JPS581032A - Production of hydrogen absorbing metallic material - Google Patents
Production of hydrogen absorbing metallic materialInfo
- Publication number
- JPS581032A JPS581032A JP56099083A JP9908381A JPS581032A JP S581032 A JPS581032 A JP S581032A JP 56099083 A JP56099083 A JP 56099083A JP 9908381 A JP9908381 A JP 9908381A JP S581032 A JPS581032 A JP S581032A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- hydrogen absorbing
- activation
- metallic material
- alloys
- 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.)
- Granted
Links
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
Abstract
Description
【発明の詳細な説明】
本発明は水嵩吸蔵特性の優れた金属材料の製造に関する
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of metal materials with excellent water bulk storage properties.
水素は古くから化学原料、還元性雰囲気ガス。Hydrogen has long been a chemical raw material and a reducing atmosphere gas.
金属精錬用還元剤などに広く使用されている◎まだ、近
年においてはエネルギー媒体としての利用、さらに近い
将来には二次エネルギーとしての大巾な利用が考えられ
ている。Although it is widely used as a reducing agent for metal refining, in recent years it has been used as an energy medium, and in the near future it is being considered for widespread use as secondary energy.
このような多種多様な水素の利用における問題点の一つ
として、水素の貯蔵・輸送がある。従来水素を貯蔵ある
いは輸送する場合、高圧縮して耐圧容器で貯蔵あるいは
輸送することが一般的であり、特殊な場合に一２５３℃
という極低温の液体水素として貯蔵・輸送する方法がと
られていた。One of the problems in using such a wide variety of hydrogen is the storage and transportation of hydrogen. Conventionally, when storing or transporting hydrogen, it is common to store or transport it in a pressure-resistant container after being highly compressed.
The method used was to store and transport hydrogen as cryogenic liquid hydrogen.
これらの方法においては、耐圧、耐極低温など特殊な容
器が必要であったり、冷却のために多量のエネルギーを
要したり、又、安全性の面で部属がある。These methods require special containers such as those that can withstand pressure or cryogenic temperatures, require a large amount of energy for cooling, and have some limitations in terms of safety.
近年、水素をある種の金属あるいは合金に吸蔵させて金
属水素化物という形で貯蔵・輸送する方法が考られてお
り、この金属水素化物は蓄熱、ヒ−）／ンデ、冷暖房シ
ステム材料などのエネルギー変換媒体としての利用も考
えられるようになった。代表的な水素吸蔵合金としてＬ
ａＮ１３ 、ＴＩＦ・などが開発されている。しかしな
がら、これらの材料においては次のような欠点があり、
実用面で不十分であった。すなわち、ＬａＮ１５系にお
いてはＬａが資源的に豊富でなく、非常に高価であるた
めに広汎な多量の使用には耐えられない。また、ＴｉＦ
・においては、Ｔｉ単体に比べて水素吸収、放出が容易
になり九とはいえ、なお４５０℃の高温、水素圧３０〜
６０嬌−２，１遍間程度の長期間に及ぶ活性化の操作が
必要であシ、合金を耐圧容器に入れて、Ｗｋ１０ＫＩＩ
７がの水素圧で微１００℃に加熱する操作は材料面、安
全面で大きな制約を受け、かつ活性化に要するエネルギ
ー量も神霊に大きくなり、やはり実用性に欠ける。これ
らの欠点を改善する目的で水素吸蔵合金としてＴｉ−Ｍ
層系が開発されたが、これは活性化の面では優れている
ものの、合金が微粉化し易いこと、残留水素量が多いな
どの欠点がある。また、Ｔｉ−Ｆ・の活性化を容易にす
る目的でＦ・のｌθ〜２０襲をＭｕで置換した合金ＴＩ
Ｆ・・、＠ Ｍｕ ＠、１ などが開発された。この合
金の場合には、やはり活性化は容易になるものの、水素
の平衡解腫圧が一定にならなくなり（プラトーが無い）
。また水素放出量が減少するなどの欠点があるＯ
本発明者等は水素＠蔵のための活性化の容易な、そして
合金本来の優れた吸蔵特性を変えない金属材料を得るべ
く種々研究を行い、本方法を見い出した。In recent years, methods have been developed to store and transport hydrogen in the form of metal hydrides by occluding hydrogen in certain metals or alloys, and these metal hydrides can be used for heat storage, heat storage, heating and cooling system materials, etc. It is now possible to consider its use as an energy conversion medium. L as a typical hydrogen storage alloy
aN13, TIF, etc. have been developed. However, these materials have the following drawbacks:
It was insufficient in practical terms. That is, in the LaN15 system, La is not abundant as a resource and is very expensive, so it cannot withstand widespread use in large quantities. Also, TiF
・Although it is easier to absorb and release hydrogen compared to Ti alone, it still remains at a high temperature of 450°C and a hydrogen pressure of 30~
It is necessary to perform an activation operation for a long period of about 60 to 2.1 times, and the alloy must be placed in a pressure container and the Wk10KII
The operation of heating to a microscopic 100 degrees Celsius under the same hydrogen pressure is subject to major restrictions in terms of materials and safety, and the amount of energy required for activation is also extremely large, making it impractical. In order to improve these drawbacks, Ti-M is used as a hydrogen storage alloy.
A layer system has been developed, but although this is superior in terms of activation, it has disadvantages such as easy pulverization of the alloy and a large amount of residual hydrogen. In addition, in order to facilitate the activation of Ti-F, alloy TI in which lθ~20 of F was replaced with Mu
F..., @Mu @, 1, etc. were developed. In the case of this alloy, activation is still easy, but the hydrogen equilibrium decomposition pressure is not constant (there is no plateau).
. In addition, there are drawbacks such as a decrease in the amount of hydrogen released. The present inventors have conducted various studies in order to obtain a metal material that is easy to activate for hydrogen storage and does not change the excellent storage properties inherent to the alloy. , discovered this method.
本発明は、活性化の困難な、たとえばＴｉｔ・合金表面
にＮｌ 、 Ｃｍ 、 Ｃ・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具い元素をメッキによシコ
ーティングするものである。活性化が容易になる理由は
、水素雰囲気によって容易に還元された金属Ｎｉ 、
Ｃｕなどが水素分子を原子状態に解離して金属内部に侵
入させ、内部のＴｌｌ’・合金に吸蔵させることによる
と考えている。The present invention is to coat the surface of a Ti alloy, which is difficult to activate, with an element whose oxide is relatively easily reduced in a hydrogen atmosphere, such as Nl, Cm, or C, by plating. . The reason why activation is easy is because metal Ni, which is easily reduced by hydrogen atmosphere,
It is believed that this is because Cu or the like dissociates hydrogen molecules into atomic states, allows them to enter the metal, and causes them to be occluded by the internal Tll' alloy.
本発明によシ、従来活性化に４５０〜５００℃の高温で
、水素圧３０〜６０ ｋｌｉｍｌで加圧、あるいは真空
排気のくシ返し操作を１週間程度行う必要があったもの
が、２００℃以下、水素圧２９〜３０ ｋｌＶＩｌ’で
１日以内と、処理温度、水素圧力、所要時間の全ての面
で飛躍的に性能向上が計られ実用性の高い水素吸蔵金属
材料が得られるようになった。また本発明によ）水素吸
蔵合金の耐錆性を向上させ、外観も曳好になる。According to the present invention, activation at a high temperature of 450 to 500 degrees Celsius, pressurization with a hydrogen pressure of 30 to 60 kiloml, or repeated evacuation operations for about a week was required to be performed at a high temperature of 450 to 500 degrees Celsius. Below, a hydrogen storage metal material with high practicality has been obtained, with dramatic improvements in performance in all aspects of processing temperature, hydrogen pressure, and required time, within one day at a hydrogen pressure of 29 to 30 klVIl'. Ta. Furthermore, according to the present invention, the rust resistance of the hydrogen storage alloy is improved and the appearance becomes more attractive.
なお、メッキ方法は無電解メッキあるいは電気メッキに
より、１種あるいは２種以上（合金メッキ）の金属を水
素吸蔵金属材料表面に被覆する。The plating method is to coat the surface of the hydrogen storage metal material with one or more metals (alloy plating) by electroless plating or electroplating.
実施例Ｉ
ＴｉＦ・合金を６０メ、シ、以下に粉砕した粉末２０ｇ
を、塩化ニッケル２Ｉｉを含む１ｔｓ塩酸水溶液１００
５１７中に約５分間浸漬し、無電解メッキを行った。そ
の後、水洗し、大気中で自然乾燥させ水素吸蔵・放出能
実験装置に入れ、２００℃、２０ Ｖノの水素雰囲気中
で３０分間、後真空排気３０分間、この繰返しを１０回
行い活性化させた０この１０回の活性化処現によって十
分水素吸蔵を行うようになることが認められた。ＴｉＦ
・−Ｎ１メ。Example I 20g of TiF alloy powder pulverized to 60mm or less
, 1ts hydrochloric acid aqueous solution containing nickel chloride 2Ii 100
517 for about 5 minutes to perform electroless plating. After that, it was washed with water, air-dried in the air, placed in a hydrogen absorption/desorption capacity experimental device, and activated in a hydrogen atmosphere of 200°C and 20 V for 30 minutes, followed by vacuum evacuation for 30 minutes, and this process was repeated 10 times. It was found that sufficient hydrogen storage was achieved by performing the activation treatment 10 times. TiF
・-N1me.
キ水素吸蔵材料の２５℃における水素吸蔵能、水素化物
の平衡解離圧を測定し、ＴｉＦ・合金と同様の良好なｌ
ラド−領域をもつ平衡解離圧が得られた。The hydrogen storage capacity and equilibrium dissociation pressure of hydrides at 25°C of the hydrogen storage material were measured, and it was found that the hydrogen storage material had a good l
An equilibrium dissociation pressure with a Rad-region was obtained.
第１図に吸蔵能、放出能を示す組成−水素圧力等電線を
示した。参考に従来のＴＩＦ・、 ＴＩＦ・。、？ＭＩ
Ｋ、）、１゜Ｔ１７１ｇ４Ｎ１０Ｊ Ｉ ＴＩＦ＠Ｃｕ
ｇ、１の組成−水素圧力等温線を第２図に示し丸。FIG. 1 shows composition-hydrogen pressure isoelectric lines showing storage capacity and desorption capacity. For reference, conventional TIF・, TIF・. ,? M.I.
K,), 1゜T171g4N10J I TIF@Cu
The composition-hydrogen pressure isotherm of g, 1 is shown in FIG. 2 as a circle.
実施例２
ＴＩＦ・合金を６０メッシ、以下に粉砕し九粉末２ Ｏ
ｌ１ｔｌｉａｌｌ鋼２Ｉｉｔ含ｔｒｌ−硫酸水溶１１１
ＧＯｄ中に約す分間浸漬してメッキし、その後水洗、大
気中で自然乾燥させ、水素吸蔵放出能実験装置に入れ、
２００℃、３０ ｋｆｅＪの水素雰囲気中で３０分間、
後真空排気３０分間、この繰返しを１０回行い、活性化
させた。実施例１と同様に、従来のＴＩＦ・で４５０℃
以上の高温を必要としていたのに対し２００℃で嵐＜、
又水素圧力も低くて良く、処理時間も大巾に改善できる
ことが認められた。また、Ｃｏメ、キについても第１図
のように曳好な結果が得られ九〇
第２図に示されるように、従来活性化を容易にさせる目
的で開発されたＴｉｔ・。、？Ｍｌ。、１などはいずれ
も解離圧にグラトー領域を持たなくなってしまうか改は
解離圧が極端に低下してしまうが、本発明による水素吸
蔵金属材料はＴＩＦ・の優れた性質を失う事なく、活性
化性能を飛躍的に向上させることができた。Example 2 TIF/alloy was pulverized to 60 mesh or less, and 9 powders were 2 O
l1treall steel 2Iit containing trl-sulfuric acid aqueous solution 111
It was immersed in GOd for about a minute for plating, then washed with water, air-dried in the air, and placed in a hydrogen storage/release capacity experimental device.
200℃, 30 minutes in hydrogen atmosphere of 30 kfeJ,
This process was repeated 10 times during post-evacuation for 30 minutes for activation. Similar to Example 1, 450°C with conventional TIF
Although it required a high temperature of 200℃, it was a storm.
It has also been found that the hydrogen pressure can be low and the processing time can be greatly improved. In addition, good results were obtained for Co and K, as shown in Figure 1, and as shown in Figure 2, Tit, which was conventionally developed for the purpose of facilitating activation, was obtained. ,? Ml. , 1, etc. either have no gratau region in their dissociation pressure or their dissociation pressure is extremely low, but the hydrogen storage metal material according to the present invention maintains its activity without losing the excellent properties of TIF. We were able to dramatically improve the conversion performance.
以上のように、本発明は実用性、経済性の面で多大な効
果をもたらすものであるから、産業界に稗益するところ
が極めて大である。As described above, the present invention brings about great effects in terms of practicality and economic efficiency, and therefore will greatly benefit the industrial world.
第１図は本発明による水素吸蔵材料の１１１Ｎ、能。
放出能を示す２５℃における組成−水素圧力等電線、第
２図は従来のＴＩＰ・、及び活性化を容易にする目的で
開発されたＴＩＰ・系合金の組成−水素圧力等温線を示
すものである・Figure 1 shows the 111N capacity of the hydrogen storage material according to the present invention. Figure 2 shows the composition-hydrogen pressure isotherm at 25°C showing the release ability, and the composition-hydrogen pressure isotherm of conventional TIP and the TIP-based alloy developed for the purpose of facilitating activation. be·
Claims (1)
ーティングすることを特徴とする水素吸蔵金属材料の製
造方法。1. A method for producing a hydrogen-absorbing metal material, which comprises coating a hydrogen-absorbing metal surface with a metal of a different type.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56099083A JPS581032A (en) | 1981-06-27 | 1981-06-27 | Production of hydrogen absorbing metallic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56099083A JPS581032A (en) | 1981-06-27 | 1981-06-27 | Production of hydrogen absorbing metallic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS581032A true JPS581032A (en) | 1983-01-06 |
| JPS6159241B2 JPS6159241B2 (en) | 1986-12-15 |
Family
ID=14238008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56099083A Granted JPS581032A (en) | 1981-06-27 | 1981-06-27 | Production of hydrogen absorbing metallic material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS581032A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5935001A (en) * | 1982-08-23 | 1984-02-25 | Mitsubishi Steel Mfg Co Ltd | Preparation of hydrogen storing material |
| JPS60190570A (en) * | 1984-03-09 | 1985-09-28 | Agency Of Ind Science & Technol | Production of hydrogen occluding alloy material |
| JPS6119063A (en) * | 1984-07-05 | 1986-01-27 | Sanyo Electric Co Ltd | Hydrogen occlusion electrode |
| JPS6130682A (en) * | 1984-07-23 | 1986-02-12 | Daido Steel Co Ltd | Hydrogen occluding material |
| JPS6227301A (en) * | 1985-07-26 | 1987-02-05 | Nippon Yakin Kogyo Co Ltd | Hydrogen occluding and releasing material having superior resistance to poisoning by impure gas |
| JPH0196301A (en) * | 1987-10-08 | 1989-04-14 | Sharp Corp | Production of hydrogen-storing alloy material |
| JPH0382734A (en) * | 1989-08-25 | 1991-04-08 | Nippon Yakin Kogyo Co Ltd | Rare earth metal-series hydrogen storage alloy |
| JPH0398260A (en) * | 1989-09-11 | 1991-04-23 | Agency Of Ind Science & Technol | Manufacture of hydrogen storage electrode |
| JPH07118704A (en) * | 1993-10-25 | 1995-05-09 | Matsushita Electric Ind Co Ltd | Hydrogen storage alloy powder, nickel-hydrogen battery having the powder in negative electrode active material and production of the powder |
| JPH08302475A (en) * | 1995-05-10 | 1996-11-19 | Sumitomo Metal Mining Co Ltd | Production of metal-coated rare-earth element-containing powder |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51148624A (en) * | 1975-06-17 | 1976-12-21 | Mitsubishi Heavy Ind Ltd | Method of fabricating hydrogen occlusive metals |
-
1981
- 1981-06-27 JP JP56099083A patent/JPS581032A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51148624A (en) * | 1975-06-17 | 1976-12-21 | Mitsubishi Heavy Ind Ltd | Method of fabricating hydrogen occlusive metals |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS624321B2 (en) * | 1982-08-23 | 1987-01-29 | Mitsubishi Steel Mfg | |
| JPS5935001A (en) * | 1982-08-23 | 1984-02-25 | Mitsubishi Steel Mfg Co Ltd | Preparation of hydrogen storing material |
| JPH0312121B2 (en) * | 1984-03-09 | 1991-02-19 | Kogyo Gijutsu Incho | |
| JPS60190570A (en) * | 1984-03-09 | 1985-09-28 | Agency Of Ind Science & Technol | Production of hydrogen occluding alloy material |
| JPH0580106B2 (en) * | 1984-07-05 | 1993-11-05 | Sanyo Electric Co | |
| JPS6119063A (en) * | 1984-07-05 | 1986-01-27 | Sanyo Electric Co Ltd | Hydrogen occlusion electrode |
| JPS6130682A (en) * | 1984-07-23 | 1986-02-12 | Daido Steel Co Ltd | Hydrogen occluding material |
| JPS6227301A (en) * | 1985-07-26 | 1987-02-05 | Nippon Yakin Kogyo Co Ltd | Hydrogen occluding and releasing material having superior resistance to poisoning by impure gas |
| JPH0224764B2 (en) * | 1985-07-26 | 1990-05-30 | Nippon Yakin Kogyo Co Ltd | |
| JPH0196301A (en) * | 1987-10-08 | 1989-04-14 | Sharp Corp | Production of hydrogen-storing alloy material |
| US5085944A (en) * | 1989-08-25 | 1992-02-04 | Nippon Yakin Kogyo Co., Ltd. | Rare earth metal-series alloys for storage of hydrogen |
| JPH0382734A (en) * | 1989-08-25 | 1991-04-08 | Nippon Yakin Kogyo Co Ltd | Rare earth metal-series hydrogen storage alloy |
| JPH0398260A (en) * | 1989-09-11 | 1991-04-23 | Agency Of Ind Science & Technol | Manufacture of hydrogen storage electrode |
| JPH0812778B2 (en) * | 1989-09-11 | 1996-02-07 | 工業技術院長 | Method for manufacturing hydrogen storage electrode |
| JPH07118704A (en) * | 1993-10-25 | 1995-05-09 | Matsushita Electric Ind Co Ltd | Hydrogen storage alloy powder, nickel-hydrogen battery having the powder in negative electrode active material and production of the powder |
| JPH08302475A (en) * | 1995-05-10 | 1996-11-19 | Sumitomo Metal Mining Co Ltd | Production of metal-coated rare-earth element-containing powder |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6159241B2 (en) | 1986-12-15 |
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