JP3088133B2 - Hydrogen storage electrode - Google Patents
Hydrogen storage electrodeInfo
- Publication number
- JP3088133B2 JP3088133B2 JP03141850A JP14185091A JP3088133B2 JP 3088133 B2 JP3088133 B2 JP 3088133B2 JP 03141850 A JP03141850 A JP 03141850A JP 14185091 A JP14185091 A JP 14185091A JP 3088133 B2 JP3088133 B2 JP 3088133B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- cobalt
- electrode
- alloy
- metal
- 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
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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
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、サイクル特性、高温特
性が共に優れた水素吸蔵電極に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogen storage electrode having excellent cycle characteristics and high temperature characteristics.
【０００２】[0002]
【従来の技術】水素吸蔵合金からなる水素吸蔵電極を用
いたニッケル水素蓄電池は、従来の蓄電池に比してエネ
ルギー密度が高く、特にニッケルカドミウム蓄電池の比
較においては、カドミウムを含まないクリーンな蓄電池
として近年非常に注目を集めている。2. Description of the Related Art A nickel-metal hydride storage battery using a hydrogen storage electrode made of a hydrogen storage alloy has a higher energy density than a conventional storage battery. In particular, in comparison with a nickel cadmium storage battery, it is a clean storage battery containing no cadmium. In recent years, it has attracted much attention.
【０００３】[0003]
【発明が解決しようとする問題点】蓄電池に用いる水素
吸蔵電極に要求される条件としては、電極として大気
圧下又は数気圧の密閉容器内で反応させる必要があるの
で、常温、常圧付近で水素の吸蔵放出が可能なこと、
電解液中であってもスムーズに電気化学的な水素の吸蔵
放出反応即ち充放電反応が可能なこと、サイクル寿命
の観点から合金が電解液中で長期間安定に存在し得るこ
と、実用化に即して水素吸蔵合金のコストが小さいこ
と、等が挙げられる。The conditions required for the hydrogen storage electrode used in the storage battery are that the electrode must be reacted under atmospheric pressure or in a closed vessel at a few atmospheric pressures. Capable of storing and releasing hydrogen,
To be able to smoothly perform electrochemical hydrogen absorption / desorption reactions, that is, charge / discharge reactions, even in electrolytes; to be able to stably exist alloys in electrolytes for a long period of time from the viewpoint of cycle life; That is, the cost of the hydrogen storage alloy is small.
【０００４】ところで当初、水素吸蔵電極として用いら
れてきた水素吸蔵合金は、ＬａＮｉ5であったが、これ
はサイクル寿命が短く、しかもＬａを用いるために高価
であるという欠点を有していた。そこでＬａの代わり
に、希土類金属の混合物であるＭｍ（ミッシュメタル）
が用いられるようになった。しかしそれでは水素吸蔵圧
が非常に高くなる。そこでＡｌを添加することにより水
素吸蔵圧を常温で常圧付近にまで低下させ、電池として
使用できるようにしていた。水素吸蔵電極は、温度の影
響を受け易いものであるが、Ａｌによる置換量を増す
と、高温でも特性の低下が少なくなる。しかしＡｌはア
ルカリ電解液中で容易に酸化され、電解液中に溶出して
しまう。このためＡｌにより多量に置換された水素吸蔵
合金では、サイクル寿命が短くなるという問題があっ
た。従って現実的には高温特性を犠牲にして合金組成が
決定されており、その改良が望まれていた。At first, the hydrogen storage alloy used as the hydrogen storage electrode was LaNi 5 , which had the drawback that it had a short cycle life and was expensive due to the use of La. Therefore, instead of La, Mm (Misch metal), which is a mixture of rare earth metals
Came to be used. However, in that case, the hydrogen storage pressure becomes very high. Therefore, by adding Al, the hydrogen storage pressure is reduced to near normal pressure at normal temperature, so that the battery can be used. The hydrogen storage electrode is easily affected by temperature. However, when the replacement amount with Al is increased, the deterioration of the characteristics is reduced even at a high temperature. However, Al is easily oxidized in an alkaline electrolyte and elutes into the electrolyte. For this reason, the hydrogen storage alloy replaced with a large amount of Al has a problem that the cycle life is shortened. Therefore, in reality, the alloy composition is determined at the expense of high-temperature characteristics, and improvement thereof has been desired.
【０００５】[0005]
【発明の目的】本発明は、上記〜の条件を満たすこ
とができ、特にＡｌにより多量に置換されていてもサイ
クル特性及び高温特性の両方に優れている水素吸蔵電極
を提供することを目的とする。An object of the present invention is to provide a hydrogen storage electrode which satisfies the above-mentioned conditions and, in particular, has excellent cycle characteristics and high-temperature characteristics even when substituted by a large amount of Al. I do.
【０００６】[0006]
【目的を達成するための手段】本発明の水素吸蔵電極
は、原子数比による示性式がＬｎＮｉxＡｌyＭv（Ｌｎ
はミッシュメタル又は希土類金属の混合物であり、Ｍは
Ｆｅ、Ｃｏ、Ｍｎ、Ｃｕ、Ｃｒ、Ｓｉ、Ｎｂ、Ｂの内の
少なくとも１種であり、ｘ、ｙ、ｖは、３．５＜ｘ≦
５．０、０．９＜ｙ≦２．５、０＜ｖ＜１．６、４．４
＜ｘ＋ｙ＋ｖ≦６．０である）である水素吸蔵合金の粉
末に、金属コバルト粉末を３〜２０重量％の範囲で物理
的に混合することにより添加して形成されたことを特徴
とするものである。Hydrogen storage electrodes of the present invention, in order to achieve the object] is rational formula by an atomic ratio of LnNi x Al y M v (Ln
Is a mixture of a misch metal or a rare earth metal, M is at least one of Fe, Co, Mn, Cu, Cr, Si, Nb, and B, and x, y, and v are 3.5 <x ≦
5.0, 0.9 <y ≦ 2.5, 0 <v <1.6, 4.4
<X + y + v ≦ 6.0) is formed by adding a metallic cobalt powder by physically mixing it in a range of 3 to 20% by weight to a powder of the hydrogen storage alloy. is there.
【０００７】[0007]
【作用】Ａｌの水素吸蔵合金の特性に対する作用はＡＢ
5型金属間化合物の結晶格子間隔を拡大し、水素吸蔵放
出を容易にすることである。このためＡｌによる多量置
換により、水素吸蔵は、高温充電時において競合反応で
ある水素ガス発生よりもスムーズに行なわれる。従って
電極の温度特性を向上させるためには、Ａｌ量を増加さ
せること（望ましくは０．９＜ｙ）が顕著な効果を得る
ための方法であった。しかし前述したように、Ａｌ量の
増加とともにサイクル数が低下するという問題があっ
た。このためＡｌ置換量は自ずと制限されていた。しか
し本発明においては、コバルトを添加することによりサ
イクル特性が著しく向上するため、Ａｌにより多量置換
しても、高温特性とサイクル特性の両立が図られること
となる。但し、Ａｌ＞２．５となると、電解液へのＡｌ
の溶出が激しくなるので、コバルトを添加してもサイク
ル特性の低下は防ぎきれないこととなる。The effect of Al on the properties of the hydrogen storage alloy is AB
The purpose is to increase the crystal lattice spacing of the type 5 intermetallic compound to facilitate hydrogen storage and release. For this reason, due to the large amount of replacement with Al, hydrogen storage is performed more smoothly than hydrogen gas generation which is a competitive reaction during high-temperature charging. Therefore, in order to improve the temperature characteristics of the electrode, increasing the amount of Al (preferably 0.9 <y) has been a method for obtaining a remarkable effect. However, as described above, there is a problem that the number of cycles decreases with an increase in the amount of Al. For this reason, the amount of Al substitution was naturally limited. However, in the present invention, the cycle characteristics are remarkably improved by adding cobalt. Therefore, even when a large amount of Al is substituted, both high temperature characteristics and cycle characteristics can be achieved. However, if Al> 2.5, the Al
Elutes intensely, so that even if cobalt is added, deterioration of cycle characteristics cannot be prevented.
【０００８】コバルトの作用機構はまだ明確になっては
いないが、遊離コバルトはＡｌの溶出を減少させる作用
を有している。このためＡｌにより多量に置換されてい
ても、水素吸蔵合金の耐食性を向上させ且つ長期サイク
ルを可能にしていると考えられる。またコバルトが利用
率を向上させる機構としては、次の(a) 〜(c) が考えら
れる。(a) 前述のようにＡｌの溶出が抑えられることに
より、電極表面や内部において放電時にアルミン酸カリ
ウムなどとしてＡｌがコロイド状に析出し、電解液の拡
散を阻害したり放電反応を妨げたりしないこと、(b) 添
加コバルトが一旦Ｃｏ(II)錯イオンとなり、充電時に還
元され、水素吸蔵合金粒子間にコバルト単体又はコバル
ト酸化物による導電性ネットワークが形成され、これに
より充放電時の電荷移動反応抵抗が小さくなっているこ
と、(c) コバルトの最外殻３ｄ軌道が放電時の水素のイ
オン化にエネルギーを付与し、放電反応をスムーズにす
ること。[0008] Although the mechanism of action of cobalt has not been elucidated yet, free cobalt has an effect of reducing the elution of Al. Therefore, it is considered that the corrosion resistance of the hydrogen-absorbing alloy is improved and a long-term cycle is possible even if a large amount of Al is substituted. The following (a) to (c) can be considered as mechanisms for improving the utilization rate of cobalt. (a) As described above, the elution of Al is suppressed, so that Al is precipitated in a colloidal manner as potassium aluminate or the like at the time of discharge on the electrode surface or inside, and does not hinder diffusion of the electrolyte solution or hinder the discharge reaction. (B) The added cobalt once becomes Co (II) complex ion, which is reduced at the time of charging, and a conductive network formed of simple cobalt or cobalt oxide is formed between the hydrogen storage alloy particles. (C) The outermost 3d orbit of cobalt imparts energy to the ionization of hydrogen at the time of discharge to smooth the discharge reaction.
【０００９】また合金組成におけるｘ、ｖの限定理由は
次の通りである。なおｙについては前述している。Ｎｉ
は本合金の基本的な示性式ＡＢ5型金属間化合物の結晶
格子における基本的骨格をなす元素である。ｘ＞５．０
では、平衡水素吸蔵圧が高くなるため、気体水素及び電
気化学的水素の吸蔵放出可能な容量が減少する。ｘ≦
３．５では、水素吸蔵量の低下が起こり、またＮｉは水
素の吸蔵放出電位において耐食性が高いので、Ｎｉが減
ると電解液に対する耐食性が低下する。従って３．５＜
ｘ≦５．０が好ましい。元素ＭのうちＦｅ、Ｃｏ、Ｃ
ｕ、Ｃｒはアルカリ水溶液に強く、これらの所定範囲の
量を置換すると、合金の水素吸蔵量（負極の電気容量）
が増し、水素吸蔵量の電気変換効率が良くなる。またＭ
ｎ、Ｎｂ、Ｓｉ、Ｂは所定範囲の量を置換すると、合金
の水素吸蔵量が増し、電気変換効率が良くなる。ｖ≧
１．６では、これらの元素量が過剰になりすぎ、Ｌｎ、
Ｎｉ、Ａｌとの適量バランスが崩れ、水素吸蔵量が却っ
て減少し、電気変換効率も悪くなる。ｖ＝０では、これ
らの元素の置換効果がなくなる。４．４＜ｘ＋ｙ＋ｖ≦
６．０の範囲外では、合金が擬２元系の結晶状態となり
得ず、水素吸蔵量が減少し、電極に使用できる合金とは
ならない。The reasons for limiting x and v in the alloy composition are as follows. Note that y has been described above. Ni
Is an element constituting the basic skeleton in the crystal lattice of the basic rational formula AB 5 type intermetallic compound of the present alloy. x> 5.0
In this case, since the equilibrium hydrogen storage pressure becomes higher, the capacity capable of storing and releasing gaseous hydrogen and electrochemical hydrogen decreases. x ≦
In the case of 3.5, the hydrogen storage amount decreases, and Ni has a high corrosion resistance at the hydrogen storage / release potential. Therefore, when Ni decreases, the corrosion resistance to the electrolytic solution decreases. Therefore, 3.5 <
x ≦ 5.0 is preferred. Fe, Co, C among the elements M
u and Cr are strong against an alkaline aqueous solution, and when these amounts are replaced in a predetermined range, the hydrogen storage capacity of the alloy (electric capacity of the negative electrode)
And the efficiency of the electric conversion of the hydrogen storage amount is improved. Also M
When n, Nb, Si, and B are replaced in amounts within a predetermined range, the hydrogen storage amount of the alloy increases, and the electric conversion efficiency improves. v ≧
At 1.6, the amounts of these elements become excessive, and Ln,
The proper balance between Ni and Al is lost, the hydrogen storage amount is rather reduced, and the electric conversion efficiency is also deteriorated. When v = 0, the effect of replacing these elements disappears. 4.4 <x + y + v ≦
Outside the range of 6.0, the alloy cannot be in a quasi-binary crystal state, the hydrogen storage amount decreases, and the alloy cannot be used as an electrode.
【００１０】また添加するコバルト量は生成するＣｏ(I
I)錯イオンの量に関係するので、３〜２０重量％が適当
である。これより少ないと添加効果が小さく、これより
大きいとエネルギー密度の低下を引き起こす。The amount of cobalt to be added depends on the amount of Co (I
I) Since it depends on the amount of complex ions, 3 to 20% by weight is appropriate. If it is less than this, the effect of addition is small, and if it is more than this, the energy density is reduced.
【００１１】[0011]
【実施例】以下、本発明を実施例に基づいて説明する。
Ｍｍ、Ｎｉ、Ａｌ、Ｆｅ、Ｃｕを所定量秤量し、高周波
溶解炉にて不活性雰囲気で溶解し、ＭｍＮｉ3.7Ａｌ1.2
Ｆｅ0.1Ｃｕ0.1で示される組成の均質な合金を作製し
た。これを機械的に粉砕後、篩いにかけて３００メッシ
ュ通過の粉末を得た。この合金粉末に、コバルト単体、
一酸化コバルト、水酸化コバルトをそれぞれ１０重量％
ずつ加えて物理的に混合し、更に３重量％のポリビニル
アルコール水溶液を加えてペースト状にした後、ニッケ
ル繊維基板に充填し、乾燥後、プレスして本発明の電極
とした。一方、合金粉末に何も添加せず、その他は同様
にして従来電極を作製した。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.
Predetermined amounts of Mm, Ni, Al, Fe, and Cu are weighed and melted in an inert atmosphere in a high-frequency melting furnace to obtain MmNi 3.7 Al 1.2
A homogeneous alloy having a composition represented by Fe 0.1 Cu 0.1 was produced. This was mechanically pulverized and then sieved to obtain a powder passing through 300 mesh. Cobalt simple substance,
10% by weight each of cobalt monoxide and cobalt hydroxide
The mixture was physically added, and the mixture was physically mixed. Further, a 3% by weight aqueous solution of polyvinyl alcohol was added to form a paste, filled in a nickel fiber substrate, dried, and pressed to obtain an electrode of the present invention. On the other hand, a conventional electrode was produced in the same manner as above except that nothing was added to the alloy powder.
【００１２】本発明電極及び従来電極を、電解液過剰の
開放形セルにより、充電７５ｍＡ／ｇ、４．５時間、放
電２５０ｍＡ／ｇの条件で充放電した。図１にその結果
を示す。Ａ〜Ｃは本発明電極、Ｄは従来電極である。な
お図１において、横軸はサイクル数、縦軸は放電容量
（％）を示す。放電容量は３サイクル目を１００とした
割合で示した。The electrode of the present invention and the conventional electrode were charged and discharged in an open cell with excess electrolyte under the conditions of charging 75 mA / g, 4.5 hours, and discharging 250 mA / g. FIG. 1 shows the results. A to C are electrodes of the present invention, and D is a conventional electrode. In FIG. 1, the horizontal axis indicates the number of cycles, and the vertical axis indicates the discharge capacity (%). The discharge capacity was shown as a ratio with the third cycle as 100.
【００１３】図１から明らかなように、本発明電極Ａ〜
Ｃは従来電極Ｄに比して、長寿命であり且つ放電容量が
大きい。またこの電解液を調べたところ、従来電極Ｄで
はＡｌが多量に溶出しており、本発明電極Ａ〜Ｃではコ
バルトを添加することによってＡｌの溶出が抑えられ、
電極の耐食性が向上されていることがわかった。またコ
バルトイオンの溶出も小さいので、添加したコバルトは
水素吸蔵合金粒子間にとどまっており、水素吸蔵放出電
位から金属状態に還元されているものと推定された。As is apparent from FIG.
C has a longer life and a larger discharge capacity than the conventional electrode D. Further, when this electrolytic solution was examined, a large amount of Al was eluted in the conventional electrode D, and elution of Al was suppressed by adding cobalt in the electrodes A to C of the present invention,
It was found that the corrosion resistance of the electrode was improved. Further, since the elution of cobalt ions was small, it was estimated that the added cobalt remained between the hydrogen storage alloy particles and was reduced to a metal state from the hydrogen storage / release potential.
【００１４】次に電極の温度特性を調べるため、Ａｌ置
換量の少ないＭｍＮｉ3.9Ａｌ0.3Ｆｅ0.3Ｃｕ0.1を従来
電極Ｅとして作製し、本発明電極Ａ〜Ｃと従来電極Ｅと
の２０℃と４０℃における放電容量を比較した。表１に
その結果を示す。Next, in order to examine the temperature characteristics of the electrodes, MmNi 3.9 Al 0.3 Fe 0.3 Cu 0.1 having a small Al substitution amount was prepared as the conventional electrode E, and the electrodes A to C of the present invention and the conventional electrode E were heated at 20 ° C. and 40 ° C. The discharge capacity at ° C. was compared. Table 1 shows the results.
【００１５】[0015]
【表１】 [Table 1]
【００１６】表１から明らかなように、本発明電極は従
来電極に比して、高温時の放電特性（高温特性）が優れ
ている。As is clear from Table 1, the electrode of the present invention has better discharge characteristics at high temperatures (high temperature characteristics) than the conventional electrodes.
【００１７】以上のように本発明電極は、サイクル特性
及び高温特性の両方に優れている。As described above, the electrode of the present invention is excellent in both cycle characteristics and high-temperature characteristics.
【００１８】また上記実施例では、ＬｎとしてＭｍを用
いているが、希土類金属単体の混合物でも同様の効果が
得られた。また水素吸蔵合金表面のコバルトが酸化物や
ＮｉＣｏ合金等であっても、また添加したコバルトが酸
化物、水酸化物、合金等であっても、電解液中でＣｏ(I
I)錯イオンを生成でき且つ充電時に還元されるものであ
れば、得られた結果に差はみられなかった。In the above embodiment, Mm is used as Ln. However, a similar effect can be obtained with a mixture of a single rare earth metal. Further, even if the cobalt on the surface of the hydrogen storage alloy is an oxide or a NiCo alloy, or the added cobalt is an oxide, a hydroxide, an alloy, or the like, Co (I
I) There was no difference in the results obtained as long as complex ions could be generated and reduced during charging.
【００１９】なお上記実施例では、ニッケル繊維基板を
用いているが、これに限らず、エキスパンドメタル、メ
タルメッシュ、ニッケルめっきパンチングメタル等を基
板として用いてもよい。また添加するコバルトとして
は、他のコバルト化合物、例えばアルカリ電解液中で溶
解し得るコバルト含有合金を用いてもよい。Although a nickel fiber substrate is used in the above embodiment, the present invention is not limited to this, and an expanded metal, a metal mesh, a nickel-plated punched metal, or the like may be used as the substrate. As the cobalt to be added, another cobalt compound, for example, a cobalt-containing alloy that can be dissolved in an alkaline electrolyte may be used.
【００２０】[0020]
【発明の効果】以上説明したように本発明の水素吸蔵電
極によれば、Ａｌにより置換してなる水素吸蔵合金の粉
末に、金属コバルトの粉末を物理的に混合することによ
り添加したので、サイクル特性と高温特性を共に向上さ
せることができる。As described above, according to the hydrogen storage electrode of the present invention, since the metal cobalt powder is added to the hydrogen storage alloy powder replaced by Al by physically mixing the powder, the cycle is increased. Both characteristics and high temperature characteristics can be improved.
【図１】 本発明の水素吸蔵電極のサイクル特性を示す
図である。FIG. 1 is a view showing cycle characteristics of a hydrogen storage electrode of the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 綿田 正治 大阪府高槻市城西町６番６号 湯浅電池 株式会社内 (72)発明者 押谷 政彦 大阪府高槻市城西町６番６号 湯浅電池 株式会社内 (72)発明者 田村 敬二 神奈川県川崎市川崎区小島町４番２号 日本冶金工業株式会社研究開発本部技術 研究所内 (72)発明者 岡登 信義 神奈川県川崎市川崎区小島町４番２号 日本冶金工業株式会社研究開発本部技術 研究所内 (72)発明者 峠 竹弥 神奈川県川崎市川崎区小島町４番２号 日本冶金工業株式会社研究開発本部技術 研究所内 (56)参考文献 特開 平１−197965（ＪＰ，Ａ) 特開 昭61−233969（ＪＰ，Ａ) 特開 昭62−119864（ＪＰ，Ａ) 特開 平１−115061（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/24 - 4/26 H01M 4/38,4/62 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shoji Watada 6-6 Josaicho, Takatsuki-shi, Osaka Yuasa Battery Co., Ltd. (72) Inventor Masahiko 6-6 Josaicho, Takatsuki-shi, Osaka Yuasa Battery Co., Ltd. (72) Inventor Keiji Tamura 4-2 Kojimacho, Kawasaki-ku, Kawasaki-shi, Kanagawa Nippon Yakin Industry Co., Ltd. No. Nippon Yakin Kogyo Co., Ltd. Research and Development Headquarters Technology Research Institute (72) Inventor Takeya Toge 4-2 Kojimacho, Kawasaki-ku, Kawasaki City, Kanagawa Prefecture Nippon Yakin Kogyo Co., Ltd. Research and Development Headquarters Technology Research Laboratory (56) References JP JP-A-1-197965 (JP, A) JP-A-61-233969 (JP, A) JP-A-62-119864 (JP, A) JP-A-1-1155061 (JP, A) ) Surveyed field (Int.Cl. 7 , DB name) H01M 4/24-4/26 H01M 4 / 38,4 / 62
Claims (2)
Ｍv（Ｌｎはミッシュメタル又は希土類金属の混合物で
あり、ＭはＦｅ、Ｃｏ、Ｍｎ、Ｃｕ、Ｃｒ、Ｓｉ、Ｎ
ｂ、Ｂの内の少なくとも１種であり、ｘ、ｙ、ｖは、
３．５＜ｘ≦５．０、０．９＜ｙ≦２．５、０＜ｖ＜
１．６、４．４＜ｘ＋ｙ＋ｖ≦６．０である）である水
素吸蔵合金の粉末に、金属コバルト粉末を３〜２０重量
％の範囲で物理的に混合することにより添加して形成さ
れたことを特徴とする水素吸蔵電極。1. The descriptive formula based on the atomic ratio is LnNi x Al y
M v (Ln is a mixture of misch metal or rare earth metal, M is Fe, Co, Mn, Cu, Cr, Si, N
b, at least one of B, x, y, and v are
3.5 <x ≦ 5.0, 0.9 <y ≦ 2.5, 0 <v <
1.6, 4.4 <x + y + v ≦ 6.0) is formed by adding a metal cobalt powder by physically mixing it in the range of 3 to 20% by weight to the powder of the hydrogen storage alloy. A hydrogen storage electrode, characterized in that:
を含有する化合物、又はこれらの混合物である請求項１
記載の水素吸蔵電極。2. The metal cobalt is a simple substance of cobalt, a compound containing cobalt, or a mixture thereof.
The hydrogen storage electrode as described in the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03141850A JP3088133B2 (en) | 1990-10-29 | 1991-06-13 | Hydrogen storage electrode |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29256790 | 1990-10-29 | ||
| JP2-292567 | 1990-10-29 | ||
| JP03141850A JP3088133B2 (en) | 1990-10-29 | 1991-06-13 | Hydrogen storage electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0536405A JPH0536405A (en) | 1993-02-12 |
| JP3088133B2 true JP3088133B2 (en) | 2000-09-18 |
Family
ID=26474016
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03141850A Expired - Lifetime JP3088133B2 (en) | 1990-10-29 | 1991-06-13 | Hydrogen storage electrode |
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| Country | Link |
|---|---|
| JP (1) | JP3088133B2 (en) |
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|---|---|---|---|---|
| CN103667837A (en) * | 2013-12-09 | 2014-03-26 | 内蒙古科技大学 | Nanometer TiF3 catalyzed high-volume hydrogen-storing alloy and preparation method thereof |
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1991
- 1991-06-13 JP JP03141850A patent/JP3088133B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0536405A (en) | 1993-02-12 |
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