JPH1131512A - Fluororesin dispersed solution, manufacture thereof and manufacture of hydrogen storage alloy electrode using the dispersed solution - Google Patents
Fluororesin dispersed solution, manufacture thereof and manufacture of hydrogen storage alloy electrode using the dispersed solutionInfo
- Publication number
- JPH1131512A JPH1131512A JP9182856A JP18285697A JPH1131512A JP H1131512 A JPH1131512 A JP H1131512A JP 9182856 A JP9182856 A JP 9182856A JP 18285697 A JP18285697 A JP 18285697A JP H1131512 A JPH1131512 A JP H1131512A
- Authority
- JP
- Japan
- Prior art keywords
- fluororesin
- hydrogen storage
- storage alloy
- slurry
- dispersion
- 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
-
- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、フッ素樹脂分散液
およびその製造方法ならびにこのフッ素樹脂分散液を用
いた水素吸蔵合金電極の製造方法に係り、特に、水素吸
蔵合金電極に撥水性を付与するために添加するフッ素樹
脂分散液およびその製造方法ならびにこの製造方法によ
り得られたフッ素樹脂分散液を水素吸蔵合金電極に添加
して同水素吸蔵合金電極に撥水性を付与する水素吸蔵合
金電極の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluororesin dispersion, a method for producing the same, and a method for producing a hydrogen storage alloy electrode using the fluororesin dispersion, and particularly to imparting water repellency to the hydrogen storage alloy electrode. Of a fluororesin dispersion to be added for the production of the hydrogen storage alloy electrode, and a fluororesin dispersion obtained by the production method being added to the hydrogen storage alloy electrode to impart water repellency to the hydrogen storage alloy electrode It is about the method.
【０００２】[0002]
【従来の技術】近年、携帯用電子・通信機器の急速な普
及により従来に増して高性能な蓄電池が要請されてい
る。このような背景にあって、従来のニッケル−カドミ
ウム蓄電池、鉛蓄電池より軽量かつ高容量で高エネルギ
ー密度が得られ、しかもクリーンな蓄電池となることか
ら負極に水素吸蔵合金を用いたニッケル−水素蓄電池が
注目されるようになった。2. Description of the Related Art In recent years, with the rapid spread of portable electronic and communication equipment, there has been a demand for higher performance storage batteries than ever. Against this background, a nickel-hydrogen storage battery using a hydrogen-absorbing alloy for the negative electrode can provide a lighter weight, higher capacity, higher energy density and higher energy density than conventional nickel-cadmium storage batteries and lead storage batteries. Came to attention.
【０００３】このようなニッケル−水素蓄電池において
は、正極側で容量が規制されるようになされているの
で、電池を充電すると、まず容量の小さい正極が満充電
となり、さらに充電を続けると過充電状態となって、正
極から酸素ガスが発生する。正極より発生した酸素ガス
は負極で消費されて水（Ｈ2Ｏ）が生成される。この生
成された水は負極表面が親水性であると、負極表面が濡
れた状態となって、酸素ガスの負極表面への拡散が阻害
され、酸素ガスの負極での消費速度が遅くなる。このた
め、電池内圧が上昇し、安全弁が作動して電池内のガス
を放出するとともに、電解液も電池外へ漏出する。その
結果、セパレータ中の電解液が枯渇し、電池のサイクル
特性が低下するという問題があった。In such a nickel-hydrogen storage battery, the capacity is regulated on the positive electrode side. Thus, when the battery is charged, the positive electrode having a small capacity is first fully charged, and when the battery is further charged, it is overcharged. In this state, oxygen gas is generated from the positive electrode. Oxygen gas generated from the positive electrode is consumed by the negative electrode to generate water (H 2 O). When the surface of the negative electrode is hydrophilic, the generated water is in a wet state on the surface of the negative electrode, diffusion of oxygen gas to the surface of the negative electrode is inhibited, and the consumption rate of oxygen gas at the negative electrode is reduced. As a result, the internal pressure of the battery increases, the safety valve operates to release the gas in the battery, and the electrolyte also leaks out of the battery. As a result, there has been a problem that the electrolyte in the separator is depleted and the cycle characteristics of the battery deteriorate.
【０００４】このようなことから、水素吸蔵合金粉末に
撥水性を付与するフッ素樹脂を混合したり、フッ素樹脂
を水素吸蔵合金電極に塗布して撥水処理を施すことが提
案されるようになった。この撥水処理により、酸素ガ
ス、電解液および水素吸蔵合金表面の、いわゆる気相、
液相、固相の３相界面が形成され、酸素ガスの消費反応
が円滑に行われるようになる。In view of the above, it has been proposed to mix a hydrogen storage alloy powder with a fluororesin which imparts water repellency, or to apply a fluororesin to the hydrogen storage alloy electrode to perform a water repellency treatment. Was. By this water repellent treatment, the so-called gas phase on the surface of the oxygen gas, the electrolytic solution and the hydrogen storage alloy,
A three-phase interface of a liquid phase and a solid phase is formed, and the oxygen gas consumption reaction can be smoothly performed.
【０００５】このような撥水処理を施すに際しては、フ
ッ素樹脂を分散させる必要がある。例えば、フッ素樹脂
を有機溶剤に分散させて有機フッ素樹脂分散液とした
り、フッ素樹脂を水中に分散させて水溶性フッ素樹脂分
散液とし、このようなフッ素樹脂分散液と水素吸蔵合金
粉末と水溶性結着剤とを混合して水素吸蔵合金電極とし
たり、あるいは水素吸蔵合金電極の表面にこのようなフ
ッ素樹脂分散液を塗布するようにしている。In performing such a water-repellent treatment, it is necessary to disperse a fluororesin. For example, a fluororesin is dispersed in an organic solvent to form an organic fluororesin dispersion, or a fluororesin is dispersed in water to form a water-soluble fluororesin dispersion. A hydrogen storage alloy electrode is prepared by mixing with a binder, or such a fluororesin dispersion is applied to the surface of the hydrogen storage alloy electrode.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、一般的
に、水素吸蔵合金粉末は水溶性結着剤とともに用いられ
るので、有機フッ素樹脂分散液を用いる場合、有機フッ
素樹脂分散液は水溶性結着剤と均一に混合することが難
しく、また有機フッ素樹脂分散液を水素吸蔵合金電極の
表面に均一に塗布することが難しいため、水素吸蔵合金
電極に不均一な撥水相が形成されて、充分な酸素ガス消
費反応が行われないという問題を生じるとともに、有機
溶剤のみで水素吸蔵合金電極を作製することは製造設備
が複雑になって、水素吸蔵合金電極の製造コストが上昇
するという問題も生じた。However, since the hydrogen storage alloy powder is generally used together with a water-soluble binder, when an organic fluororesin dispersion is used, the organic fluororesin dispersion is generally dissolved in a water-soluble binder. And it is difficult to uniformly apply the organic fluororesin dispersion to the surface of the hydrogen storage alloy electrode, so that a non-uniform water-repellent phase is formed on the hydrogen storage alloy electrode. In addition to the problem that the oxygen gas consumption reaction is not performed, the production of the hydrogen-absorbing alloy electrode using only the organic solvent complicates the production equipment and raises the problem that the production cost of the hydrogen-absorbing alloy electrode increases. .
【０００７】一方、水溶性フッ素樹脂分散液を用いる
と、フッ素樹脂は疎水性であるため、水中に均一に分散
させることが難しく、また水溶性フッ素樹脂分散液は凝
集を起こしやすいために、水素吸蔵合金電極の表面に均
一に塗布することが難しく、撥水性が不均一となって充
分に酸素ガス消費反応が行われないという問題も生じ
た。On the other hand, when a water-soluble fluororesin dispersion is used, it is difficult to uniformly disperse it in water because the fluororesin is hydrophobic, and the water-soluble fluororesin dispersion is liable to agglomerate. It is difficult to apply uniformly on the surface of the occlusion alloy electrode, and the water repellency becomes non-uniform, which causes a problem that the oxygen gas consumption reaction is not sufficiently performed.
【０００８】このようなことから、フッ素樹脂を界面活
性剤によって水中に分散させたフッ素樹脂の水性ディス
パージョンと有機溶剤との混合溶液に水素吸蔵合金負極
を浸漬もしはこの混合溶液を水素吸蔵合金負極表面に塗
着するようにしたものが特開平８−８８００３号公報に
おいて提案された。For this reason, the hydrogen-absorbing alloy negative electrode is immersed in a mixed solution of an aqueous dispersion of a fluorocarbon resin in which water is dispersed with a surfactant and an organic solvent, or the mixed solution is hydrogen-absorbed. One coated on the surface of the negative electrode has been proposed in JP-A-8-88003.
【０００９】この特開平８−８８００３号公報において
提案された方法においては、界面活性剤によって水中に
分散させたフッ素樹脂の水性ディスパージョンに有機溶
剤を混合させると、均一に分散しているフッ素樹脂同士
を凝集させることができる。このため、水素吸蔵合金粒
子間の隙間にフッ素樹脂が入り込みにくくなって電極表
面の水素吸蔵合金粒子上に付着し、電極内部に混合溶液
が浸透しにくくなる。したがって、電極表面に確実に撥
水性を付与でき、電極の空孔をフッ素樹脂が閉塞せず、
均一な充放電反応が進行するようになるというものであ
る。In the method proposed in Japanese Patent Application Laid-Open No. Hei 8-88803, when an organic solvent is mixed with an aqueous dispersion of a fluororesin dispersed in water with a surfactant, the fluororesin uniformly dispersed is obtained. They can be aggregated. For this reason, the fluororesin hardly enters the gaps between the hydrogen storage alloy particles, adheres to the hydrogen storage alloy particles on the electrode surface, and the mixed solution hardly permeates inside the electrode. Therefore, it is possible to reliably impart water repellency to the electrode surface, and the pores of the electrode are not blocked by the fluororesin,
That is, a uniform charge / discharge reaction proceeds.
【００１０】しかしながら、上記特開平８−８８００３
号公報において提案された方法においても、フッ素樹脂
が水中に分散し、この水中に分散したフッ素樹脂が有機
溶剤に分散しているため、フッ素樹脂は水素吸蔵合金電
極の表面に不均一に分布することとなって充分な酸素ガ
ス消費反応が行われないという問題を生じた。[0010] However, Japanese Patent Application Laid-Open No. H8-88003 describes
In the method proposed in Japanese Patent Application Laid-Open Publication No. H10-157, the fluororesin is dispersed in water, and the fluororesin dispersed in the water is dispersed in the organic solvent, so that the fluororesin is unevenly distributed on the surface of the hydrogen storage alloy electrode. As a result, there was a problem that a sufficient oxygen gas consumption reaction was not performed.
【００１１】そこで、本発明は上記問題点に鑑みてなさ
れたものであり、フッ素樹脂を水素吸蔵合金電極の表面
に均一に分布させることができる分散液を得るととも
に、この分散液を用いてフッ素樹脂を水素吸蔵合金電極
の表面に均一に分布させるようにすることにある。In view of the above, the present invention has been made in view of the above problems, and provides a dispersion capable of uniformly dispersing a fluororesin on the surface of a hydrogen-absorbing alloy electrode. An object of the present invention is to uniformly distribute the resin on the surface of the hydrogen storage alloy electrode.
【００１２】[0012]
【課題を解決するための手段およびその作用・効果】本
発明は、水素吸蔵合金電極に撥水性を付与するために添
加するフッ素樹脂分散液であって、上記課題を解決する
ために、請求項１に記載の発明においては、有機溶剤中
に均一に分散させたフッ素樹脂粉末と、このフッ素樹脂
粉末が均一に分散した有機溶剤を均一に分散させた水溶
液とを含有するようにしている。SUMMARY OF THE INVENTION The present invention relates to a fluororesin dispersion added for imparting water repellency to a hydrogen storage alloy electrode. In the invention described in 1, the fluororesin powder uniformly dispersed in the organic solvent and the aqueous solution in which the organic solvent in which the fluororesin powder is uniformly dispersed are uniformly dispersed are contained.
【００１３】このような分散液は、有機溶剤中にフッ素
樹脂が分散しているため、フッ素樹脂の凝集が生じるこ
とがなく、かつ水中油滴型分散液となっていることから
水溶性結着剤との親和性がよくなり、均一に水素吸蔵合
金粉末と混合できるようになるとともに、均一に水素吸
蔵合金電極に塗布することが可能となって、このような
水素吸蔵合金粉末を用いた電極の酸素ガス吸収能力が格
段に向上する。また、水中油滴型分散液は水溶液として
取り扱うことができるため、その取り扱いが簡単になっ
て、この種の水素吸蔵合金電極の製造が容易となる。In such a dispersion, since the fluororesin is dispersed in the organic solvent, no aggregation of the fluororesin occurs, and since the dispersion is an oil-in-water type dispersion, a water-soluble binder is formed. The affinity with the agent is improved, and it becomes possible to uniformly mix with the hydrogen storage alloy powder, and it is possible to uniformly apply the hydrogen storage alloy powder to the electrode. Greatly improves the oxygen gas absorption capacity. Further, since the oil-in-water dispersion can be handled as an aqueous solution, the handling is simplified, and the production of this type of hydrogen storage alloy electrode is facilitated.
【００１４】請求項２に記載の発明においては、上述の
水溶液は界面活性剤を含有するようにしている。界面活
性剤は水中油滴型分散剤となるため、水溶液に界面活性
剤を含有させることにより、フッ素樹脂を均一に分散さ
せた有機溶剤（有機溶剤油滴）は水溶液に均一に分散す
ることとなって、有機溶剤油滴の凝集が起こりにくいた
め、より均一に水素吸蔵合金粉末と混合できるようにな
るとともに、より均一に水素吸蔵合金電極に塗布するこ
とが可能となって、このような水素吸蔵合金粉末を用い
た電極の酸素ガス吸収能力が一層向上する。[0014] In the second aspect of the present invention, the above-mentioned aqueous solution contains a surfactant. Since the surfactant is an oil-in-water type dispersant, by adding the surfactant to the aqueous solution, the organic solvent (organic solvent oil droplets) in which the fluororesin is uniformly dispersed can be uniformly dispersed in the aqueous solution. This makes it difficult for the oil droplets of the organic solvent to agglomerate, so that it can be more uniformly mixed with the hydrogen storage alloy powder and can be more uniformly applied to the hydrogen storage alloy electrode. The oxygen gas absorbing ability of the electrode using the storage alloy powder is further improved.
【００１５】請求項３に記載の発明においては、上述の
水溶液は水溶性結着剤を含有するようにしている。水溶
性結着剤に水溶液を含有させると水溶液の粘度が増大す
るため、これを水素吸蔵合金電極に塗布しても電極の内
部まで浸透し過ぎることが抑制されるので、このような
水素吸蔵合金粉末を用いた電極の酸素ガス吸収能力がさ
らに向上する。In the third aspect of the present invention, the above-mentioned aqueous solution contains a water-soluble binder. When an aqueous solution is contained in a water-soluble binder, the viscosity of the aqueous solution increases, so that even if the aqueous solution is applied to a hydrogen storage alloy electrode, it is suppressed from excessively penetrating into the inside of the electrode. The oxygen gas absorbing ability of the electrode using the powder is further improved.
【００１６】また、本発明は、水素吸蔵合金電極に撥水
性を付与するために添加するフッ素樹脂分散液の製造方
法であって、上記課題を解決するために、請求項４に記
載の発明においては、有機溶剤中にフッ素樹脂粉末を分
散させる工程と、このフッ素樹脂粉末を分散させた有機
溶剤を水溶液に分散させる工程とを備え、フッ素樹脂粉
末を水溶液に均一に分散させてフッ素樹脂分散液とする
ようにしている。The present invention also relates to a method for producing a fluororesin dispersion to be added for imparting water repellency to a hydrogen storage alloy electrode. Comprises a step of dispersing the fluororesin powder in an organic solvent, and a step of dispersing the organic solvent in which the fluororesin powder is dispersed in an aqueous solution. And so on.
【００１７】このように分散液を製造すると、有機溶剤
中にフッ素樹脂が分散しているため、フッ素樹脂に凝集
が生じることが防止できるようになるとともに、水中油
滴型分散液となるため、水溶性結着剤との親和性が向上
する。そのため、水素吸蔵合金粉末と均一に混合できる
ようになるとともに、水素吸蔵合金電極に均一に塗布す
ることが可能となるので、酸素ガス吸収能力が格段に向
上した水素吸蔵合金粉末を用いた電極を製造することが
可能になる。また、水中油滴型分散液は水溶液として取
り扱うことができるため、その取り扱いが簡単になっ
て、この種の水素吸蔵合金電極の製造が容易となる。When the dispersion is produced in this manner, since the fluororesin is dispersed in the organic solvent, it is possible to prevent the flocculation of the fluororesin from occurring, and to form an oil-in-water type dispersion. The affinity with the water-soluble binder is improved. Therefore, it becomes possible to mix the hydrogen storage alloy powder uniformly with the hydrogen storage alloy powder, and it becomes possible to apply the hydrogen storage alloy powder uniformly to the hydrogen storage alloy electrode. It becomes possible to manufacture. Further, since the oil-in-water dispersion can be handled as an aqueous solution, the handling is simplified, and the production of this type of hydrogen storage alloy electrode is facilitated.
【００１８】請求項５に記載の発明においては、上述の
水溶液に界面活性剤を添加するようにしている。界面活
性剤は水中油滴型分散剤となるため、水溶液に界面活性
剤を含有させることにより、フッ素樹脂を均一に分散さ
せた有機溶剤（有機溶剤油滴）は水溶液に均一に分散す
ることとなって、有機溶剤油滴の凝集が起こりにくいた
め、より均一に水素吸蔵合金粉末と混合できるようにな
るとともに、より均一に水素吸蔵合金電極に塗布するこ
とが可能となって、このような水素吸蔵合金粉末を用い
た電極の酸素ガス吸収能力が一層向上する。In the invention according to claim 5, a surfactant is added to the aqueous solution. Since the surfactant is an oil-in-water type dispersant, by adding the surfactant to the aqueous solution, the organic solvent (organic solvent oil droplets) in which the fluororesin is uniformly dispersed can be uniformly dispersed in the aqueous solution. This makes it difficult for the oil droplets of the organic solvent to agglomerate, so that it can be more uniformly mixed with the hydrogen storage alloy powder and can be more uniformly applied to the hydrogen storage alloy electrode. The oxygen gas absorbing ability of the electrode using the storage alloy powder is further improved.
【００１９】請求項６に記載の発明においては、上述の
水溶液に水溶性結着剤を添加するようにしている。水溶
液に水溶性結着剤を含有させると水溶液の粘度が増大す
るため、これを水素吸蔵合金電極に塗布しても電極の内
部まで浸透し過ぎることが抑制されるので、このような
水素吸蔵合金粉末を用いた電極の酸素ガス吸収能力がさ
らに向上する。In the invention according to claim 6, a water-soluble binder is added to the above-mentioned aqueous solution. When a water-soluble binder is contained in the aqueous solution, the viscosity of the aqueous solution increases, so that even if the solution is applied to the hydrogen-absorbing alloy electrode, it is suppressed from excessively penetrating into the inside of the electrode. The oxygen gas absorbing ability of the electrode using the powder is further improved.
【００２０】さらに、本発明は、フッ素樹脂分散液を水
素吸蔵合金粉末に混合して水素吸蔵合金電極に撥水性を
付与する水素吸蔵合金電極の製造方法であって、上記課
題を解決するために、請求項７に記載の発明において
は、フッ素樹脂粉末を均一に分散させた有機溶剤を水溶
液に均一に分散させてフッ素樹脂分散液とする分散工程
と、この分散工程により得られたフッ素樹脂分散液と水
素吸蔵合金粉末と水溶性結着剤とを混練してスラリーと
するスラリー工程と、このスラリー工程により得られた
スラリーを集電体に塗着する塗着工程と、この塗着工程
により集電体に塗着されたスラリーを乾燥する乾燥工程
と、この乾燥工程により乾燥された水素吸蔵電極を圧延
する圧延工程とを備えるようにしている。Further, the present invention relates to a method for producing a hydrogen storage alloy electrode for imparting water repellency to a hydrogen storage alloy electrode by mixing a fluororesin dispersion liquid with the hydrogen storage alloy powder. In the invention according to claim 7, a dispersion step of uniformly dispersing an organic solvent in which a fluororesin powder is uniformly dispersed in an aqueous solution to obtain a fluororesin dispersion, and a dispersion of the fluororesin obtained by the dispersion step A slurry step of kneading the liquid, the hydrogen storage alloy powder and the water-soluble binder to form a slurry, a coating step of coating the slurry obtained in the slurry step on a current collector, A drying step of drying the slurry applied to the current collector and a rolling step of rolling the hydrogen storage electrode dried in the drying step are provided.
【００２１】このように分散液を製造した後、この分散
液と水素吸蔵合金粉末と水溶性結着剤とを混練してスラ
リーとすると、有機溶剤中にフッ素樹脂が分散している
ため、フッ素樹脂に凝集が生じることなく水素吸蔵合金
粉末に均一に分散するようになる。また、この分散液は
水中油滴型分散液となるため、水溶性結着剤との親和性
も向上する。このため、フッ素樹脂と水素吸蔵合金粉末
と水溶性結着剤とが均一に混合できるようになるので、
酸素ガス吸収能力が格段に向上した水素吸蔵合金電極を
製造することが可能になる。また、水中油滴型分散液は
水溶液として取り扱うことができるため、その取り扱い
が簡単になって、この種の水素吸蔵合金電極の製造が容
易になる。After the dispersion liquid is manufactured as described above, the dispersion liquid, the hydrogen storage alloy powder, and the water-soluble binder are kneaded to form a slurry. Since the fluororesin is dispersed in the organic solvent, The resin is uniformly dispersed in the hydrogen storage alloy powder without causing aggregation. Further, since this dispersion is an oil-in-water dispersion, the affinity with the water-soluble binder is also improved. For this reason, since it becomes possible to uniformly mix the fluororesin, the hydrogen storage alloy powder, and the water-soluble binder,
It becomes possible to manufacture a hydrogen storage alloy electrode having a remarkably improved oxygen gas absorption capacity. Further, since the oil-in-water dispersion can be handled as an aqueous solution, the handling is simplified, and the production of this type of hydrogen storage alloy electrode is facilitated.
【００２２】また、本発明は、フッ素樹脂分散液を水素
吸蔵合金電極に塗布して同水素吸蔵合金電極に撥水性を
付与する水素吸蔵合金電極の製造方法であって、上記課
題を解決するために、請求項８に記載の発明において
は、フッ素樹脂粉末を均一に分散させた有機溶剤を水溶
液に均一に分散させてフッ素樹脂分散液とする分散工程
と、水素吸蔵合金粉末と水溶性結着剤とを混練してスラ
リーとするスラリー工程と、このスラリー工程により得
られたスラリーを集電体に塗着する塗着工程と、この塗
着工程により集電体に塗着されたスラリー上に先の分散
工程により得られたフッ素樹脂分散液を塗着する分散液
塗着工程と、スラリーおよび同スラリー上に塗着された
フッ素樹脂分散液を乾燥する乾燥工程と、この乾燥工程
により乾燥された水素吸蔵電極を圧延する圧延工程とを
備えるようにしている。Another object of the present invention is to provide a method for producing a hydrogen storage alloy electrode in which a fluororesin dispersion is applied to a hydrogen storage alloy electrode to impart water repellency to the hydrogen storage alloy electrode. In the invention according to claim 8, a dispersion step of uniformly dispersing an organic solvent in which the fluororesin powder is uniformly dispersed in an aqueous solution to obtain a fluororesin dispersion liquid, and a water-soluble binding to the hydrogen storage alloy powder A slurry step of kneading the agent with the slurry, a coating step of coating the slurry obtained by the slurry step on the current collector, and a slurry step of coating the slurry on the current collector by the coating step. The dispersion liquid application step of applying the fluororesin dispersion liquid obtained in the previous dispersion step, the drying step of drying the slurry and the fluororesin dispersion liquid applied on the slurry, and the drying step Water So that and a rolling step of rolling the absorbing electrode.
【００２３】このように分散液を製造し、スラリー工程
により得られたスラリーを集電体に塗着した後、このス
ラリー上にフッ素樹脂分散液を塗着すると、フッ素樹脂
は有機溶剤中に均一分散しているのでフッ素樹脂に凝集
が生じることなくスラリー上に均一に塗布されることと
なる。そのため、水素吸蔵合金電極上に均一にフッ素樹
脂が分布することとなって、酸素ガス吸収能力が格段に
向上した水素吸蔵合金電極を製造することが可能にな
る。After the dispersion liquid is manufactured as described above, the slurry obtained by the slurry process is applied to the current collector, and then the fluororesin dispersion liquid is applied on the slurry, whereby the fluororesin is uniformly dispersed in the organic solvent. Since they are dispersed, they are uniformly applied on the slurry without aggregation of the fluororesin. For this reason, the fluororesin is uniformly distributed on the hydrogen storage alloy electrode, and it is possible to manufacture a hydrogen storage alloy electrode having a remarkably improved oxygen gas absorption capacity.
【００２４】請求項９に記載の発明においては、上述の
フッ素樹脂分散液にガス吸収触媒を添加するようにして
いる。フッ素樹脂が分散液に均一に分散していると、こ
の分散液にガス吸収触媒を添加して混合すると、フッ素
樹脂と水素吸蔵合金とガス吸収触媒とが互いに接触する
接触面積が増大するようになるため、この水素吸蔵合金
電極の酸素ガスの吸収能力が格段に向上するようにな
る。In the ninth aspect of the present invention, a gas absorption catalyst is added to the fluororesin dispersion. When the fluororesin is uniformly dispersed in the dispersion, a gas absorption catalyst is added to and mixed with the dispersion so that the contact area between the fluororesin, the hydrogen storage alloy, and the gas absorption catalyst is increased. Therefore, the ability of the hydrogen storage alloy electrode to absorb oxygen gas is significantly improved.
【００２５】[0025]
ａ．フッ素樹脂分散液の作製 （１）実施例１ シクロヘキサン（有機溶剤）にフッ素樹脂、例えばポリ
テトラフルオロエチレン（ＰＴＦＥ）を１５重量％分散
させた有機中分散液を作製する。この有機中分散液７０
重量％をホモジナイザー（機械的攪拌、超音波照射など
により２液相を混合分散してエマルジョンとする装置）
を用いて３０重量％の水中に分散させてフッ素樹脂分散
液を作製する。このようにして作製されたフッ素樹脂分
散液を実施例１のフッ素樹脂分散液Ａとする。a. Preparation of Fluororesin Dispersion (1) Example 1 An organic dispersion in which 15% by weight of a fluororesin, for example, polytetrafluoroethylene (PTFE) is dispersed in cyclohexane (organic solvent) is prepared. This organic dispersion 70
Weight% homogenizer (device for mixing and dispersing two liquid phases by mechanical stirring, ultrasonic irradiation, etc. to form an emulsion)
Is dispersed in 30% by weight of water to prepare a fluororesin dispersion. The fluororesin dispersion thus prepared is referred to as a fluororesin dispersion A of Example 1.
【００２６】（２）実施例２ シクロヘキサンにフッ素樹脂、例えばポリテトラフルオ
ロエチレン（ＰＴＦＥ）を１５重量％分散させた有機中
分散液を作製する。この有機中分散液７０重量％をホモ
ジナイザー（機械的攪拌、超音波照射などにより２液相
を混合分散してエマルジョンとする装置）を用いて、４
重量％の界面活性剤（ポリオキシエチレンソルビタンモ
ノラウラート（キシダ化学製，商品名：Ｔｗｅｅｎ２
０））を含有する３０重量％の水中に分散させてフッ素
樹脂分散液を作製する。このようにして作製されたフッ
素樹脂分散液を実施例２のフッ素樹脂分散液Ｂとする。(2) Example 2 An organic dispersion in which a fluororesin, for example, polytetrafluoroethylene (PTFE) is dispersed at 15% by weight in cyclohexane is prepared. 70% by weight of this organic dispersion is homogenized using a homogenizer (a device for mixing and dispersing two liquid phases by mechanical stirring, ultrasonic irradiation or the like to form an emulsion).
% By weight of a surfactant (polyoxyethylene sorbitan monolaurate (trade name: Tween2, manufactured by Kishida Chemical Co., Ltd.)
0)) is dispersed in 30% by weight of water to prepare a fluororesin dispersion. The fluororesin dispersion thus prepared is referred to as a fluororesin dispersion B of Example 2.
【００２７】（３）実施例３ 上述のフッ素樹脂分散液Ａに１０重量％のカーボン粉末
（ガス吸収触媒）を混合したものを実施例３のフッ素樹
脂分散液Ｃとする。(3) Example 3 A mixture of the fluororesin dispersion A described above and 10% by weight of carbon powder (gas absorption catalyst) is referred to as a fluororesin dispersion C of Example 3.
【００２８】（４）実施例４ 上述のフッ素樹脂分散液Ａに１０重量％のニッケル粉末
（ガス吸収触媒）を混合したものを実施例４のフッ素樹
脂分散液Ｄとする。(4) Example 4 A mixture of the above-mentioned fluororesin dispersion liquid A and 10% by weight of nickel powder (gas absorption catalyst) is referred to as a fluororesin dispersion liquid D of Example 4.
【００２９】（５）実施例５ 上述のフッ素樹脂分散液Ａに５重量％のカーボン粉末
（ガス吸収触媒）と５重量％のニッケル粉末（ガス吸収
触媒）を混合したものを実施例５のフッ素樹脂分散液Ｅ
とする。(5) Example 5 A mixture of 5% by weight of carbon powder (gas absorbing catalyst) and 5% by weight of nickel powder (gas absorbing catalyst) in the above-mentioned fluororesin dispersion liquid A was mixed with fluorine of Example 5. Resin dispersion liquid E
And
【００３０】（６）実施例６ 上述のフッ素樹脂分散液Ｂに１０重量％のカーボン粉末
（ガス吸収触媒）を混合したものを実施例６のフッ素樹
脂分散液Ｆとする。(6) Example 6 A mixture of the above-mentioned fluororesin dispersion B and 10% by weight of carbon powder (gas absorption catalyst) is referred to as a fluororesin dispersion F of Example 6.
【００３１】（７）実施例７ 上述のフッ素樹脂分散液Ｂに１０重量％のニッケル粉末
（ガス吸収触媒）を混合したものを実施例７のフッ素樹
脂分散液Ｇとする。(7) Example 7 A mixture of the fluororesin dispersion B described above and 10% by weight of nickel powder (gas absorption catalyst) is referred to as a fluororesin dispersion G of Example 7.
【００３２】（８）実施例８ 上述のフッ素樹脂分散液Ｂに５重量％のカーボン粉末
（ガス吸収触媒）と５重量％のニッケル粉末（ガス吸収
触媒）を混合したものを実施例８のフッ素樹脂分散液Ｈ
とする。(8) Example 8 A mixture of 5% by weight of carbon powder (gas absorbing catalyst) and 5% by weight of nickel powder (gas absorbing catalyst) in the above-mentioned fluororesin dispersion B was mixed with fluorine of Example 8. Resin dispersion liquid H
And
【００３３】（９）比較例１ シクロヘキサンにフッ素樹脂、例えばポリテトラフルオ
ロエチレン（ＰＴＦＥ）を１５重量％分散させたものを
比較例１のフッ素樹脂分散液Ｉとする。(9) Comparative Example 1 A fluororesin dispersion liquid I of Comparative Example 1 was prepared by dispersing a fluororesin, for example, polytetrafluoroethylene (PTFE) at 15% by weight in cyclohexane.
【００３４】（１０）比較例２ 水に４重量％の界面活性剤（ポリオキシエチレンソルビ
タンモノラウラート（キシダ化学製，商品名：Ｔｗｅｅ
ｎ２０））とフッ素樹脂、例えばポリテトラフルオロエ
チレン（ＰＴＦＥ）を１５重量％分散させたものを比較
例２のフッ素樹脂分散液Ｊとする。(10) Comparative Example 2 4% by weight of a surfactant (polyoxyethylene sorbitan monolaurate (manufactured by Kishida Chemical Co., trade name: Tween) in water
n20)) and 15% by weight of a fluororesin, for example, polytetrafluoroethylene (PTFE) dispersed therein, is referred to as a fluororesin dispersion J of Comparative Example 2.
【００３５】（１１）比較例３ 水に４重量％の界面活性剤（ポリオキシエチレンソルビ
タンモノラウラート（キシダ化学製，商品名：Ｔｗｅｅ
ｎ２０））とフッ素樹脂、例えばポリテトラフルオロエ
チレン（ＰＴＦＥ）を１５重量％分散させて水中分散液
を作製する。この水中分散液５０重量％とシクロヘキサ
ン５０重量％を混合したものを比較例３のフッ素樹脂分
散液Ｋとする。(11) Comparative Example 3 4% by weight of a surfactant (polyoxyethylene sorbitan monolaurate (manufactured by Kishida Chemical, trade name: Tween) in water
n20)) and a fluororesin, for example, polytetrafluoroethylene (PTFE) at 15% by weight, to prepare a dispersion in water. A mixture of 50% by weight of this dispersion in water and 50% by weight of cyclohexane is referred to as a fluororesin dispersion K of Comparative Example 3.
【００３６】ｂ．負極の作製 （１）実施例１ ミッシュメタル（Ｍｍ：希土類元素の混合物）、ニッケ
ル、コバルト、アルミニウム、およびマンガンを元素比
で１：３．２：１．０：０．２：０．６の比率で混合
し、この混合物をアルゴンガス雰囲気の高周波誘導炉で
誘導加熱して合金溶湯となす。この合金溶湯を公知の方
法で冷却し、組成式Ｍｍ1.0Ｎｉ3.2Ｃｏ1.0Ａｌ0.2Ｍｎ
0.6で表される水素吸蔵合金のインゴットを作製する。
この水素吸蔵合金インゴットを機械的に粉砕し、平均粒
子径が約１００μｍの水素吸蔵合金粉末となし、この水
素吸蔵合金粉末に水溶性結着剤、例えばポリエチレンオ
キサイド（ＰＥＯ）１重量％と、上述のフッ素樹脂分散
液Ａ（水素吸蔵合金に対してフッ素樹脂固形分が１重量
％となる）と、適量の水を加えて混練して水素吸蔵合金
スラリーを作製する。このスラリーをパンチングメタル
に塗布し、乾燥した後、厚み０．４ｍｍに圧延して実施
例１の水素吸蔵合金負極を作製する。B. Production of Negative Electrode (1) Example 1 Mish metal (Mm: mixture of rare earth elements), nickel, cobalt, aluminum and manganese in an element ratio of 1: 3.2: 1.0: 0.2: 0.6 The mixture is mixed in a ratio, and the mixture is induction-heated in a high-frequency induction furnace in an argon gas atmosphere to form a molten alloy. The molten alloy is cooled by a known method, and the composition formula is Mm 1.0 Ni 3.2 Co 1.0 Al 0.2 Mn.
A hydrogen storage alloy ingot represented by 0.6 is produced.
The hydrogen storage alloy ingot is mechanically pulverized to form a hydrogen storage alloy powder having an average particle diameter of about 100 μm. The hydrogen storage alloy powder is mixed with a water-soluble binder, for example, 1 wt% of polyethylene oxide (PEO) and And a suitable amount of water and kneaded with a fluororesin dispersion liquid A (the fluororesin solid content is 1% by weight based on the hydrogen storage alloy) to prepare a hydrogen storage alloy slurry. This slurry is applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce the hydrogen storage alloy negative electrode of Example 1.
【００３７】（２）実施例２ 実施例１と同様に作製した水素吸蔵合金粉末に水溶性結
着剤、例えばポリエチレンオキサイド（ＰＥＯ）１重量
％と、上述のフッ素樹脂分散液Ｂ（水素吸蔵合金に対し
てフッ素樹脂固形分が１重量％となる）と、適量の水を
加えて混練して水素吸蔵合金スラリーを作製する。この
スラリーをパンチングメタルに塗布し、乾燥した後、厚
み０．４ｍｍに圧延して実施例２の水素吸蔵合金負極を
作製する。(2) Example 2 A hydrogen-absorbing alloy powder prepared in the same manner as in Example 1 was mixed with a water-soluble binder, for example, 1% by weight of polyethylene oxide (PEO), and the above-mentioned fluororesin dispersion B (hydrogen-absorbing alloy) The solid content of the fluororesin becomes 1% by weight), and an appropriate amount of water is added and kneaded to prepare a hydrogen storage alloy slurry. This slurry is applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode of Example 2.
【００３８】（３）実施例３ 実施例１と同様に作製した水素吸蔵合金粉末に水溶性結
着剤、例えばポリエチレンオキサイド（ＰＥＯ）１重量
％と、上述のフッ素樹脂分散液Ｃ（水素吸蔵合金に対し
てフッ素樹脂固形分が１重量％となる）と、適量の水を
加えて混練して水素吸蔵合金スラリーを作製する。この
スラリーをパンチングメタルに塗布し、乾燥した後、厚
み０．４ｍｍに圧延して実施例３の水素吸蔵合金負極を
作製する。(3) Example 3 A hydrogen-absorbing alloy powder prepared in the same manner as in Example 1 was mixed with a water-soluble binder, for example, 1% by weight of polyethylene oxide (PEO), and the above-mentioned fluororesin dispersion C (hydrogen-absorbing alloy). The solid content of the fluororesin becomes 1% by weight), and an appropriate amount of water is added and kneaded to prepare a hydrogen storage alloy slurry. This slurry was applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode of Example 3.
【００３９】（４）実施例４ 実施例１と同様に作製した水素吸蔵合金粉末に水溶性結
着剤、例えばポリエチレンオキサイド（ＰＥＯ）１重量
％と、上述のフッ素樹脂分散液Ｄ（水素吸蔵合金に対し
てフッ素樹脂固形分が１重量％となる）と、適量の水を
加えて混練して水素吸蔵合金スラリーを作製する。この
スラリーをパンチングメタルに塗布し、乾燥した後、厚
み０．４ｍｍに圧延して実施例４の水素吸蔵合金負極を
作製する。(4) Example 4 A hydrogen-absorbing alloy powder prepared in the same manner as in Example 1 was mixed with a water-soluble binder, for example, 1% by weight of polyethylene oxide (PEO), and the above-mentioned fluororesin dispersion D (hydrogen-absorbing alloy). The solid content of the fluororesin becomes 1% by weight), and an appropriate amount of water is added and kneaded to prepare a hydrogen storage alloy slurry. The slurry was applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode of Example 4.
【００４０】（５）実施例５ 実施例１と同様に作製した水素吸蔵合金粉末に水溶性結
着剤、例えばポリエチレンオキサイド（ＰＥＯ）１重量
％と、上述のフッ素樹脂分散液Ｅ（水素吸蔵合金に対し
てフッ素樹脂固形分が１重量％となる）と、適量の水を
加えて混練して水素吸蔵合金スラリーを作製する。この
スラリーをパンチングメタルに塗布し、乾燥した後、厚
み０．４ｍｍに圧延して実施例５の水素吸蔵合金負極を
作製する。(5) Example 5 A hydrogen-absorbing alloy powder prepared in the same manner as in Example 1 was mixed with a water-soluble binder, for example, 1% by weight of polyethylene oxide (PEO), and the above-mentioned fluororesin dispersion E (hydrogen-absorbing alloy). The solid content of the fluororesin becomes 1% by weight), and an appropriate amount of water is added and kneaded to prepare a hydrogen storage alloy slurry. This slurry was applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode of Example 5.
【００４１】（６）実施例６ 実施例１と同様に作製した水素吸蔵合金粉末に水溶性結
着剤、例えばポリエチレンオキサイド（ＰＥＯ）１重量
％と、上述のフッ素樹脂分散液Ｆ（水素吸蔵合金に対し
てフッ素樹脂固形分が１重量％となる）と、適量の水を
加えて混練して水素吸蔵合金スラリーを作製する。この
スラリーをパンチングメタルに塗布し、乾燥した後、厚
み０．４ｍｍに圧延して実施例６の水素吸蔵合金負極を
作製する。(6) Example 6 A hydrogen-absorbing alloy powder prepared in the same manner as in Example 1 was mixed with a water-soluble binder, for example, 1% by weight of polyethylene oxide (PEO), and the above-mentioned fluororesin dispersion F (hydrogen-absorbing alloy). The solid content of the fluororesin becomes 1% by weight), and an appropriate amount of water is added and kneaded to prepare a hydrogen storage alloy slurry. This slurry is applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode of Example 6.
【００４２】（７）実施例７ 実施例１と同様に作製した水素吸蔵合金粉末に水溶性結
着剤、例えばポリエチレンオキサイド（ＰＥＯ）１重量
％と、上述のフッ素樹脂分散液Ｇ（水素吸蔵合金に対し
てフッ素樹脂固形分が１重量％となる）と、適量の水を
加えて混練して水素吸蔵合金スラリーを作製する。この
スラリーをパンチングメタルに塗布し、乾燥した後、厚
み０．４ｍｍに圧延して実施例７の水素吸蔵合金負極を
作製する。(7) Example 7 A hydrogen-absorbing alloy powder prepared in the same manner as in Example 1 was mixed with a water-soluble binder, for example, 1% by weight of polyethylene oxide (PEO), and the above-mentioned fluororesin dispersion G (hydrogen-absorbing alloy). The solid content of the fluororesin becomes 1% by weight), and an appropriate amount of water is added and kneaded to prepare a hydrogen storage alloy slurry. This slurry was applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode of Example 7.
【００４３】（８）実施例８ 実施例１と同様に作製した水素吸蔵合金粉末に水溶性結
着剤、例えばポリエチレンオキサイド（ＰＥＯ）１重量
％と、上述のフッ素樹脂分散液Ｈ（水素吸蔵合金に対し
てフッ素樹脂固形分が１重量％となる）と、適量の水を
加えて混練して水素吸蔵合金スラリーを作製する。この
スラリーをパンチングメタルに塗布し、乾燥した後、厚
み０．４ｍｍに圧延して実施例８の水素吸蔵合金負極を
作製する。(8) Example 8 A hydrogen-absorbing alloy powder prepared in the same manner as in Example 1 was mixed with a water-soluble binder, for example, 1% by weight of polyethylene oxide (PEO), and the above-mentioned fluororesin dispersion H (hydrogen-absorbing alloy). The solid content of the fluororesin becomes 1% by weight), and an appropriate amount of water is added and kneaded to prepare a hydrogen storage alloy slurry. This slurry is applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode of Example 8.
【００４４】（９）実施例９ 実施例１と同様に作製した水素吸蔵合金粉末に水溶性結
着剤、例えばポリエチレンオキサイド（ＰＥＯ）０．５
％重量と、適量の水を加えて混練して水素吸蔵合金スラ
リーを作製する。このスラリーをパンチングメタルに塗
布し、乾燥した後、厚み０．４ｍｍに圧延して水素吸蔵
合金負極を作製する。このようにして作製した水素吸蔵
合金負極の表面に上述のフッ素樹脂分散液Ａ（水素吸蔵
合金に対してフッ素樹脂固形分が１重量％となる）にポ
リエチレンオキサイド（ＰＥＯ）０．５％重量を混合し
たスラリーを塗布し、乾燥して実施例９の水素吸蔵合金
負極とする。(9) Example 9 A water-soluble binder, for example, polyethylene oxide (PEO) 0.5 was added to the hydrogen storage alloy powder produced in the same manner as in Example 1.
% Hydrogen and an appropriate amount of water are added and kneaded to prepare a hydrogen storage alloy slurry. This slurry is applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode. 0.5% by weight of polyethylene oxide (PEO) was added to the surface of the thus prepared hydrogen storage alloy negative electrode in the above-mentioned fluororesin dispersion A (the fluororesin solid content was 1% by weight with respect to the hydrogen storage alloy). The mixed slurry was applied and dried to obtain a hydrogen storage alloy negative electrode of Example 9.
【００４５】（１０）実施例１０ 実施例１と同様に作製した水素吸蔵合金粉末に水溶性結
着剤、例えばポリエチレンオキサイド（ＰＥＯ）０．５
重量％と、適量の水を加えて混練して水素吸蔵合金スラ
リーを作製する。このスラリーをパンチングメタルに塗
布し、乾燥した後、厚み０．４ｍｍに圧延して水素吸蔵
合金負極を作製する。このようにして作製した水素吸蔵
合金負極の表面に上述のフッ素樹脂分散液Ｂ（水素吸蔵
合金に対してフッ素樹脂固形分が１重量％となる）にポ
リエチレンオキサイド（ＰＥＯ）０．５％重量を混合し
たスラリーを塗布し、乾燥して実施例１０の水素吸蔵合
金負極とする。(10) Example 10 A water-soluble binder, for example, polyethylene oxide (PEO) 0.5 was added to the hydrogen storage alloy powder prepared in the same manner as in Example 1.
A hydrogen storage alloy slurry is prepared by adding and mixing the weight% and an appropriate amount of water. This slurry is applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode. 0.5% by weight of polyethylene oxide (PEO) was added to the above-mentioned fluororesin dispersion B (the fluororesin solid content was 1% by weight with respect to the hydrogen storage alloy) on the surface of the hydrogen storage alloy negative electrode thus produced. The mixed slurry was applied and dried to obtain a hydrogen storage alloy negative electrode of Example 10.
【００４６】（１１）実施例１１ 実施例１と同様に作製した水素吸蔵合金粉末に水溶性結
着剤、例えばポリエチレンオキサイド（ＰＥＯ）１重量
％と、適量の水を加えて混練して水素吸蔵合金スラリー
を作製する。このスラリーをパンチングメタルに塗布
し、乾燥した後、厚み０．４ｍｍに圧延して水素吸蔵合
金負極を作製する。このようにして作製した水素吸蔵合
金負極の表面に上述のフッ素樹脂分散液Ｃ（水素吸蔵合
金に対してフッ素樹脂固形分が１重量％となる）にポリ
エチレンオキサイド（ＰＥＯ）０．５％重量を混合した
スラリーを塗布し、乾燥して実施例１１の水素吸蔵合金
負極とする。(11) Example 11 A hydrogen-absorbing alloy powder prepared in the same manner as in Example 1 was mixed with a water-soluble binder, for example, 1% by weight of polyethylene oxide (PEO) and an appropriate amount of water, and kneaded. Prepare an alloy slurry. This slurry is applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode. 0.5% by weight of polyethylene oxide (PEO) was added to the surface of the thus-prepared hydrogen storage alloy negative electrode in the fluororesin dispersion liquid C (the fluororesin solid content was 1% by weight with respect to the hydrogen storage alloy). The mixed slurry was applied and dried to obtain a hydrogen storage alloy negative electrode of Example 11.
【００４７】（１２）実施例１２ 実施例１と同様に作製した水素吸蔵合金粉末に水溶性結
着剤、例えばポリエチレンオキサイド（ＰＥＯ）１重量
％と、適量の水を加えて混練して水素吸蔵合金スラリー
を作製する。このスラリーをパンチングメタルに塗布
し、乾燥した後、厚み０．４ｍｍに圧延して水素吸蔵合
金負極を作製する。このようにして作製した水素吸蔵合
金負極の表面に上述のフッ素樹脂分散液Ｄ（水素吸蔵合
金に対してフッ素樹脂固形分が１重量％となる）にポリ
エチレンオキサイド（ＰＥＯ）０．５％重量を混合した
スラリーを塗布し、乾燥して実施例１２の水素吸蔵合金
負極とする。(12) Example 12 A hydrogen-absorbing alloy powder prepared in the same manner as in Example 1 was mixed with a water-soluble binder, for example, 1% by weight of polyethylene oxide (PEO) and an appropriate amount of water, and kneaded. Prepare an alloy slurry. This slurry is applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode. 0.5% by weight of polyethylene oxide (PEO) was added to the above-mentioned fluororesin dispersion D (the fluororesin solid content was 1% by weight with respect to the hydrogen-absorbing alloy) on the surface of the hydrogen-absorbing alloy negative electrode thus produced. The mixed slurry was applied and dried to obtain a hydrogen storage alloy negative electrode of Example 12.
【００４８】（１３）実施例１３ 実施例１と同様に作製した水素吸蔵合金粉末に水溶性結
着剤、例えばポリエチレンオキサイド（ＰＥＯ）１重量
％と、適量の水を加えて混練して水素吸蔵合金スラリー
を作製する。このスラリーをパンチングメタルに塗布
し、乾燥した後、厚み０．４ｍｍに圧延して水素吸蔵合
金負極を作製する。このようにして作製した水素吸蔵合
金負極の表面に上述のフッ素樹脂分散液Ｅ（水素吸蔵合
金に対してフッ素樹脂固形分が１重量％となる）にポリ
エチレンオキサイド（ＰＥＯ）０．５％重量を混合した
スラリーを塗布し、乾燥して実施例１３の水素吸蔵合金
負極とする。(13) Example 13 A hydrogen-absorbing alloy powder prepared in the same manner as in Example 1 was mixed with a water-soluble binder, for example, 1% by weight of polyethylene oxide (PEO) and an appropriate amount of water, and kneaded. Prepare an alloy slurry. This slurry is applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode. 0.5% by weight of polyethylene oxide (PEO) was added to the surface of the thus prepared hydrogen storage alloy negative electrode in the above-mentioned fluororesin dispersion E (the fluororesin solid content was 1% by weight with respect to the hydrogen storage alloy). The mixed slurry was applied and dried to obtain a hydrogen storage alloy negative electrode of Example 13.
【００４９】（１４）実施例１４ 実施例１と同様に作製した水素吸蔵合金粉末に水溶性結
着剤、例えばポリエチレンオキサイド（ＰＥＯ）１重量
％と、適量の水を加えて混練して水素吸蔵合金スラリー
を作製する。このスラリーをパンチングメタルに塗布
し、乾燥した後、厚み０．４ｍｍに圧延して水素吸蔵合
金負極を作製する。このようにして作製した水素吸蔵合
金負極の表面に上述のフッ素樹脂分散液Ｆ（水素吸蔵合
金に対してフッ素樹脂固形分が１重量％となる）にポリ
エチレンオキサイド（ＰＥＯ）０．５％重量を混合した
スラリーを塗布し、乾燥して実施例１４の水素吸蔵合金
負極とする。(14) Example 14 A hydrogen-absorbing alloy powder prepared in the same manner as in Example 1 was mixed with a water-soluble binder, for example, 1% by weight of polyethylene oxide (PEO) and an appropriate amount of water, and kneaded. Prepare an alloy slurry. This slurry is applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode. 0.5% by weight of polyethylene oxide (PEO) was added to the surface of the thus prepared hydrogen storage alloy negative electrode in the above-mentioned fluororesin dispersion F (the fluororesin solid content was 1% by weight with respect to the hydrogen storage alloy). The mixed slurry was applied and dried to obtain a hydrogen storage alloy negative electrode of Example 14.
【００５０】（１５）実施例１５ 実施例１と同様に作製した水素吸蔵合金粉末に水溶性結
着剤、例えばポリエチレンオキサイド（ＰＥＯ）１重量
％と、適量の水を加えて混練して水素吸蔵合金スラリー
を作製する。このスラリーをパンチングメタルに塗布
し、乾燥した後、厚み０．４ｍｍに圧延して水素吸蔵合
金負極を作製する。このようにして作製した水素吸蔵合
金負極の表面に上述のフッ素樹脂分散液Ｇ（水素吸蔵合
金に対してフッ素樹脂固形分が１重量％となる）にポリ
エチレンオキサイド（ＰＥＯ）０．５％重量を混合した
スラリーを塗布し、乾燥して実施例１５の水素吸蔵合金
負極とする。(15) Example 15 A hydrogen-absorbing alloy powder prepared in the same manner as in Example 1 was mixed with a water-soluble binder, for example, 1% by weight of polyethylene oxide (PEO) and an appropriate amount of water, and kneaded. Prepare an alloy slurry. This slurry is applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode. 0.5% by weight of polyethylene oxide (PEO) was added to the surface of the thus prepared hydrogen storage alloy negative electrode in the above-mentioned fluororesin dispersion G (the fluororesin solid content was 1% by weight with respect to the hydrogen storage alloy). The mixed slurry was applied and dried to obtain a hydrogen storage alloy negative electrode of Example 15.
【００５１】（１６）実施例１６ 実施例１と同様に作製した水素吸蔵合金粉末に水溶性結
着剤、例えばポリエチレンオキサイド（ＰＥＯ）１重量
％と、適量の水を加えて混練して水素吸蔵合金スラリー
を作製する。このスラリーをパンチングメタルに塗布
し、乾燥した後、厚み０．４ｍｍに圧延して水素吸蔵合
金負極を作製する。このようにして作製した水素吸蔵合
金負極の表面に上述のフッ素樹脂分散液Ｈ（水素吸蔵合
金に対してフッ素樹脂固形分が１重量％となる）にポリ
エチレンオキサイド（ＰＥＯ）０．５％重量を混合した
スラリーを塗布し、乾燥して実施例１６の水素吸蔵合金
負極とする。(16) Example 16 A hydrogen-absorbing alloy powder prepared in the same manner as in Example 1 was mixed with a water-soluble binder, for example, 1% by weight of polyethylene oxide (PEO) and an appropriate amount of water, and kneaded. Prepare an alloy slurry. This slurry is applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode. 0.5% by weight of polyethylene oxide (PEO) was added to the surface of the thus-prepared hydrogen storage alloy negative electrode in the fluororesin dispersion liquid H (the fluororesin solid content was 1% by weight with respect to the hydrogen storage alloy). The mixed slurry was applied and dried to obtain a hydrogen storage alloy negative electrode of Example 16.
【００５２】（１７）実施例１７ 実施例１と同様に作製した水素吸蔵合金粉末に水溶性結
着剤、例えばポリエチレンオキサイド（ＰＥＯ）１重量
％と、適量の水を加えて混練して水素吸蔵合金スラリー
を作製する。このスラリーをパンチングメタルに塗布
し、乾燥した後、厚み０．４ｍｍに圧延して水素吸蔵合
金負極を作製する。上述のフッ素樹脂分散液Ｂ（水素吸
蔵合金に対してフッ素樹脂固形分が１重量％となる）を
塗布し、乾燥して実施例１７の水素吸蔵合金負極とす
る。(17) Example 17 A hydrogen-absorbing alloy powder prepared in the same manner as in Example 1 was mixed with a water-soluble binder, for example, 1% by weight of polyethylene oxide (PEO) and an appropriate amount of water, and kneaded. Prepare an alloy slurry. This slurry is applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode. The above-mentioned fluororesin dispersion liquid B (the fluororesin solid content is 1% by weight with respect to the hydrogen storage alloy) is applied and dried to obtain a hydrogen storage alloy negative electrode of Example 17.
【００５３】（１８）比較例１ 実施例１と同様に作製した水素吸蔵合金粉末にポリエチ
レンオキサイド（ＰＥＯ）１重量％と、上述のフッ素樹
脂分散液Ｉ（水素吸蔵合金に対してフッ素樹脂固形分が
１重量％となる）と、適量の水を加えて混練して水素吸
蔵合金スラリーを作製する。このスラリーをパンチング
メタルに塗布し、乾燥した後、厚み０．４ｍｍに圧延し
て比較例１の水素吸蔵合金負極を作製する。(18) Comparative Example 1 1% by weight of polyethylene oxide (PEO) was added to a hydrogen storage alloy powder prepared in the same manner as in Example 1, and the above-mentioned fluororesin dispersion liquid I (solid content of the fluororesin relative to the hydrogen storage alloy) Is 1% by weight), and an appropriate amount of water is added and kneaded to prepare a hydrogen storage alloy slurry. This slurry is applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode of Comparative Example 1.
【００５４】（１９）比較例２ 実施例１と同様に作製した水素吸蔵合金粉末にポリエチ
レンオキサイド（ＰＥＯ）１重量％と、上述のフッ素樹
脂分散液Ｊ（水素吸蔵合金に対してフッ素樹脂固形分が
１重量％となる）と、適量の水を加えて混練して水素吸
蔵合金スラリーを作製する。このスラリーをパンチング
メタルに塗布し、乾燥した後、厚み０．４ｍｍに圧延し
て比較例２の水素吸蔵合金負極を作製する。(19) Comparative Example 2 1% by weight of polyethylene oxide (PEO) was added to the hydrogen storage alloy powder prepared in the same manner as in Example 1, Is 1% by weight), and an appropriate amount of water is added and kneaded to prepare a hydrogen storage alloy slurry. This slurry is applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode of Comparative Example 2.
【００５５】（２０）比較例３ 実施例１と同様に作製した水素吸蔵合金粉末にポリエチ
レンオキサイド（ＰＥＯ）１重量％と、上述のフッ素樹
脂分散液Ｋ（水素吸蔵合金に対してフッ素樹脂固形分が
１重量％となる）と、適量の水を加えて混練して水素吸
蔵合金スラリーを作製する。このスラリーをパンチング
メタルに塗布し、乾燥した後、厚み０．４ｍｍに圧延し
て比較例３の水素吸蔵合金負極を作製する。(20) Comparative Example 3 1% by weight of polyethylene oxide (PEO) was added to the hydrogen-absorbing alloy powder prepared in the same manner as in Example 1, and the above-mentioned fluororesin dispersion liquid K (the fluororesin solid content with respect to the hydrogen-absorbing alloy) Is 1% by weight), and an appropriate amount of water is added and kneaded to prepare a hydrogen storage alloy slurry. This slurry was applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode of Comparative Example 3.
【００５６】（２１）比較例４ 実施例１と同様に作製した水素吸蔵合金粉末にポリエチ
レンオキサイド（ＰＥＯ）１重量％と、１重量％のフッ
素樹脂粉末（Ｌ）と、適量の水を加えて混練して水素吸
蔵合金スラリーを作製する。このスラリーをパンチング
メタルに塗布し、乾燥した後、厚み０．４ｍｍに圧延し
て比較例４の水素吸蔵合金負極を作製する。(21) Comparative Example 4 1% by weight of polyethylene oxide (PEO), 1% by weight of a fluororesin powder (L) and an appropriate amount of water were added to a hydrogen storage alloy powder prepared in the same manner as in Example 1. The mixture is kneaded to produce a hydrogen storage alloy slurry. This slurry is applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode of Comparative Example 4.
【００５７】（２２）比較例５ 実施例１と同様に作製した水素吸蔵合金粉末にポリエチ
レンオキサイド（ＰＥＯ）０．５重量％と、適量の水を
加えて混練して水素吸蔵合金スラリーを作製する。この
スラリーをパンチングメタルに塗布し、乾燥した後、厚
み０．４ｍｍに圧延して水素吸蔵合金負極を作製する。
このようにして作製した水素吸蔵合金負極の表面に上述
のフッ素樹脂分散液Ｉ（水素吸蔵合金に対してフッ素樹
脂固形分が１重量％となる）にポリエチレンオキサイド
（ＰＥＯ）０．５％重量を混合したスラリーを塗布し、
乾燥して比較例５の水素吸蔵合金負極とする。(22) Comparative Example 5 A hydrogen storage alloy slurry is prepared by adding 0.5% by weight of polyethylene oxide (PEO) and an appropriate amount of water to a hydrogen storage alloy powder prepared in the same manner as in Example 1, and kneading the mixture. . This slurry is applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode.
0.5% by weight of polyethylene oxide (PEO) was added to the above-mentioned fluororesin dispersion liquid I (the fluororesin solid content was 1% by weight with respect to the hydrogen-absorbing alloy) on the surface of the hydrogen storage alloy negative electrode thus produced. Apply the mixed slurry,
Drying was performed to obtain a hydrogen storage alloy negative electrode of Comparative Example 5.
【００５８】（２３）比較例６ 実施例１と同様に作製した水素吸蔵合金粉末にポリエチ
レンオキサイド（ＰＥＯ）０．５重量％と、適量の水を
加えて混練して水素吸蔵合金スラリーを作製する。この
スラリーをパンチングメタルに塗布し、乾燥した後、厚
み０．４ｍｍに圧延して水素吸蔵合金負極を作製する。
このようにして作製した水素吸蔵合金負極の表面に上述
のフッ素樹脂分散液Ｊ（水素吸蔵合金に対してフッ素樹
脂固形分が１重量％となる）にポリエチレンオキサイド
（ＰＥＯ）０．５％重量を混合したスラリーを塗布し、
乾燥して比較例６の水素吸蔵合金負極とする。(23) Comparative Example 6 A hydrogen storage alloy slurry is prepared by adding 0.5% by weight of polyethylene oxide (PEO) and an appropriate amount of water to a hydrogen storage alloy powder prepared in the same manner as in Example 1 and kneading the mixture. . This slurry is applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode.
0.5% by weight of polyethylene oxide (PEO) was added to the fluororesin dispersion J (the fluororesin solid content was 1% by weight with respect to the hydrogen storage alloy) on the surface of the hydrogen storage alloy negative electrode thus prepared. Apply the mixed slurry,
Drying was performed to obtain a hydrogen storage alloy negative electrode of Comparative Example 6.
【００５９】（２４）比較例７ 実施例１と同様に作製した水素吸蔵合金粉末にポリエチ
レンオキサイド（ＰＥＯ）０．５重量％と、適量の水を
加えて混練して水素吸蔵合金スラリーを作製する。この
スラリーをパンチングメタルに塗布し、乾燥した後、厚
み０．４ｍｍに圧延して水素吸蔵合金負極を作製する。
このようにして作製した水素吸蔵合金負極の表面に上述
のフッ素樹脂粉末Ｋ（水素吸蔵合金に対してフッ素樹脂
固形分が１重量％となる）にポリエチレンオキサイド
（ＰＥＯ）０．５％重量を混合したスラリーを塗布し、
乾燥して比較例７の水素吸蔵合金負極とする。(24) Comparative Example 7 A hydrogen storage alloy slurry is prepared by adding 0.5% by weight of polyethylene oxide (PEO) and an appropriate amount of water to the hydrogen storage alloy powder prepared in the same manner as in Example 1, and kneading the mixture. . This slurry is applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode.
0.5% by weight of polyethylene oxide (PEO) is mixed with the above-mentioned fluororesin powder K (the fluororesin solid content is 1% by weight with respect to the hydrogen-absorbing alloy) on the surface of the hydrogen-absorbing alloy negative electrode thus produced. And apply the slurry
Drying was performed to obtain a hydrogen storage alloy negative electrode of Comparative Example 7.
【００６０】（２５）比較例８ 実施例１と同様に作製した水素吸蔵合金粉末にポリエチ
レンオキサイド（ＰＥＯ）０．５重量％と、適量の水を
加えて混練して水素吸蔵合金スラリーを作製する。この
スラリーをパンチングメタルに塗布し、乾燥した後、厚
み０．４ｍｍに圧延して水素吸蔵合金負極を作製する。
このようにして作製した水素吸蔵合金負極の表面に１重
量％のフッ素樹脂粉末を塗布し、乾燥して比較例８の水
素吸蔵合金負極とする。(25) Comparative Example 8 A hydrogen storage alloy slurry is prepared by adding 0.5% by weight of polyethylene oxide (PEO) and an appropriate amount of water to a hydrogen storage alloy powder prepared in the same manner as in Example 1, and kneading the mixture. . This slurry is applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode.
The surface of the thus-prepared hydrogen storage alloy negative electrode was coated with 1% by weight of a fluororesin powder and dried to obtain a hydrogen storage alloy negative electrode of Comparative Example 8.
【００６１】（２６）比較例９ 実施例１と同様に作製した水素吸蔵合金粉末にポリエチ
レンオキサイド（ＰＥＯ）１重量％と、１重量％のフッ
素樹脂粉末と、適量の水を加えて混練して水素吸蔵合金
スラリーを作製する。このスラリーをパンチングメタル
に塗布し、乾燥した後、厚み０．４ｍｍに圧延して比較
例９の水素吸蔵合金負極を作製する。(26) Comparative Example 9 1% by weight of polyethylene oxide (PEO), 1% by weight of a fluororesin powder, and an appropriate amount of water were added to a hydrogen storage alloy powder produced in the same manner as in Example 1 and kneaded. Prepare a hydrogen storage alloy slurry. This slurry is applied to a punching metal, dried, and then rolled to a thickness of 0.4 mm to produce a hydrogen storage alloy negative electrode of Comparative Example 9.
【００６２】ｃ．ニッケル電極の作製 水酸化ニッケルを主成分とする活物質スラリーを多孔度
９５％で、厚み１．６ｍｍの発泡ニッケルからなる基板
に充填し、ＰＴＦＥ（ポリテトラフルオロエチレン）水
溶液に浸漬した後、乾燥を行う。乾燥後、厚み０．６０
ｍｍとなるように圧延を行い非焼結式ニッケル正極を作
製した。C. Preparation of Nickel Electrode An active material slurry containing nickel hydroxide as a main component is filled into a 1.6 mm thick substrate made of foamed nickel having a porosity of 95%, immersed in an aqueous PTFE (polytetrafluoroethylene) solution, and then dried. I do. After drying, thickness 0.60
mm to obtain a non-sintered nickel positive electrode.
