JPS6149374A - Nickel positive electrode for alkali cell - Google Patents
Nickel positive electrode for alkali cellInfo
- Publication number
- JPS6149374A JPS6149374A JP59172185A JP17218584A JPS6149374A JP S6149374 A JPS6149374 A JP S6149374A JP 59172185 A JP59172185 A JP 59172185A JP 17218584 A JP17218584 A JP 17218584A JP S6149374 A JPS6149374 A JP S6149374A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- powder
- positive electrode
- active material
- cobalt hydroxide
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- 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
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明はアルカリ蓄電池用ニッケル正極に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a nickel positive electrode for alkaline storage batteries.
従来技術とその問題点
アルカリ蓄電池用ニッケル正極は、２つの型に分類され
る。その１つは、シンター型と呼ばれているものである
。２〜６μの微細なニッケル粉末茶穿孔調板あるいは、
ニッケルネット等に焼結させた１０数μの微孔性焼結基
板に硝酸ニッケル溶液を含浸させる。その後アルカリ溶
液中で水酸化ニッケルに変化させることによって、活物
質を充填させるいわゆる溶液含浸法を用いるものである
。Prior art and its problems Nickel positive electrodes for alkaline storage batteries are classified into two types. One of them is called the sinter type. 2~6μ fine nickel powder brown perforated tone plate or
A microporous sintered substrate of 10-odd microns sintered into a nickel net or the like is impregnated with a nickel nitrate solution. A so-called solution impregnation method is then used to fill the active material by changing it into nickel hydroxide in an alkaline solution.
他の１つは、水酸化ニッケル活物質そのものを水等によ
ってペースト状にして、これを数十〜数百ミクロンの細
孔からなるニッケル繊維焼結体に、直接充填するペース
ト型や−あるいは水酸化ニッケル粉末に合剤を少量加え
てプレスし、ベレット状にして使用するボタン型である
。又穿孔鋼板を加工しホ゛ケット部を作り、その中に水
酸化ニアケル粉末を充填するポケット型もこの類である
。The other is a paste type in which the nickel hydroxide active material itself is made into a paste with water etc., and this is directly filled into a nickel fiber sintered body consisting of pores of several tens to hundreds of microns. It is a button type that is used by adding a small amount of the mixture to nickel oxide powder and pressing it into a pellet shape. Another type of pocket type is a pocket type in which a perforated steel plate is processed to form a socket and Niacel hydroxide powder is filled into the socket.
後者の水酸化ニッケル固体粉末を直接充填するものは、
溶液含浸法と異なり、微孔性焼結体を使用しない為集電
性に乏しく、５０〜６０％程度の活物質利用率しか得ら
れず、シンタ一式の活物質利用率９０％に比べて性能的
に大巾に劣っていた。これを改良するべく、水酸化ニッ
ケル粉末とカーボニルニッケル粉末の如き微細な粒子を
混合して用いられている。しかしこの場合でも約１０％
程度の性能向上するにすぎない。この様に正極に混合さ
れたニッケル粉末が有効に作用しない原因は、正極充放
電４位でニッケル粉末の表面に電導性の悪いニッケル水
酸化物が形成されるため□゛である。The latter, which is directly filled with nickel hydroxide solid powder, is
Unlike the solution impregnation method, it does not use a microporous sintered body, so it has poor current collecting properties, and the active material utilization rate is only about 50 to 60%, which is lower than the 90% active material utilization rate of a complete sinter set. It was inferior to Ohin in terms of performance. In order to improve this, a mixture of fine particles such as nickel hydroxide powder and carbonyl nickel powder is used. However, even in this case, about 10%
It only improves performance to a certain degree. The reason why the nickel powder mixed in the positive electrode does not work effectively is that nickel hydroxide with poor conductivity is formed on the surface of the nickel powder at the fourth stage of charging and discharging the positive electrode.
発明の目的
本発明は）アルカリ蓄電池用ニッケル正極、才、７に水
酸化ニンケル活物質粉末を直接充填させる正極において
、活物質利用率を向上させ、高性能で且つ生産性の高い
ニッケルーカドミウム蓄電池を提供することを目的とす
る。Purpose of the Invention The present invention is to provide a nickel-cadmium storage battery with improved active material utilization rate, high performance, and high productivity in a positive electrode in which a nickel positive electrode for an alkaline storage battery is directly filled with nickel hydroxide active material powder. The purpose is to provide
発明の構成
すなわち、本発明は上記の目的を達成するために、従来
のカーボニルニッケル粉末の添加に代えて、２価の水酸
化コバルトを添加するものである。水酸化ニッケル粉末
と２価の水酸化コバルト粉末を混合したニンケル正極活
物質である。Components of the Invention In order to achieve the above object, the present invention adds divalent cobalt hydroxide in place of the conventional addition of carbonyl nickel powder. Ninkel positive electrode active material is a mixture of nickel hydroxide powder and divalent cobalt hydroxide powder.
実す山側 以下本発明の一実施椀について詳述する。fruit mountain side An embodiment of the present invention will be described in detail below.
硫酸コバルト水溶液を室温でγルカリ’ｔＢ液と中和さ
せて水酸化コバルトを沈澱させた。The cobalt sulfate aqueous solution was neutralized with the gamma alkali'tB solution at room temperature to precipitate cobalt hydroxide.
この沈澱物を水洗した後真空乾操すると、表面が薄く６
価の水酸化コバルトで覆われた２価の水酸化コバルトが
得られた。この２価の水酸化コバルトは、６価の水酸化
コバルトで波器さねている為、空気中で長期間安定に存
在した。この粉末１０％と水酸化ニッケル粉末９０％と
を粉砕混合した後、カルボキシメチル七ルローズを少量
溶解した水を加えてペースト状にした０このペーストを
繊維径が約２５μのニッケル繊維をエアーレード法で分
布した後、還元性雰囲気下で焼結した厚み２間、多孔度
９５％の基板に充填した。その後乾燥、厚み調節してＱ
、７ｍｍの正極板とした。After washing this precipitate with water and drying it in vacuum, the surface became thin and 6
A divalent cobalt hydroxide coated with a divalent cobalt hydroxide was obtained. Since this divalent cobalt hydroxide was corrugated with hexavalent cobalt hydroxide, it existed stably in the air for a long period of time. After pulverizing and mixing 10% of this powder and 90% of nickel hydroxide powder, water in which a small amount of carboxymethyl hexarurose was dissolved was added to make a paste.The paste was made into a paste using nickel fibers with a fiber diameter of about 25μ by the airlaid method. After distributing the mixture, it was filled into a substrate having a thickness of 2 mm and a porosity of 95%, which was sintered under a reducing atmosphere. Then dry, adjust the thickness and
, and a 7 mm positive electrode plate.
４Ｘ４Ｃｍのこの正極１枚と、正極よりも容責大なる２
枚のカドミウム負極および比ｆｆ１１．２０の水酸化カ
リウム電解液を用いて、ニッケルーカドミウム蓄電池を
作成した。そしてこれを充放電して正極板の活物質利用
率を測定した。なお比較のために、同一寸法で１０％ニ
ッケル粉末、９０％水酸化ニッケル粉末の混合組成から
なる正極板についても測定した。This one positive electrode of 4X4Cm and two with greater tolerance than the positive electrode
A nickel-cadmium storage battery was prepared using two cadmium negative electrodes and a potassium hydroxide electrolyte with a ratio of ff 11.20. Then, this was charged and discharged to measure the active material utilization rate of the positive electrode plate. For comparison, a positive electrode plate having the same dimensions and a mixed composition of 10% nickel powder and 90% nickel hydroxide powder was also measured.
第１図はこれらの結果を示したものである。FIG. 1 shows these results.
すなわち、これら極板を０．１Ｃ電流で１５時間充電し
た後、０．２ Ｇ ７１流でＯＶ ＶＳ、 Ｈ９／ＨＧ
Ｉ Ｏまで放電させた時の正極板の活物質利用率を比１
咬した０
第１図の１はニッケル粉末と水酸化ニッケル粉末からな
る正極であり、■は２価の水酸化コバルト粉末と水酸化
ニッケル粉末からなる本発明の正極である。図より明ら
かな如く、２価の水酸化コバルトを添加したものは、利
用率９０％程度を示し、従来のシンタ一式とほとんど変
らない高性能を示した。その他のコバルト化合物として
、６価のＣｏ２０３やＣ０（ＯＨ）３の添加を試みたが
、はとんど効果が認められなかった。なぜ一般に不安定
とされる２ １ｉｌｌｉの水酸化コバルトＣＯ（ＯＨ）
２のみ有効であるかは明確ではないが、おそら＜ Ｃｉ
ｏ （ＯＨ） ２を出発物質として充放電中に電導性の
優れたコバルト化合物に変化するためと考えられた。That is, after charging these plates with 0.1C current for 15 hours, OV VS, H9/HG with 0.2G 71 current.
The active material utilization rate of the positive electrode plate when discharged to I O is compared to 1
0 In Fig. 1, 1 is a positive electrode made of nickel powder and nickel hydroxide powder, and ■ is a positive electrode of the present invention made of divalent cobalt hydroxide powder and nickel hydroxide powder. As is clear from the figure, the one to which divalent cobalt hydroxide was added showed a utilization rate of about 90%, showing almost the same high performance as the conventional sinter set. As other cobalt compounds, attempts were made to add hexavalent Co203 and C0(OH)3, but no effect was observed. Why 2 1illi cobalt hydroxide CO(OH) is generally considered unstable
Although it is not clear whether only 2 is effective, it is probably < Ci
This is thought to be because o (OH) 2 is used as a starting material and changes into a cobalt compound with excellent conductivity during charging and discharging.
発明の効果
上述の如く、本発明は水酸化ニッケル粉末と２価の水酸
化コバルト粉末を混合することにより、大巾に活物質利
用率を向上させた高性能な電池となり、しかもシンター
型と比べて、生産性の高い電池であり、その工業的価値
は非常に大である。Effects of the Invention As described above, the present invention provides a high-performance battery with a greatly improved active material utilization rate by mixing nickel hydroxide powder and divalent cobalt hydroxide powder, and moreover, compared to the sintered type. Therefore, it is a highly productive battery, and its industrial value is extremely large.
第１図は活物質利用率と充放電サイクルとの関係を示し
た図であり、Ｉはニッケル粉末が添加された正極活物質
よりなるニッケルーカドミウム電池であり、■は２価の
水酸化コバルトを添加した本発明による正極板を用いた
ニッケルーカドミウム電池である。Figure 1 is a diagram showing the relationship between active material utilization rate and charge/discharge cycle, where I is a nickel-cadmium battery made of a positive electrode active material to which nickel powder is added, and ■ is divalent cobalt hydroxide. This is a nickel-cadmium battery using a positive electrode plate according to the present invention containing .
Claims (1)
酸化コバルト粉末を混合することを特徴としたアルカリ
蓄電池用ニッケル正極。A nickel positive electrode for an alkaline storage battery, characterized in that the nickel positive electrode active material is a mixture of nickel hydroxide powder and divalent cobalt hydroxide powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59172185A JPS6149374A (en) | 1984-08-17 | 1984-08-17 | Nickel positive electrode for alkali cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59172185A JPS6149374A (en) | 1984-08-17 | 1984-08-17 | Nickel positive electrode for alkali cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6149374A true JPS6149374A (en) | 1986-03-11 |
| JPH0429189B2 JPH0429189B2 (en) | 1992-05-18 |
Family
ID=15937150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59172185A Granted JPS6149374A (en) | 1984-08-17 | 1984-08-17 | Nickel positive electrode for alkali cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6149374A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0284333A2 (en) * | 1987-03-25 | 1988-09-28 | Matsushita Electric Industrial Co., Ltd. | Sealed type nickel-hydride battery and production process thereof |
| EP0721229A1 (en) | 1994-12-19 | 1996-07-10 | Matsushita Electric Industrial Co., Ltd. | Alkaline storage battery and method of producing Ni/Co hydroxide active mass for positive electrode |
| US6576368B1 (en) | 1998-10-02 | 2003-06-10 | Sanyo Electric Co., Ltd. | Positive active material for use in sealed alkaline storage batteries |
| US6608465B2 (en) | 2001-10-31 | 2003-08-19 | Matsushita Electric Industrial Co., Ltd. | Positive electrode for alkaline storage battery and alkaline storage battery using the same |
| US7166391B2 (en) | 2000-11-15 | 2007-01-23 | Matsushita Electric Industrial Co., Ltd. | Cobalt compound for use in alkaline storage battery, method for manufacturing the same, and positive electrode plate of alkaline storage battery employing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5045246A (en) * | 1973-08-13 | 1975-04-23 |
-
1984
- 1984-08-17 JP JP59172185A patent/JPS6149374A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5045246A (en) * | 1973-08-13 | 1975-04-23 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0284333A2 (en) * | 1987-03-25 | 1988-09-28 | Matsushita Electric Industrial Co., Ltd. | Sealed type nickel-hydride battery and production process thereof |
| EP0721229A1 (en) | 1994-12-19 | 1996-07-10 | Matsushita Electric Industrial Co., Ltd. | Alkaline storage battery and method of producing Ni/Co hydroxide active mass for positive electrode |
| US5759718A (en) * | 1994-12-19 | 1998-06-02 | Matsushita Electric Industrial Co., Ltd. | Alkaline storage battery and method for making same |
| US6576368B1 (en) | 1998-10-02 | 2003-06-10 | Sanyo Electric Co., Ltd. | Positive active material for use in sealed alkaline storage batteries |
| US7166391B2 (en) | 2000-11-15 | 2007-01-23 | Matsushita Electric Industrial Co., Ltd. | Cobalt compound for use in alkaline storage battery, method for manufacturing the same, and positive electrode plate of alkaline storage battery employing the same |
| US6608465B2 (en) | 2001-10-31 | 2003-08-19 | Matsushita Electric Industrial Co., Ltd. | Positive electrode for alkaline storage battery and alkaline storage battery using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0429189B2 (en) | 1992-05-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |