties in use in the high temperature range of 200°C or higher.
そこで本発明は、上記の問題点を解決し、２００°Ｃ以
上においても、安全で操作し易い１〜ｌＯａｔｍの水素
吸蔵、放出圧力をもち、しかも可逆的な水素吸蔵、放出
に必要な水素吸蔵圧力と放出圧力との差が小さく、２０
０°Ｃ以上の高温域で作動する熱の利用システムへの使
用に適した水素吸蔵合金を提供することを目的とする。Therefore, the present invention solves the above problems and has hydrogen storage and release pressures of 1 to 1 Oatm that are safe and easy to operate even at temperatures above 200°C, as well as hydrogen storage and release necessary for reversible hydrogen storage and release. The difference between pressure and discharge pressure is small, 20
The purpose of the present invention is to provide a hydrogen storage alloy suitable for use in heat utilization systems that operate in a high temperature range of 0°C or higher.
（ニ）問題点を解決するための手段
本発明の水素吸蔵合金は、ＭｇＺｎ２型ラベス相（六方
晶系の結晶構造をもつ合金材）構造を有するＺｒＭｎ２
合金のＭｎの一部がＣｏで置換されると共に、バナジウ
ム■が添加されてなる合金Ｚｒ（Ｍｎニー！Ｇｏｌｔ）
ｙｖ２である。(d) Means for solving the problems The hydrogen storage alloy of the present invention is a ZrMn2 alloy having a MgZn2-type Laves phase (alloy material having a hexagonal crystal structure) structure.
Alloy Zr (Mnney!Golt) in which part of the Mn in the alloy is replaced with Co and vanadium ■ is added.
It is yv2.
（作 用）
このようにＭｇｚｎｚ型ラベス相構造を有するＺｒＭｎ
２合金に対し、Ｖを添加することにより、水素吸蔵圧力
と水素放出圧力との差が小さくなりヒステリシスが減少
すると同時に水素吸蔵及び放出圧力が双方共に低下する
。また、にｎの一部をＣｏで置換することにより、プラ
ト一部（水素吸蔵圧力の変化に対し水素吸蔵放出圧力が
ほとんど変化しない領域）の傾斜が減少する。(Function) As described above, ZrMn having the Mgznz-type Laves phase structure
By adding V to the two alloys, the difference between the hydrogen storage pressure and the hydrogen release pressure becomes smaller, the hysteresis decreases, and at the same time, both the hydrogen storage and release pressures decrease. Furthermore, by substituting a portion of n with Co, the slope of a portion of the plateau (a region where the hydrogen storage and release pressure hardly changes with respect to changes in the hydrogen storage pressure) is reduced.
このように、Ｖ添加の圧力低下作用により、２００°Ｃ
以上においても安全で操作し易い１〜１０ａｔｍの水素
吸蔵及び放出圧力が得られる。In this way, due to the pressure reduction effect of V addition, 200°C
Even in the above manner, a hydrogen storage and release pressure of 1 to 10 atm, which is safe and easy to operate, can be obtained.
また、■のヒステリシス減少作用及びＣｏのプラトー傾
斜減少作用により一定量の水素の可逆的な吸蔵及び放出
に必要な水素吸蔵圧力と放出圧力との差を小さくするこ
とができる。しかも、このような組成多元化によっても
ＺｒＭｎ２合金のもつ優れた初期活性化特性は損なわれ
ることはない。従って、この水素吸蔵合金を２００℃以
上で作動する熱輸送システム等の熱利用システムに利用
すれば、安全で操作し易い１〜ｌｏａｔｍの圧力範囲で
、しかも僅かな圧力差で可逆的に水素吸蔵、放出を行う
ことができ、極めて熱効率のよいしかも安全なシステム
が実現可能となる。Moreover, the difference between the hydrogen storage pressure and the release pressure required for reversibly storing and releasing a certain amount of hydrogen can be reduced by the hysteresis reducing effect of (2) and the plateau slope reducing effect of Co. Moreover, even with such compositional diversification, the excellent initial activation characteristics of the ZrMn2 alloy are not impaired. Therefore, if this hydrogen storage alloy is used in heat utilization systems such as heat transport systems that operate at temperatures above 200°C, it will be possible to reversibly absorb hydrogen within a safe and easy-to-operate pressure range of 1 to 1 loatm and with a small pressure difference. , an extremely thermally efficient and safe system can be realized.
（ハ）実施例
［実施例１コ
水素吸蔵合金の原料金属としてＺｒ 、 Ｍｎ 、 Ｃ
ｏ 、 Ｖの各粉末を秤量したのち、これを混合し、更
に適当な大きさにプレス成形し、水冷銅鋳型内にてアル
ゴンアークにより溶解後、鋳造して
Ｚｒ （Ｍｎ、 、、Ｃｏ、 −ｘ）ｚ −＠ｖｌｌ−
ｚの金属鋳塊を得た。次いで、これを１００メツシユ程
度に粉砕し、粉末状の水素吸蔵合金Ｚｒ（Ｍｎ、 ａｇ
ｃＯｌ） 、ｘ）ｔ 、５Ｖｏ−ｚを得た。この水素吸
蔵合金の結晶構造を粉末Ｘ線回折法により調べたところ
、ＭｇＺｎ２型ラベス相単一相構造であることを確認し
た。(c) Example [Example 1] Zr, Mn, C as raw material metals of hydrogen storage alloy
After weighing the respective powders of Zr (Mn, , Co, - x)z -@vll-
A metal ingot of Z was obtained. Next, this is crushed into about 100 meshes, and powdered hydrogen storage alloy Zr (Mn, ag
cOl), x)t, 5Vo-z were obtained. When the crystal structure of this hydrogen storage alloy was examined by powder X-ray diffraction, it was confirmed that it had a MgZn2 type Laves phase single phase structure.
次に、以上の実施例により作製した水素吸蔵合金と従来
公知の水素吸蔵合金との特性比較のため、以下の水素吸
蔵合金を作製した。Next, in order to compare the characteristics of the hydrogen storage alloy produced in the above example with a conventionally known hydrogen storage alloy, the following hydrogen storage alloy was produced.
［比較例］
原料金属としてＣｏ、Ｖを用いない他は上記［実施例１
］に準じて原料金属Ｚｒ、Ｍｎの混合粉末より水素吸蔵
合金ＺｒＭｎ、を得た。[Comparative Example] Same as above [Example 1] except that Co and V were not used as raw material metals.
] A hydrogen storage alloy ZrMn was obtained from a mixed powder of raw metals Zr and Mn.
上記［実施例１］および［比較例］で得られた各水素吸
蔵合金に対して、公知のジーベルツの反応装置を用いて
、初期活性化及び２００℃における平衡水素圧カー水素
吸蔵量の測定を行ない、合金の水素吸蔵、放出特性を調
べた。その結果、先ず初期活性化に付いては、［実施例
１］におけるこの合金Ｚｒ（Ｍｎ０．、Ｃｏ。−□）ｚ
−ａｖｏ、ｚは常温テノ真空排気ノ後。For each of the hydrogen storage alloys obtained in [Example 1] and [Comparative Example], initial activation and measurement of equilibrium hydrogen pressure and hydrogen storage capacity at 200°C were carried out using a known Sieverts reaction apparatus. The hydrogen storage and release characteristics of the alloy were investigated. As a result, first of all, regarding the initial activation, this alloy Zr(Mn0., Co.-□)z in [Example 1]
-avo and z are after vacuum evacuation at room temperature.
常温で水素をｌｏａｔｍ加圧することにより１合金は容
易に水素吸蔵を開始した。そして１次の２００℃におけ
る平衡水素圧カー水素吸蔵量の測定結果に関しては、第
１図に示すような各曲線が得られた。By pressurizing hydrogen to loatm at room temperature, Alloy 1 easily started absorbing hydrogen. Regarding the measurement results of the first-order equilibrium hydrogen pressure hydrogen storage amount at 200° C., curves as shown in FIG. 1 were obtained.
同図に於いて、実線Ａは［実施例１］に係る本発明のＺ
ｒ（Ｍｎｏ−ｓｃＯｏ−ｉ）ｔ、５Ｖｏ−ｚ合金、破線
Ｂは従来公知のＺｒＭｎ、合金の平衡水素圧カー水素吸
蔵量曲線をそれぞれ示している。また、同図中、右向き
の矢印は水素吸蔵曲線、左向きの矢印は水素放出曲線を
示している。In the figure, the solid line A indicates Z of the present invention according to [Example 1].
r(Mno-scOo-i)t, 5Vo-z alloy, and the broken line B shows the equilibrium hydrogen pressure Curr hydrogen storage amount curve of the conventionally known ZrMn and alloy, respectively. In addition, in the figure, the rightward arrow indicates the hydrogen absorption curve, and the leftward arrow indicates the hydrogen release curve.
この第１図から、公知の合金であるＺｒＭｎ２合金及び
本発明のＺｒ（Ｍｎｏ−ｓｃＯｏ、ｘ）ｘ、ｓＶｏ、ｚ
合金は共に２００℃で操作し易く、安全な圧力範囲であ
る１〜１０ａｔｍの圧力範囲にその平衡水素吸収及び放
出圧力を示していることが判る。しかし、一定量の水素
を可逆的に吸収、放出するたノ、に必要な圧力差（自然
対数差；以後Ｈ５と記す）に関しては、公知のＺｒＭｎ
。From FIG. 1, it can be seen that the known alloy ZrMn2 alloy and the present invention Zr(Mno-scOo, x)
It can be seen that both alloys are easy to operate at 200 DEG C. and exhibit their equilibrium hydrogen absorption and release pressures in the pressure range of 1 to 10 atm, which is a safe pressure range. However, regarding the pressure difference (natural log difference; hereinafter referred to as H5) required to reversibly absorb and release a certain amount of hydrogen, the known ZrMn
.
合金では１．５以上であるのに対し、本発明のＺｒ（Ｍ
ｎｆｌｌｓｃｏｏＴｌ）１６＠ＶＯｊ２合金では０．５
以下となり、大きく改善されていることが測定の結果、
判明した。While it is 1.5 or more for alloys, Zr(M
nfllscooTl) 16@VOj2 alloy is 0.5
As a result of the measurement, it is found that the following is a significant improvement.
found.
［実施例２］
前記［実施例１］では、合金Ｚｒ （Ｍｎ、 、５ｃＯ
ａ−４） １．５ＶＯ−２を作製して、その特性につい
て調べたが、今度は前記［実施例１］と同じ方法でＺ
ｒ ＋ Ｍ ｎ ｔ Ｃｏｒ Ｖ粉末のうち、Ｚｒと（
Ｍｎ＋Ｃｏ）粉末の配分比を種々変えて、Ｚｒに対する
（Ｍｎ＋Ｃｏ）の量論比、が種々に異なる水素吸蔵合金
Ｚｒ（Ｍｎ、 、、Ｃｏ、 、、）ＹＶ、 、、を作製
した。[Example 2] In the above [Example 1], alloy Zr (Mn, , 5cO
a-4) 1.5VO-2 was produced and its properties were investigated, but this time Z was produced using the same method as [Example 1].
r + M n t Cor V powder, Zr and (
Hydrogen storage alloys Zr(Mn, , , Co, , , ) YV, , with various stoichiometric ratios of (Mn+Co) to Zr were prepared by varying the distribution ratio of Mn+Co) powder.
これらの水素吸蔵合金の結晶構造を粉末Ｘ線回折法によ
り調べたところ、いずれの合金もＭｇＺｎ。When the crystal structure of these hydrogen storage alloys was investigated by powder X-ray diffraction method, all alloys were found to be MgZn.
型ラベス相単一相構造であること、および、初期活性化
はいずれの合金においても容易であって、常温での真空
排気後１０ａｔｍの水素ガスを加圧することにより容易
に水素吸蔵を開始する点は、前記［実施例１］同様であ
った。It has a Laves-type single-phase structure, and initial activation is easy for any alloy, and hydrogen storage can be easily started by pressurizing hydrogen gas at 10 atm after evacuation at room temperature. was the same as in [Example 1] above.
次に、これら合金の水素吸蔵、放出特性を調べてみた。Next, we investigated the hydrogen storage and release characteristics of these alloys.
その結果得られた量論比、と０．７ｔｇｔ％の水素吸蔵
量に相当する水素を可逆的に吸蔵、放出するだめの圧力
差（自然対数差戸１Ｓとの関係を第２図に示す。The relationship between the stoichiometric ratio obtained as a result and the pressure difference (natural logarithm difference door 1S) for reversibly storing and releasing hydrogen corresponding to a hydrogen storage amount of 0.7 tgt% is shown in FIG.
この図から明らかなように、量論比、が１．７より小、
あるいは２．３より大となると前記の圧力差Ｈ３が急激
に大きくなることが判る。また、これは、量論比、が１
．７より小さい場合はプラト一部の傾斜の増加、２．３
より大きい場合はプラト一部の傾斜の増加及び水素吸蔵
量の減少に起因することが判った・
［実施例３］
前記［実施例１コと同じ方法で、Ｚｒ、Ｍｎ、Ｃｏ、Ｖ
粉末のうち、Ｍｎに対するＣｏの置換量、とＶの添加量
２を種々変えて水素吸蔵合金
Ｚｒ（Ｍｎ１−ｘｃＯｘ）ｚ−ａＶｇを作製し、８と、
の値の異なる各種合金の水素吸蔵、放出特性を調べた。As is clear from this figure, the stoichiometric ratio is smaller than 1.7,
Alternatively, it can be seen that when the pressure difference H3 becomes larger than 2.3, the pressure difference H3 increases rapidly. Also, this means that the stoichiometric ratio is 1
．． If smaller than 7, increase in slope of part of Plato, 2.3
It was found that the larger value was caused by an increase in the slope of a part of the plateau and a decrease in the amount of hydrogen storage. [Example 3] Using the same method as in Example 1 above, Zr, Mn, Co, V
Hydrogen storage alloy Zr(Mn1-xcOx)z-aVg was prepared by varying the amount of Co substituted for Mn and the amount of V added 2 among the powders, and 8 and
The hydrogen storage and release characteristics of various alloys with different values of were investigated.
なお、これらの合金も、構造はＭｇｘｎ２ラベス相単一
相構造であること、および初期活性化はいずれの合金に
おいても容易であって、常温での真空排気後１０ａｔｍ
の水素ガスを５１１圧することにより合金が容易に水素
吸蔵を開始する点は前記［実施例１］同様であった。It should be noted that these alloys also have a Mgxn2 Laves phase single-phase structure, and initial activation is easy for any of the alloys, and after evacuation at room temperature 10 atm
This was the same as in Example 1 above, in that the alloy easily started absorbing hydrogen by applying 511 pressures of hydrogen gas.
まず、肚に対するｃｏの置換量８による水素吸蔵、放出
特性について述べる。第３図は、■添加量２＝０゜２と
したときの、ｒ（Ｍｎ１−ｘｃＯｘ”）、＊ｔｌＶｏ、
ｘ合金のＣｏ置換量、と水素吸蔵量との関係を示してい
る。同図から明らかなように、水素吸蔵量は、Ｃｏ置換
量、が０゜５より大きくなると急激に減少することが判
る。First, the hydrogen absorption and release characteristics depending on the amount of co replaced with 8 in the abdomen will be described. Figure 3 shows r(Mn1-xcOx”), *tlVo, when ■addition amount 2 = 0°2.
It shows the relationship between the amount of Co substitution in the x alloy and the amount of hydrogen storage. As is clear from the figure, the amount of hydrogen storage decreases rapidly when the amount of Co substitution becomes larger than 0.5.
次にＶ添加量２による水素吸蔵、放出特性について述べ
る。第４図は、Ｃｏｉ換１ｘ＝０．５としたときのＺｒ
（Ｍｎｏ、５ｃＯａ、ｓ）ｔ、ａＶｚ合金のＶ添加量、
と可逆的に水素を吸蔵、放出するために必要な圧力（自
然対数差）Ｈ３との関係を示している。Next, the hydrogen absorption and release characteristics with V addition amount of 2 will be described. Figure 4 shows Zr when Coi exchange 1x = 0.5.
(Mno, 5cOa, s)t, V addition amount of aVz alloy,
It shows the relationship between H3 and the pressure (natural logarithmic difference) H3 required to reversibly absorb and release hydrogen.
この図から言えることは、プラト一部（水素吸蔵量の変
化に対し水素吸蔵放出圧力がほとんど変化しない領域）
の平坦化に効果を発揮するＣｏの置換量を徐々に増やし
、最大０．５とした場合においても、■の添加量、が１
より大きくなるとプラト傾斜が大きくなり、１１Ｓ値が
急激に増加することが判る。それ故、Ｚが１より大きく
なる範囲では可逆的に水素を吸蔵、放出するのに大きな
圧力差を要することとなって操作し難くなくなる。なお
、本発明の水素吸蔵合金はＣｏ及びＶの置換、添加量に
より平衡水素圧力の！１８１整が可能である。そこで本
発明の水素吸蔵合金であって、■を前記の限界量である
１、０まで添加し、圧力を低下させたＺｒ（Ｍｎｏ−ｓ
ｃＯａ−ｓ）ｔ、ｓＶｘ、ａ合金にライてその平衡水素
圧力の温度依存特性を調べたところ６００°Ｃ付近では
じめて１０ａｔｍ〜以上を示した。従って、本発明の水
素吸蔵合金は６００℃程度までの高温域で使用可能であ
る。What can be said from this figure is the plateau part (region where hydrogen storage and release pressure hardly changes with changes in hydrogen storage amount).
Even when the amount of Co substitution, which is effective in flattening the surface area, is gradually increased to a maximum of 0.5, the amount of addition of
It can be seen that as the value becomes larger, the plateau slope becomes larger and the 11S value increases rapidly. Therefore, in a range where Z is greater than 1, a large pressure difference is required to reversibly absorb and release hydrogen, making it difficult to operate. In addition, the hydrogen storage alloy of the present invention has an equilibrium hydrogen pressure depending on the substitution and addition amount of Co and V. 181 arrangements are possible. Therefore, in the hydrogen storage alloy of the present invention, Zr (Mno-s
When we examined the temperature dependence of the equilibrium hydrogen pressure on cOa-s)t, sVx, and a alloys, we found that it first showed 10 atm or more at around 600°C. Therefore, the hydrogen storage alloy of the present invention can be used in a high temperature range up to about 600°C.
以上の各実施例から、従来のＭｇＺｎ２型ラベス相構造
をもつＺｒＭｎ２合金に対し、Ｖを添加すると、可逆的
に水素を吸蔵、放出するために必要な水素吸蔵圧力と水
素放出圧力との差の主要原因であるヒステリシス（同一
量の水素吸蔵時における水素吸蔵圧力と水素放出圧力と
の差）を減少させ、同時に平衡水素吸蔵及び放出圧力を
低下させる。更に、このＶｌ添加したｚｒＭｎ、Ｖ、合
金に対し、肚の一部をＣｏで置換した組成式がＺｒ（Ｍ
ｎ、−ｘＣｏ、）ｙＩ／ｚで表わされる合金とし、特に
Ｃｏ＠換量ア、 Ｚｒに対する（Ｍｎ＋Ｃｏ）の旦論比
Ｖ＋Ｖ添加量、の値をＯ＜、＜０．５．１．７くう＜２
．３． Ｏ＜、＜１．０の範囲に入るようにすると、グ
ラ１−−傾斜を減少させることができる。From the above examples, it is clear that when V is added to a ZrMn2 alloy with a conventional MgZn2-type Laves phase structure, the difference between the hydrogen storage pressure and the hydrogen release pressure required to reversibly store and release hydrogen increases. It reduces the main cause of hysteresis (the difference between hydrogen storage pressure and hydrogen release pressure when the same amount of hydrogen is stored), and at the same time reduces the equilibrium hydrogen storage and release pressure. Furthermore, for this Vl-added zrMn, V, alloy, a part of the belly is replaced with Co, and the composition formula is Zr(M
n, -xCo, )yI/z, and in particular, the value of Co@conversion amount a, the theoretical ratio V+V addition amount of (Mn+Co) to Zr, is O<,<0.5.1.7. <2
．． 3. If it falls within the range of O<, <1.0, the gradient can be reduced.
この結果、僅かな圧力差で可逆的に水素吸蔵、放出を行
なうことができ、かつ２００’Ｃ以上６００°Ｃ程度ま
での高温域で操作し易い１〜１０ａｔｍの水素吸蔵放出
圧力を有し、しかも初期活性化処理の極めて容易な熱利
用システムに最適な水素吸蔵合金が得られるようになる
。As a result, it can reversibly store and release hydrogen with a small pressure difference, and has a hydrogen storage and release pressure of 1 to 10 atm, which is easy to operate in a high temperature range of 200°C to 600°C. Moreover, it becomes possible to obtain a hydrogen storage alloy that is most suitable for a heat utilization system and has an extremely easy initial activation treatment.
（ト）発明の効果
以」二のように本発明によれば、従来のＺｒ−Ｍｎ系合
金やＭｇ−Ｎｉ系合金あるいは希土類−Ｎｉ系合金では
得られなかった初期活性化処理の容易さ、並びに２００
℃以上６００℃程度までの高温域で操作し易いｌ〜１０
ａｔｍの平衡水素圧力、及びわずかな圧力差で水素吸蔵
、放出を行なうことのできる優れた可逆性を同時に兼ね
備えた水素吸蔵合金を得ることができる。この結果、本
発明の合金を可逆的な水素の吸蔵、放出を利用する２０
０℃以上６００℃程度までの高温域で作動する水素貯蔵
システムや蓄熱システム、ヒートポンプなどの熱利用シ
ステムなどに使用すれば、効率が良く、しかも安全性の
高いシステムが実現できる。(g) Effects of the Invention According to the present invention, the ease of initial activation treatment that could not be obtained with conventional Zr-Mn alloys, Mg-Ni alloys, or rare earth-Ni alloys, as described in 2. and 200
Easy to operate in the high temperature range from ℃ to 600℃ l~10
It is possible to obtain a hydrogen storage alloy that simultaneously has the equilibrium hydrogen pressure of ATM and excellent reversibility that allows hydrogen storage and release with a small pressure difference. As a result, the alloy of the present invention can be used to utilize reversible hydrogen storage and desorption.
If used in hydrogen storage systems, heat storage systems, and heat utilization systems such as heat pumps that operate in the high temperature range from 0°C to about 600°C, highly efficient and highly safe systems can be realized.
第１図は［実施例１］に係る本発明のＺｒ（Ｍｎ０．ｇ
Ｃｏｏ。
ｉＬ＋ｓＶｏ、ｚ合金及び公知のＺｎＭｎ２合金の２０
０°Ｃにおける平衡水素圧カー水素吸蔵量曲線を各々実
′ａＡ及び破線Ｂで示した図、第２図は［実施例２コに
示す本発明の合金Ｚｒ （Ｍｎｏ−ｓ Ｃｏ。、Ｌ ）
ｙＶａ 、ｚにおける量論比アと可逆的に水素を吸蔵、
放出するための圧力差（自然対数差）Ｈ５との関係を示
すグラフ図、第３図は［実施例３コに示す本発明の合金
Ｚｒ（Ｍｎ、−ｙｃｏｘ）ｔ −８ＶＯ１２のＣｏ置換
量。と水素吸蔵量との関係を示すグラフ図、第４図は［
実施例３］に示す本発明の合金Ｚｒ（Ｍｎ６．５ Ｃｏ
ｏ −ｓ ）０９．■２のＶ添加量、と可逆的に水素を
吸蔵、放出するための圧力差（自然対数差）Ｉｔｓとの
関係を示すグラフ図である。
第１図
第３図
第２図
（Ｍｎ ＋ Ｃｏ ）／Ｚｒ 量論比（ｙ）
■添加量（Ｚ）
手続ｎｕ正書（自発）
昭和６３年１２月２８日FIG. 1 shows Zr (Mn0.g
Coo. iL+sVo, 20 of z alloy and known ZnMn2 alloy
Figure 2 shows the equilibrium hydrogen pressure Curr hydrogen storage capacity curves at 0°C shown by solid lines aA and broken lines B, respectively.
yVa, reversibly absorbs hydrogen with the stoichiometric ratio a at z,
FIG. 3 is a graph showing the relationship with the pressure difference (natural logarithmic difference) H5 for discharging. Figure 4 is a graph showing the relationship between hydrogen storage capacity and hydrogen storage capacity.
The alloy Zr (Mn6.5 Co
o-s)09. 2 is a graph showing the relationship between the amount of V added in 2 and the pressure difference (natural logarithm difference) Its for reversibly occluding and releasing hydrogen. Fig. 1 Fig. 3 Fig. 2 (Mn + Co)/Zr stoichiometric ratio (y) ■Amount added (Z) Procedure nu official document (spontaneous) December 28, 1988
Claims (3)
のＭｎの一部がＣｏで置換されかつＶが添加されて組成
式Ｚｒ（Ｍｎ＿１＿−＿ｘＣｏ＿ｘ）＿ｙＶ＿ｚで表わ
されることを特徴とする水素吸蔵合金。(1) A hydrogen storage alloy characterized in that a part of Mn in a ZrMn_2 alloy having a MgZn_2-type Laves phase structure is replaced with Co and V is added, so that it is represented by the compositional formula Zr(Mn_1_-_xCo_x)_yV_z.
）／Ｚｒの量論比ｙが１．７＜ｙ＜２．３であることを
特徴とする水素吸蔵合金。(2) In claim 1, (Mn+Co
)/Zr stoichiometric ratio y of 1.7<y<2.3.
が０＜ｘ＜０．５、Ｖ添加量ｚが０＜ｚ＜１．０である
ことを特徴とする水素吸蔵合金。(3) Co substitution amount x in claim 1
is 0<x<0.5, and the amount of V added z is 0<z<1.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26046688A JPH02107740A (en) | 1988-10-18 | 1988-10-18 | Hydrogen storage alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26046688A JPH02107740A (en) | 1988-10-18 | 1988-10-18 | Hydrogen storage alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02107740A true JPH02107740A (en) | 1990-04-19 |
Family
ID=17348341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26046688A Pending JPH02107740A (en) | 1988-10-18 | 1988-10-18 | Hydrogen storage alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02107740A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5825453A (en) * | 1982-07-26 | 1983-02-15 | Matsushita Electric Ind Co Ltd | Metallic material for storing hydrogen |
| JPS59208036A (en) * | 1983-05-11 | 1984-11-26 | Agency Of Ind Science & Technol | Alloy for hydrogen storage |
| JPS6152336A (en) * | 1984-08-18 | 1986-03-15 | Matsushita Electric Ind Co Ltd | Hydrogen occluding alloy |
| JPS61276945A (en) * | 1985-06-03 | 1986-12-06 | Nippon Yakin Kogyo Co Ltd | Hydrogen occluding zirconium alloy |
-
1988
- 1988-10-18 JP JP26046688A patent/JPH02107740A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5825453A (en) * | 1982-07-26 | 1983-02-15 | Matsushita Electric Ind Co Ltd | Metallic material for storing hydrogen |
| JPS59208036A (en) * | 1983-05-11 | 1984-11-26 | Agency Of Ind Science & Technol | Alloy for hydrogen storage |
| JPS6152336A (en) * | 1984-08-18 | 1986-03-15 | Matsushita Electric Ind Co Ltd | Hydrogen occluding alloy |
| JPS61276945A (en) * | 1985-06-03 | 1986-12-06 | Nippon Yakin Kogyo Co Ltd | Hydrogen occluding zirconium alloy |
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