JPH0931575A - Hydrogen storage alloy and its production - Google Patents
Hydrogen storage alloy and its productionInfo
- Publication number
- JPH0931575A JPH0931575A JP7202771A JP20277195A JPH0931575A JP H0931575 A JPH0931575 A JP H0931575A JP 7202771 A JP7202771 A JP 7202771A JP 20277195 A JP20277195 A JP 20277195A JP H0931575 A JPH0931575 A JP H0931575A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- storage alloy
- powder
- hydrogen
- laves phase
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000001257 hydrogen Substances 0.000 title claims abstract description 52
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 52
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 36
- 239000000956 alloy Substances 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229910001068 laves phase Inorganic materials 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 abstract description 7
- 238000013329 compounding Methods 0.000 abstract 4
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- 238000010298 pulverizing process Methods 0.000 abstract 1
- RZJQYRCNDBMIAG-UHFFFAOYSA-N [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] Chemical class [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] RZJQYRCNDBMIAG-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 150000004681 metal hydrides Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ＡＢ2 型ラーベス
相水素吸蔵合金の水素吸蔵量を増加した水素吸蔵合金お
よびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogen storage alloy in which the hydrogen storage capacity of an AB 2 type Laves phase hydrogen storage alloy is increased, and a method for producing the same.
【０００２】[0002]
【従来の技術】従来から、水素を貯蔵・輸送するため
に、金属水素化物として固形化する技術が開発されてき
た。金属水素化物は金属結晶の格子中に水素が侵入して
結合するのでその水素密度は高く、液体水素のそれ以上
のもので、重量的にもボンベにつめた水素ガスよりも有
利なことが知られている。2. Description of the Related Art Conventionally, a technique for solidifying a metal hydride has been developed in order to store and transport hydrogen. It is known that metal hydride has a high hydrogen density because hydrogen penetrates and bonds with the lattice of the metal crystal, and is more than liquid hydrogen, and it is also advantageous in terms of weight over hydrogen gas filled in a cylinder. Has been.
【０００３】水素吸蔵合金としてはチタン系合金、ニッ
ケル系合金、マンガン系合金、マグネシウム系合金など
色々と提案されている。中でもマグネシウム系合金は密
度が小さく、安価である点で開発が進められている（特
開平４−１８７５０３号公報、特開平４−２６２５０１
号公報）。Various hydrogen storage alloys such as titanium alloys, nickel alloys, manganese alloys and magnesium alloys have been proposed. Among them, magnesium alloys are under development because they have a low density and are inexpensive (Japanese Patent Laid-Open Nos. 4-187503 and 4-262501).
Issue).
【０００４】[0004]
【発明が解決しようとする課題】しかし、従来の水素吸
蔵合金は、水素吸蔵量が十分でなく、またＭｇ2 Ｎｉ合
金は水素吸蔵量が２．０ｗｔ％以上であるが、２００℃
以上の高温環境下でないと吸蔵しなという欠点があっ
た。本発明は、高温環境下でなくても水素吸蔵量が多い
水素吸蔵合金およびその製造方法を提供することを目的
としている。However, the conventional hydrogen storage alloys do not have a sufficient hydrogen storage capacity, and the Mg 2 Ni alloy has a hydrogen storage capacity of 2.0 wt% or more.
There is a drawback that it does not occlude unless it is under the above high temperature environment. An object of the present invention is to provide a hydrogen storage alloy having a large hydrogen storage capacity even under a high temperature environment and a method for producing the same.
【０００５】[0005]
【課題を解決するための手段】上記目的を達成するた
め、本発明の水素吸蔵合金においては、ＡＢ2 型ラーベ
ス相水素吸蔵合金粉末８０〜９５重量％とマグネシウム
粉末５〜２０重量％とを複合化、すなわちＡＢ2 型ラー
ベス相水素吸蔵合金粉末の表面にマグネシウムを被覆
し、一部を合金化することである。To achieve the above object, in the hydrogen storage alloy of the present invention, a mixture of AB 2 type Laves phase hydrogen storage alloy powder of 80 to 95% by weight and magnesium powder of 5 to 20% by weight is used. That is, the surface of the AB 2 type Laves phase hydrogen storage alloy powder is coated with magnesium to partially alloy it.
【０００６】また、本発明の水素吸蔵合金においては、
ＡＢ2 型ラーベス相水素吸蔵合金として、次式で示され
る組成からなるものを用いることである。 ＴｉX Ｚｒ1-X ＭY 但しＭ：Ｎｉ，Ｆｅ，Ｍｎ，Ｖ，Ｃｏ，Ｓｍ，Ｃｒ，Ａ
ｌ，Ｃｕ，Ｍｏ，Ｗの一種以上 ｘ＝０〜０．３ ａｔｍ％ ｙ＝１．６〜２．４ ａｔｍ％ また、本発明の水素吸蔵合金の製造方法においては、Ａ
Ｂ2 型ラーベス相水素吸蔵合金粉末８０〜９５重量％
と、マグネシウム粉末５〜２０重量％とをボールミル内
において不活性雰囲気中で混合−粉砕−複合化すること
である。さらに、本発明の水素吸蔵合金の製造方法にお
いては、ボールミルとして横型ボールミルを使用するこ
とである。Further, in the hydrogen storage alloy of the present invention,
As the AB 2 type Laves phase hydrogen storage alloy, one having a composition represented by the following formula is used. Ti X Zr 1-X M Y However, M: Ni, Fe, Mn, V, Co, Sm, Cr, A
1 or more of 1, Cu, Mo, W x = 0 to 0.3 atm% y = 1.6 to 2.4 atm% In the method for producing a hydrogen storage alloy of the present invention, A
B 2 type Laves phase hydrogen storage alloy powder 80 to 95 wt%
And 5 to 20% by weight of magnesium powder in a ball mill in an inert atmosphere by mixing-grinding-compositing. Furthermore, in the method for producing a hydrogen storage alloy of the present invention, a horizontal ball mill is used as the ball mill.
【０００７】[0007]
【作用】本発明の水素吸蔵合金は、通常のラーベス相合
金粉末とマグネシウム粉末を不活性雰囲気のボールミル
中で混合−粉砕処理を行なうことにより、ラーベス相合
金とマグネシウムとがその表面で機械的に接触し、複合
化、すなわちメカニカルアロイイングしたもので、複合
化することによってきわめて活性な表面状態となったも
のと推測される。その結果、室温以下の穏和な環境にお
ける原料合金単体の場合、水素吸蔵量が１．４ｗｔ％程
度であったものが、２．３ｗｔ％程度にまで増大した。
次に、原料粉末の混合物中のマグネシウム粉末含有割合
を５〜２０重量％に限定した理由を説明すると、マグネ
シウム粉末が５％未満の添加では水素吸蔵量が増加せ
ず、また２０％を超えるとボールミルの内壁にマグネシ
ウムが付着して複合化できないからである。In the hydrogen storage alloy of the present invention, the ordinary Laves phase alloy powder and the magnesium powder are mixed and pulverized in a ball mill in an inert atmosphere, so that the Laves phase alloy and magnesium are mechanically bonded on the surface. It is assumed that it was brought into contact with the composite, that is, mechanically alloyed, and the composite was brought into an extremely active surface state. As a result, in the case of the raw material alloy alone in a mild environment at room temperature or lower, the hydrogen storage amount increased from about 1.4 wt% to about 2.3 wt%.
Next, the reason why the content ratio of the magnesium powder in the mixture of the raw material powders is limited to 5 to 20% by weight will be explained. If the addition amount of the magnesium powder is less than 5%, the hydrogen storage amount does not increase, and if it exceeds 20%. This is because magnesium adheres to the inner wall of the ball mill and cannot be composited.
【０００８】[0008]
【発明の実施の形態】本発明の実施例を説明するが、こ
れらによって本発明が限定されるものではない。原料と
して、通常のラーベス相合金粉末とマグネシウム粉末を
準備する。ラーベス相合金粉末として化学式Ｔｉ0.24Ｚ
ｒ0.76（Ｎｉ0.55Ｆｅ0.085 Ｍｎ0.3 Ｖ0.065 ）2.1 で
表されるラーベス相合金を用いた。この合金は、成分均
一化の為、真空中で１０８０℃×１０ｈｒ熱処理されて
おり、粒径は１００μｍ以下である。マグネシウムは試
薬級で、粒径１５０μｍ以下である。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described, but the present invention is not limited by these embodiments. Normal Laves phase alloy powder and magnesium powder are prepared as raw materials. Chemical formula Ti 0.24 Z as Laves phase alloy powder
A Laves phase alloy represented by r 0.76 (Ni 0.55 Fe 0.085 Mn 0.3 V 0.065 ) 2.1 was used. This alloy has been heat-treated at 1080 ° C. for 10 hours in a vacuum in order to make the components uniform, and has a grain size of 100 μm or less. Magnesium is reagent grade and has a particle size of 150 μm or less.
【０００９】前記合金粉末９０ｇとマグネシウム粉末１
０ｇとをステンレス鋼製ボールと一緒に内径１８８ｍｍ
のボールミル容器に入れ、容器内部を不活性ガスのアル
ゴンで置換する。次に前記ボールミル容器を横型ボール
ミル装置にセットし、７０ｒｐｍで２０時間と１１０時
間処理して混合−粉砕−複合化した。その結果マグネシ
ウムが被覆された７５μｍ以下の混合粉末が得られた。
これらの混合粉末を次のようにしてその特性を測定し
た。90 g of the alloy powder and 1 of magnesium powder
0g together with stainless steel balls, inner diameter 188mm
Then, the inside of the container is replaced with an inert gas of argon. Next, the ball mill container was set in a horizontal ball mill device and treated at 70 rpm for 20 hours and 110 hours to carry out mixing-grinding-compositing. As a result, a mixed powder of 75 μm or less coated with magnesium was obtained.
The characteristics of these mixed powders were measured as follows.
【００１０】測定にはジーベルツ式ＰＣＴ測定装置を使
用し、試料を２５０℃で活性化させた後、測定試料容器
を真空に排気し、真空原点法により水素吸蔵量を測定し
た。測定結果を図１に示す。室温以下の０℃という穏和
な環境における原料合金単体の場合、水素吸蔵量が１．
４５ｗｔ％であったものが、２０時間処理したものでは
１．６ｗｔ％、１１０時間処理したものでは２．３ｗｔ
％になり、１１０時間処理したものでは約１．６倍の吸
蔵量になった。For the measurement, a Sibelts type PCT measuring device was used. After activating the sample at 250 ° C., the measurement sample container was evacuated to a vacuum and the hydrogen storage amount was measured by the vacuum origin method. FIG. 1 shows the measurement results. In the case of a raw material alloy alone in a mild environment of 0 ° C. below room temperature, the hydrogen storage capacity is 1.
What was 45 wt% was 1.6 wt% when treated for 20 hours and 2.3 wt% when treated for 110 hours
%, And the amount of occlusion was about 1.6 times when treated for 110 hours.
【００１１】本例では、図１の特性曲線からみて、絶対
的な水素吸蔵量は大きくなったものの有効水素量が少な
く、プラトー領域の平坦性が良くないため、急速な水素
の吸収・放出には適しているといえないが、気体状化学
反応原料から不要な水素を除去する場合などのゲッター
材として有効であり、またヒートポンプ、水素貯蔵容器
等にも使用できる。In this example, as seen from the characteristic curve of FIG. 1, although the absolute hydrogen storage amount is large, the effective hydrogen amount is small and the flatness of the plateau region is not good, which results in rapid hydrogen absorption / desorption. Is not suitable, but it is effective as a getter material when removing unnecessary hydrogen from a gaseous chemical reaction raw material, and can also be used for a heat pump, a hydrogen storage container and the like.
【００１２】[0012]
【発明の効果】本発明の水素吸蔵合金は、室温以下の０
℃という穏和な環境における水素吸蔵量が従来の水素吸
蔵合金に比べ大幅に増加するという優れた効果を奏す
る。The hydrogen storage alloy of the present invention has a temperature of room temperature or lower.
It has an excellent effect that the hydrogen storage amount in a mild environment of ℃ significantly increases compared to the conventional hydrogen storage alloy.
【図１】本発明による水素吸蔵合金の特性を示す説明図
である。FIG. 1 is an explanatory diagram showing characteristics of a hydrogen storage alloy according to the present invention.
Claims (4)
０〜９５重量％とマグネシウム粉末５〜２０重量％とを
複合化した水素吸蔵合金。1. AB 2 type Laves phase hydrogen storage alloy powder 8
A hydrogen storage alloy that is a composite of 0 to 95% by weight and 5 to 20% by weight of magnesium powder.
式で示される組成からなることを特徴とする請求項１記
載の水素吸蔵合金。 ＴｉX Ｚｒ1-X ＭY 但しＭ：Ｎｉ，Ｆｅ，Ｍｎ，Ｖ，Ｃｏ，Ｓｍ，Ｃｒ，Ａ
ｌ，Ｃｕ，Ｍｏ，Ｗの一種以上 ｘ＝０〜０．３ ａｔｍ％ ｙ＝１．６〜２．４ ａｔｍ％2. The hydrogen storage alloy according to claim 1, wherein the AB 2 type Laves phase hydrogen storage alloy has a composition represented by the following formula. Ti X Zr 1-X M Y However, M: Ni, Fe, Mn, V, Co, Sm, Cr, A
1 or more of 1, Cu, Mo, W x = 0 to 0.3 atm% y = 1.6 to 2.4 atm%
０〜９５重量％と、マグネシウム粉末５〜２０重量％と
をボールミル内において不活性雰囲気中で混合−粉砕−
複合化することを特徴とする請求項１または請求項２記
載の水素吸蔵合金の製造方法。3. AB 2 type Laves phase hydrogen storage alloy powder 8
Mixing 0 to 95% by weight and 5 to 20% by weight of magnesium powder in an inert atmosphere in a ball mill-grinding-
The method for producing a hydrogen storage alloy according to claim 1, wherein the hydrogen storage alloy is compounded.
を特徴とする請求項３記載の水素吸蔵合金の製造方法。4. The method for producing a hydrogen storage alloy according to claim 3, wherein the ball mill is a horizontal ball mill.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7202771A JPH0931575A (en) | 1995-07-18 | 1995-07-18 | Hydrogen storage alloy and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7202771A JPH0931575A (en) | 1995-07-18 | 1995-07-18 | Hydrogen storage alloy and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0931575A true JPH0931575A (en) | 1997-02-04 |
Family
ID=16462910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7202771A Pending JPH0931575A (en) | 1995-07-18 | 1995-07-18 | Hydrogen storage alloy and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0931575A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6902845B2 (en) * | 2001-03-09 | 2005-06-07 | Canon Kabushiki Kaisha | Alkaline rechargeable battery and process for the production thereof |
| CN111621673A (en) * | 2020-07-22 | 2020-09-04 | 江苏美特林科特殊合金股份有限公司 | Intermediate alloy and preparation method thereof |
-
1995
- 1995-07-18 JP JP7202771A patent/JPH0931575A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6902845B2 (en) * | 2001-03-09 | 2005-06-07 | Canon Kabushiki Kaisha | Alkaline rechargeable battery and process for the production thereof |
| CN111621673A (en) * | 2020-07-22 | 2020-09-04 | 江苏美特林科特殊合金股份有限公司 | Intermediate alloy and preparation method thereof |
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