JPH0784636B2 - Hydrogen storage alloy - Google Patents
Hydrogen storage alloyInfo
- Publication number
- JPH0784636B2 JPH0784636B2 JP21514086A JP21514086A JPH0784636B2 JP H0784636 B2 JPH0784636 B2 JP H0784636B2 JP 21514086 A JP21514086 A JP 21514086A JP 21514086 A JP21514086 A JP 21514086A JP H0784636 B2 JPH0784636 B2 JP H0784636B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- alloy
- hydrogen storage
- storage alloy
- powder
- 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
Links
Landscapes
- Powder Metallurgy (AREA)
- Hydrogen, Water And Hydrids (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、水素吸蔵合金に関し、更に詳細にはMg−Ni系
水素吸蔵合金に関する。TECHNICAL FIELD The present invention relates to a hydrogen storage alloy, and more particularly to a Mg—Ni-based hydrogen storage alloy.
（従来の技術） 上記したNg−Ni系水素吸蔵合金は、比重が小さく、水素
吸蔵量が大きいので、水素自動車の貯蔵材料として有望
であるが、反応速度が遅く、反応温度が高いなどの問題
点がある。水素吸蔵合金の吸収・放出速度を高める方法
としては、従来、添加元素により組成を変化させる方法
が主流である。この方法では速度は大きくなるが単位重
量当りの吸蔵量が小さくなり、またMg系合金の場合、比
重が大きくなるので、自動車用など軽量化が要求される
部門への適用には不利である。この他、Mg表面にNi鍍金
を施す方法も試みられているが、Mg粒子全体を覆ってし
まうため初期活性化等に不利である。(Prior Art) The Ng-Ni-based hydrogen storage alloys described above are promising as storage materials for hydrogen automobiles because of their low specific gravity and large hydrogen storage capacity, but they have problems such as slow reaction speed and high reaction temperature. There is a point. As a method for increasing the absorption / desorption rate of a hydrogen storage alloy, a method in which the composition is changed by an additive element has hitherto been the mainstream. In this method, the speed is increased, but the amount of occlusion per unit weight is decreased, and in the case of the Mg-based alloy, the specific gravity is increased, which is disadvantageous for application to automobiles and other departments requiring weight reduction. In addition, a method of applying Ni plating on the Mg surface has been attempted, but it is disadvantageous for initial activation and the like because it covers the entire Mg particle.
（発明の目的等） 水素吸蔵合金の水素化・脱水素化機構は、解明されてな
いが、合金粒子最表面に亀裂が入り、そのため水分や酸
化被毒されていない、合金の純金属部分が露出し、これ
が水素分子の解離、或は水素原子の結合に際し触媒的役
割を果たすと考えられている。Ni超微粒子は、化学的に
活性でその優れた触媒特性から有機化学反応の水素化等
に適用が試みられている。(Purpose of the Invention) Although the hydrogenation / dehydrogenation mechanism of the hydrogen storage alloy has not been clarified, the pure metal part of the alloy is not cracked at the outermost surface of the alloy particles, and thus is not poisoned by water or oxidation. It is exposed and it is believed that it plays a catalytic role in the dissociation of hydrogen molecules or the bonding of hydrogen atoms. Ultrafine Ni particles are chemically active and have been attempted to be applied to hydrogenation of organic chemical reactions due to their excellent catalytic properties.
本発明は、このNi超微粒子の特異な触媒機能を生かし、
水素吸蔵合金の水素吸収・放出速度を高めることを目的
とするものである。The present invention takes advantage of the unique catalytic function of the Ni ultrafine particles,
The purpose is to increase the hydrogen absorption / desorption rate of the hydrogen storage alloy.
（発明の構成等） 本発明の水素吸蔵合金は、第１図に示したように、Mg−
Ni水素吸蔵合金粉末１にNi超微粒子２を混合し、初期活
性化処理により合金粉末表面にNi超微粒子２を付着せし
め、その特異な触媒機能により水素の吸収・放出速度を
高めたことを特徴とするものである。なお、Ni超微粉末
は、Mg−Ni2元系合金の融点以下で溶融するので、付着
・熱処理によっても、母材への影響が少ない。(Structure of the Invention, etc.) The hydrogen storage alloy of the present invention, as shown in FIG.
Ni hydrogen storage alloy powder 1 is mixed with Ni ultrafine particles 2, and the initial activation treatment causes the Ni ultrafine particles 2 to adhere to the surface of the alloy powder, and its unique catalytic function enhances the absorption and desorption rate of hydrogen. It is what Since the ultrafine Ni powder melts below the melting point of the Mg-Ni binary alloy, the adhesion and heat treatment have little effect on the base material.
以下、本発明の水素吸蔵合金を更に詳細に説明する。Hereinafter, the hydrogen storage alloy of the present invention will be described in more detail.
水素吸蔵合金の組成は、吸蔵量の極端な低下を防ぐた
め、Niを15〜54.7重量％とし、Mgを残余とする。このMg
−Ni合金を、32メッシュ以下、100メッシュ以上に粉砕
する。これは、充分な比表面積を得るとともに、水素の
吸収・放出による格子定数の変化に伴い、合金粉に亀裂
が入り、徐々に微粉化して飛散するのを防ぐ範囲であ
る。Ni超微粒子は、その粒径を0.02〜1.0ミクロンとす
る。これ以下では、粒子の飛散によりその取扱いが難し
く、これ以上の粒径のものは一般に超微粒子とは言わ
ず、その活性な特性を充分に生かすことができない。ま
た、経済的にも、この範囲が望ましい。超微粒子は一般
のその他の粒子に比べ、かさ密度、比表面積が非常に大
きく、少量の添加により大きな効果を得ることができ
る。従って添加すべき割合は、水素吸蔵合金に対し0.5
〜2.0重量％とする。0.5重量％未満では十分な効果がな
い。2.0重量％を越えると効果が飽和し経済的でない。
これらの原料を混合し、水素吸蔵用材料として用いる。
この混合粉末の表面の水分や吸着ガスの影響を取除き、
容易に水素の吸収・放出をし始めるようにするため初期
活性化処理を行う。これは、密閉できる反応容器に試料
を装填し、約30分〜２時間真空引きした後、約30kgf/cm
2の水素を印加し、300〜500℃において約30分〜２時間
保持する。これを300℃にした後、系を真空引き、約30k
gf/cm2の水素印加なる、水素の出入れを１サイクル約10
分〜１時間をもって１〜10回行い、処理を完了するもの
である。The composition of the hydrogen storage alloy is such that Ni is 15 to 54.7 wt% and Mg is the balance, in order to prevent an extreme decrease in the storage amount. This Mg
-Ni alloy is crushed to 32 mesh or less and 100 mesh or more. This is a range in which a sufficient specific surface area is obtained, and the alloy powder is prevented from cracking, gradually becoming finer and scattering due to a change in lattice constant due to absorption / desorption of hydrogen. The Ni ultrafine particles have a particle size of 0.02 to 1.0 micron. Below this, handling is difficult due to scattering of particles, and particles with a particle size above this are not generally called ultrafine particles, and their active characteristics cannot be fully utilized. Further, economically, this range is desirable. Ultrafine particles have a very large bulk density and specific surface area as compared with other general particles, and a large effect can be obtained by adding a small amount. Therefore, the ratio to be added is 0.5 for hydrogen storage alloys.
~ 2.0% by weight. If it is less than 0.5% by weight, no sufficient effect is obtained. If it exceeds 2.0% by weight, the effect is saturated and it is not economical.
These raw materials are mixed and used as a hydrogen storage material.
Remove the influence of moisture and adsorbed gas on the surface of this mixed powder,
An initial activation process is performed to make it easy to start absorbing and desorbing hydrogen. It is about 30kgf / cm after loading the sample in a reaction container that can be closed and evacuating for about 30 minutes to 2 hours.
Apply 2 of hydrogen and hold at 300-500 ° C. for about 30 minutes to 2 hours. After setting this to 300 ° C, vacuum the system to about 30k.
Approximately 10 cycles of hydrogen inflow and outflow with gf / cm 2 hydrogen applied
The treatment is completed by repeating the treatment 1 to 10 times in 1 minute to 1 hour.
この初期活性化処理を行った後、合金からの水素の吸収
・放出にかかる時間を短縮するのが本発明の効果であ
る。この時間は、水素の飽和吸収量に到達するまでの時
間をもって表わすが、便宜上、水素の飽和吸収量の95原
子％到達する時間をもって示す。It is an effect of the present invention to shorten the time required for absorbing and desorbing hydrogen from the alloy after performing this initial activation treatment. This time is represented by the time until the saturated absorption amount of hydrogen is reached, but for convenience, it is shown as the time when 95 atomic% of the saturated absorption amount of hydrogen is reached.
第１図を参照して、本発明の水素吸蔵合金における水素
吸収の仕組説明する。合金１表面に到達した水素分子Ｈ
は、水素原子Ｈ′に解離する。この反応に際し、Ni超微
粒子２は触媒機能を果たす。この水素原子は合金粉末内
部に拡散し、金属水素化物として貯蔵する。The mechanism of hydrogen absorption in the hydrogen storage alloy of the present invention will be described with reference to FIG. Hydrogen molecule H reaching the surface of alloy 1
Dissociates into hydrogen atoms H '. During this reaction, the Ni ultrafine particles 2 fulfill a catalytic function. This hydrogen atom diffuses inside the alloy powder and is stored as a metal hydride.
放出は、この過程を逆にたどる。Release follows this process in reverse.
実施例 （１） 純度99％、32メッシュ以上、100メッシュ以上
のMg粉末に、純度99.5％、平均粒径500ÅのNi超微粒子
をMgの1.0重量％添加、混合し、反応容器に装填する。Example (1) Ni powder having a purity of 99.5% and an average particle size of 500Å was added to Mg powder having a purity of 99%, 32 mesh or more and 100 mesh or more at 1.0 wt% of Mg, mixed, and charged into a reaction vessel.
活性化処理は、常温にて１時間排気後、約30kgf/cm2の
水素を印加し、約１時間で300℃に昇温、１時間保持
後、真空排気、約30kgf/cm2の水素印加のサイクルを２
回繰り返す。For activation, after evacuation at room temperature for 1 hour, apply hydrogen of about 30 kgf / cm 2 , raise to 300 ° C in about 1 hour, hold for 1 hour, evacuation, apply hydrogen of about 30 kgf / cm 2 . The cycle of 2
Repeat times.
次に系を真空排気し、水素を充分に放出させた後、30kg
f/cm2の水素を印加し、時間経過に対し、飽和吸蔵量の
何％を吸収したかにより、速度をみる。Then, the system is evacuated to release hydrogen sufficiently, then 30kg
Apply f / cm 2 of hydrogen and check the speed according to the percentage of the saturated storage amount over time.
（２） 上記（１）式において、吸蔵用合金に、32メッ
シュ以上、100メッシュ以下、Mg:45.3重量％、Ni:54.7
重量％のMg−Ni合金を用い、以下同様に水素の吸蔵を行
う。(2) In the above formula (1), the occlusion alloy contains 32 mesh or more and 100 mesh or less, Mg: 45.3 wt%, Ni: 54.7
Hydrogen is occluded in the same manner as below using a Mg-Ni alloy in a weight percentage.
上記２件の吸蔵速度曲線を第２図に示す。比較のため
に、Ni超微粒子無添加の曲線も示す。The above two storage speed curves are shown in FIG. A curve without addition of Ni ultrafine particles is also shown for comparison.
この図より、吸蔵速度が大きく改善されていることがわ
かる。From this figure, it can be seen that the storage speed is greatly improved.
なお、合金の水素吸蔵速度の測定にあたっては、まず初
期活性化を行ない、次いて測定を行なう。When measuring the hydrogen absorption rate of the alloy, first the initial activation is performed, and then the measurement is performed.
初期活性化 試料表面の水分や吸着ガスは、試料の水素化に大きな防
げとなるので、これを除去しなくてはならない。これを
初期活性化処理という。試料をセルに装填後、ロータリ
ーポンプで約１時間排気する。次に約50kg/cm2の水素を
印加し、室温から500℃まで約２時間で昇温後、300℃ま
で放冷する。この温度で10時間程度保持する。Initial activation Moisture and adsorbed gas on the surface of the sample greatly prevent hydrogenation of the sample and must be removed. This is called initial activation processing. After loading the sample into the cell, evacuate with a rotary pump for about 1 hour. Next, about 50 kg / cm 2 of hydrogen is applied, the temperature is raised from room temperature to 500 ° C in about 2 hours, and then allowed to cool to 300 ° C. Hold at this temperature for about 10 hours.
更に、ロータリーポンプでの排気、約50kg/cm2の水素の
印加を約７時間のサイクルで２回繰り返して活性化処理
の終了とする。Further, exhaustion with a rotary pump and application of hydrogen of about 50 kg / cm 2 are repeated twice in a cycle of about 7 hours to complete the activation treatment.
吸蔵速度の測定 活性化処理を施した試料について、吸蔵速度の測定を行
う。水素化した試料を10〜15時間、ロータリーポンプで
排気し、試料中の水素を完全に放出させる。次に約30kg
/cm2の水素を印加して、圧力の低下から合金1molに吸収
された水素原子のmol数を計算する。これを、Mgに対す
る理論飽和吸蔵量との引で表わす。Measurement of occlusion rate The occlusion rate of the activated sample is measured. The hydrogenated sample is evacuated with a rotary pump for 10-15 hours to completely release the hydrogen in the sample. Next about 30 kg
Applying hydrogen / cm 2 , calculate the mol number of hydrogen atoms absorbed in 1 mol of the alloy from the decrease in pressure. This is expressed by subtraction from the theoretical saturated storage amount with respect to Mg.
第１図は、本発明の水素吸蔵合金の構造とその水素吸蔵
の仕組を説明する図、 第２図は、本発明の水素吸蔵合金の効果を示すためのグ
ラフである。 １……Mg−Ni合金粉末、 ２……Ni超微粒子、 Ｈ……水素分子、 Ｈ′……水素原子。FIG. 1 is a diagram for explaining the structure of the hydrogen storage alloy of the present invention and the mechanism for hydrogen storage, and FIG. 2 is a graph showing the effect of the hydrogen storage alloy of the present invention. 1 ... Mg-Ni alloy powder, 2 ... Ni ultrafine particles, H ... hydrogen molecule, H '... hydrogen atom.
Claims (1)
末と、この粉末に対し、0.5〜2.0重量％の平均粒径0.02
〜1.0μのNi超微粒子とを混在させてなる水素吸蔵合
金。1. An Ng-Ni alloy powder containing 15 to 54.7% by weight of Ni, and an average particle diameter of 0.5 to 2.0% by weight based on the powder, 0.02.
Hydrogen storage alloy that is mixed with ~ 1.0μ Ni ultrafine particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21514086A JPH0784636B2 (en) | 1986-09-12 | 1986-09-12 | Hydrogen storage alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21514086A JPH0784636B2 (en) | 1986-09-12 | 1986-09-12 | Hydrogen storage alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6372849A JPS6372849A (en) | 1988-04-02 |
| JPH0784636B2 true JPH0784636B2 (en) | 1995-09-13 |
Family
ID=16667357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21514086A Expired - Lifetime JPH0784636B2 (en) | 1986-09-12 | 1986-09-12 | Hydrogen storage alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0784636B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3383692B2 (en) * | 1993-02-22 | 2003-03-04 | マツダ株式会社 | Composite hydrogen storage metal member and method of manufacturing the same |
| KR100318370B1 (en) * | 1999-05-21 | 2001-12-22 | 유철호 | Mg2NiHx Hydrogen absorbing materials prepared from Mg and Ni chips by using hydrogen induced mechanical alloying, and a process and device for preparing the same |
| US7694419B2 (en) * | 2005-04-27 | 2010-04-13 | The Gillette Company | Battery-operated appliances |
| JP4462301B2 (en) | 2007-07-27 | 2010-05-12 | トヨタ自動車株式会社 | Method for producing hydrogen storage material |
| WO2011027462A1 (en) * | 2009-09-04 | 2011-03-10 | 株式会社アツミテック | Hydrogen storage unit |
| CN102596451B (en) * | 2009-09-04 | 2015-01-07 | 株式会社渥美精机 | Hydrogen storage alloy and hydrogen storage unit using same |
-
1986
- 1986-09-12 JP JP21514086A patent/JPH0784636B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6372849A (en) | 1988-04-02 |
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