JP3276730B2 - Manufacturing method of alkaline storage battery - Google Patents
Manufacturing method of alkaline storage batteryInfo
- Publication number
- JP3276730B2 JP3276730B2 JP20944693A JP20944693A JP3276730B2 JP 3276730 B2 JP3276730 B2 JP 3276730B2 JP 20944693 A JP20944693 A JP 20944693A JP 20944693 A JP20944693 A JP 20944693A JP 3276730 B2 JP3276730 B2 JP 3276730B2
- Authority
- JP
- Japan
- Prior art keywords
- active material
- slurry
- ptfe
- storage battery
- alkaline storage
- 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
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ニッケル−カドミウム
蓄電池、ニッケル−亜鉛蓄電池、ニッケル−水素蓄電池
等のアルカリ蓄電池の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an alkaline storage battery such as a nickel-cadmium storage battery, a nickel-zinc storage battery, and a nickel-hydrogen storage battery.
【０００２】[0002]
【従来の技術】ニッケル−カドミウム蓄電池等のアルカ
リ蓄電池に用いられる正極としては、従来、焼結式ニッ
ケル正極が広く用いられていた。この焼結式ニッケル正
極は、パンチングメタル等の導電性芯体の表面にニッケ
ル粉末を主体とするスラリーを塗着し、焼結して多孔性
焼結基板を得、この基板内に、硝酸ニッケル等のニッケ
ル塩溶液を含浸し、アルカリ処理することにより、活物
質である水酸化ニッケルを生成させることによって製造
される。2. Description of the Related Art A sintered nickel positive electrode has been widely used as a positive electrode for an alkaline storage battery such as a nickel-cadmium storage battery. This sintered nickel positive electrode is obtained by applying a slurry mainly composed of nickel powder to the surface of a conductive core such as punching metal and sintering to obtain a porous sintered substrate. It is produced by impregnating with a nickel salt solution such as that described above and subjecting it to an alkali treatment to produce nickel hydroxide as an active material.
【０００３】このような含浸及びアルカリ処理を経て、
基板内に活物質を生成する工程は煩雑であり、本来は活
物質を基板内に直接充填するのが望ましいが、多孔性焼
結基板はその孔径が小さいので、活物質を基板内に直接
充填することはできない。After such impregnation and alkali treatment,
The process of generating the active material in the substrate is complicated, and it is originally desirable to directly fill the active material into the substrate. However, since the porous sintered substrate has a small pore size, the active material is directly charged into the substrate. I can't.
【０００４】そこで、スポンジ状あるいはフェルト状金
属体のように孔径の大きい基板が、活物質保持体として
注目されるようになった。即ち、結着剤と混合した活物
質スラリーを、孔径の大きいスポンジ状あるいはフェル
ト状の金属体に充填した後、乾燥、圧延して非焼結式ニ
ッケル正極を得ている。Accordingly, a substrate having a large hole diameter such as a sponge-like or felt-like metal body has been attracting attention as an active material holder. That is, a non-sintered nickel positive electrode is obtained by filling a sponge-like or felt-like metal body having a large pore diameter with an active material slurry mixed with a binder, followed by drying and rolling.
【０００５】前記結着剤としてはポリテトラフロロエチ
レン樹脂（以下ＰＴＦＥと云う）が用いられているが、
スラリーを調合する際や活物質保持体へ充填させる際に
ＰＴＦＥが繊維化し、活物質スラリーの粘度が急激に上
昇する。この結果、活物質スラリーを活物質保持体へ均
一に充填しにくいという問題点を有していた。[0005] Polytetrafluoroethylene resin (hereinafter referred to as PTFE) is used as the binder.
When preparing the slurry or filling the slurry into the active material holder, the PTFE fiberizes, and the viscosity of the active material slurry sharply increases. As a result, there is a problem that it is difficult to uniformly fill the active material holding body with the active material slurry.
【０００６】この問題点の対策として、特開平４−２４
８３６５号公報には、球状の水酸化ニッケル、水、増粘
剤、ＰＴＦＥディスパージョンを混練して、活物質スラ
リーを作製する方法が記載されている。As a countermeasure against this problem, Japanese Patent Laid-Open No.
No. 8,365 describes a method for producing an active material slurry by kneading spherical nickel hydroxide, water, a thickener, and a PTFE dispersion.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、通常用
いられているＰＴＦＥの分子量は１０００万程度と大き
く、前記特開平４−２４８３６５号公報に記載されてい
る方法を用いても、活物質スラリーを活物質保持体へ充
填させる際のＰＴＦＥの繊維化を充分に抑制することは
できず、活物質スラリーを均一に充填することは困難で
あった。However, the molecular weight of PTFE, which is usually used, is as large as about 10 million, and the active material slurry can be activated even by using the method described in JP-A-4-248365. It was not possible to sufficiently suppress PTFE fiberization when filling the material holding body, and it was difficult to uniformly fill the active material slurry.
【０００８】本発明は、前記に鑑みて成されたものであ
り、ＰＴＦＥが持つ優れた結着剤としての能力を維持し
つつ、活物質スラリー粘度の急激な上昇を抑制し、容易
に活物質スラリーを活物質保持体へ均一に充填できるア
ルカリ蓄電池の製造方法を提供することを課題とする。The present invention has been made in view of the above, and it is intended to suppress the rapid increase in the viscosity of the active material slurry while maintaining the excellent binding ability of PTFE as an active material. It is an object of the present invention to provide a method for manufacturing an alkaline storage battery capable of uniformly filling a slurry into an active material holder.
【０００９】[0009]
【課題を解決するための手段】本発明のアルカリ蓄電池
の製造方法は、水酸化ニッケル粉末を主成分とする活物
質スラリーをスポンジ状あるいはフェルト状金属多孔体
からなる活物質保持体に充填する第１ステップと、前記
活物質保持体を圧延する第２ステップとからなり、前記
第１ステップの活物質スラリーに分子量が約３００万以
下のポリテトラフロロエチレンを添加することを特徴と
する。According to a method of manufacturing an alkaline storage battery of the present invention, an active material slurry containing nickel hydroxide powder as a main component is sponge-like or felt-like porous metal.
A first step of filling the active material holding body made of the result and a second step of rolling the active material retainer, the molecular weight of the active material slurry of the first step is about 3,000,000 polytetrafluoroethylene It is characterized by being added.
【００１０】[0010]
【作用】ＰＴＦＥは、せん断力を加えると繊維化する性
質を有している。このため、活物質保持体にＰＴＦＥを
含む活物質スラリーを充填し、圧延することにより、Ｐ
ＴＦＥが繊維化し、活物質粒子同士及び活物質粒子−保
持体間と絡み合い、活物質保持体からの活物質の脱落を
防止できる。The PTFE has the property that it becomes fibrous when a shearing force is applied. For this reason, the active material holding body is filled with an active material slurry containing PTFE, and is rolled, whereby P
The TFE becomes fibrous and becomes entangled with the active material particles and between the active material particles and the support, thereby preventing the active material from dropping from the active material support.
【００１１】しかし、活物質保持体に活物質スラリーを
連続的に充填する際には、活物質スラリーの物性の安定
化が不可欠となる。特に、スラリーの流動性の指標とな
るスラリー粘度の変動は活物質保持体中へのスラリーの
導入の難易を変動させるため、充填中には一定に保つ必
要があり、スラリーへの添加剤等を選択するにあたって
は、この点について考慮する必要がある。However, when the active material slurry is continuously filled in the active material holder, it is essential to stabilize the physical properties of the active material slurry. In particular, fluctuations in the slurry viscosity, which is an indicator of the fluidity of the slurry, change the difficulty of introducing the slurry into the active material holding body, so it is necessary to keep the slurry constant during filling. This must be taken into account when making a selection.
【００１２】この点からＰＴＦＥの添加について考える
と、従来のような分子量１０００万程度のものの使用は
スラリーの調合時や、充填中に生じるせん断力の印加に
よりＰＴＦＥの繊維化が生じ、スラリー粘度を上昇させ
るという不具合いを有しており、スラリーへの添加剤と
しては適さない。Considering the addition of PTFE from this point, the use of PTFE having a molecular weight of about 10,000,000 as in the prior art causes PTFE fiberization due to the application of a shear force generated during the preparation of the slurry or during filling, and the slurry viscosity is reduced. It has the disadvantage of raising the temperature and is not suitable as an additive to the slurry.
【００１３】これに対し、本発明のように分子量約３０
０万以下のＰＴＦＥを用いれば、スラリーの調合時や充
填中にＰＴＦＥの繊維化を抑制し、スラリー粘度の変動
を防止できる。On the other hand, as in the present invention, the molecular weight is about 30.
If PTFE of 50,000 or less is used, fibrillation of PTFE can be suppressed at the time of preparing and filling the slurry, and fluctuation of the slurry viscosity can be prevented.
【００１４】更に、前記活物質保持体を圧延する第２ス
テップ時には、ＰＴＦＥは繊維化し、活物質粒子同士及
び活物質粒子−保持体間と絡み合い、活物質保持体から
の活物質の脱落を防止することができる。Further, at the time of the second step of rolling the active material holder, the PTFE is fibrillated and entangled with the active material particles and between the active material particles and the support to prevent the active material from falling off from the active material holder. can do.
【００１５】[0015]
（実施例１）粒径が約１０μｍの球状の水酸化ニッケル
粉末５５重量％と、粒径が約１μｍの水酸化コバルト粉
末５重量％と、メチルセルロースを１重量部含有したメ
チルセルロース水溶液３９重量％と、分子量が１０万の
ＰＴＦＥを１重量％とを混合して活物質スラリーａを作
製した。(Example 1) 55% by weight of spherical nickel hydroxide powder having a particle size of about 10 μm, 5% by weight of cobalt hydroxide powder having a particle size of about 1 μm, and 39% by weight of a methylcellulose aqueous solution containing 1 part by weight of methylcellulose. An active material slurry (a) was prepared by mixing PTFE having a molecular weight of 100,000 with 1% by weight.
【００１６】（実施例２）分子量が１０万のＰＴＦＥの
代わりに、分子量が３００万のＰＴＦＥを用いた他は前
記実施例１と同様にして、活物質スラリーｂを作製し
た。(Example 2) An active material slurry b was prepared in the same manner as in Example 1 except that PTFE having a molecular weight of 3,000,000 was used instead of PTFE having a molecular weight of 100,000.
【００１７】（比較例１）分子量が１０万のＰＴＦＥの
代わりに、分子量が１０００万のＰＴＦＥを用いた他は
前記実施例１と同様にして、活物質スラリーｘを作製し
た。Comparative Example 1 An active material slurry x was prepared in the same manner as in Example 1 except that PTFE having a molecular weight of 10,000,000 was used instead of PTFE having a molecular weight of 100,000.
【００１８】前記各活物質スラリーａ、ｂ、ｘを円筒状
容器に入れ、プロペラにより撹拌を行い、撹拌時間と活
物質スラリー粘度の関係を測定した。Each of the active material slurries a, b, and x was placed in a cylindrical container and stirred with a propeller, and the relationship between the stirring time and the viscosity of the active material slurry was measured.
【００１９】この測定結果を図１に示す。図１より、分
子量が１０万及び３００万のＰＴＦＥを用いた活物質ス
ラリーａ、ｂは、粘度の上昇はほとんど見られず、安定
した粘度が得られることがわかる。FIG. 1 shows the measurement results. FIG. 1 shows that the active material slurries a and b using PTFE having a molecular weight of 100,000 and 3,000,000 show almost no increase in viscosity, and stable viscosity can be obtained.
【００２０】一方、分子量が１０００万のＰＴＦＥを用
いた活物質スラリーｘは、撹拌時間を３時間を越える
と、活物質スラリー粘度の上昇が著しいことがわかる。On the other hand, it can be seen that the viscosity of the active material slurry x of the active material slurry x using PTFE having a molecular weight of 10,000,000 significantly increases when the stirring time exceeds 3 hours.
【００２１】前記各活物質スラリーａ、ｂ、ｘを、発泡
ニッケル基体に充填し、乾燥、圧延を行い、非焼結式ニ
ッケル正極板を作製した。Each of the active material slurries a, b, and x was filled in a foamed nickel substrate, dried and rolled to produce a non-sintered nickel positive electrode plate.
【００２２】また、酸化カドミウムと金属カドミウムを
糊料液と混合して、ペースト状とし、パンチングメタル
に塗布し、乾燥、圧延を行った。更に、これを０．２Ｃ
の電流で１５０％まで充電し、０．２Ｃの電流で放電す
ることにより化成し、水洗乾燥して、非焼結式カドミウ
ム負極板を作製した。Cadmium oxide and metal cadmium were mixed with a paste liquid to form a paste, applied to a punching metal, dried and rolled. Furthermore, this is 0.2C
The battery was charged to a current of 150% and discharged at a current of 0.2 C to form a chemical, washed with water and dried to produce a non-sintered cadmium negative electrode plate.
【００２３】前記にて作製した非焼結式ニッケル正極板
を、ポリプロピレン不織セパレータを介して、前記非焼
結式カドミウム負極板と組み合わせ、水酸化カリウム水
溶液を電解液として用いて、公称容量１．２Ａｈの密閉
型ニッケル−カドミウム蓄電池を作製した。The non-sintered nickel positive electrode plate prepared above was combined with the non-sintered cadmium negative plate through a polypropylene non-woven separator, and a potassium hydroxide aqueous solution was used as an electrolyte to obtain a nominal capacity of 1%. A sealed nickel-cadmium storage battery of 0.2 Ah was produced.
【００２４】こうして作製した電池を使用した活物質ス
ラリーの符号に対応させ、夫々Ａ、Ｂ、Ｘとする。The symbols A, B, and X correspond to the signs of the active material slurries using the batteries thus manufactured.
【００２５】前記各電池Ａ、Ｂ、Ｘについて充放電サイ
クル（充電：１．２Ａ×１．５時間、放電：１．２Ａ）
を行い、電池容量が１サイクル目の容量に対し５０％以
下となるサイクル数を測定し、この結果を表１に示す。A charge / discharge cycle for each of the batteries A, B, and X (charge: 1.2 A × 1.5 hours, discharge: 1.2 A)
And the number of cycles at which the battery capacity becomes 50% or less of the capacity of the first cycle was measured. The results are shown in Table 1.
【００２６】[0026]
【表１】 [Table 1]
【００２７】表１より、いずれの電池もほぼ６００サイ
クルにおいて容量が、１サイクル目の容量に対し５０％
以下となり、充放電サイクル寿命はほぼ同等であること
がわかる。According to Table 1, the capacity of each of the batteries in almost 600 cycles was 50% of the capacity in the first cycle.
The results are as follows, and it can be seen that the charge / discharge cycle life is almost the same.
【００２８】これは、充放電サイクル時に活物質保持体
からの活物質の脱落により、サイクル寿命に至るという
不具合が生じていないことを示している。即ち、分子量
が３００万以下のＰＴＦＥを用いることにより充分な結
着剤としての効果を得ることができる。 This means that the active material falls off from the active material holder during the charge / discharge cycle, leading to a cycle life.
Indicates that no problem has occurred . That is, by using PTFE having a molecular weight of 3,000,000 or less, sufficient
The effect as an adhesive can be obtained.
【００２９】[0029]
【発明の効果】本発明により、ＰＴＦＥが持つ優れた結
着剤としての能力を維持しながら、活物質スラリーを活
物質保持体に均一に充填することが困難であるという極
板製造時の不具合いを解消することが可能となる。Industrial Applicability According to the present invention, it is difficult to uniformly fill an active material holder with an active material slurry while maintaining the excellent binding ability of PTFE, which is a disadvantage at the time of manufacturing an electrode plate. Can be eliminated.
【図１】各活物質スラリーａ、ｂ、ｘの撹拌時間とスラ
リー粘度の関係図である。FIG. 1 is a diagram showing the relationship between the stirring time of each active material slurry a, b, and x and the slurry viscosity.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平５−47376（ＪＰ，Ａ) 特開 平２−288157（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/14 - 4/34 H01M 4/62 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-47376 (JP, A) JP-A-2-288157 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 4/14-4/34 H01M 4/62
Claims (1)
るアルカリ蓄電池の製造方法において、 水酸化ニッケル粉末を主成分とする活物質スラリーをス
ポンジ状あるいはフェルト状金属多孔体からなる活物質
保持体に充填する第１ステップと、 前記活物質保持体を圧延する第２ステップとを有し、 前記第１ステップの活物質スラリーに分子量が約３００
万以下のポリテトラフロロエチレンを添加することを特
徴とするアルカリ蓄電池の製造方法。1. A method for manufacturing an alkaline storage battery using a non-sintered nickel positive electrode as a positive electrode, comprising the steps of :
A first step of filling the active material holder made of a porous or felt-like porous metal body, and a second step of rolling the active material holder, wherein the active material slurry of the first step has a molecular weight of about 300
A method for producing an alkaline storage battery, comprising adding 10,000 or less polytetrafluoroethylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20944693A JP3276730B2 (en) | 1993-08-24 | 1993-08-24 | Manufacturing method of alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20944693A JP3276730B2 (en) | 1993-08-24 | 1993-08-24 | Manufacturing method of alkaline storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0765830A JPH0765830A (en) | 1995-03-10 |
| JP3276730B2 true JP3276730B2 (en) | 2002-04-22 |
Family
ID=16573002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20944693A Expired - Fee Related JP3276730B2 (en) | 1993-08-24 | 1993-08-24 | Manufacturing method of alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3276730B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7683432B2 (en) | 2004-06-25 | 2010-03-23 | Rohm Co., Ltd. | Semiconductor device having high-k gate dielectric layer and method for manufacturing the same |
-
1993
- 1993-08-24 JP JP20944693A patent/JP3276730B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7683432B2 (en) | 2004-06-25 | 2010-03-23 | Rohm Co., Ltd. | Semiconductor device having high-k gate dielectric layer and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0765830A (en) | 1995-03-10 |
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