JPH063733B2 - Hydrogen storage electrode - Google Patents
Hydrogen storage electrodeInfo
- Publication number
- JPH063733B2 JPH063733B2 JP60016862A JP1686285A JPH063733B2 JP H063733 B2 JPH063733 B2 JP H063733B2 JP 60016862 A JP60016862 A JP 60016862A JP 1686285 A JP1686285 A JP 1686285A JP H063733 B2 JPH063733 B2 JP H063733B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- electrode
- hydrogen
- storage electrode
- battery
- 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
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)
Description
【発明の詳細な説明】 (イ)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。TECHNICAL 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 so as to maintain a high capacity for a long period of time.
(ロ)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及びニッ
ケル−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、特に
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。(B) Conventional technology Conventionally frequently used storage batteries include lead batteries and nickel-cadmium batteries, but in recent years they are lighter than these batteries and may have a higher capacity, so especially at low voltage A metal using an electrode provided with a hydrogen storage alloy capable of reversibly storing and releasing hydrogen as an active material as a negative electrode, and an electrode having a metal oxide such as nickel hydroxide as a positive electrode active material for a positive electrode Hydrogen alkaline storage batteries are receiving 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
吸蔵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
おり、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Ｍｇ−Ｎｉ系
合金がある。しかしながら、このＭｇ−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, a hydrogen storage electrode provided 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 an alloy powder storing hydrogen and acetylene black and an electrode as proposed in JP-A-53-103541. It is produced by a method in which a support and a support are bonded to each other with an electrolytic solution-resistant particulate binder to form a hydrogen storage electrode. One of the hydrogen storage alloys used for these electrodes is JP-B-59-31180. There is a Mg-Ni type alloy as shown by. However, this Mg-Ni alloy has a small discharge capacity because it can store a small amount of hydrogen, and has a short cycle life due to charge and discharge.
(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、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。(C) Problems to be Solved by the Invention The present invention is intended to obtain a hydrogen storage electrode that has a large amount of hydrogen stored and released and has a long cycle life due to charging and discharging.
(ニ)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、Ｃｅ、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。(D) Means for Solving Problems The hydrogen storage electrode of the present invention comprises a hydrogen storage material made of a magnesium alloy containing at least one rare earth element selected from La, Ce, Pr, Nd and Sm. is there.
(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、負極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) Operation 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.
(ヘ)実 施 例 市販のランタン及びマグネシウムを組成比でＬａ：Ｍｇ
＝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Ｌａ2Ｍｇ17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た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) Actual Example Commercially available lanthanum and magnesium in a composition ratio of La: Mg
= 2: 17, mixed in an arc melting furnace, heated, melted, alloyed, and pulverized to obtain La 2 Mg 17 powder. Further, materials containing magnesium were mixed and similarly alloyed by heating and melting and then pulverized to obtain various hydrogen storage alloy powders 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維持化する。そして得られた混
練物をニッケル金網で包み込み３ton／cm2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
金が水素を吸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約1.5ｇ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 with a mixer and the fluororesin is maintained. Then, the obtained kneaded product was wrapped in a nickel wire mesh and pressure-molded at 3 ton / cm 2 , to prepare various hydrogen storage electrodes having an outer surface covered with the nickel wire mesh. The hydrogen storage electrode having a structure in which the outer surface is covered with a nickel wire mesh, the hydrogen storage alloy in the electrode absorbs hydrogen during charging and mechanically suppresses the expansion of the electrode generated by generating hydrogen gas by the nickel wire mesh, The deterioration of mechanical strength due to the expansion of the electrode and the accompanying drop of the hydrogen storage alloy are suppressed, and the early deterioration of the performance due to the charge / discharge cycle is suppressed. The alloy powder used for these hydrogen storage electrodes is about 1.5 g each.
次いで上記水素吸蔵電極を理論容量が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−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0.1Ｃ電流で１６時間充
電した後、0.2Ｃ電流で放電して電池電圧が1.0Ｖ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、各電池の放電容量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, the above hydrogen storage electrode was combined with a sintered nickel positive electrode having a theoretical capacity of 600 mAH, and various sealed nickel-hydrogen alkaline storage batteries were prepared by using an aqueous solution of potassium hydroxide as an electrolytic solution, depending on the type of hydrogen storage material used for the negative electrode. The batteries are A to G. After charging these batteries with 0.1C current for 16 hours, discharge them with 0.2C current and stop charging when the battery voltage becomes 1.0V. Repeat charging and discharging under the cycle condition, and show the discharge capacity of each battery in the table. The cycle characteristics are shown and the initial capacity of each battery is shown as 100 in the drawing.
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た電池Ａ乃至Ｆは、Ｍｇ２Ｎ
ｉ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おり、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。ま
た電池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Ｍｇ２Ｎｉを水素吸蔵材として用い
た時より放電容量及びサイルウ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。 From the table and the drawings, the batteries A to F using the magnesium alloy containing a rare earth element as the hydrogen storage material of the negative electrode are Mg2N.
Compared to the battery G using i as the hydrogen storage material of the negative electrode, the discharge capacity and the cycle characteristics were both improved. The discharge capacity was the battery A and the cycle characteristics were the batteries A and B.
It can be seen that F and F show particularly excellent performance. Further, as is clear from the measurement result of the battery F, when the magnesium alloy containing two or more kinds of rare earth elements is used as the hydrogen storage material of the negative electrode, the discharge capacity and the Silu characteristics are better than those when Mg2Ni is used as the hydrogen storage material. It has been improved, and it is clear that the same effect can be obtained even if plural kinds of rare earth elements are contained in the magnesium alloy.
(ト)発明の効果 本発明の水素吸蔵電極は、Ｌａ、Ｃｅ、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。(G) Effect of the Invention The hydrogen storage electrode of the present invention is a hydrogen storage material made of a magnesium alloy containing at least one rare earth element selected from La, Ce, Pr, Nd and Sm, and has an increased discharge capacity and cycle characteristics. Therefore, by using the electrode, a storage battery with excellent performance can be provided, and 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 provided with the hydrogen storage electrode of the present invention and a comparative battery.
Claims (1)
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水素吸蔵電極。1. A hydrogen storage electrode comprising 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 JPS61176066A (en) | 1986-08-07 |
| JPH063733B2 true 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) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1404633A (en) * | 2000-11-27 | 2003-03-19 | 皇家菲利浦电子有限公司 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61176066A (en) | 1986-08-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |