JPH07268514A - Hydrogen occluding alloy and hydrogen occluding alloy electrode - Google Patents
Hydrogen occluding alloy and hydrogen occluding alloy electrodeInfo
- Publication number
- JPH07268514A JPH07268514A JP6057514A JP5751494A JPH07268514A JP H07268514 A JPH07268514 A JP H07268514A JP 6057514 A JP6057514 A JP 6057514A JP 5751494 A JP5751494 A JP 5751494A JP H07268514 A JPH07268514 A JP H07268514A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- phase
- hydrogen storage
- solid solution
- hydrogen
- 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
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/383—Hydrogen absorbing alloys
-
- 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
- Y02E60/10—Energy storage using batteries
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、水素吸蔵合金及び水素
吸蔵合金電極に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogen storage alloy and a hydrogen storage alloy electrode.
【０００２】[0002]
【従来技術とその課題】水素吸蔵合金は、大量の水素を
可逆的に吸蔵・放出することができるため、水素ガスの
貯蔵用材料、ヒートポンプ等の熱利用システム用の材
料、ニッケル−水素電池用の負極用材料などとして幅広
い用途への利用が期待されている。BACKGROUND OF THE INVENTION Hydrogen storage alloys are capable of reversibly storing and releasing a large amount of hydrogen. Therefore, hydrogen storage materials, materials for heat utilization systems such as heat pumps, nickel-hydrogen batteries, etc. It is expected to be used in a wide range of applications as a negative electrode material.
【０００３】水素吸蔵合金には、ＬａＮｉ5 等のＡＢ5
型合金、ＺｒＭｎ2 等のＡＢ2 型ラーベス合金、ＴｉＦ
ｅ等のＡＢ型合金、Ｍｇ2 Ｎｉ等のＡ2 Ｂ型合金、Ｔｉ
−Ｖ等の固溶体合金などが知られている。この中でも、
特に、固溶体合金は、水素吸蔵量が非常に大きく、しか
もコスト面において他の合金に比べて有利であるという
特徴がある。For hydrogen storage alloys, AB 5 such as LaNi 5 is used.
Type alloy, AB 2 type Laves alloy such as ZrMn 2 , TiF
AB type alloys such as e, A 2 B type alloys such as Mg 2 Ni, Ti
Solid solution alloys such as -V are known. Among these,
In particular, the solid solution alloy is characterized in that it has a very large hydrogen storage capacity and is more advantageous in cost than other alloys.
【０００４】しかしながら、固溶体合金は、水素の吸蔵
・放出を繰り返す際のサイクル寿命が短く、またニッケ
ル−水素電池用の負極として用いる場合の電気化学的な
反応が比較的遅いため、これらの点において未だ改善の
余地がある。However, the solid solution alloy has a short cycle life when hydrogen is repeatedly occluded and released, and the electrochemical reaction when it is used as a negative electrode for a nickel-hydrogen battery is relatively slow. There is still room for improvement.
【０００５】[0005]
【発明が解決しようとする課題】従って、本発明は、水
素吸蔵特性に優れ、電池の負極用材料としても好適な水
素吸蔵合金を提供することを主な目的とする。SUMMARY OF THE INVENTION Therefore, the main object of the present invention is to provide a hydrogen storage alloy which has excellent hydrogen storage characteristics and is suitable as a material for a negative electrode of a battery.
【０００６】[0006]
【課題を解決するための手段】本発明者は、上記従来技
術の問題に鑑み、Ｔｉ−Ｖ系固溶体合金にニッケルを添
加することによってその電気化学的反応を促進させ、水
素吸蔵特性の改善を試みた。しかし、ニッケル単独の添
加では、例えばニッケル−水素電池用の負極として用い
た場合、バナジウムの電解液中への溶解が著しいため、
サイクル寿命が短く、放電容量も小さく、上記特性を十
分改善できないことが判明した。In view of the above problems of the prior art, the inventor of the present invention improves the hydrogen storage characteristics by adding nickel to a Ti-V solid solution alloy to accelerate its electrochemical reaction. I tried. However, with the addition of nickel alone, when used as a negative electrode for a nickel-hydrogen battery, for example, because the dissolution of vanadium in the electrolytic solution is remarkable,
It was found that the cycle life was short, the discharge capacity was small, and the above characteristics could not be sufficiently improved.
【０００７】そこで、本発明者は、さらに特定の元素を
ニッケルと併用して添加したところ、従来では見られな
かった特異な構造をもつ水素吸蔵合金が得られ、この合
金はサイクル寿命、放電容量等の水素吸蔵特性が大幅に
改善されることを見出し、本発明を完成するに至った。Therefore, the present inventor further added a specific element together with nickel to obtain a hydrogen storage alloy having a peculiar structure which was not seen in the past, and this alloy has a cycle life and a discharge capacity. The inventors have found that the hydrogen storage characteristics such as the above are significantly improved, and have completed the present invention.
【０００８】即ち、本発明は、Ｔｉ−Ｖ系固溶体合金に
おいて、Ｔｉ−Ｖ系固溶体合金からなる母相中に、ＡＢ
2 型ラーベス合金相を主相とする相が３次元網目骨格を
形成して存在することを特徴とする水素吸蔵合金に係る
ものである。That is, according to the present invention, in a Ti-V type solid solution alloy, AB is added in a mother phase composed of the Ti-V type solid solution alloy.
The present invention relates to a hydrogen storage alloy characterized in that a phase having a type 2 Laves alloy phase as a main phase forms and exists in a three-dimensional network skeleton.
【０００９】以下、本発明について詳細に説明する。The present invention will be described in detail below.
【００１０】本発明の水素吸蔵合金は、上記のようにＴ
ｉ−Ｖ系固溶体合金からなる母相中に、ＡＢ2 型ラーベ
ス合金相を主相とする相が３次元網目骨格を形成して存
在するという特異な構造を有するものである。The hydrogen storage alloy of the present invention has the above-mentioned T content.
It has a peculiar structure in which a phase having an AB 2 type Laves alloy phase as a main phase exists in a matrix consisting of an i-V type solid solution alloy to form a three-dimensional network skeleton.
【００１１】上記Ｔｉ−Ｖ系固溶体合金は、合金全体と
してＴｉＶαＮｉβＡγＭδなる組成を有することが望
ましい。上記組成式中Ａは、Ｚｒ、Ｈｆ及びＴａの少な
くとも１種の元素を示す。これら元素（Ａ）が全く含ま
れていない場合には、３次元網目骨格を形成すべき相が
析出しなくなるおそれがあるので好ましくない。上記Ｍ
は、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｃｕ及びＮｂの少なくと
も１種の元素を示す。なお、本発明の効果を低減させな
い限り、上記以外の他の元素が含まれていても良い。上
記組成式中αは１〜１０、βは０．２〜２、γは０．０
５〜１、δは０〜２の範囲であることが好ましい。上記
α、β、γ及びδのうち１つでも、これらの数値範囲外
となる場合は、水素吸蔵量が低下するか、或いはＡＢ2
型ラーベス相を主相とする相が三次元網目骨格として析
出しなくなるおそれがあるので好ましくない。The above Ti-V type solid solution alloy preferably has a composition of TiVαNiβAγMδ as the whole alloy. In the above composition formula, A represents at least one element of Zr, Hf, and Ta. When these elements (A) are not contained at all, the phase for forming the three-dimensional network skeleton may not be precipitated, which is not preferable. M above
Indicates at least one element of Cr, Mn, Fe, Co, Cu and Nb. In addition, as long as the effect of the present invention is not reduced, elements other than the above may be contained. In the above composition formula, α is 1 to 10, β is 0.2 to 2, and γ is 0.0.
It is preferable that 5-1 and δ are in the range of 0-2. If even one of α, β, γ, and δ is out of these numerical ranges, the hydrogen storage amount is reduced or AB 2
This is not preferable because the phase having the Laves phase as the main phase may not precipitate as a three-dimensional network skeleton.
【００１２】本発明合金中のＡＢ2 型ラーベス合金相を
主相とする相（以下「第２相」という。）は、ＴｉεＡ
ζＮｉηＶθＭιなる組成を有する。上記組成式中Ａは
Ｚｒ、Ｈｆ及びＴａの少なくとも１種の元素を示す。こ
れらの元素が含まれていない場合は、ラーベス合金相そ
のものが析出しなくなるので好ましくない。また、同式
中Ｍは、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｃｕ及びＮｂの
少なくとも１種の元素を示す。なお、本発明の効果に悪
影響を及ぼさない範囲であれば、これらの元素以外の元
素が含まれていても差支えない。また、上記組成式中ε
は０．１〜０．４、ζは０．１〜０．４、ηは０．１〜
０．６、θは０．１〜０．５、ιは０〜０．２、かつε
＋ζ＋η＋θ＋ι＝１であることが望ましい。これらの
いずれかが上記の数値範囲外となる場合は、耐久性の低
下又は水素吸蔵反応の阻害を招くおそれがあるので好ま
しくない。The phase having the AB 2 type Laves alloy phase as the main phase (hereinafter referred to as “second phase”) in the alloy of the present invention is TiεA.
It has a composition of ζNiηVθMι. In the above composition formula, A represents at least one element of Zr, Hf, and Ta. When these elements are not contained, the Laves alloy phase itself does not precipitate, which is not preferable. In the formula, M represents at least one element selected from V, Cr, Mn, Fe, Co, Cu, and Nb. In addition, as long as the effect of the present invention is not adversely affected, elements other than these elements may be contained. In the composition formula above, ε
Is 0.1 to 0.4, ζ is 0.1 to 0.4, and η is 0.1 to
0.6, θ is 0.1 to 0.5, ι is 0 to 0.2, and ε
It is desirable that + ζ + η + θ + ι = 1. If any of these is out of the above numerical range, durability may be deteriorated or hydrogen storage reaction may be hindered, which is not preferable.
【００１３】第２相中、ＡＢ2 型ラーベス合金相の含有
率は通常５体積％以上であり、残部は他の相を含んでい
ても良い。The content of the AB 2 type Laves alloy phase in the second phase is usually 5% by volume or more, and the balance may contain other phases.
【００１４】上記第２相は、上記のＴｉＶαＮｉβＡγ
Ｍδ系固溶体合金からなる母相中に３次元網目骨格を形
成している。Ｔｉ−Ｖ系固溶体合金における第２相の占
める体積割合は、合金全体の組成、製造条件等によって
異なり、合金の用途等に応じて適宜設定すれば良い。The second phase is TiVαNiβAγ.
A three-dimensional network skeleton is formed in the mother phase composed of the Mδ-based solid solution alloy. The volume ratio of the second phase in the Ti-V solid solution alloy varies depending on the composition of the entire alloy, manufacturing conditions, etc., and may be appropriately set according to the application of the alloy and the like.
【００１５】本発明の水素吸蔵合金は、上記ＴｉＶαＮ
ｉβＡγＭδなる組成に調製した原料粉末を、アーク溶
解法等の公知の方法により加熱溶解させ、これを冷却す
ることによって得ることができる。上記の原料粉末は、
市販の原料粉末をそのまま適用することができる。ま
た、必要に応じて、ＣａＢ6 等のように、溶湯から酸化
物を除去する働きをもつ添加剤を配合することもでき
る。The hydrogen storage alloy of the present invention is the above TiVαN.
It can be obtained by heating and melting a raw material powder prepared to have a composition of iβAγMδ by a known method such as an arc melting method, and then cooling this. The above raw material powder is
A commercially available raw material powder can be applied as it is. Further, if necessary, an additive having a function of removing oxides from the molten metal, such as CaB 6 , can be added.
【００１６】本発明の水素吸蔵合金電極は、上記の本発
明の水素吸蔵合金を含有するものである。例えば、上記
のＴｉＶαＮｉβＡγＭδなる組成に調製した原料粉末
に銅粉等を配合し、これを所定の形状にプレス成形等に
より成形すれば得られる。The hydrogen storage alloy electrode of the present invention contains the above hydrogen storage alloy of the present invention. For example, it can be obtained by mixing raw material powder prepared to have the composition of TiVαNiβAγMδ with copper powder or the like, and press-molding the powder into a predetermined shape.
【００１７】[0017]
【発明の効果】このように、本発明の水素吸蔵合金は、
母相に対して第２相が３次元網目骨格を形成して存在し
ているので、当該第２相がＴｉ−Ｖ系固溶体合金をマイ
クロカプセル化したような状態となり、これにより水素
の吸蔵・放出に伴う微粉化が大幅に抑制されることとな
る。As described above, the hydrogen storage alloy of the present invention is
Since the second phase exists with respect to the mother phase in the form of a three-dimensional network skeleton, the second phase becomes a state in which the Ti-V based solid solution alloy is microencapsulated. The pulverization associated with the release will be greatly suppressed.
【００１８】また、第２相が保護膜となって水素吸蔵合
金の主要元素であるバナジウムの溶解を抑制乃至防止す
ることができるので、耐アルカリ性が改善される結果、
サイクル寿命を向上させることができる。さらに、第２
相は、反応触媒相としての役割も果たすため、本発明水
素吸蔵合金を電極として使用する場合には、放電時の反
応速度を増大させることも可能となる。Further, since the second phase serves as a protective film and can suppress or prevent the dissolution of vanadium which is the main element of the hydrogen storage alloy, the alkali resistance is improved.
The cycle life can be improved. Furthermore, the second
Since the phase also serves as a reaction catalyst phase, when the hydrogen storage alloy of the present invention is used as an electrode, it becomes possible to increase the reaction rate during discharge.
【００１９】[0019]
【実施例】以下、実施例を示し、本発明の特徴とすると
ころをより明確にする。EXAMPLES Examples will be shown below to clarify the characteristics of the present invention.
【００２０】実施例１ 市販のＴｉ、Ｖ、Ｎｉ及びＺｒを用いて、組成がＴｉＶ
3 Ｎｉ0.56Ｚｒ0.05となるように秤量して混合し、アー
ク溶解法により加熱溶解させて合金を作製した。得られ
た合金を樹脂に封入して断面を研磨した後、走査型電子
顕微鏡及びＥＰＭＡにより合金断面の元素分析を行っ
た。その断面の状態を図１に示す。Example 1 Commercially available Ti, V, Ni and Zr were used, and the composition was TiV.
3 Ni 0.56 Zr 0.05 was weighed and mixed so as to be melted by heating by an arc melting method to prepare an alloy. After sealing the obtained alloy in a resin and polishing the cross section, elemental analysis of the cross section of the alloy was performed by a scanning electron microscope and EPMA. The state of the cross section is shown in FIG.
【００２１】上記の結果、Ｔｉ−Ｖ系固溶体合金相Ｔｉ
Ｖ5.76Ｎｉ0.32Ｚｒ0.02の粒界部分にＡＢ2 型ラーベス
合金相を主相とする相Ｔｉ0.25Ｚｒ0.16Ｎｉ0.32Ｖ0.27
（白い部分）が析出し、母相に対して３次元網目骨格を
形成していることが確認された。As a result of the above, Ti--V type solid solution alloy phase Ti
V 5.76 Ni 0.32 Zr 0.02 A phase having an AB 2 type Laves alloy phase as a main phase at the grain boundary portion Ti 0.25 Zr 0.16 Ni 0.32 V 0.27
It was confirmed that (white portion) was precipitated and formed a three-dimensional network skeleton with respect to the matrix.
【００２２】実施例２ 市販のＴｉ、Ｖ、Ｎｉ及びＨｆを用いて、組成がＴｉＶ
3 Ｎｉ0.56Ｈｆ0.24となるように秤量して混合し、アー
ク溶解法により加熱溶解させて合金を作製した。得られ
た合金を樹脂に封入して断面を研磨した後、走査型電子
顕微鏡及びＥＰＭＡにより合金断面の元素分析を行っ
た。Example 2 Commercially available Ti, V, Ni and Hf were used, and the composition was TiV.
3 Ni 0.56 Hf 0.24 was weighed and mixed so as to be melted by heating by an arc melting method to prepare an alloy. After sealing the obtained alloy in a resin and polishing the cross section, elemental analysis of the cross section of the alloy was performed by a scanning electron microscope and EPMA.
【００２３】その結果、Ｔｉ−Ｖ系固溶体合金相ＴｉＶ
5.34Ｎｉ0.30Ｈｆ0.09の粒界部分にＡＢ2 型ラーベス合
金相を主相とする相Ｔｉ0.25Ｈｆ0.18Ｎｉ0.29Ｖ0.28が
析出し、母相に対して３次元網目骨格を形成しているこ
とが確認された。As a result, Ti--V type solid solution alloy phase TiV
5.34 Ni 0.30 Hf 0.09 At the grain boundary part, the phase Ti 0.25 Hf 0.18 Ni 0.29 V 0.28 having the AB 2 type Laves alloy phase as the main phase is precipitated and forms a three-dimensional network skeleton with respect to the parent phase. confirmed.
【００２４】実施例３ 表１に示す組成の本発明合金（試料Ｎｏ．１〜１２）で
電極を作製し、この電極を用いて電池を作製した。Example 3 An electrode was prepared from the alloy of the present invention (Sample Nos. 1 to 12) having the composition shown in Table 1, and a battery was prepared using this electrode.
【００２５】試料Ｎｏ．１〜１５の組成の合金粉末０．
２ｇを電解銅粉０．６ｇと混合して直径１３ｍｍのペレ
ット状にプレスした電極を負極とし、水酸化ニッケル電
極を正極とし、６Ｍ水酸化カリウム水溶液を電解液とし
てニッケル−水素電池を作製した。この電池を２０ｍＡ
の電流で５時間充電した後、１０ｍＡの電流で放電させ
た際の充放電サイクル試験の結果を表１に示す。Sample No. Alloy powder having a composition of 1 to 15
A nickel-hydrogen battery was prepared by mixing 2 g with 0.6 g of electrolytic copper powder and pressing it into a pellet having a diameter of 13 mm as a negative electrode, a nickel hydroxide electrode as a positive electrode, and a 6 M potassium hydroxide aqueous solution as an electrolytic solution. This battery is 20mA
Table 1 shows the results of the charge / discharge cycle test when the battery was charged with the current of 5 hours for 5 hours and then discharged with the current of 10 mA.
【００２６】なお、比較のため、本発明合金の組成をも
たない合金粉末を用いて上記と同様にして作製した電極
（比較試料Ｎｏ．１〜４）を用いて同様の電池を作製
し、充放電サイクル試験をした。その結果も表１に併記
する。For comparison, a similar battery was prepared using the electrodes (Comparative Sample Nos. 1 to 4) prepared in the same manner as described above by using the alloy powder having no composition of the alloy of the present invention, A charge / discharge cycle test was conducted. The results are also shown in Table 1.
【００２７】[0027]
【表１】 [Table 1]
【図１】実施例１の水素吸蔵合金の結晶構造を走査型電
子顕微鏡で観察した状態を示す図である。FIG. 1 is a diagram showing a state in which a crystal structure of a hydrogen storage alloy of Example 1 is observed with a scanning electron microscope.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 高橋 国男 愛知県刈谷市八軒町５丁目50番地 株式会 社イムラ材料開発研究所内 (72)発明者 三島 貴弘 愛知県刈谷市八軒町５丁目50番地 株式会 社イムラ材料開発研究所内 (72)発明者 磯村 秋人 愛知県刈谷市八軒町５丁目50番地 株式会 社イムラ材料開発研究所内 (72)発明者 境 哲男 大阪府池田市緑丘１丁目８番31号 工業技 術院大阪工業技術研究所内 (72)発明者 宮村 弘 大阪府池田市緑丘１丁目８番31号 工業技 術院大阪工業技術研究所内 (72)発明者 上原 斎 大阪府池田市緑丘１丁目８番31号 工業技 術院大阪工業技術研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kunio Takahashi 5-50 Hachiken-cho, Kariya city, Aichi Prefectural Institute for Imla Materials Development (72) Inventor Takahiro Mishima 5-chome Hachiken-cho, Kariya city, Aichi prefecture Address: Imla Material Development Laboratory (72) Inventor Akito Isomura 5-50, Hachiken-cho, Kariya City, Aichi Prefecture Imla Material Development Laboratory (72) Inventor Tetsuo Sakai 1-chome, Midorigaoka, Ikeda, Osaka 8-31 Industrial Technology Institute Osaka Industrial Technology Research Institute (72) Inventor Hiroshi Miyamura 1-831 Midorigaoka, Ikeda City, Osaka Prefecture Industrial Technology Institute Osaka Industrial Technology Research Institute (72) Inventor Sai Uehara Ikeda, Osaka Prefecture 1-8-31 Midorigaoka, Yokohama-shi Industrial Technology Institute Osaka Industrial Technology Research Institute
Claims (6)
系固溶体合金からなる母相中に、ＡＢ2 型ラーベス合金
相を主相とする相が３次元網目骨格を形成して存在する
ことを特徴とする水素吸蔵合金。1. A Ti-V solid solution alloy comprising Ti-V
A hydrogen storage alloy, characterized in that a matrix having an AB 2 type Laves alloy phase as a main phase is present in a matrix consisting of a solid solution alloy forming a three-dimensional network skeleton.
ＴｉＶαＮｉβＡγＭδ（但し、ＡはＺｒ、Ｈｆ及びＴ
ａの少なくとも１種の元素、ＭはＣｒ、Ｍｎ、Ｆｅ、Ｃ
ｏ、Ｃｕ及びＮｂの少なくとも１種の元素、１≦α≦１
０、０．２≦β≦２、０．０５≦γ≦１、０＜δ≦２）
なる組成を有する請求項１記載の水素吸蔵合金。2. A Ti-V based solid solution alloy comprising TiVαNiβAγMδ (where A is Zr, Hf and T) as a whole alloy.
at least one element of a, M is Cr, Mn, Fe, C
o, at least one element of Cu and Nb, 1 ≦ α ≦ 1
0, 0.2 ≦ β ≦ 2, 0.05 ≦ γ ≦ 1, 0 <δ ≦ 2)
The hydrogen storage alloy according to claim 1, having the following composition.
が、ＴｉεＡζＮｉηＶθＭι（但し、ＡはＺｒ、Ｈｆ
及びＴａの少なくとも１種の元素、ＭはＣｒ、Ｍｎ、Ｆ
ｅ、Ｃｏ、Ｃｕ及びＮｂの少なくとも１種の元素、０．
１≦ε≦０．４、０．１≦ζ≦０．４、０．１≦η≦
０．６、０．１≦θ≦０．５、０＜ι≦０．２、かつε
＋ζ＋η＋θ＋ι＝１）なる組成である請求項１又は２
に記載の水素吸蔵合金。3. A phase having an AB 2 type Laves alloy phase as a main phase is TiεAζNiηVθMι (where A is Zr, Hf
And at least one element of Ta, M is Cr, Mn, F
e, Co, Cu and Nb, at least one element, 0.
1 ≦ ε ≦ 0.4, 0.1 ≦ ζ ≦ 0.4, 0.1 ≦ η ≦
0.6, 0.1 ≦ θ ≦ 0.5, 0 <ι ≦ 0.2, and ε
The composition is + ζ + η + θ + ι = 1).
Hydrogen storage alloy according to.
ｉＶαＮｉβＡγ（但し、ＡはＺｒ、Ｈｆ及びＴａの少
なくとも１種の元素、１≦α≦１０、０．２≦β≦２、
０．０５≦γ≦１）なる組成を有する請求項１記載の水
素吸蔵合金。4. A Ti-V solid solution alloy containing T as a whole alloy.
iVαNiβAγ (where A is at least one element of Zr, Hf, and Ta, 1 ≦ α ≦ 10, 0.2 ≦ β ≦ 2,
The hydrogen storage alloy according to claim 1, having a composition of 0.05 ≦ γ ≦ 1).
が、ＴｉεＡζＮｉηＶθ（但し、ＡはＺｒ、Ｈｆ及び
Ｔａの少なくとも１種の元素、０．１≦ε≦０．４、
０．１≦ζ≦０．４、０．１≦η≦０．６、０．１≦θ
≦０．５、かつε＋ζ＋η＋θ＝１）なる組成である請
求項１、２及び４のいずれかに記載の水素吸蔵合金。5. A phase having an AB 2 type Laves alloy phase as a main phase is TiεAζNiηVθ (where A is at least one element of Zr, Hf and Ta, 0.1 ≦ ε ≦ 0.4,
0.1 ≦ ζ ≦ 0.4, 0.1 ≦ η ≦ 0.6, 0.1 ≦ θ
The hydrogen storage alloy according to claim 1, having a composition of ≦ 0.5 and ε + ζ + η + θ = 1).
系固溶体合金からなる母相中に、ＡＢ2 型ラーベス合金
相を主相とする相が３次元網目骨格を形成して存在する
水素吸蔵合金を含有することを特徴とする水素吸蔵合金
電極。6. A Ti-V-based solid solution alloy containing Ti-V
A hydrogen storage alloy electrode, comprising a hydrogen storage alloy in which a phase having an AB 2 type Laves alloy phase as a main phase forms a three-dimensional network skeleton in a mother phase composed of a solid solution alloy.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6057514A JPH07268514A (en) | 1994-03-28 | 1994-03-28 | Hydrogen occluding alloy and hydrogen occluding alloy electrode |
| US08/410,798 US5690799A (en) | 1994-03-28 | 1995-03-27 | Hydrogen-occluding alloy and hydrogen-occluding alloy electrode |
| US08/822,043 US5776626A (en) | 1994-03-28 | 1997-03-24 | Hydrogen-occluding alloy and hydrogen-occluding alloy electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6057514A JPH07268514A (en) | 1994-03-28 | 1994-03-28 | Hydrogen occluding alloy and hydrogen occluding alloy electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07268514A true JPH07268514A (en) | 1995-10-17 |
Family
ID=13057853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6057514A Pending JPH07268514A (en) | 1994-03-28 | 1994-03-28 | Hydrogen occluding alloy and hydrogen occluding alloy electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07268514A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07268513A (en) * | 1994-03-28 | 1995-10-17 | Imura Zairyo Kaihatsu Kenkyusho:Kk | Hydrogen occluding alloy and hydrogen occluding alloy electrode |
| EP1026763A1 (en) * | 1997-09-30 | 2000-08-09 | Sanyo Electric Co., Ltd. | Hydrogen absorbing allow electrode and method of producing the same |
| US6309779B1 (en) | 1999-02-17 | 2001-10-30 | Matsushita Electric Industrial Co., Ltd. | Hydrogen storage alloy electrode and method for manufacturing the same |
| US6338764B1 (en) | 1998-04-30 | 2002-01-15 | Toyota Jidosha Kabushiki Kaisha | Hydrogen-absorbing alloy and hydrogen-absorbing alloy electrode |
| US6632567B2 (en) * | 2000-03-23 | 2003-10-14 | Sanyo Electric Co., Ltd. | Nickel-metal hydride storage battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01119636A (en) * | 1986-12-29 | 1989-05-11 | Energy Conversion Devices Inc | Charge holding and strengthening electrochemical hydrogen occlusion alloy and cell |
| JPH01165737A (en) * | 1987-11-17 | 1989-06-29 | Kuochih Hong | Hydrogen storing method and hydride electrode material |
| JPH03294405A (en) * | 1990-04-11 | 1991-12-25 | Energy Conversion Devices Inc | Continuous production of negative electrode consisting of finely pulverized hydrogen occluded alloy material |
| JPH05247568A (en) * | 1990-10-11 | 1993-09-24 | Hitachi Maxell Ltd | Hydrogen storage alloy electrode and battery using them |
| JPH07268513A (en) * | 1994-03-28 | 1995-10-17 | Imura Zairyo Kaihatsu Kenkyusho:Kk | Hydrogen occluding alloy and hydrogen occluding alloy electrode |
-
1994
- 1994-03-28 JP JP6057514A patent/JPH07268514A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01119636A (en) * | 1986-12-29 | 1989-05-11 | Energy Conversion Devices Inc | Charge holding and strengthening electrochemical hydrogen occlusion alloy and cell |
| JPH01165737A (en) * | 1987-11-17 | 1989-06-29 | Kuochih Hong | Hydrogen storing method and hydride electrode material |
| JPH03294405A (en) * | 1990-04-11 | 1991-12-25 | Energy Conversion Devices Inc | Continuous production of negative electrode consisting of finely pulverized hydrogen occluded alloy material |
| JPH05247568A (en) * | 1990-10-11 | 1993-09-24 | Hitachi Maxell Ltd | Hydrogen storage alloy electrode and battery using them |
| JPH07268513A (en) * | 1994-03-28 | 1995-10-17 | Imura Zairyo Kaihatsu Kenkyusho:Kk | Hydrogen occluding alloy and hydrogen occluding alloy electrode |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07268513A (en) * | 1994-03-28 | 1995-10-17 | Imura Zairyo Kaihatsu Kenkyusho:Kk | Hydrogen occluding alloy and hydrogen occluding alloy electrode |
| JP2719884B2 (en) * | 1994-03-28 | 1998-02-25 | 株式会社イムラ材料開発研究所 | Hydrogen storage alloy and hydrogen storage alloy electrode |
| EP1026763A1 (en) * | 1997-09-30 | 2000-08-09 | Sanyo Electric Co., Ltd. | Hydrogen absorbing allow electrode and method of producing the same |
| EP1026763A4 (en) * | 1997-09-30 | 2004-12-22 | Sanyo Electric Co | Hydrogen absorbing allow electrode and method of producing the same |
| US6338764B1 (en) | 1998-04-30 | 2002-01-15 | Toyota Jidosha Kabushiki Kaisha | Hydrogen-absorbing alloy and hydrogen-absorbing alloy electrode |
| DE19918329B4 (en) * | 1998-04-30 | 2008-02-14 | Toyota Jidosha Kabushiki Kaisha, Toyota | A hydrogen absorbing alloy and electrode comprising the hydrogen absorbing alloy |
| US6309779B1 (en) | 1999-02-17 | 2001-10-30 | Matsushita Electric Industrial Co., Ltd. | Hydrogen storage alloy electrode and method for manufacturing the same |
| US6632567B2 (en) * | 2000-03-23 | 2003-10-14 | Sanyo Electric Co., Ltd. | Nickel-metal hydride storage battery |
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