JPH0773052B2 - Non-sintered electrode manufacturing method - Google Patents
Non-sintered electrode manufacturing methodInfo
- Publication number
- JPH0773052B2 JPH0773052B2 JP61159002A JP15900286A JPH0773052B2 JP H0773052 B2 JPH0773052 B2 JP H0773052B2 JP 61159002 A JP61159002 A JP 61159002A JP 15900286 A JP15900286 A JP 15900286A JP H0773052 B2 JPH0773052 B2 JP H0773052B2
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- tank
- nickel hydroxide
- aqueous solution
- powder
- 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
- H01M4/48—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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (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】 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適用しう
る、非焼結式ニッケル正極の製造法に関するものであ
る。Description: TECHNICAL FIELD The present invention relates to a method for producing a non-sintered nickel positive electrode applicable to a nickel positive electrode for alkaline storage batteries.
従来の技術 従来、この種のアルカリ電池用ニッケル正極に使用する
非焼結式ニッケル正極、つまり水酸化ニッケル粉末を活
物質として直接使用する正極にはニッケル塩水溶液に化
学量論的に過剰で一定量のか性アルカリを加え、水酸化
ニッケルとして沈澱析出させて製造する方法、すなわ
ち、水酸化ニッケルをバッチ式で製造している。また、
電池用活物質として特性の優れたものにするため、結晶
をある程度成長、安定化する目的で一定時間熟成する必
要があった。これらの理由により、この方法では、製造
工程が連続化することが困難で、製造コストが高くなる
欠点を有している。Conventional technology Conventionally, a non-sintered nickel positive electrode used for this type of nickel positive electrode for alkaline batteries, that is, a positive electrode that directly uses nickel hydroxide powder as an active material, is stoichiometrically excessive and constant in a nickel salt aqueous solution. A method of producing a nickel hydroxide by adding a certain amount of caustic alkali and precipitating it out as nickel hydroxide, that is, nickel hydroxide is produced in a batch system. Also,
In order to obtain excellent characteristics as a battery active material, it was necessary to age the crystals for a certain period of time in order to grow and stabilize the crystals to some extent. For these reasons, this method has a drawback that it is difficult to make the manufacturing process continuous and the manufacturing cost becomes high.
発明が解決しようとする問題点 このような従来の製法では、水酸化ニッケル粉末を連続
的に製造することが困難で、水酸化ニッケル粉末が高価
になるという問題があった。Problems to be Solved by the Invention In such a conventional production method, it is difficult to continuously produce nickel hydroxide powder, and the nickel hydroxide powder becomes expensive.
本発明は水溶性のニッケル塩の転化と結晶を成長させる
熟成の２段階を同一槽で連続的に行ない、低コストの水
酸化ニッケル粉末を製造することを目的とするものであ
る。An object of the present invention is to produce a low-cost nickel hydroxide powder by continuously performing the two steps of conversion of a water-soluble nickel salt and aging for growing crystals in the same tank.
問題点を解決するための手段 この問題点を解決するために本発明は、非焼結式ニッケ
ル極に使用される水酸化ニッケル粉末の製法をつぎに示
す方法で製造するものである。すなわち、ニッケル塩の
水溶液とか性アルカリ水溶液を同一槽に導入して十分攪
拌し、水酸化ニッケルに転化してこの槽の上部より、オ
ーバーフローさせて取り出す工程を採用し、この工程に
おいて前記水溶液の濃度、供給量および槽内温度を一定
にするとともに、槽内のPH値を10.4〜10.7の範囲内に制
御して水酸化ニッケル粉末を得るものである。Means for Solving the Problems In order to solve this problem, the present invention is to manufacture the nickel hydroxide powder used for the non-sintered nickel electrode by the following method. That is, a step of introducing an aqueous solution of nickel salt and a caustic alkaline solution into the same tank, stirring them sufficiently, converting them into nickel hydroxide, and taking out by overflowing from the upper part of this tank is adopted. The nickel hydroxide powder is obtained by keeping the supply amount and the temperature in the tank constant and controlling the PH value in the tank within the range of 10.4 to 10.7.
作用 この構成では上記の供給水溶液の濃度、供給量および槽
内の温度を一定にして槽内のPH値を10.4〜10.7の範囲内
に制御することにより、得られる水酸化ニッケルの比表
面積を大きくして利用率を向上させるとともに、基板に
充てんする際の充てん密度を大きくすることができ、電
池用活物質として優れた特性を有する水酸化ニッケルを
得ることができる。Function In this configuration, the specific surface area of the nickel hydroxide obtained is increased by controlling the PH value in the tank within the range of 10.4 to 10.7 while keeping the concentration of the above-mentioned aqueous solution supplied, the supply amount and the temperature in the tank constant. Thus, it is possible to improve the utilization rate and increase the packing density at the time of filling the substrate, and it is possible to obtain nickel hydroxide having excellent characteristics as a battery active material.
また、本構成では水酸化ニッケルへの転化と熟成を同一
の槽内で連続的に行うことができるので、水酸化ニッケ
ルの製造工程を簡素化して安価に水酸化ニッケルを得る
ことができる。Further, in this configuration, since conversion into nickel hydroxide and aging can be continuously performed in the same tank, the manufacturing process of nickel hydroxide can be simplified and nickel hydroxide can be obtained at low cost.
実 施 例 水酸化ニッケルを製造する析出槽としては、100のタ
ンクを用いて、ニッケル塩、か性アルカリ水溶液とし
て、各々180g/のニッケル金属を溶解した硝酸ニッケ
ルと、20重量％の水酸化ナトリウム水溶液を用いた。こ
のタンク内へニッケル塩溶液を1.5/hrの一定流量で導
入し、槽内温度を40℃一定に保ち、十分攪拌しながら、
水酸化ナトリウム水溶液を一定範囲内のPH値を保持する
ために間欠的に添加した。この一定範囲のPH値として、
10.3〜10.4,10.4〜10.5,10.5〜10.6,10.6〜10.7,10.7〜
10.8の５段階に変化させて得られた水酸化ニッケルＡ〜
Ｅを作り、水洗、乾燥し粉末とした。Example: As a precipitation tank for producing nickel hydroxide, 100 tanks were used, and nickel nitrate in which 180 g / nickel metal was dissolved in nickel salt and caustic alkaline aqueous solution, respectively, and 20% by weight of sodium hydroxide were used. An aqueous solution was used. The nickel salt solution was introduced into this tank at a constant flow rate of 1.5 / hr, the temperature inside the tank was kept constant at 40 ° C., with sufficient stirring,
Aqueous sodium hydroxide solution was added intermittently to keep the PH value within a certain range. As the PH value in this fixed range,
10.3 ~ 10.4, 10.4 ~ 10.5, 10.5 ~ 10.6, 10.6 ~ 10.7, 10.7 ~
Nickel hydroxide A obtained by changing to 5 steps of 10.8
E was prepared, washed with water and dried to obtain a powder.
このＡ〜Ｅの粉末を用いて、それぞれ水酸化ニッケル10
0gに対して、金属コバルト8g混合し、水を加えてペース
ト状にし、発泡状ニッケル多孔体（多孔度95％）に充て
んし、乾燥後一定条件で加圧プラスを行ない、非焼結式
ニッケル正極を得た。この正極を用い、負極として公知
のカドミウム負極と組みあわせ、公称容量700mAhのAAサ
イズの密閉形ニッケルカドミウム蓄電池を構成した。Using the powders A to E, nickel hydroxide 10
Mix 0 g of metallic cobalt with 8 g of metallic cobalt, add water to form a paste, fill a foamed nickel porous body (porosity 95%), pressurize plus after drying under constant conditions, non-sintered nickel A positive electrode was obtained. This positive electrode was used in combination with a known negative electrode of cadmium as a negative electrode to form an AA size sealed nickel cadmium storage battery having a nominal capacity of 700 mAh.
この電池を20℃の一定温度で0.1Cで20時間充電し、0.2C
で放電を繰りかえし、２サイクル目の放電容量（終止電
圧を1Vにした場合）で電池特性を評価した。これらの結
果を第１表に示す。Charge this battery at 0.1C for 20 hours at a constant temperature of 20 ℃
Discharging was repeated and the battery characteristics were evaluated by the discharge capacity at the second cycle (when the final voltage was 1 V). The results are shown in Table 1.
この表において、析出PH値は、たとえばＡの場合であれ
ば、下限値が10.3であり、上限値が10.4の範囲で変化し
ている。実際にはPH値が10.33になると水酸化ナトリウ
ムの水溶液が添加され、PH値が10.37になれば水酸化ナ
トリウム水溶液の供給ポンプが停止するように設計され
ている。また、粉末の充てん密度の測定は水酸化ニッケ
ル粉末を十分乾燥後、一定高さより落下させる工程を決
められた回数だけ繰りかえした時の粉末の密度を示した
もので、電極にした場合の同一体積中に充てんされる水
酸化ニッケル量に関連してくる。したがって、高容量の
電池を作るには充てん密度の大きい粉末が望ましい。 In this table, for example, in the case of A, the precipitated PH value has a lower limit value of 10.3 and an upper limit value of 10.4. In practice, when the PH value reaches 10.33, the sodium hydroxide aqueous solution is added, and when the PH value reaches 10.37, the sodium hydroxide aqueous solution supply pump is stopped. Further, the measurement of the packing density of the powder shows the density of the powder when the step of dropping the nickel hydroxide powder from a certain height is repeated a predetermined number of times after the nickel hydroxide powder has been sufficiently dried. It is related to the amount of nickel hydroxide filled in. Therefore, a powder having a high packing density is desirable for producing a high capacity battery.
活物質の利用率については、PH値の大きい範囲で析出さ
せた水酸化ニッケルが良かった。この粉末においては、
粉末の粒子が小さくなり、比表面積の大きな粉末が形成
されたことに起因する。しかし、電極として充てんした
場合、充てん密度が低くなり、容量密度としては低下し
た。Regarding the utilization rate of the active material, nickel hydroxide deposited in the range of large PH value was good. In this powder,
This is due to the fact that the particles of the powder became small and a powder having a large specific surface area was formed. However, when it was filled as an electrode, the packing density was low and the capacity density was low.
実施例においてはニッケル塩濃度、ニッケル塩流量（析
出槽内に滞留している時間）、析出温度を固定して、PH
値を変化させて得られた粉末について比較したが、前記
３条件が異なることにより、最適PH値が異なってくる。
したがって、PH値だけで本発明を規正することは困難
で、４項目を関連づけて決定することが必要である。ま
た、使用するニッケル塩の種類を変更しても、上記４項
目を限定することにより最適範囲が存在することが確認
でき、この方法は水溶性のニッケル塩たとえば、硫酸ニ
ッケル，塩化ニッケルでも適用できることがわかった。In the examples, the nickel salt concentration, the nickel salt flow rate (the time of staying in the deposition tank), the deposition temperature were fixed, and the PH
The powders obtained by changing the values were compared, but the optimum PH value differs due to the difference in the above three conditions.
Therefore, it is difficult to regulate the present invention only by the PH value, and it is necessary to determine the four items in association with each other. Further, even if the type of nickel salt used is changed, it can be confirmed that the optimum range exists by limiting the above four items, and this method can be applied to water-soluble nickel salts such as nickel sulfate and nickel chloride. I understood.
さらに、実施例においては発泡状ニッケル多孔体へ、充
てんして電極を構成する例を示したが、金属基板とし
て、ニッケルのネット、エキスパンドメタルの両面に塗
着する方法により得られたニッケル正極および多数の細
孔を有する金属ケース内へ充てんして得られるポケット
式ニッケル正極においても本発明は有効な手段であっ
た。Further, in the examples, an example in which the foamed nickel porous body is filled to form the electrodes, but as the metal substrate, a nickel net, a nickel positive electrode obtained by a method of coating both surfaces of the expanded metal and The present invention was also an effective means for a pocket-type nickel positive electrode obtained by filling a metal case having a large number of pores.
発明の効果 以上のように本構成ではニッケル塩水溶液とか性アルカ
リ水溶液を同一槽内に導入して攪拌する際、前記供給水
溶液の濃度、供給量および槽内の温度を一定にして槽内
のPH値を10.4〜10.7の範囲内に制御することにより、得
られる水酸化ニッケルの比表面積を大きくして利用率を
向上させるとともに、基板に充てんする際の充てん密度
を大きくすることができ、電池用活物質として優れた特
性を有する水酸化ニッケルを得ることができる。As described above, in this configuration, when the nickel salt aqueous solution and the caustic alkaline aqueous solution are introduced into the same tank and stirred, the concentration of the supplied aqueous solution, the supply amount, and the temperature in the tank are kept constant and the pH in the tank is kept constant. By controlling the value within the range of 10.4 to 10.7, it is possible to increase the specific surface area of the obtained nickel hydroxide and improve the utilization rate, and also to increase the packing density when filling the substrate. It is possible to obtain nickel hydroxide having excellent properties as an active material.
また、本構成では水酸化ニッケルへの転化と熟成を同一
の槽内で連続的に行うことができるので、水酸化ニッケ
ルの製造工程を簡素化して安価に水酸化ニッケルを得る
ことができる。Further, in this configuration, since conversion into nickel hydroxide and aging can be continuously performed in the same tank, the manufacturing process of nickel hydroxide can be simplified and nickel hydroxide can be obtained at low cost.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 生駒 宗久 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 松本 功 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Munehisa Ikoma 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Isao Matsumoto 1006 Kadoma, Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd.
Claims (2)
物を乾燥状態もしくはペースト状態で金属基板または支
持体内部に充てんしたニッケル正極であって、この正極
に用いる水酸化ニッケル粉末はニッケル塩の水溶液とか
性アルカリ水溶液を同一槽内に導入し十分攪拌して水酸
化ニッケルに転化し、この槽内から連続的に水酸化ニッ
ケルを取り出す工程により得られ、前記水溶液の濃度、
供給量および槽内の温度を一定にするとともに槽内のPH
値を10.4〜10.7の範囲内に制御する非焼結式電極の製造
法。1. A nickel positive electrode in which a powder mixture mainly composed of nickel hydroxide powder is filled in a dry state or a paste state inside a metal substrate or a support, and the nickel hydroxide powder used for the positive electrode is an aqueous solution of nickel salt. Obtained by the step of introducing a caustic alkaline aqueous solution into the same tank and sufficiently stirring to convert it into nickel hydroxide, and continuously taking out nickel hydroxide from the tank, the concentration of the aqueous solution,
The supply amount and the temperature in the tank are kept constant and the PH in the tank is
A method for manufacturing non-sintered electrodes whose value is controlled within the range of 10.4 to 10.7.
の範囲第１項に記載の非焼結式電極の製造法。2. The method for producing a non-sintered electrode according to claim 1, wherein the nickel salt is nickel nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61159002A JPH0773052B2 (en) | 1986-07-07 | 1986-07-07 | Non-sintered electrode manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61159002A JPH0773052B2 (en) | 1986-07-07 | 1986-07-07 | Non-sintered electrode manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6316556A JPS6316556A (en) | 1988-01-23 |
| JPH0773052B2 true JPH0773052B2 (en) | 1995-08-02 |
Family
ID=15684083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61159002A Expired - Lifetime JPH0773052B2 (en) | 1986-07-07 | 1986-07-07 | Non-sintered electrode manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0773052B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01187768A (en) * | 1988-01-19 | 1989-07-27 | Yuasa Battery Co Ltd | Nickel electrode for alkali battery |
| JPH0724218B2 (en) * | 1988-04-11 | 1995-03-15 | 株式会社ユアサコーポレーション | Nickel electrode for alkaline battery and battery using the same |
| JPH026340A (en) * | 1988-04-13 | 1990-01-10 | Kansai Shokubai Kagaku Kk | Production of nickel hydroxide |
| CA2133906A1 (en) | 1993-10-20 | 1995-04-21 | Kuninobu Makimoto | Method for the preparation of nickel hydroxide particles |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS604149B2 (en) * | 1977-06-10 | 1985-02-01 | 電気化学工業株式会社 | Dry spray method |
-
1986
- 1986-07-07 JP JP61159002A patent/JPH0773052B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6316556A (en) | 1988-01-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |