JPH01201401A - Hydrogen storage alloy powder - Google Patents
Hydrogen storage alloy powderInfo
- Publication number
- JPH01201401A JPH01201401A JP63026366A JP2636688A JPH01201401A JP H01201401 A JPH01201401 A JP H01201401A JP 63026366 A JP63026366 A JP 63026366A JP 2636688 A JP2636688 A JP 2636688A JP H01201401 A JPH01201401 A JP H01201401A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- storage alloy
- alloy powder
- hydrogen
- rare earth
- 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
- 239000001257 hydrogen Substances 0.000 title claims abstract description 91
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 91
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000000956 alloy Substances 0.000 title claims abstract description 82
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 82
- 239000000843 powder Substances 0.000 title claims abstract description 30
- 150000002910 rare earth metals Chemical group 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 14
- 229910010340 TiFe Inorganic materials 0.000 abstract description 5
- 229910018561 MmNi5 Inorganic materials 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 229910002335 LaNi5 Inorganic materials 0.000 abstract description 3
- 229910010389 TiMn Inorganic materials 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000001994 activation Methods 0.000 description 10
- 230000004913 activation Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
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
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は水素貯蔵合金粉末に関し、さらに詳しくは、金
属水素化物の形態で多量の水素を極めて速やかに吸蔵で
き、そして、僅かの加熱で容易に、かつ、速やかに水素
を放出することができる水素貯蔵合金粉末に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a hydrogen storage alloy powder, and more specifically, it is capable of absorbing a large amount of hydrogen in the form of a metal hydride very quickly and can be easily absorbed by a small amount of heating. The present invention relates to a hydrogen storage alloy powder that can quickly release hydrogen.
［従来の技術］
従来において、ＴｉＦｅ、ＴｉＭｎ等に代表されるＴｉ
系の水素貯蔵合金は、水素吸蔵、放出特性に優れ、かつ
、安価であることから、実用化に近い水素貯蔵合金とし
て注目されてきているが、活性化処理、即ち、合金の表
面にある酸化物、吸着ガス、吸着水分等の抑制する物質
を除去するために、高温・高圧処理を行う必要があるこ
と、および、水素純度の影響を受は易いという問題があ
る。[Prior art] In the past, Ti, represented by TiFe, TiMn, etc.
This type of hydrogen storage alloy has excellent hydrogen storage and release characteristics and is inexpensive, so it has been attracting attention as a hydrogen storage alloy that is close to being put into practical use. There are problems in that it is necessary to perform high temperature and high pressure treatment to remove suppressing substances such as gases, adsorbed gases, and adsorbed moisture, and that it is easily affected by hydrogen purity.
また、１ａＮｉｓ、ＭｍＮｉ５等に代表される希土類系
の水素貯蔵合金は、水素吸蔵、放出特性が優れ、かつ、
活性化処理を必要とせず、また、水素純度の影響ら受け
にくく、極めて取り扱いの容易な水素貯蔵合金であるが
、非常に高価であるという欠点がある。In addition, rare earth hydrogen storage alloys such as 1aNis and MmNi5 have excellent hydrogen storage and release characteristics, and
It is a hydrogen storage alloy that does not require activation treatment, is not easily affected by hydrogen purity, and is extremely easy to handle, but it has the drawback of being extremely expensive.
［発明が解決しようとする課題］
本発明は上記の従来の水素貯蔵合金、Ｔｉ系水素貯蔵合
金や希土類系水素貯蔵合金の個々の問題点に鑑み、本発
明者が鋭意研究を行った結果、活性化処理を必要とせず
、さらに、安価である水素貯蔵合金粉末を開発したので
ある。[Problems to be Solved by the Invention] The present invention has been made as a result of intensive research conducted by the present inventors in view of the individual problems of the conventional hydrogen storage alloys, Ti-based hydrogen storage alloys, and rare earth-based hydrogen storage alloys. They have developed a hydrogen storage alloy powder that does not require activation treatment and is also inexpensive.
［課題を解決するための手段］
本発明に係る水素貯蔵合金粉末の特徴とするところは、
１゛ｉ系水素貯蔵合金粉末の外表面上に、希土類系水素
貯蔵合金を被覆を設けたことにある。[Means for Solving the Problems] The hydrogen storage alloy powder according to the present invention is characterized by:
1. The outer surface of the 1.i-based hydrogen storage alloy powder is coated with a rare earth hydrogen storage alloy.
本発明に係る水素貯蔵合金粉末について、以下詳細に説
明する。The hydrogen storage alloy powder according to the present invention will be explained in detail below.
本発明に係る水素貯蔵合金粉末において使用するＴｉ系
水素貯蔵合金粉末として、ＴｉｄｅおよびＴｉＭｎ等に
代表されるＴｉ系の水素貯蔵合金は、水素吸蔵、水素放
出特性に優れている材料であり、この材料は水素貯蔵合
金として使用する場合、活性化処理を必要とする表面特
性に難点があるので、基本的には外部雰囲気に接するこ
とのないように、水素貯蔵合金の内部の構成材料とした
。As the Ti-based hydrogen storage alloy powder used in the hydrogen storage alloy powder according to the present invention, Ti-based hydrogen storage alloys such as Tide and TiMn are materials with excellent hydrogen storage and hydrogen release characteristics. When the material is used as a hydrogen storage alloy, it has a drawback in its surface properties that require activation treatment, so it is basically used as an internal constituent material of the hydrogen storage alloy so that it does not come into contact with the external atmosphere.
また、本発明の係る水素貯蔵合金粉末において使用する
被覆材料の希土類系水素貯蔵合金として、Ｌ ａＮ ｉ
ｓ、ＭｍＮｉ５等に代表される希土類系の水素貯蔵合金
は、水素吸蔵、放出特性が優れ、かつ、活性化処理を必
要とせず、また、水素純度の影響も受けにくく、極めて
取り扱いの容易な水素貯蔵合金であることから被覆の構
成材料とし、さらに、Ｔｉ系水素貯蔵合金と同じ温度範
囲でその機能を発揮すること、および、Ｔｉ系水素貯蔵
合金と比べて表面特性に優れていることから、このＴｉ
系水素貯蔵合金の外表面に存在させるのである。In addition, as a rare earth hydrogen storage alloy for the coating material used in the hydrogen storage alloy powder according to the present invention, L aN i
Rare earth hydrogen storage alloys, such as MmNi5 and MmNi5, have excellent hydrogen storage and release characteristics, do not require activation treatment, are not easily affected by hydrogen purity, and are extremely easy to handle hydrogen storage alloys. Since it is a storage alloy, it is used as a constituent material of the coating, and furthermore, it performs its function in the same temperature range as Ti-based hydrogen storage alloys, and has superior surface properties compared to Ti-based hydrogen storage alloys. This Ti
The hydrogen storage alloy is made to exist on the outer surface of the hydrogen storage alloy.
そして、希土類系水素貯蔵合金はＴｉ系水素貯蔵合金に
対して、必ずしも完全に被覆されている必要はないが、
その被覆率が高いほど水素貯蔵合金としては有利である
。Although the rare earth hydrogen storage alloy does not necessarily have to be completely coated with the Ti hydrogen storage alloy,
The higher the coverage, the more advantageous it is as a hydrogen storage alloy.
さらに、Ｔｉ系水素貯蔵合金の外表面に希土類系水素貯
蔵合金を被覆しても、水素の吸収能はＴｉ系水素貯蔵合
金が希土類系水素貯蔵合金より大きいから、Ｔｉ系水素
貯蔵合金の外表面に希土類系水素貯蔵合金か被覆されて
いてし、水素はＴｉ系水素貯蔵合金に吸蔵される。即ち
、１回当たりの水素の吸収能自体は各単独粉の混合した
粉末と変わりがない（劣らない。）。Furthermore, even if the outer surface of the Ti-based hydrogen storage alloy is coated with a rare earth-based hydrogen storage alloy, the hydrogen absorption capacity of the Ti-based hydrogen storage alloy is greater than that of the rare-earth hydrogen storage alloy. The hydrogen storage alloy is coated with a rare earth hydrogen storage alloy, and hydrogen is stored in the Ti hydrogen storage alloy. That is, the hydrogen absorption capacity per one time itself is the same (not inferior) to that of a mixed powder of each individual powder.
また、吸蔵水素の放出は、水素分圧を変える（真空）、
または、加熱による方法が採用できるが、何れの場合で
も希土類系水素貯蔵合金の被覆による悪影響はない。In addition, the release of stored hydrogen changes the hydrogen partial pressure (vacuum),
Alternatively, a heating method can be employed, but in either case, coating with a rare earth hydrogen storage alloy does not have any adverse effects.
さらに、希土類系水素貯蔵合金をＴｉ系水素貯蔵合金の
外表面に被覆する方法として、スパッタリングを使用で
きるが、他の被覆方法でもよい。Furthermore, although sputtering can be used as a method for coating the outer surface of the Ti-based hydrogen storage alloy with the rare earth hydrogen storage alloy, other coating methods may also be used.
そして、スパッタリングでは完全にＴｉ系水素貯蔵合金
の外表面に希土類系水素貯蔵合金を完全に被覆できない
が、１００％完全に被覆しなくてもよく、単に、被覆さ
れない部分があるというだけである。Although it is not possible to completely coat the outer surface of the Ti-based hydrogen storage alloy with the rare earth-based hydrogen storage alloy by sputtering, it is not necessary to completely cover the outer surface of the Ti-based hydrogen storage alloy, but there is simply a portion that is not covered.
このようにして製造された水素貯蔵合金粉末は、吸着用
タンクに充填して使用される。The hydrogen storage alloy powder produced in this manner is used by filling an adsorption tank.
［実 施 例］
本発明に係る水素貯蔵合金粉末の実施例を比較例ととも
に説明する。[Example] Examples of the hydrogen storage alloy powder according to the present invention will be described together with comparative examples.
実施例 比較合金の実施例。Example Examples of comparative alloys.
市販のＴｉとＦｅを原子数比Ｔｉ：Ｆｅ＝ｌ：１となる
ように分取し、各々高真空アーク溶解炉に挿入し、炉内
を高純度アルゴン雰囲気とした後、加熱溶解して、Ｔｔ
Ｆｅの組成の合金を製造した。Commercially available Ti and Fe were separated so that the atomic ratio Ti:Fe=1:1, each was inserted into a high vacuum arc melting furnace, the inside of the furnace was made into a high purity argon atmosphere, and then heated and melted. Tt
An alloy with a composition of Fe was produced.
製造されたＴｉｄｅ合金を１００〜２００メツシユに粉
砕して、その５ｇを５ＵＳ３１６鋼製反応容器に採取し
、この容器を排気装置に接続して減圧し、また、１００
℃に加熱保持して脱ガスを行った。次いで、器内に５ナ
インの水素ガスを導入し水素圧を５０ ｋｇｒ／ｃｒｎ
”に保持して、水素の吸蔵させた。その後、再び排気し
て水素を放出して、所謂、活性化処理を完了した。The produced Tide alloy was crushed into 100-200 meshes, 5 g of which was collected in a 5US316 steel reaction vessel, and this vessel was connected to an exhaust system to reduce the pressure.
Degassing was performed by heating and maintaining the temperature at °C. Next, 5 nines of hydrogen gas was introduced into the vessel and the hydrogen pressure was increased to 50 kgr/crn.
'' to absorb hydrogen. Thereafter, it was evacuated again to release hydrogen, completing the so-called activation process.
その後、この粉末合金を取り出して、常温、大気中に２
週間放置し、以下説明する測定試験に供した。After that, this powder alloy was taken out and placed in the atmosphere at room temperature for 2 hours.
The sample was left for a week and then subjected to the measurement test described below.
本発明に係る水素貯蔵合金粉末の実施例。Examples of hydrogen storage alloy powder according to the present invention.
市販のＬａとＮｉを原子数比Ｌａ：Ｎ１＝１：５となる
ように分取し、高真空アーク溶解炉に挿入し、炉内を高
純度アルゴン雰囲気とした後、加熱溶解して、ＬａＮｉ
５の組成の合金を製造した。Commercially available La and Ni are separated so that the atomic ratio La:N1=1:5, inserted into a high-vacuum arc melting furnace, and after creating a high-purity argon atmosphere inside the furnace, they are heated and melted to form LaNi.
An alloy of composition No. 5 was produced.
このＬａＮｉ５をスパッタリングターゲット材料として
、マグネトロン型スパッタリング装置に装着した。This LaNi5 was used as a sputtering target material and was installed in a magnetron type sputtering device.
また、上記比較合金として製作したＴｉＦｅ合金粉末（
上記の活性化処理を行なっていない物）を、このスパッ
タリング装置に挿入し、装置内で上記と全（同様の活性
化処理（脱ガス−水素吸蔵−水素放出）を行なった後、
直ちに、Ｌ ａＮ ｉｓ金合金スパッタし、ＴｉＦｅ合
金粉末上にＬａＮｉ５合金の皮膜を約０．５μｍ平均厚
さで被覆した。In addition, TiFe alloy powder (
After inserting the above-mentioned material (which has not been subjected to the activation treatment) into this sputtering apparatus and performing the same activation treatment (degassing - hydrogen absorption - hydrogen release) as above in the apparatus,
Immediately, LaNi5 alloy was sputtered to coat the TiFe alloy powder with an average thickness of about 0.5 μm.
その後、このようにして製作された粉末合金を取り出し
て、常温、大気中に２週間放置し、以下説明する測定試
験に供した。Thereafter, the powder alloy produced in this manner was taken out, left in the atmosphere at room temperature for two weeks, and subjected to the measurement test described below.
本発明に係る水素貯蔵合金粉末と比較合金の水素化反応
速度の測定。Measurement of hydrogenation reaction rate of hydrogen storage alloy powder according to the present invention and comparative alloy.
本発明に係る水素貯蔵合金粉末および比較合金について
、各々別個に２５℃の温度に保持されている反応容器に
入れ、５ Ｘ １０−’Ｔｏｒｒまで減圧してから、６
０ ｋｇｆ／ｃｍ”の水素を挿入し、水素の吸収量を系
内の圧力変化から測定して、各々の水素化反応速度を求
めた。The hydrogen storage alloy powder according to the present invention and the comparative alloy were separately placed in a reaction vessel maintained at a temperature of 25°C, and the pressure was reduced to 5 x 10-' Torr, and then the mixture was heated to 6.
0 kgf/cm'' of hydrogen was inserted, and the amount of hydrogen absorbed was measured from the pressure change in the system to determine each hydrogenation reaction rate.
水素化反応速度の測定結果を第１図に示す。The measurement results of the hydrogenation reaction rate are shown in FIG.
この第１図から、比較合金のＴｉＦｅ合金は大さ・）暴
露によって活性化が失われているが、本発明に係る水素
貯蔵合金粉末で活性化状態にあることがわかる。即ち、
比較合金では一度大気に暴露される場合には、その度に
活性化処理を必要とするが、本発明に係る水素貯蔵合金
粉末ではその必要がなく、容易に何時でも使用できるの
である。From FIG. 1, it can be seen that the comparative TiFe alloy loses its activation due to exposure, but the hydrogen storage alloy powder according to the present invention is in an activated state. That is,
Comparative alloys require activation treatment each time they are exposed to the atmosphere, but the hydrogen storage alloy powder according to the present invention does not require such activation and can be used easily at any time.
また、水素貯蔵合金では、水素吸蔵・放出の繰り返しに
伴う微粉化ら使用する上で問題となっているが、本発明
に係る水素貯蔵合金粉末は比較合金に比べて、この耐微
粉化性にも優れていることも確認している。これは希土
類系水素貯蔵合金の被覆効果によるものであると考えら
れる。In addition, hydrogen storage alloys have problems in use due to pulverization due to repeated hydrogen absorption and release, but the hydrogen storage alloy powder according to the present invention has better resistance to pulverization than comparative alloys. It has also been confirmed that it is also excellent. This is thought to be due to the coating effect of the rare earth hydrogen storage alloy.
第１図は本発明に係る水素貯蔵合金粉末と比較合金を２
５℃の温度で測定した水素化反応曲線である。Figure 1 shows two hydrogen storage alloy powders according to the present invention and a comparative alloy.
It is a hydrogenation reaction curve measured at a temperature of 5°C.
Claims (1)
蔵合金の被覆を設けたことを特徴とする水素貯蔵合金粉
末。A hydrogen storage alloy powder characterized in that a coating of a rare earth hydrogen storage alloy is provided on the outer surface of the Ti-based hydrogen storage alloy powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63026366A JPH01201401A (en) | 1988-02-06 | 1988-02-06 | Hydrogen storage alloy powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63026366A JPH01201401A (en) | 1988-02-06 | 1988-02-06 | Hydrogen storage alloy powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01201401A true JPH01201401A (en) | 1989-08-14 |
Family
ID=12191501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63026366A Pending JPH01201401A (en) | 1988-02-06 | 1988-02-06 | Hydrogen storage alloy powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01201401A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04246138A (en) * | 1991-01-29 | 1992-09-02 | Sharp Corp | Hydrogen storage alloy material and its production |
-
1988
- 1988-02-06 JP JP63026366A patent/JPH01201401A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04246138A (en) * | 1991-01-29 | 1992-09-02 | Sharp Corp | Hydrogen storage alloy material and its production |
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