JPH0682553B2 - Method for producing nickel hydroxide for alkaline battery - Google Patents
Method for producing nickel hydroxide for alkaline batteryInfo
- Publication number
- JPH0682553B2 JPH0682553B2 JP62181834A JP18183487A JPH0682553B2 JP H0682553 B2 JPH0682553 B2 JP H0682553B2 JP 62181834 A JP62181834 A JP 62181834A JP 18183487 A JP18183487 A JP 18183487A JP H0682553 B2 JPH0682553 B2 JP H0682553B2
- Authority
- JP
- Japan
- Prior art keywords
- nickel hydroxide
- amount
- nickel
- mol
- active material
- 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 - Fee Related
Links
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000003518 caustics Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 238000011049 filling Methods 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000011149 active material Substances 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000005245 sintering Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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
- H01M4/32—Nickel oxide or hydroxide electrodes
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (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、アルカリ蓄電池の正極側活物質として用いら
れる水酸化ニッケルの製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing nickel hydroxide used as a positive electrode side active material of an alkaline storage battery.
従来の技術 アルカリ電池用ニッケル電極の製造法には、焼結式，ポ
ケット式などがあるが、寿命が長い点，高率放電特性が
優れている点から焼結式が広く使われている。一方、焼
結式により得られるニッケル極板は寿命が長く高率放電
特性に優れているものの工程が煩雑であるため、これに
かわる法として金属多孔体を用いる方法が提案されてい
る（特開昭58−161252号公報）。2. Description of the Related Art Conventional methods for manufacturing nickel electrodes for alkaline batteries include a sintering method and a pocket method, but the sintering method is widely used because of its long life and excellent high rate discharge characteristics. On the other hand, the nickel electrode plate obtained by the sintering method has a long life and excellent high rate discharge characteristics, but the process is complicated. Therefore, a method using a metal porous body has been proposed as an alternative method (Japanese Patent Application Laid-Open No. 2000-242242). 58-161252).
金属多孔体は、多孔度95〜98％を有し、孔径が数10〜数
100ミクロンと大きく、この孔径が大きいことにより活
物質粉末である水酸化ニッケルをそのまま充填すること
ができる利点がある。活物質の金属多孔体への充填方法
としては、予じめ金属多孔体に水を付着させた後活物質
を充填するのが通例であるが、この方法では0.9g/cc vo
id程度の充填率であり、焼結式のニッケル極板の2.0g/c
c voidに比べて非常に小さなものとなる。活物質充填率
が低いと、電池容量によって決まる所要活物質量を得る
ために、金属多孔体の厚みを厚くせねばならない不利益
がある。従って、厚みを厚くすることなく所要活物質量
を確保するためには、活物質充填後に極板をプレスする
必要がある。この活物質充填後のプレスは初期の活物質
充填量が大きい程容易であり、また極板強度が大きくそ
の後の工程で扱いやすくなる。The porous metal has a porosity of 95 to 98% and a pore size of several tens to several.
The size is as large as 100 microns, and the large pore size has an advantage that nickel hydroxide as the active material powder can be directly filled. As a method for filling the active material into the metal porous body, it is customary to deposit the active material after adhering water to the metal porous body in advance, but in this method, 0.9 g / cc vo
The filling rate is about id, and it is 2.0g / c of the sintering type nickel plate.
It is much smaller than c void. If the filling rate of the active material is low, there is a disadvantage that the thickness of the porous metal body must be increased in order to obtain the required amount of active material determined by the battery capacity. Therefore, in order to secure the required amount of active material without increasing the thickness, it is necessary to press the electrode plate after filling the active material. The pressing after filling with the active material is easier as the filling amount of the active material in the initial stage is larger, and the strength of the electrode plate is larger and the pressing is easier in the subsequent steps.
そこで、初期の活物質充填量の大きいことが望ましいの
であるが、活物質として従来の方法で合成・生成される
水酸化ニッケルを用いたのでは充分な充填量を得ること
が困難であった。Therefore, it is desirable that the initial amount of the active material is large, but it is difficult to obtain a sufficient amount of the active material by using nickel hydroxide synthesized and produced by a conventional method.
それ故、本発明は金属多孔体への充填量の高い水酸化ニ
ッケルを得ることのできる製造方法を提供することを主
たる目的としている。Therefore, the main object of the present invention is to provide a manufacturing method capable of obtaining nickel hydroxide having a high filling amount in a porous metal body.
問題点を解決するための手段 上記の目的は、ニッケル塩とカセイアルカリを混合し、
その生成物に対し残留分を含めて総量が10〜50mol％の
カセイアルカリを混合させた後乾燥工程をへて水酸化ニ
ッケルを製造することによって達成される。Means for Solving Problems The purpose of the above is to mix nickel salt and caustic
This is achieved by mixing nickel hydroxide with a total amount of 10 to 50 mol% caustic for the product, including the residue, followed by a drying step to produce nickel hydroxide.
作用 ニッケル塩とカセイアルカリ混合させ、生成した水酸化
ニッケルに過剰量のカセイアルカリを添加し乾燥を行な
うと、水酸化ニッケルの結晶性が上がる。又、乾燥の段
階で水酸化ニッケルの凝集が促進され粒径が大きくな
る。その為、金属多孔体への充填量が高くなり、その後
の工程が容易なものとなる。但し、ニッケル塩に対し添
加するカセイアルカリの量があまり過剰すぎると、水酸
化ニッケルの粒子が分解されて、粒形の小さいものが出
来てしまう。そのためカセイアルカリの添加量は適切な
範囲に保つ必要があり、実験によれば、上記のように総
量が10〜50mol％の範囲に保てばよいことがわかった。Action The crystallinity of nickel hydroxide increases when nickel salt and caustic alkali are mixed and an excess amount of caustic alkali is added to the produced nickel hydroxide and drying is performed. In addition, agglomeration of nickel hydroxide is promoted during the drying stage, and the particle size increases. Therefore, the filling amount in the porous metal becomes high, and the subsequent steps become easy. However, if the amount of caustic alkali added to the nickel salt is too excessive, the nickel hydroxide particles will be decomposed and small particles will be formed. Therefore, it is necessary to keep the amount of caustic alkali added in an appropriate range, and according to experiments, it was found that the total amount should be kept in the range of 10 to 50 mol% as described above.
実施例 次に本発明の実施例を詳述する。Example Next, an example of the present invention will be described in detail.
先ず、4mol％／の水酸化ナトリウム１中に、1mol％
／の硝酸ニッケル１を徐々に添加させていき、水酸
化ニッケルの合成を行った。合成した水酸化ニッケルを
充分水洗して残留不純物を取り除き、その後、水酸化ニ
ッケルのろ過を行ない、定量の水酸化ナトリウム粉末を
添加して均一に混合した。ここで水酸化ナトリウムの添
加量は0mol％、5mol％、10mol％、20mol％、
30mol％、40mol％、50mol％、60mol％の８通りと
した。但し、各場合とも水酸化ナトリウムの添加量は、
残量も含めて水酸化ニッケルに対する総量を意味してい
る。かくして、各通りの添加量のものについて中間乾燥
を行なって後、水を加えて混合しろ過する工程を４〜５
回繰返し（デカンテーションろ過）、本乾燥、粉砕を行
なって完成水酸化ニッケルとした。図は水酸化ナトリウ
ムの添加量が上記〜の各場合のものの水酸化ニッケ
ルの平均粒径（破線）及び金属多孔体への充填率（実
線）を表わしている。図から水酸化ナトリウム量が10mo
l％（対水酸化ニッケル量）から充填率の向上が見られ
るが、他方50mol％よりも多く添加を行うと充填率が低
下してしまうことがわかる。First, 1 mol% in 4 mol% / sodium hydroxide 1
Nickel nitrate 1 of / was gradually added to synthesize nickel hydroxide. The synthesized nickel hydroxide was thoroughly washed with water to remove residual impurities, and then nickel hydroxide was filtered, and a fixed amount of sodium hydroxide powder was added and uniformly mixed. Here, the addition amount of sodium hydroxide is 0 mol%, 5 mol%, 10 mol%, 20 mol%,
Eight kinds of 30 mol%, 40 mol%, 50 mol% and 60 mol% were used. However, in each case, the amount of sodium hydroxide added is
It means the total amount of nickel hydroxide, including the remaining amount. Thus, after performing intermediate drying for each of the added amounts, 4 to 5 steps of adding water, mixing and filtering are performed.
Repeated times (decantation filtration), main drying and pulverization were carried out to obtain finished nickel hydroxide. The figure shows the average particle size of nickel hydroxide (broken line) and the filling rate into the porous metal body (solid line) in the cases where the added amount of sodium hydroxide is in each of the above cases. From the figure, the amount of sodium hydroxide is 10mo
It can be seen that the filling rate is improved from 1% (amount of nickel hydroxide), but on the other hand, if the addition amount is more than 50 mol%, the filling rate decreases.
ここで、充填率（g/cc void）とは、金属多孔体の空間
体積中に占める水酸化ニッケル量をいう。また、充填
は、水酸化ニッケルに水，糊料を添加したスラリー状に
し、金属多孔体にこすりつけて行った。金属多孔体とし
てはNi繊維焼結体を使用した。Here, the filling rate (g / cc void) refers to the amount of nickel hydroxide in the space volume of the metal porous body. Further, the filling was performed by making a slurry in which water and a paste were added to nickel hydroxide and rubbing it on the porous metal body. A Ni fiber sintered body was used as the metal porous body.
水酸化ナトリウム添加量が0mol％と20mol％の水酸化ニ
ッケルを用いてAAサイズのニッケル・カドミウム電池を
作製し、電池容量の比較を行ったところ、下表のような
結果がえられ、本発明方法の場合、大幅な容量の増加が
みられた。When nickel-cadmium batteries of AA size were prepared by using nickel hydroxide containing 0 mol% and 20 mol% of sodium hydroxide and the battery capacities were compared, the results shown in the table below were obtained. In the case of the method, a significant increase in capacity was observed.
尚、実施例では、水酸化ナトリウムの添加方法として粉
末状で添加する方法をとったが、これは中間乾燥時の乾
燥の条件を一定にするためであり、水溶液として添加し
ても良い。また中間乾燥後のデカンテーションろ過は残
留不純物を更に取り除くために行ったもので、本発明を
実施する上での必須条件ではない。更に、実施例におい
ては添加物として水酸化ナトリウムを選択しているが、
他のカセイアルカリでも同様に使用できることはいうま
でもない。また、金属多孔体としてニッケル繊維焼結体
を用いたが、発泡ニッケル等も使用できる。また糊料等
を添加してパンチングメタル等に本発明による水酸化ニ
ッケルを塗着しても良い。 In the examples, the method of adding sodium hydroxide was used in the form of powder, but this is to keep the drying conditions during the intermediate drying constant and may be added as an aqueous solution. The decantation filtration after the intermediate drying is performed to further remove the residual impurities and is not an essential condition for carrying out the present invention. Furthermore, although sodium hydroxide is selected as an additive in the examples,
It goes without saying that other caustic alkalis can be used as well. Further, although the nickel fiber sintered body is used as the metal porous body, foamed nickel or the like can also be used. Alternatively, a paste or the like may be added to the punching metal or the like to apply the nickel hydroxide according to the present invention.
発明の効果 以上述べたように本発明によるアルカリ電池用水酸化ニ
ッケルの製造方法はニッケル塩とカセイアルカリを混合
し、その生成物に対し残留分を含めて総量が10〜50mol
％のカセイアルカリを混合させた後乾燥工程をへて水酸
化ニッケルを製造するものであるから、活物質としての
水酸化ニッケルの平均粒径が大きく、金属多孔体への活
物質充填率を高めることができ、その分金属多孔体の厚
みを厚くすることなく活物質充填量を増大することがで
き、電池容量の増加が図れるといった効果がある。As described above, in the method for producing nickel hydroxide for alkaline batteries according to the present invention, the nickel salt and caustic are mixed, and the total amount of the product including the residual amount is 10 to 50 mol.
% Nickel hydroxide is produced by mixing the caustic alkali with a caustic alkali, and the average particle size of nickel hydroxide as the active material is large, and the filling rate of the active material in the metal porous body is increased. Therefore, the active material filling amount can be increased without increasing the thickness of the porous metal body, and the battery capacity can be increased.
図は水酸化ナトリウムの添加量を変化させたときの平均
粒径及び金属多孔体への充填率の変化を示す図である。The figure is a diagram showing changes in the average particle diameter and the filling rate in the porous metal body when the amount of sodium hydroxide added is changed.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 富田 正仁 大阪府守口市京阪本通２丁目18番地 三洋 電機株式会社内 (72)発明者 浜松 太計男 大阪府守口市京阪本通２丁目18番地 三洋 電機株式会社内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Masahito Tomita, 2-18 Keihan Hon-dori, Moriguchi City, Osaka Prefecture Sanyo Electric Co., Ltd. (72) Takeio Hamamatsu 2--18, Keihan Hon-dori, Moriguchi City, Osaka Sanyo Electric Co., Ltd.
Claims (1)
の生成物に対し残留分を含めて総量が10〜50mol％のカ
セイアルカリを混合させた後乾燥工程をへて水酸化ニッ
ケルを製造することを特徴とするアルカリ電池用水酸化
ニッケルの製造方法。1. A method for producing nickel hydroxide by mixing a nickel salt and caustic alkali and mixing the product with caustic alkali in a total amount of 10 to 50 mol% including a residual amount, followed by a drying step. A method for producing nickel hydroxide for alkaline batteries, which comprises:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62181834A JPH0682553B2 (en) | 1987-07-20 | 1987-07-20 | Method for producing nickel hydroxide for alkaline battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62181834A JPH0682553B2 (en) | 1987-07-20 | 1987-07-20 | Method for producing nickel hydroxide for alkaline battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6424362A JPS6424362A (en) | 1989-01-26 |
| JPH0682553B2 true JPH0682553B2 (en) | 1994-10-19 |
Family
ID=16107631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62181834A Expired - Fee Related JPH0682553B2 (en) | 1987-07-20 | 1987-07-20 | Method for producing nickel hydroxide for alkaline battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0682553B2 (en) |
-
1987
- 1987-07-20 JP JP62181834A patent/JPH0682553B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6424362A (en) | 1989-01-26 |
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| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |