JPS62113359A - Metal-hydrogen alkaline storage battery - Google Patents
Metal-hydrogen alkaline storage batteryInfo
- Publication number
- JPS62113359A JPS62113359A JP60253253A JP25325385A JPS62113359A JP S62113359 A JPS62113359 A JP S62113359A JP 60253253 A JP60253253 A JP 60253253A JP 25325385 A JP25325385 A JP 25325385A JP S62113359 A JPS62113359 A JP S62113359A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- electrode
- negative electrode
- hydrogen storage
- occluded
- 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
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/242—Hydrogen storage electrodes
-
- 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】
ｔ（］ 産業上の利用分計
本発明は活物質の水素を吸蔵及び放出することのできる
水素吸蔵電極を負極に用い、金［酸化物からなる活物質
を備えた電極を正極に用いる金属−水素アルカリ蓄電池
Ｉ：関する。[Detailed Description of the Invention] t() Industrial Application The present invention uses a hydrogen storage electrode capable of absorbing and desorbing hydrogen in an active material as a negative electrode, and comprises an active material made of gold [oxide]. Metal-hydrogen alkaline storage battery I using an electrode as a positive electrode: Related.
（Ｃ７）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
ケルーカドミクム電池があるが、近年これら電池より軽
量で且つ高容駄となる可能性があるということで、特Ｃ
：低圧（−於いて活物質である水嵩を吸蔵及び放出する
ことのできる水素吸蔵合金を備えた電極を負極に用い、
水散化ニッケルなどの金属酸化物からなる活物質を備え
た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。(C7) Conventional technology Lead-acid batteries and nickel-cadmium batteries have traditionally been commonly used storage batteries, but in recent years special C
: An electrode equipped with a hydrogen storage alloy that can absorb and release water, which is an active material, at low pressure (-) is used as the negative electrode,
Metal-hydrogen alkaline storage batteries that use, as a positive electrode, an electrode comprising an active material made of a metal oxide such as water-dispersed nickel are attracting attention.
一般にこの種蓄電池（：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（：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ζ：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、金属−水素アルカリ蓄電池はこれら電極を
負極に用いて特開昭５３−１１１４３９号公報で示され
るように、充電時に正極で発生する酸素を、負極の水素
吸蔵合金に吸蔵した水素と反応させて消費するよう構成
される。Hydrogen storage electrodes equipped with hydrogen storage alloys, which are generally used in this type of storage battery, are proposed in Japanese Patent Publication No. 58-46827 (1988-46827). A method of sintering a mixture to produce a sintered porous body and using this as a hydrogen storage electrode, or a method of using an alloy powder that stores hydrogen and acetylene black as proposed in JP-A-53-103541. A metal-hydrogen alkaline storage battery uses these electrodes as a negative electrode to form a hydrogen storage electrode. As shown in Japanese Patent No. 53-111439, the battery is configured so that oxygen generated at the positive electrode during charging is consumed by reacting with hydrogen stored in the hydrogen storage alloy of the negative electrode.
しかしながら、このような金属−水素アルカリＶ電池で
は、負極である水素吸蔵電極の表面近傍Ｉ：於いて、電
池系内のＩｔＸが水軍吸蔵合金に吸蔵されている活性な
水素と極めて迅速に反応して消費され、これによって、
水素吸蔵電極の水素吸蔵量が減少するため、保存中の負
極容量のは少速度が著しく大きいという問題があった。However, in such metal-hydrogen alkaline V batteries, ItX in the battery system reacts extremely quickly with active hydrogen stored in the hydrogen storage alloy near the surface of the hydrogen storage electrode, which is the negative electrode. is consumed, thereby
Since the hydrogen storage capacity of the hydrogen storage electrode decreases, there is a problem in that the capacity of the negative electrode decreases significantly during storage.
（ハ）発明が解決しようとする問題点
本発明は金属−水素アルカリ蓄電池に於いて保存中に酸
素が迅速に負極の水素吸蔵電極で消費されることによっ
て生じる負極容量の急速な低下を抑制しようとするもの
である。(c) Problems to be Solved by the Invention The present invention aims to suppress the rapid decrease in negative electrode capacity caused by rapid consumption of oxygen in the negative electrode hydrogen storage electrode during storage in metal-hydrogen alkaline storage batteries. That is.
に）問題点を解決する六めの手段
本発明の金属−水素アルカリ蓄電池は、水素吸蔵合金が
局部的に存在する水素吸蔵電極を負極に用いたものであ
る。B) Sixth means for solving the problem The metal-hydrogen alkaline storage battery of the present invention uses a hydrogen storage electrode in which a hydrogen storage alloy is locally present as a negative electrode.
庫）作 用
水素吸蔵合金が局部的に存在する水素吸蔵電極は、従来
の水素吸蔵合金が均一に存在する水素吸蔵電極に比べて
、有効反応面積が小さくなシ、電池系内の酸素と負極の
水素吸蔵電極との反応速度を減少することができ、保存
中の負極の水素吸蔵量の低下を抑制することができる。Hydrogen storage electrodes in which hydrogen storage alloys are present locally have a smaller effective reaction area than conventional hydrogen storage electrodes in which hydrogen storage alloys are distributed uniformly. It is possible to reduce the reaction rate of the negative electrode with the hydrogen storage electrode, and it is possible to suppress a decrease in the hydrogen storage amount of the negative electrode during storage.
（へ）実施例
水素吸蔵能力を有するＬａＮｉ５ ｆ機械的に５０μｍ
以下（：粉砕した後、このＬＩＬＮｉ５粉末８０重粉末
８尋
１ｌｉｔｓ及び結着剤としてのポリテトラフルオロエチ
レン１０重ｔ１％を加えて混合機で均一に混合すると共
にポリテトラフルオロエチレンを繊維化する。(f) Example: LaNi5 with hydrogen storage capacity mechanically 50 μm
Following (: After pulverization, 1 liter of 8 fat of this LILNi5 powder 80 weight powder and 1% of polytetrafluoroethylene 10 weight t as a binder are added and mixed uniformly with a mixer, and the polytetrafluoroethylene is made into fibers.
次いでこのようにポリテトラフルオロエチレンを繊維化
した混合物に水を加えてペース） ［ＳＬ＋を得る。Next, water was added to the mixture in which polytetrafluoroethylene was made into fibers to obtain paste) [SL+].
また同様にシて前記ＬＩＬＮｉ５をアセチレングラツク
に代え．その他は同一条件でペースト１ｌｌ）を得。Similarly, the LILNi5 was replaced with acetylene black. Otherwise, 1 liter of paste was obtained under the same conditions.
９Ｊ４１図に示すように負極集電体（１）の両面中央部
にペース）（ＩＬｌｔ−貼り付け．その周辺部分の集電
体（１）にペースト１ｔ）ｌを貼り付けて負極全面積の
４０％がペースト（ＩＬ）で占められた水素吸蔵電極を
得た。9J41 As shown in Figure 9J41, paste 1 t of paste on the central part of both sides of the negative electrode current collector (1) (ILlt- Paste. Paste 1 t of paste on the current collector (1) in the surrounding area to cover 40% of the total area of the negative electrode. A hydrogen storage electrode was obtained in which % was occupied by paste (IL).
このようにして得た水素吸蔵電極と，放電容量が１２０
０ｍＡＨのニッケル正極をセパレータを介して巻回する
こと（：より電極体を形成し，この電極体を電池外装罐
に挿入し．アルカリ電解液の注入などを行なった後封口
して本発明のニッケルー水素電池（Ａ）を作製した。The hydrogen storage electrode obtained in this way has a discharge capacity of 120
The nickel positive electrode of the present invention is formed by winding a 0mAH nickel positive electrode through a separator to form an electrode body, inserting this electrode body into a battery exterior can, and sealing it after injecting an alkaline electrolyte. A hydrogen battery (A) was produced.
また比較として．前記ペースト（＆）を実施例と同一寸
法の集電体の両面全面に貼り付けて水素吸蔵電極会得．
同様にシて比較電池（Ｂｌを作製した。尚前記電池内及
び（ＢＩ Ｃ用いた水素吸蔵電極は共に理論容置が２４
００ｍＡＨであり，電池（Ｂ１（：用イタ水素吸蔵電極
では，電極の厚みを調節することにより負極集電体の全
面をペースト（ａｌで覆っている。Also as a comparison. A hydrogen storage electrode was obtained by pasting the paste (&) on both sides of a current collector having the same dimensions as in the example.
A comparative battery (Bl) was prepared in the same manner.The theoretical capacity of both the battery and the hydrogen storage electrode (using BIC) was 24.
00 mAH, and in the Ita hydrogen storage electrode for the battery (B1), the entire surface of the negative electrode current collector is covered with paste (Al) by adjusting the thickness of the electrode.
第２図は上記本発明電池内及び比較電池（Ｂｌを夫々満
充電した後１０日曲保存した時の残存容量の経時変化を
示したものであり１本発明電池囚は比較電池ｔＢｌに比
較して残存容量の減少率が小さくなシ，保存特性が著し
く向上していることがわかる。Figure 2 shows the change in remaining capacity over time when the battery of the present invention and the comparative battery (Bl) were fully charged and stored for 10 days. It can be seen that the rate of decrease in remaining capacity is small and the storage characteristics are significantly improved.
本発明電池内の保存特性がこのように比較電池（Ｂｌよ
り優れているのは次の理由によるものと考えられる。す
なわち、比較電池ＩＢＩでは水素吸蔵合金が負極に均一
に存在しておシ．負極の有効反応面積が大きいため．水
素吸蔵合金に吸蔵された活性な水素と電池系内の酸素の
反応が迅速に進み，これによって負極の水素吸蔵量が急
速に減少して残存容量の減少率が非常Ｉ：大きくなる。The reason why the storage characteristics of the battery of the present invention are superior to that of the comparative battery (Bl) is considered to be due to the following reason: In the comparative battery IBI, the hydrogen storage alloy is uniformly present in the negative electrode. Because the effective reaction area of the negative electrode is large, the reaction between the active hydrogen stored in the hydrogen storage alloy and the oxygen in the battery system proceeds rapidly, resulting in a rapid decrease in the amount of hydrogen stored in the negative electrode, resulting in a decrease in the remaining capacity. is very serious I: becomes large.
これに対して本発明電池（Ａｌでは水素吸蔵合金が負極
Ｃ：局部的（：存在するため．実質上負極の有効反応面
積が小さくなシ，水素吸蔵合金に吸蔵された水素と電池
内の酸素の反応速度が遅くなることから，残存容量の減
少率が小さくなって保存特性が向上したものと考えられ
る。また、負極の周縁部は電池系内の酸素と反応し易く
なっているので１本発明電池囚の負極のよう（：、水素
吸蔵合金を負極の周縁部を除く中央付近に局在させると
，前記酸素との反応速度を効率よく減少でき有効である
。On the other hand, in the battery of the present invention (Al), the hydrogen storage alloy exists locally in the negative electrode (C), so the effective reaction area of the negative electrode is practically small, and the hydrogen stored in the hydrogen storage alloy and the oxygen in the battery It is thought that the rate of decrease in remaining capacity is reduced and the storage characteristics are improved because the reaction rate of As in the case of the negative electrode of the invention battery, it is effective to localize the hydrogen storage alloy near the center of the negative electrode, excluding the periphery, to efficiently reduce the rate of reaction with oxygen.
上述したよう（：水素吸蔵合金を負極に均一（−存在さ
せるより１局部的に存在させた方が保存特性が向上する
が，その局部的；二存在させる範囲については広すぎる
と負極と酸素の反応速度を充分に減少することができず
．逆に狭すぎると負極容量が小さくなるため．負極全面
積の３０％から７０チＣ：することが望ましい。As mentioned above, the storage characteristics will be improved if the hydrogen storage alloy is present locally on the negative electrode rather than uniformly, but if the hydrogen storage alloy is present locally and over a wide range, the contact between the negative electrode and oxygen will increase. The reaction rate cannot be sufficiently reduced.On the other hand, if it is too narrow, the negative electrode capacity will be small.It is desirable that the area is between 30% and 70 cm of the total area of the negative electrode.
尚１本発明電池（Ａｌの負極は充電時に水素吸蔵合金が
存在しない部分から水素ガスが発生するが。Note that when the battery of the present invention (Al negative electrode) is charged, hydrogen gas is generated from the portion where the hydrogen storage alloy is not present.
電池系内の水素分圧が水素吸蔵合金の水素吸蔵圧以上に
なると、水素吸蔵合金が系内の水素を吸蔵する友め、負
極容量を大きくとっておくことによシ、水素ガス発生に
よる系内の内圧の上昇を抑えることができる。When the hydrogen partial pressure in the battery system exceeds the hydrogen storage pressure of the hydrogen storage alloy, the hydrogen storage alloy absorbs the hydrogen in the system, so by keeping a large negative electrode capacity, the system due to hydrogen gas generation It is possible to suppress the increase in the internal pressure inside.
また、上記実施例では水素吸蔵合金としてＬｓＬＮｉ５
を、正極としてニッケル電極を用いたが。In addition, in the above embodiment, LsLNi5 is used as the hydrogen storage alloy.
However, a nickel electrode was used as the positive electrode.
本発明はこれに限定されるものではなく、他の水素吸蔵
合金を用いてなる水素吸蔵電極、あるいは他の金属酸化
物を備えた正極を用いた場合Ｌ：も同様の効果が得られ
ることは明らかである。The present invention is not limited to this, and the same effect can be obtained by using a hydrogen storage electrode made of another hydrogen storage alloy or a positive electrode equipped with another metal oxide. it is obvious.
（ト）発明の効果
本発明の金属−水素アルカリ蓄電池は、水素吸蔵合金が
局部的に存在する水素吸蔵電極を負極Ｃ二用い友もので
あるため、負極と酸素との反応速度を減少することがで
き、負極の水素吸蔵量の低下を抑制できるため、電池の
保存特性が向上する。(G) Effects of the Invention The metal-hydrogen alkaline storage battery of the present invention uses a hydrogen storage electrode in which a hydrogen storage alloy is locally present as a negative electrode C2, so that the reaction rate between the negative electrode and oxygen can be reduced. This makes it possible to suppress a decrease in the hydrogen storage capacity of the negative electrode, thereby improving the storage characteristics of the battery.
第１図は本発明電池の負極の斜視図、＄２図は本発明電
池込）と比較電池［ＢＩの保存時の残存容量の経時変化
を示した図面である。
（１）・・・集電体。FIG. 1 is a perspective view of the negative electrode of the battery of the present invention, and Figure 2 is a diagram showing the change over time in the remaining capacity of the battery of the present invention (including the battery of the present invention) and the comparative battery (BI) during storage. (1)... Current collector.
Claims (2)
負極に用いた金属−水素アルカリ蓄電池。(1) A metal-hydrogen alkaline storage battery using a hydrogen storage electrode in which a hydrogen storage alloy is locally present as a negative electrode.
在する特許請求の範囲第（１）項記載の金属−水素アル
カリ蓄電池。(2) The metal-hydrogen alkaline storage battery according to claim (1), wherein the hydrogen storage alloy is present in a portion of the negative electrode excluding the peripheral portion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60253253A JPH0636362B2 (en) | 1985-11-12 | 1985-11-12 | Metal-hydrogen alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60253253A JPH0636362B2 (en) | 1985-11-12 | 1985-11-12 | Metal-hydrogen alkaline storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62113359A true JPS62113359A (en) | 1987-05-25 |
| JPH0636362B2 JPH0636362B2 (en) | 1994-05-11 |
Family
ID=17248697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60253253A Expired - Lifetime JPH0636362B2 (en) | 1985-11-12 | 1985-11-12 | Metal-hydrogen alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0636362B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006076304A (en) * | 2004-09-08 | 2006-03-23 | Heidelberger Druckmas Ag | Printing sheet gripper (lead edge clamp) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60130053A (en) * | 1983-12-15 | 1985-07-11 | Toshiba Corp | Sealed secondary battery having a negative electrode consisting of hydrogen-absorbing alloy electrode |
| JPS60136162A (en) * | 1983-12-26 | 1985-07-19 | Toshiba Corp | Sealed secondary battery having hydrogen-absorbing alloy electrode as negative electrode |
| JPS60198056A (en) * | 1984-03-22 | 1985-10-07 | Toshiba Corp | Hydrogen-absorbing alloy electrode |
-
1985
- 1985-11-12 JP JP60253253A patent/JPH0636362B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60130053A (en) * | 1983-12-15 | 1985-07-11 | Toshiba Corp | Sealed secondary battery having a negative electrode consisting of hydrogen-absorbing alloy electrode |
| JPS60136162A (en) * | 1983-12-26 | 1985-07-19 | Toshiba Corp | Sealed secondary battery having hydrogen-absorbing alloy electrode as negative electrode |
| JPS60198056A (en) * | 1984-03-22 | 1985-10-07 | Toshiba Corp | Hydrogen-absorbing alloy electrode |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006076304A (en) * | 2004-09-08 | 2006-03-23 | Heidelberger Druckmas Ag | Printing sheet gripper (lead edge clamp) |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0636362B2 (en) | 1994-05-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |