JPS61176066A - Hydrogen occlusion electrode - Google Patents
Hydrogen occlusion electrodeInfo
- Publication number
- JPS61176066A JPS61176066A JP60016862A JP1686285A JPS61176066A JP S61176066 A JPS61176066 A JP S61176066A JP 60016862 A JP60016862 A JP 60016862A JP 1686285 A JP1686285 A JP 1686285A JP S61176066 A JPS61176066 A JP S61176066A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- hydrogen storage
- hydrogen
- hydrogen occlusion
- magnesium 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.)
- Granted
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】
（イ１ 産業上の利用分野
本発明はアルカリ蓄電池の負極として用いられる水素吸
蔵電極に関し、特に高容量を長期にわたって維持するよ
う改良された水素吸蔵電極に関する。DETAILED DESCRIPTION OF THE INVENTION (1) Industrial Application Field The present invention relates to a hydrogen storage electrode used as a negative electrode of an alkaline storage battery, and more particularly to a hydrogen storage electrode improved to maintain high capacity over a long period of time.
（口ｌ 従来の技術
従来からよく用いられる蓄電池としては鉛電池ｌ’ニッ
ケルーカドミウム電池があるが、近年これら電池より軽
量で且つ高容量となる可能性があるということで、４？
に低圧に於いて負極活物質である水素を可逆的に吸蔵及
び放出することのできる水素吸蔵合金を備えた電極を負
極に用い、水酸化ニッケルなどの金属酸化物を正極活物
質とする電極を正極に用いた金属−水素アルカリ蓄電池
が注目されている。(1) Conventional technology Lead-acid batteries and nickel-cadmium batteries are conventionally commonly used storage batteries, but in recent years, there is a possibility that they will be lighter and have higher capacity than these batteries.
An electrode with a hydrogen storage alloy that can reversibly absorb and release hydrogen as a negative electrode active material at low pressure is used as the negative electrode, and an electrode with a metal oxide such as nickel hydroxide as the positive electrode active material. Metal-hydrogen alkaline storage batteries using positive electrodes are attracting attention.
一般にこの種蓄電池に用いられる水素吸蔵合金を備えた
水素吸蔵電極は特公昭５８−４６８２７号公報に於いて
提案されているように水素を吸蔵する合金粉末と水素を
＠薦しない合金粉末との混合物を焼結して焼結多孔体を
作製し、これを水素吸蔵電極とする方法、あるいは特開
昭５３−１０３５４１号公報に於いて提案されているよ
うに水素を吸蔵する合金粉末とアセチレンブラック及び
電極支持体とを耐電解液性の粒子状結着剤により相互に
結合させて水素吸蔵電極とする方法によって作製されて
訃り、これら電極に用いる水素吸蔵合金の１つに特公昭
５９−３１１８０号公報で示されるようなＭＰ−Ｎｉ系
合金がある。しかしながら、このＭＰ−Ｎｉ系合金は吸
蔵できる水素量が少ないため放電容量が小さく、充放電
によるサイクル寿命も短かった。Generally, the hydrogen storage electrode equipped with a hydrogen storage alloy used in this type of storage battery is a mixture of an alloy powder that stores hydrogen and an alloy powder that does not store hydrogen, as proposed in Japanese Patent Publication No. 58-46827. A method of producing a sintered porous body by sintering and using this as a hydrogen storage electrode, or a method of combining hydrogen storage alloy powder, acetylene black and Hydrogen storage electrodes were produced by bonding the electrode support and the electrolyte-resistant particulate binder to each other, and one of the hydrogen storage alloys used for these electrodes was published in Japanese Patent Publication No. 59-31180. There is an MP-Ni alloy as shown in the above publication. However, this MP-Ni alloy has a small amount of hydrogen that can be occluded, so its discharge capacity is small, and its cycle life due to charging and discharging is also short.
（ハ）発明が解決しようとする問題点 本発明は、吸蔵及び放出する水素量が多く。(c) Problems that the invention attempts to solve The present invention absorbs and releases a large amount of hydrogen.
また充放電によるサイクル寿命の長い水素吸蔵電極を得
ようとするものである。It is also an attempt to obtain a hydrogen storage electrode that has a long cycle life during charging and discharging.
に）問題点を解決するための手段 本発明の水素吸蔵電極は、Ｌａ、Ｏｅ、Ｐｒ。) measures to resolve the problem; The hydrogen storage electrode of the present invention includes La, Oe, and Pr.
Ｎｄ及びＳｍから選ばれる少なくとも一種の希土類元素
を含むマグネシウム合金からなる水素吸蔵材を備えたも
のである。It is equipped with a hydrogen storage material made of a magnesium alloy containing at least one rare earth element selected from Nd and Sm.
（ホ）作 用
負極の水素吸蔵材として前記希土類元素を含むマグネシ
ウム合金を用いると、負唖の水素吸蔵電極のサイクル寿
命が伸び、放電容量が増大する。(E) Function When the magnesium alloy containing the rare earth element is used as the hydrogen storage material of the negative electrode, the cycle life of the negative electrode hydrogen storage electrode is extended and the discharge capacity is increased.
（へ）実施例
市販のランタン及びマグネシウムを組成比でＬａ：ＭＰ
−２：１７になるよう混合し、アーク溶解炉に入れ加熱
、溶解して合金化した後粉砕してＬａ ２ＭｊＦ １７
粉末を得た。またマグネシウムを含む材料を混合し、同
様にして加熱溶解によって合金化しに後粉砕して表に示
すような各種水素吸蔵合金粉末を得た。(f) Example Commercially available lanthanum and magnesium in a composition ratio of La:MP
La 2MjF 17
A powder was obtained. Further, a material containing magnesium was mixed, alloyed by heating and melting in the same manner, and then crushed to obtain various hydrogen storage alloy powders as shown in the table.
こうして得られた各種水素吸蔵合金粉末８０重量％、導
電材としてのアセチレンブラック１０重量％及び結着剤
としてのフッ素樹脂粉末１０重量％を混合機で均一に混
合すると共にフッ素樹脂を繊維化する。そして得られた
混線物をニッケル金網で包み込み３ｔｏｎ／−で加圧成
型することにより、外面がニッケル金網で覆われた水素
吸蔵電極を種々作製した。上記外面がニッケル金網で覆
われた構造の水素吸蔵電極は、充電時に電極中の水素吸
蔵合金が水素をｒ４Ｉｉ蔵すると共に水素ガスを発生し
て生じる電極の膨張を前記ニッケル金網によって機械的
に抑え、この電極の膨張による機械的強度の劣化及びそ
れに伴う水素吸蔵合金の脱落が抑えられて充放電サイク
ルによる性能の早期低下を抑制する。尚、これら水素吸
蔵電極に用いた合金粉末は夫々的ｔｓｙである。80% by weight of the various hydrogen storage alloy powders thus obtained, 10% by weight of acetylene black as a conductive material, and 10% by weight of fluororesin powder as a binder are uniformly mixed in a mixer, and the fluororesin is made into fibers. The resulting mixed material was wrapped in a nickel wire mesh and press-molded at 3 tons/- to produce various hydrogen storage electrodes whose outer surfaces were covered with the nickel wire mesh. In the hydrogen storage electrode whose outer surface is covered with a nickel wire mesh, the hydrogen storage alloy in the electrode stores hydrogen during charging, and the nickel wire mesh mechanically suppresses expansion of the electrode caused by hydrogen gas generation. This suppresses the deterioration of mechanical strength due to expansion of the electrode and the resulting drop-off of the hydrogen storage alloy, thereby suppressing early deterioration of performance due to charge/discharge cycles. Incidentally, the alloy powders used for these hydrogen storage electrodes were each tsy.
次いで上記水素吸蔵電極を理論容ｌが６００ｍＡＨの焼
結式ニッケル正極と組み合わせ電解液に水酸化カリウム
水溶液を用いて密閉型ニッケルー水素アルカリ蓄電池を
種々作製し、負極に用いた水素吸蔵材の種類により電池
Ａ乃至Ｇとする。これら電池を０．１０１ｊｌ流で１６
時市充電した後、α２Ｃ電流で放電して電池′シ圧がｔ
ＯＶになった時点で放電停止するサイクル条件で充放電
を繰り返し行ない、各電池の放ｉ！容貴を表に示すと共
にそのサイクル特性を各電池の初期容量を夫々１００と
して図面に示す。Next, various sealed nickel-hydrogen alkaline storage batteries were prepared by combining the above hydrogen storage electrode with a sintered nickel positive electrode with a theoretical capacity of 600 mAH and using an aqueous potassium hydroxide solution as the electrolyte, and by combining the hydrogen storage electrode with a sintered nickel positive electrode having a theoretical capacity of 600 mAH. Let them be batteries A to G. 16 of these batteries at 0.101jl flow
After charging, the battery's pressure is reduced to t by discharging with α2C current.
Charging and discharging are repeated under cycle conditions in which discharging is stopped when OV is reached, and each battery is discharged. The capacity is shown in the table, and the cycle characteristics are shown in the drawings, with the initial capacity of each battery being 100.
表
表及び図面から希土類元素を含むマグネシウム合金を負
極の水素吸蔵材として用い九電池Ａ乃至Ｆは１Ｍｌ！２
Ｎｉを負極の水素吸蔵材に用いた電池Ｇに比し何れも放
電容量及びサイクル特性が向上して訃り、放電容量につ
いては電池Ａが、またサイクル特性については電池Ａ％
Ｂ及びＦが特に優れた性能を示していることがわかる。From the tables and drawings, nine batteries A to F using a magnesium alloy containing rare earth elements as the hydrogen storage material of the negative electrode are 1Ml! 2
Compared to Battery G, which uses Ni as the hydrogen storage material in the negative electrode, both have improved discharge capacity and cycle characteristics.
It can be seen that B and F exhibit particularly excellent performance.
ま九電池Ｆの測定結果から明らかなように、２種以上の
希土類元素を含むマグネシウム合金を負極の水素吸蔵材
として用いた場合にもＭＰＩＮｉを水素吸蔵材として用
いた時より放電容量及びサイクル特性が向上しており、
マグネシウム合金中に含有させる希土類元素が複数種で
あっても同様な効果が得られることは明白である。As is clear from the measurement results of Maku Battery F, even when a magnesium alloy containing two or more rare earth elements is used as the hydrogen storage material for the negative electrode, the discharge capacity and cycle characteristics are better than when MPINi is used as the hydrogen storage material. has improved,
It is clear that similar effects can be obtained even if multiple types of rare earth elements are contained in the magnesium alloy.
（ト１ 発明の効果 本発明の水素吸蔵電極は＊ Ｌａ、Ｏｅ、Ｐｒ。(G1. Effects of the invention The hydrogen storage electrode of the present invention is *La, Oe, Pr.
Ｎｄ及びｓｍから選ばれる少なくとも一種の希土類元素
を含むマグネシウム合金からなる水素吸蔵材であり、放
電容量の増大及びサイクル特性の向上をもたらすもので
あるから、該電極を用いることにより優れた性能の蓄電
池を提供することができその工業的価値は極めて大きい
。It is a hydrogen storage material made of a magnesium alloy containing at least one rare earth element selected from Nd and SM, and it increases discharge capacity and improves cycle characteristics, so by using this electrode, a storage battery with excellent performance can be obtained. Its industrial value is extremely large.
図面は本発明の水素吸蔵電極を備えた電池及び比較電池
のサイクル特性図である。The drawings are cycle characteristic diagrams of a battery equipped with the hydrogen storage electrode of the present invention and a comparative battery.
Claims (1)
なくとも一種の希土類元素を含むマグネシウム合金から
なる水素吸蔵材を備えた水素吸蔵電極。(1) A hydrogen storage electrode including a hydrogen storage material made of a magnesium alloy containing at least one rare earth element selected from La, Ce, Pr, Nd, and Sm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60016862A JPH063733B2 (en) | 1985-01-30 | 1985-01-30 | Hydrogen storage electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60016862A JPH063733B2 (en) | 1985-01-30 | 1985-01-30 | Hydrogen storage electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61176066A true JPS61176066A (en) | 1986-08-07 |
| JPH063733B2 JPH063733B2 (en) | 1994-01-12 |
Family
ID=11928025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60016862A Expired - Lifetime JPH063733B2 (en) | 1985-01-30 | 1985-01-30 | Hydrogen storage electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH063733B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002043170A2 (en) * | 2000-11-27 | 2002-05-30 | Koninklijke Philips Electronics N.V. | Metal hydride battery material with high storage capacity |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4915933A (en) * | 1972-04-06 | 1974-02-12 | ||
| JPS5110109A (en) * | 1974-07-16 | 1976-01-27 | Tohoku Daigaku Kinzoku Zairyo |
-
1985
- 1985-01-30 JP JP60016862A patent/JPH063733B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4915933A (en) * | 1972-04-06 | 1974-02-12 | ||
| JPS5110109A (en) * | 1974-07-16 | 1976-01-27 | Tohoku Daigaku Kinzoku Zairyo |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002043170A2 (en) * | 2000-11-27 | 2002-05-30 | Koninklijke Philips Electronics N.V. | Metal hydride battery material with high storage capacity |
| WO2002043170A3 (en) * | 2000-11-27 | 2002-08-29 | Koninkl Philips Electronics Nv | Metal hydride battery material with high storage capacity |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH063733B2 (en) | 1994-01-12 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |