JPS6129068A - Production of sintered cadmium negative electrode plate - Google Patents
Production of sintered cadmium negative electrode plateInfo
- Publication number
- JPS6129068A JPS6129068A JP59149911A JP14991184A JPS6129068A JP S6129068 A JPS6129068 A JP S6129068A JP 59149911 A JP59149911 A JP 59149911A JP 14991184 A JP14991184 A JP 14991184A JP S6129068 A JPS6129068 A JP S6129068A
- Authority
- JP
- Japan
- Prior art keywords
- cobalt
- hydroxide
- cadmium
- electrode plate
- nickel
- 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
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
- H01M4/801—Sintered carriers
-
- 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
- H01M4/246—Cadmium 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】
（イ）産業上の利用分野
本発明は焼結式カドミウム陰極板の製造方法に関し、特
にニブケルとコバルトが添加された焼結式カドミウム陰
極板の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a method for manufacturing a sintered cadmium cathode plate, and more particularly to a method for manufacturing a sintered cadmium cathode plate to which nibkel and cobalt are added.
（ロ）従来の技術
一般に焼結式カドミウム陰極板は、水、増粘剤及びニッ
ケル粉末を混合してなるスラリーを、鉄板にニッケルメ
・シキが施された導電芯体に塗着、乾燥し、次いで焼結
することにより得られる多孔性ニッケル焼結基板の多孔
部に、硝酸カドミウムまたは硫酸カドミウム等のカドミ
ウム塩溶液を含浸した後、アルカリ中で反応させ前記カ
ドミウム塩を水酸化カドミウムに変化させるか、もしく
は熱分解して酸化カドミウムに変化させることにより活
物質を充填して作製され、この一連の活物質の充填操作
を数回繰り返し行なうことで所装置の活物質が焼結基板
の多孔部に充填される。(b) Conventional technology In general, a sintered cadmium cathode plate is produced by applying a slurry made of a mixture of water, a thickener and nickel powder to a conductive core made of a nickel plated iron plate, and drying it. Next, the porous portion of the porous nickel sintered substrate obtained by sintering is impregnated with a cadmium salt solution such as cadmium nitrate or cadmium sulfate, and then the cadmium salt is converted into cadmium hydroxide by reacting in an alkali. Alternatively, it is produced by filling an active material by thermally decomposing it into cadmium oxide, and by repeating this series of active material filling operations several times, the active material of the device is filled into the porous part of the sintered substrate. Filled.
こうして作製される焼結式カドミウム陰極板は、電極内
に焼結金属からなる導電マ） １７ツクスを有するため
の活物質への電気導孤性が良く、機械的強度も大きいと
いう利点を有しているが、活物質の利用率については満
足できるものではなかった。The sintered cadmium cathode plate produced in this way has the advantage of having good electrical conductivity to the active material due to the conductive matrix made of sintered metal in the electrode, and high mechanical strength. However, the utilization rate of the active material was not satisfactory.
このカドミウム陰極板の活物質の利用率の向上を行なう
方法として、特公昭５Ｂ−３２７４５号公報に於いてペ
ースト式カドミウム陰極板にコバルト化合物またはコバ
ルト化合物及びニッケル化合物を添加することが提案さ
れており、こうして作製されたカドミウム陰極板はコバ
ルト化合物の添加により活物質の利用率は向上する。し
かしながら、充放電を繰り返すうちにコバルトは電解液
に溶出し、その結果極板容置が減少してサイクル劣化を
起こすという欠点があり、コバルト化合物と酸化カドミ
ウムと共に二・ツケル化合物を混合して極板を作製し、
た場合に於いてもサイクル寿命の向上はあまりみられな
かった。As a method of improving the utilization rate of the active material of this cadmium cathode plate, Japanese Patent Publication No. 5B-32745 proposes adding a cobalt compound or a cobalt compound and a nickel compound to a paste-type cadmium cathode plate. In the cadmium cathode plate thus prepared, the utilization rate of the active material is improved by adding a cobalt compound. However, during repeated charging and discharging, cobalt dissolves into the electrolyte, resulting in a decrease in the electrode capacity and cycle deterioration. Create a board,
Even in these cases, no significant improvement in cycle life was observed.
（ハ）発明が解決しようとする問題点
本発明は焼結式カドミウム陰極板の利用率を水酸化コバ
ルトの添加により向上させると共に前記水酸化コバルト
の電解液への溶出に伴う極板容量の劣化を抑制せしめん
とするものである。(c) Problems to be Solved by the Invention The present invention improves the utilization rate of a sintered cadmium cathode plate by adding cobalt hydroxide, and the capacity of the electrode plate deteriorates due to elution of the cobalt hydroxide into the electrolyte. The aim is to suppress this.
に）問題点を解決するための手段
水酸化カドミウムあるいは酸化カドミウムの充填操作に
加えて、ニッケル塩とコバルト塩との混合溶液を含浸し
、次いで前記ニッケル塩とコバルト塩を水酸化物に変化
させることにより、水酸化二叩ケルと水酸化コバルトを
同時に基板の多孔部に充填する操作を少なくとも一回行
なうものである。B) Measures to solve the problem In addition to the filling operation of cadmium hydroxide or cadmium oxide, impregnating with a mixed solution of nickel salt and cobalt salt, and then converting the nickel salt and cobalt salt into hydroxide. Accordingly, the operation of simultaneously filling the porous portions of the substrate with cobalt hydroxide and cobalt hydroxide is performed at least once.
（ホ）作用
焼結基板に水酸化コバルトと水酸化ニッケルを同時に充
填すると、充放電を行なった際にコバルトとニッケルの
固溶体が形成され、このコバルトニッケル固溶体は充放
電の際に溶解し難いため、コバルトの電解液への溶出が
抑制される。(e) Effect When a sintered substrate is filled with cobalt hydroxide and nickel hydroxide at the same time, a solid solution of cobalt and nickel is formed during charging and discharging, and this cobalt-nickel solid solution is difficult to dissolve during charging and discharging. , elution of cobalt into the electrolyte is suppressed.
（へ）実施例
多孔性ニッケル焼結基板を硝酸カドミウム溶液に浸漬し
、次いでアルカリ処理、水洗、乾燥を行なうという活物
質充填操作を繰り返し行なって焼結基板の多孔部に水酸
化カドミウムを充填した後、最終回のみ硝酸コバルト、
硝酸ニッケル及び水を重量比で下表のように混合してな
る含浸液に浸漬し、次いでアルカリ処理、水洗、乾燥を
行なって前記多孔部に水酸化コバルトと水酸化ニッケル
とを充填した本発明の焼結式カドミウム陰極板内及び四
を得る。比較として最終回の充填操作に用いる含浸液を
硝酸コバルト水溶液に習え、その他は前記本発明極板と
同一の操作で比較極板（Ｃ１を得、また兼終回の充填操
作を行なわず前記本発明極板と同一の操作で水酸化カド
ミウムの充填のみ行なった比較極板ｐ）を得る。これら
極板内乃至ｐ）の最終回の充填操作に用いた含浸液の組
成は各組成物の重量比で表わすと下表のとおりである。(F) Example A porous nickel sintered substrate was immersed in a cadmium nitrate solution, and then the active material filling operation of alkali treatment, water washing, and drying was repeated to fill the porous portions of the sintered substrate with cadmium hydroxide. After, cobalt nitrate only in the final episode,
The present invention, in which the pores are filled with cobalt hydroxide and nickel hydroxide by being immersed in an impregnating solution made by mixing nickel nitrate and water in the weight ratio shown in the table below, followed by alkali treatment, washing with water, and drying. A sintered cadmium cathode plate and four are obtained. For comparison, a comparison electrode plate (C1) was obtained by using a cobalt nitrate aqueous solution as the impregnating liquid used in the final filling operation, and the other operations were the same as those for the electrode plate of the present invention. A comparative electrode plate p) was obtained by carrying out the same operation as the invention electrode plate, except for filling with cadmium hydroxide. The composition of the impregnating liquid used in the final filling operation of the inside of the electrode plate (p) is as shown in the table below, expressed in weight ratio of each composition.
表
第１図はこれらカドミウム陰極板をニッケル板を対極と
して電解液リッチの状態で満充電した後、１時間率電流
にて放電するという充放電条件で充放電を行なったとき
のサイクル特性図である。図面より本発明極板内及び四
は水酸化ニッケルが添加されていない比較極板Ｃ）に比
較して容量劣化が少なく、また水酸化コバルトが添加さ
れていない比較極板σ））に比較して容量がアップして
いることがわかる。Table 1 shows the cycle characteristics when these cadmium cathode plates are fully charged in an electrolyte-rich state with a nickel plate as the counter electrode, and then charged and discharged at a 1 hour rate current. be. From the drawings, the capacity deterioration of the electrode plates of the present invention and 4 is smaller than that of the comparative electrode plate C) to which nickel hydroxide is not added, and compared to the comparative electrode plate σ)) to which cobalt hydroxide is not added. It can be seen that the capacity has increased.
第２図は前述の実施例に於いて最終回の充填操作に用い
る含浸液中のコバルトとニッケルの比率を変化させて作
製したカドミウム陰極板の利用率をコバルトに対するニ
ッケル量の変化に対応して示した図面である。最終回の
充填操作を行なわない比較極板（Ｄｌの利用率を測定し
たところ利用率が７６％であったことから、最終回のコ
バルト添加により利用率の向上がみられ、またコバルト
と同時にニッケルを添加した場合に於いても利用率の向
上がみられることがわかる。Figure 2 shows the utilization rate of the cadmium cathode plate produced by changing the ratio of cobalt and nickel in the impregnating liquid used in the final filling operation in the above-mentioned example, in response to the change in the amount of nickel to cobalt. This is a drawing shown. Comparative electrode plate without the final filling operation (Measurement of Dl utilization rate showed that the utilization rate was 76%, indicating that the utilization rate improved with the addition of cobalt in the final loading operation, and that nickel was added at the same time as cobalt. It can be seen that the utilization rate is improved even when .
第３図及び第４図は前述の実施例に於いて最終回の充填
操作に用いる含浸液中のコバルトとニッケルの比率を変
化させて作製されたカドミウム陰極板中のコバルト量を
表わした図面であり、第３図では充放電前（充填直後）
と充放電を１サイクル行なった後のコバルト量を、第４
図では充放電を１０サイクル行なった後のコバルト量を
夫々示している。尚充放電条件は前述と同様である。第
３図及び第４図から極板作製時点に於いてカドミウム陰
極板中に含有されるコバルト量は含浸液中のニッケル針
にあまり影響を受けることがないが、充放電を行なうと
含浸液中のニッケル量が増すに従ってカドミウム陰極中
に含有されるコバルト量が増加することがわかる。Figures 3 and 4 are drawings showing the amount of cobalt in cadmium cathode plates produced by varying the ratio of cobalt and nickel in the impregnating liquid used in the final filling operation in the above-mentioned example. Yes, in Figure 3, before charging and discharging (immediately after charging)
The amount of cobalt after one cycle of charging and discharging is
The figure shows the amount of cobalt after 10 cycles of charging and discharging. Note that the charging and discharging conditions are the same as described above. Figures 3 and 4 show that the amount of cobalt contained in the cadmium cathode plate at the time of electrode plate fabrication is not affected much by the nickel needles in the impregnating liquid, but when charging and discharging, the amount of cobalt contained in the impregnating liquid is It can be seen that as the amount of nickel increases, the amount of cobalt contained in the cadmium cathode increases.
これは本発明の製造方法を用いて作製されたカドミウム
陰極板は水酸化コバルトと水酸化ニッケルが同時に充填
されているため、充放電の際にニッケルとコバルトの固
溶体が形成されて電解液のな
溶出が抑制されるからであり、充放電時のコバルトの溶
出が抑制されることによりカドミウム陰極板の利用率が
抑えられて、極板容量のサイクル劣化が抑制される。こ
れに対して最終回に水酸化コバルトのみ充填したカドミ
ウム陰極板は充放電サイクルの経過に伴う極板中のコバ
ルト量の減少が著しいため、１０サイクル経過時点では
水酸化コバルト及び水酸化ニッケルが添加されていない
カドミウム陰極板と同様な容量まで極板容量が減少し、
水酸化コバルト添加の効果が失われる。This is because the cadmium cathode plate produced using the manufacturing method of the present invention is filled with cobalt hydroxide and nickel hydroxide at the same time, so a solid solution of nickel and cobalt is formed during charging and discharging, and the electrolyte becomes a solid solution. This is because elution is suppressed, and by suppressing cobalt elution during charging and discharging, the utilization rate of the cadmium cathode plate is suppressed, and cycle deterioration of the electrode plate capacity is suppressed. On the other hand, with the cadmium cathode plate filled only with cobalt hydroxide in the final cycle, the amount of cobalt in the plate decreases significantly as the charge/discharge cycle progresses, so cobalt hydroxide and nickel hydroxide are added after 10 cycles. The plate capacitance is reduced to a capacity similar to that of an untreated cadmium cathode plate,
The effect of cobalt hydroxide addition is lost.
（ト）発明の効果
本発明の焼結式カドミウム陰極板の製造方法は、水酸化
カドミウムの充填操作の他に、水酸化コバルトと水酸化
ニッケルとを同時に充填する操作を行なうものであるか
ら、水酸化コバルトの存在により極板の利用率が向上す
ると共に、水酸化コバルトは水酸化ニッケルと固溶体を
形成し電解液への溶出が防止されるためコバルトの電解
液への溶出に伴う極板容量の劣化春抑制することができ
る。(G) Effects of the Invention The method for manufacturing a sintered cadmium cathode plate of the present invention involves not only filling cadmium hydroxide but also filling cobalt hydroxide and nickel hydroxide at the same time. The presence of cobalt hydroxide improves the utilization rate of the electrode plate, and since cobalt hydroxide forms a solid solution with nickel hydroxide and prevents elution into the electrolyte, the electrode plate capacity increases due to the elution of cobalt into the electrolyte. The deterioration of spring can be suppressed.
第１図は本発明極板と比較極板のサイクル特性図、ｉＪ
２図はカドミウム陰極板の利用率と含浸液中のコバルト
に対するニッケル量との関係を示す図面、第３図及び第
４図はカドミウム陰極板中のコバルト量と含浸液中のコ
バルトに対するニッケル量との関係を示す図面である。
ｆＡｌ凹・・・本発明極板、ｔｑ鈴＋・・・比較極板。Figure 1 is a cycle characteristic diagram of the electrode plate of the present invention and the comparative electrode plate, iJ
Figure 2 shows the relationship between the utilization rate of the cadmium cathode plate and the amount of nickel relative to cobalt in the impregnating liquid, and Figures 3 and 4 show the relationship between the amount of cobalt in the cadmium cathode plate and the amount of nickel relative to cobalt in the impregnating liquid. FIG. fAl concave: present invention electrode plate, tq bell+: comparison electrode plate.
Claims (1)
次いで前記カドミウム塩を水酸化カドミウムあるいは酸
化カドミウムに変化させる操作を複数回繰り返すもので
あって、前記操作の他に前記多孔部にニッケル塩とコバ
ルト塩との混合溶液を含浸し、次いでニッケル塩とコバ
ルト塩とを水酸化ニッケルと水酸化コバルトに変化させ
る操作を少なくとも一回行なうことを特徴とする焼結式
カドミウム陰極板の製造方法。(1) Impregnating the porous part of the sintered substrate with a cadmium salt solution,
Next, the operation of changing the cadmium salt into cadmium hydroxide or cadmium oxide is repeated several times, and in addition to the above operation, the porous portion is impregnated with a mixed solution of nickel salt and cobalt salt, and then the nickel salt and cobalt salt are A method for producing a sintered cadmium cathode plate, comprising performing at least once an operation of converting a cobalt salt into nickel hydroxide and cobalt hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59149911A JPS6129068A (en) | 1984-07-18 | 1984-07-18 | Production of sintered cadmium negative electrode plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59149911A JPS6129068A (en) | 1984-07-18 | 1984-07-18 | Production of sintered cadmium negative electrode plate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6129068A true JPS6129068A (en) | 1986-02-08 |
Family
ID=15485286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59149911A Pending JPS6129068A (en) | 1984-07-18 | 1984-07-18 | Production of sintered cadmium negative electrode plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6129068A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4920819A (en) * | 1988-03-04 | 1990-05-01 | Nhk Morse Co., Ltd. | Junction unit used in dual station system |
| US5280282A (en) * | 1990-02-28 | 1994-01-18 | Sanshin Kogyo Kabushiki Kaisha | Remote control system |
-
1984
- 1984-07-18 JP JP59149911A patent/JPS6129068A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4920819A (en) * | 1988-03-04 | 1990-05-01 | Nhk Morse Co., Ltd. | Junction unit used in dual station system |
| US5280282A (en) * | 1990-02-28 | 1994-01-18 | Sanshin Kogyo Kabushiki Kaisha | Remote control system |
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