JPS61185862A - Hydrogen occlusion alloy electrode - Google Patents
Hydrogen occlusion alloy electrodeInfo
- Publication number
- JPS61185862A JPS61185862A JP60025227A JP2522785A JPS61185862A JP S61185862 A JPS61185862 A JP S61185862A JP 60025227 A JP60025227 A JP 60025227A JP 2522785 A JP2522785 A JP 2522785A JP S61185862 A JPS61185862 A JP S61185862A
- Authority
- JP
- Japan
- Prior art keywords
- palladium
- hydrogen
- hydrogen occlusion
- occlusion alloy
- alloy
- 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
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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
（発明の技術分野〕
本発明は、水素吸蔵合金電極の改良、特にその寿命特性
の向上に関する。DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to improvements in hydrogen storage alloy electrodes, particularly to improvements in their life characteristics.
水薬吸蔵合金１極は水素を可逆的に吸蔵・放出する合金
を主な活物質とする電極で、蓄電池や燃料電池の電極と
して用いられている。一般（二水素吸蔵合金は、電解液
中で酸化を彼りやすい金属を成分として含むために、従
来の水素吸蔵合金電極では充放電を繰り返すうちに合金
の一部が酸化されて性能が劣化するという問題点があっ
た。例えばＬａＮＩｍ ＋二代表される希土類系の水素
吸蔵合金では、希土類元素が酸化されることにより１合
金構造の破壊が起こる。また、水素吸蔵合金（二は水素
の吸蔵・放出を繰り返すと合金粉子が微粉化するという
性質があるために、従来の水素吸蔵合金電極では充放電
ナイクルが進むと、水素吸蔵合金粉末の電極からの脱落
や電極の崩壊が起こり、長寿命が得られないという問題
点があった。Hydrogen storage alloy single electrode is an electrode whose main active material is an alloy that reversibly stores and releases hydrogen, and is used as an electrode in storage batteries and fuel cells. General (Dihydrogen storage alloys contain metals that easily oxidize in the electrolyte, so in conventional hydrogen storage alloy electrodes, part of the alloy becomes oxidized during repeated charging and discharging, resulting in deterioration of performance. For example, in rare earth hydrogen storage alloys such as LaNIm + 2, the alloy structure 1 is destroyed due to oxidation of the rare earth element. Because the alloy powder has the property of becoming pulverized when discharged repeatedly, in conventional hydrogen storage alloy electrodes, as the charging/discharging cycle progresses, the hydrogen storage alloy powder falls off from the electrode and the electrode collapses, resulting in a long service life. There was a problem in that it was not possible to obtain
本発明は以上の問題点全考慮してなされたもので、水素
の吸蔵能は悪化させずＣ二耐酸化性を向上させ微粉化を
防止した水素吸蔵合金粉末を主材料とすることによって
、従来品と同等の放電容量乞持も、より長寿命の水素吸
蔵合金電極全提供することｔ目的とする。The present invention has been made in consideration of all the above problems, and by using a hydrogen storage alloy powder as the main material, which does not deteriorate the hydrogen storage capacity, improves C2 oxidation resistance, and prevents pulverization, it is possible to overcome the conventional The purpose is to provide a hydrogen storage alloy electrode that has a discharge capacity equivalent to that of the conventional hydrogen absorbing alloy electrode, but has a longer lifespan.
本発明は、従来の水素吸蔵合金電極に使用されていた水
素吸蔵合金（希土類金属系、テタンーマンガン糸、鉄−
チタン糸など）の粉末の表面（ニパラジウムの’ｆｆｊ
ｉｍｌ−をル成したものを主構成材料とする水素吸蔵合
金電極である。The present invention utilizes hydrogen storage alloys (rare earth metals, tetan-manganese threads, iron-
The surface of powder (such as titanium thread) (nipalladium'ffj
This is a hydrogen-absorbing alloy electrode whose main constituent material is a mixture of iml-.
パラジウムは希土類金属やＭｎ 、 Ｆｅなどに比べて
耐酸化性に優れた金属であるので、パラジウム被覆層は
内部の水素吸蔵合金粉末を酸化から保護する。まに水素
吸蔵合金は水素を吸蔵した際に膨張したり微粉化したり
するが、パラジウム被覆層は内部の合金粒子の膨５Ｅｔ
を吸収したり、微粉化した含金粒子の脱落を防ぐ。従っ
てパラジウム被覆層ンもつ水素吸蔵合金粉末を主構成材
料として用いることによって、水素吸蔵合金心極の長寿
命化が達成される。Since palladium is a metal with superior oxidation resistance compared to rare earth metals, Mn, Fe, etc., the palladium coating layer protects the internal hydrogen storage alloy powder from oxidation. Hydrogen-absorbing alloys expand or become pulverized when they absorb hydrogen, but the palladium coating layer expands due to the expansion of the internal alloy particles.
Prevents the absorption of metal particles and the falling off of finely divided gold-containing particles. Therefore, by using hydrogen storage alloy powder with a palladium coating layer as the main constituent material, a longer life of the hydrogen storage alloy core electrode can be achieved.
また、パラジウム自体が水素を吸ｊ威・放出できる金属
であるため、パラジウム被覆層を形成しても、４極とし
ての各区はほとんど減少しない。パラジウム以外の耐酸
化性に優れた金属（たとえばＣｕ 、 Ｎｉなど）は水
素の吸蔵・放出能を持にないので、パラジウム以外の金
属で被覆した水素吸蔵合鉱扮末を用いた場合には、寿命
に向上しても、電極としての単位重数・単位体積あたり
の容量が被ｉ層の金属分だけ低下する。従って被覆層と
してはパラジウムが最適である。Furthermore, since palladium itself is a metal that can absorb and release hydrogen, even if a palladium coating layer is formed, the number of quadrupole sections will hardly decrease. Metals with excellent oxidation resistance other than palladium (e.g. Cu, Ni, etc.) do not have the ability to absorb and release hydrogen, so when using a hydrogen absorbing composite powder coated with a metal other than palladium, Even if the life is improved, the capacity per unit weight and unit volume of the electrode is reduced by the metal of the i-layer. Therefore, palladium is most suitable for the coating layer.
しかし、パラジウムは比較的高価な金属であるので、少
址の使用が好ましい。水素吸蔵合金粉末の粒径としては
数十μｍ以上のものを用いる事が好ましく、パラジウム
被覆層の厚さは平均１μｍ１２Ｌ下が特に好ましい。However, since palladium is a relatively expensive metal, it is preferable to use it sparingly. The particle size of the hydrogen storage alloy powder is preferably several tens of μm or more, and the thickness of the palladium coating layer is particularly preferably 1 μm or less on average.
パラジウムによる被覆は気相から行なっても液相から行
なっても良いが、高価な装置を必要とせず、操作の容易
なことから、パラジウムを含む溶液中Ｃ：水素吸蔵合金
粉宋を投入して被覆層Ｚ形成することが好ましい。なＳ
この場合はパラジウムを含む溶液の酸性度がＰＨ５以下
であるとパラジウム被覆層形成中（：水素吸蔵合金粉末
の表面が酸化を被り水素吸蔵・放出能が低下する恐れが
あるので、ＰＨ７以上の溶液を使用することが望ましい
。Coating with palladium may be carried out from the gas phase or from the liquid phase, but since it does not require expensive equipment and is easy to operate, C: Hydrogen storage alloy powder Sung is added to the solution containing palladium. It is preferable to form a covering layer Z. NaS
In this case, if the acidity of the palladium-containing solution is below PH5, the surface of the hydrogen-absorbing alloy powder may be oxidized and the hydrogen storage/release ability may be reduced. It is preferable to use
〔発明の効果］
以上説明し定ように本発明によれば、水素の吸蔵・放出
能を損わずに、水素吸蔵合金が酸化から保ルリされ、合
金粒子の脱落や電極の崩壊が防止されるので、従来品と
同等の容量をもち、より長寿命な水素吸蔵合金電極を得
ることができる。[Effects of the Invention] As explained above, according to the present invention, the hydrogen storage alloy is protected from oxidation without impairing its ability to absorb and release hydrogen, and the falling off of alloy particles and the collapse of the electrodes are prevented. Therefore, it is possible to obtain a hydrogen storage alloy electrode that has a capacity equivalent to that of conventional products and has a longer life.
さらｌ二、パラジウムの水素吸蔵・放出の際の平衡水累
圧が低いことから、充電によって水素吸蔵合金粉末に吸
蔵された水素がパラジウム被覆層！通って抜は出すこと
は困難である。従って電極としては、自己放電が防止さ
れるという効果がある。Furthermore, since the equilibrium water cumulative pressure during hydrogen storage and release of palladium is low, the hydrogen stored in the hydrogen storage alloy powder due to charging is absorbed into the palladium coating layer! It is difficult to pass through and extract it. Therefore, the electrode has the effect of preventing self-discharge.
以上の効果に加えて、パラジウムが存在すること（二よ
り、その触媒としての作用が付加されて、Ｗｊｌ ｅ’
ｊｌ電極として使用しに場合には正極から発生する０２
をＮ２０に還元する化学反応が共存し、このためＣ二’
心’Ｉｍ内の０□址が減少して電極の酸化が防止される
という効果も期待できる。In addition to the above effects, the presence of palladium (secondarily, its catalytic action is added, and Wjl e'
02 generated from the positive electrode when used as a jl electrode
There exists a chemical reaction that reduces C2' to N20.
It is also expected that the 0□ area in the heart'Im will be reduced and the oxidation of the electrodes will be prevented.
本発明の水素吸蔵合金電極は、充放電を繰り返す二次電
池の負極に適しにものである。The hydrogen storage alloy electrode of the present invention is suitable for a negative electrode of a secondary battery that is repeatedly charged and discharged.
以下に、本発明の詳細な説明する。 The present invention will be explained in detail below.
水素吸蔵合金としテハＭｍＮ１４２Ｍｎｏ４（Ｍｍ ：
ミッシユメタル）を使用した。この合金に水ｉ’ｖａ＆
蔵・放出させ、粒径２〜５０／ｘｎ の粉末とした。Teha MmN142Mno4 (Mm:
Missy Metal) was used. Water i'va & into this alloy
It was stored and released to form a powder with a particle size of 2 to 50/xn.
一方Ｐｄ浴としては１０％Ｐｄ Ｃ１２水溶液ＣＮａＯ
Ｈ水溶液！加えＰＨＩＱ〜１２に蒜製した溶液を用いた
。On the other hand, as a Pd bath, 10% Pd C12 aqueous solution CNaO
H aqueous solution! A solution prepared by adding garlic to PHIQ ~ 12 was used.
ＭｍＮ ｉ ４ｘ Ｍｎｏ、ａ合金粉床３ｇ’、ｔ２５
℃のＰｄ浴３００ｍ１中に投入し、５分間攪拌した後濾
過する。約ＩＵｆＭの純水による洗浄全数回繰り返す。MmN i 4x Mno, a alloy powder bed 3g', t25
The mixture was poured into a 300 ml Pd bath at 0.degree. C., stirred for 5 minutes, and then filtered. Repeat washing with approximately IUfM pure water several times.
その後ホルマリン水１：、 ＮａＯＨ水溶液を加えてＰ
Ｈ８〜１１とした溶液１００ｍＩＩ中（二投入し２５℃
で数分攪拌し濾過する。得られたＰ（））きＭｍＮＩ
４．ｔ Ｍｎ ｎ、ａ合金粉床はＮ２気流中で風乾させ
る。以上のよう（ニシテ形成したＰｄ層は、ＭｍＮ ｉ
４．ｚＭｎ ｏ、ｓ粒子の表面を部分的に被覆してＳす
、その平均の厚さは１μｍ以下Ｃ二なっている。このＰ
ｄつきＭｍＮ １４１Ｍｎ合金粉末の重量に対し、４重
量パーセントのポリテトラフロロエチレンの粉末ン混合
し、混練して厚さ０．５１１＠のシートとする。このシ
ートｌ適当な大きさＣユリり、 Ｎｉネットに圧着して
水素吸蔵合金電極を得た。After that, add formalin water 1:, NaOH aqueous solution and P
H8-11 solution in 100ml (two injections at 25°C)
Stir for a few minutes and filter. The obtained P()) MmNI
4. The t Mn n,a alloy powder bed is air dried in a stream of N2. As mentioned above (the Pd layer formed in Nishite is MmN i
4. The surface of the zMno, s particles is partially coated with S, the average thickness of which is less than 1 μm. This P
MmN with d 141Mn alloy powder is mixed with 4% by weight of polytetrafluoroethylene powder and kneaded to form a sheet having a thickness of 0.511@. This sheet was cut to an appropriate size and pressed onto a Ni net to obtain a hydrogen storage alloy electrode.
上記の方法で作った水素吸蔵合金電極を負極とし１通常
のニッケル極を正極として、８Ｎ−ＫＯ）（水溶液を′
４！解液として作成した二次電池の負極の容Ｍ （Ｐ（
１つき付合粉末１ｇあたり）のチイクル特性を第１図の
曲線Ａｔ二示す。曲線Ｂは、Ｐｄ被覆層をもたないＭｍ
Ｎ ＋ ４１ Ｍｎ ｏ、ｓ合金粉末７ｆｒ：使用して
同様に作成し定電様による参照実験の結果得られた特性
である。なお充電鼠は１６８ ｍ ｈｈ−ｇ ｓ 、
放電電流３０献で測定した。チイクル初期にどいて両者
同じ容量が得られてＳす、Ｐｄ層を形成しても容置が悪
化しないことがわかる。チイクルが１１０回以上の領域
では、Ｐｄ層なしの合金から作つた電極の方が８破低下
が著しく、たとえば容量が１００ ｍＡｂ−ｇ−ｓに低
下するのは、Ｐｄ層がない場合に１７５ｆイクルである
のに対し、 Ｐｄ層ｔもつ場合シーは１９５サイクルで
ある。このように第り図から本発明により水素吸蔵合金
電極の長寿命化が達成されることがわかる。Using the hydrogen storage alloy electrode made by the above method as a negative electrode, and using a normal nickel electrode as a positive electrode,
4! The capacity M (P(
Curve At2 in FIG. Curve B is Mm without Pd coating layer.
N + 41 Mno, s alloy powder 7fr: These are the characteristics obtained as a result of a reference experiment using a constant electric current. In addition, the charging mouse is 168 m hh-gs,
The measurement was performed at a discharge current of 30%. It can be seen that the same capacitance was obtained in both cases at the initial stage of the cycle, and the capacity did not deteriorate even if the S and Pd layers were formed. In the region of 110 cycles or more, electrodes made from alloys without a Pd layer exhibit a more significant 8 failure drop.For example, the capacitance drops to 100 mAb-gs after 175 cycles without a Pd layer. On the other hand, in the case of a Pd layer t, the sea is 195 cycles. As described above, it can be seen from the diagram that the present invention achieves a longer life of the hydrogen storage alloy electrode.
第１図は、本発明２二よる水素吸蔵電極と従来の水素吸
蔵合金電極の放電容量のチイクル特性図。
代理人 弁理士 則近憲佑（ほか１名）第１図
寸イフル敞−１０FIG. 1 is a cycle characteristic diagram of the discharge capacity of the hydrogen storage electrode according to the present invention 22 and the conventional hydrogen storage alloy electrode. Agent Patent attorney Kensuke Norichika (and 1 other person) Figure 1 Dimensions 10
Claims (2)
主構成材料としたことを特徴とする水素吸蔵合金電極。(1) A hydrogen storage alloy electrode characterized in that its main constituent material is hydrogen storage alloy powder whose surface is coated with palladium.
ｍ以下としたことを特徴とする特許請求の範囲第１項記
載の水素吸蔵合金電極。(2) The average thickness of the palladium layer covering the surface is 1μ
The hydrogen storage alloy electrode according to claim 1, characterized in that the hydrogen storage alloy electrode is less than or equal to m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60025227A JPS61185862A (en) | 1985-02-14 | 1985-02-14 | Hydrogen occlusion alloy electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60025227A JPS61185862A (en) | 1985-02-14 | 1985-02-14 | Hydrogen occlusion alloy electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61185862A true JPS61185862A (en) | 1986-08-19 |
Family
ID=12160080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60025227A Pending JPS61185862A (en) | 1985-02-14 | 1985-02-14 | Hydrogen occlusion alloy electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61185862A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03247735A (en) * | 1990-02-23 | 1991-11-05 | Nippon Yakin Kogyo Co Ltd | Rare earth metal-nickel series hydrogen storage alloy and material for occluding hydrogen |
-
1985
- 1985-02-14 JP JP60025227A patent/JPS61185862A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03247735A (en) * | 1990-02-23 | 1991-11-05 | Nippon Yakin Kogyo Co Ltd | Rare earth metal-nickel series hydrogen storage alloy and material for occluding hydrogen |
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