【００６３】ｄ．電池の作製 上述のように作製した実施例１〜１７および比較例１〜
９の水素吸蔵合金負極と非焼結式ニッケル正極とをポリ
プロピレン製不織布のセパレータを介して卷回して、渦
巻状の電極群を作製した後、この電極群を外装缶に挿入
する。その後、外装缶内に電解液として３０重量％の水
酸化カリウム水溶液を注入し、更に外装缶を封口して、
ニッケル−水素蓄電池を組み立てる。このようにして作
製した電池の理論容量は１０００ｍＡＨとなる。なお、
実施例１〜１７の水素吸蔵合金負極を用いたニッケル−
水素蓄電池をそれぞれ１〜１７の電池とし、比較例１〜
９の水素吸蔵合金負極を用いたニッケル−水素蓄電池を
それぞれ１８〜２６の電池とする。D. Production of Battery Examples 1 to 17 and Comparative Examples 1 to 1 produced as described above.
After winding the hydrogen storage alloy negative electrode of No. 9 and the non-sintered nickel positive electrode through a polypropylene nonwoven fabric separator to produce a spiral electrode group, this electrode group is inserted into an outer can. Thereafter, a 30% by weight aqueous solution of potassium hydroxide was poured as an electrolytic solution into the outer can, and the outer can was sealed.
Assemble the nickel-hydrogen storage battery. The theoretical capacity of the battery manufactured in this way is 1000 mAH. In addition,
Nickel using the hydrogen storage alloy negative electrodes of Examples 1 to 17
The hydrogen storage batteries were respectively 1 to 17 batteries, and Comparative Examples 1 to
Nickel-hydrogen storage batteries using the hydrogen storage alloy negative electrode of No. 9 are referred to as batteries 18 to 26, respectively.
【００６４】ｅ．電池の活性化 上述のように作成した１〜２６のニッケル−水素蓄電池
を室温で０．１Ｃの充電電流で１６時間充電した後、
０．２Ｃの放電電流で電池電圧が１．０Ｖになるまで放
電させた後、１時間休止するサイクルを３サイクル繰り
返してニッケル−水素蓄電池を活性化する。E. Battery activation After charging the nickel-hydrogen storage batteries 1 to 26 prepared as described above at room temperature with a charging current of 0.1 C for 16 hours,
After discharging the battery with a discharge current of 0.2 C until the battery voltage reaches 1.0 V, a cycle of resting for 1 hour is repeated three cycles to activate the nickel-hydrogen storage battery.
【００６５】ｆ．電池内圧の測定 上述のようにして活性化した１〜２６のニッケル−水素
蓄電池を１０００ｍＡで充電電流で１．５時間充電した
後の電池内圧を測定すると以下の表１に示すような結果
となった。F. Measurement of battery internal pressure When the nickel-hydrogen storage batteries 1 to 26 activated as described above were charged at 1000 mA with a charging current for 1.5 hours, the battery internal pressure was measured, and the results shown in Table 1 below were obtained. Was.
【００６６】[0066]
【表１】 [Table 1]
【００６７】上記表１より以下のことが明らかとなっ
た。即ち、フッ素樹脂が無添加の負極を用いた電池２６
より、フッ素樹脂を極板の内部あるいは表面に添加した
電池１８〜２５の内圧は低下するが、それほど内圧低下
の効果は大きくない。その理由は次のように考えること
ができる。比較例１８と２２（分散液Ｉを用いたもの）
の問題点は、フッ素樹脂が有機溶剤中に分散しているた
め、有機溶剤は水溶性糊料（ＰＥＯ）と混合したときに
均一に混合できないため、フッ素樹脂の混合または塗布
が不均一となり、内圧低減効果が十分でない。また、比
較例１９と２３（分散液Ｊを用いたもの）の問題点は、
フッ素樹脂の分散が十分でないことによる。フッ素樹脂
は疎水性のため、水中に分散しにくく、凝集を起こしや
すい。そのために分散剤（界面活性剤）を用いている
が、疎水性の有機溶剤に分散させた方が良好である。The following is clear from Table 1 above. That is, the battery 26 using the negative electrode to which no fluorine resin was added was used.
As a result, the internal pressure of the batteries 18 to 25 in which the fluororesin is added to the inside or the surface of the electrode plate is reduced, but the effect of lowering the internal pressure is not so large. The reason can be considered as follows. Comparative Examples 18 and 22 (Using Dispersion I)
The problem is that because the fluororesin is dispersed in the organic solvent, the organic solvent cannot be mixed uniformly when mixed with the water-soluble paste (PEO), so that the mixing or application of the fluororesin becomes uneven, The effect of reducing the internal pressure is not sufficient. In addition, the problems of Comparative Examples 19 and 23 (using dispersion J) are as follows.
This is due to insufficient dispersion of the fluororesin. Because the fluororesin is hydrophobic, it is difficult to disperse in water and easily causes aggregation. For this purpose, a dispersant (surfactant) is used, but it is better to disperse it in a hydrophobic organic solvent.
【００６８】さらに、比較例２０と２４（分散液Ｋを用
いたもの）の問題点は、フッ素樹脂が水中に分散してい
ること、およびこの水中に分散したフッ素樹脂を有機溶
剤に混合していることから、スラリー混合時、あるいは
負極表面への塗着時にフッ素樹脂が不均一に分布するこ
とにより、内圧低減効果が十分ではない。また、比較例
２１と２５（フッ素樹脂粉末Ｌを用いたもの）の問題点
は、フッ素樹脂を粉末状態で混合したり、あるいはフッ
素樹脂粉末を負極表面へ塗着するため、フッ素樹脂が不
均一に分布することにより、内圧低減効果が十分ではな
い。The problems of Comparative Examples 20 and 24 (using dispersion K) are that the fluororesin is dispersed in water and that the fluororesin dispersed in water is mixed with an organic solvent. Therefore, the effect of reducing the internal pressure is not sufficient due to the uneven distribution of the fluororesin during the mixing of the slurry or the application to the negative electrode surface. Further, the problems of Comparative Examples 21 and 25 (using the fluororesin powder L) are that the fluororesin is mixed in a powder state or the fluororesin powder is applied to the negative electrode surface. , The effect of reducing the internal pressure is not sufficient.
【００６９】これに対して、実施例のフッ素樹脂分散液
を用いた電池１〜１７の内圧低減効果は大きい。まず、
実施例１と９は、有機溶剤中にフッ素樹脂が分散してい
るため、フッ素樹脂の凝集が起こらず、水中油滴型分散
液となっているために水溶性結着剤（ＰＥＯ）との親和
性が良く、均一に混合、塗布することができるためと考
えることができる。そして、水中油滴型分散液は水溶液
として取り扱うことができるため、取り扱いが容易とな
る。On the other hand, the batteries 1 to 17 using the fluororesin dispersions of the examples have a large internal pressure reducing effect. First,
In Examples 1 and 9, since the fluororesin is dispersed in the organic solvent, the flocculation of the fluororesin does not occur, and since the dispersion is an oil-in-water type dispersion, the dispersion with the water-soluble binder (PEO) It can be considered that the compound has good affinity and can be uniformly mixed and applied. Since the oil-in-water dispersion can be handled as an aqueous solution, the handling becomes easy.
【００７０】実施例２と１０は、さらに内圧低減効果は
大きい。これは水中油滴型分散剤（界面活性剤）により
有機溶剤油滴の凝集が起こりにくいため、より均一に混
合、塗布することができるためと考えることができる。
実施例３〜８と１１〜１６は、ガス吸収触媒（カーボン
あるいはニッケル）を混合しているために、さらに内圧
低減効果は大きい。これはフッ素樹脂が均一に分散して
いるため、水素吸蔵合金とフッ素樹脂と触媒の接触面積
が増加するためと考えることができる。In the second and tenth embodiments, the effect of reducing the internal pressure is further increased. This can be considered because the oil-in-water type dispersant (surfactant) hardly causes the oil droplets of the organic solvent to agglomerate, so that they can be more uniformly mixed and applied.
In Examples 3 to 8 and 11 to 16, since the gas absorption catalyst (carbon or nickel) is mixed, the effect of reducing the internal pressure is further increased. This can be attributed to the fact that the fluororesin is uniformly dispersed, which increases the contact area between the hydrogen storage alloy, the fluororesin, and the catalyst.
【００７１】なお、実施例１７と実施例２との比較で分
かるように、水溶性結着剤（ＰＥＯ）を添加すると、内
圧低減効果が大きくなるということができる。これは、
フッ素樹脂分散液に水溶性結着剤（ＰＥＯ）を添加する
と、フッ素樹脂分散液の粘度が増大し、フッ素樹脂が負
極内部まで浸透しすぎることが抑制されるためと考える
ことができる。As can be seen from a comparison between Example 17 and Example 2, it can be said that the addition of a water-soluble binder (PEO) increases the effect of reducing the internal pressure. this is,
It can be considered that when the water-soluble binder (PEO) is added to the fluororesin dispersion, the viscosity of the fluororesin dispersion increases and the fluororesin is prevented from permeating too far into the negative electrode.
【００７２】なお、上述した実施形態においては、有機
溶剤としてシクロヘキサンを用いる例について説明した
が、有機溶剤としては、これ以外にシクロヘプタン、ヘ
プタン、トルエン、ヘキサン等を用いるようにしてもよ
い。In the above embodiment, an example in which cyclohexane is used as the organic solvent has been described. However, as the organic solvent, cycloheptane, heptane, toluene, hexane or the like may be used.
Claims (9)
めに添加するフッ素樹脂分散液であって、 有機溶剤中に均一に分散させたフッ素樹脂粉末と、 前記フッ素樹脂粉末が均一に分散した前記有機溶剤を均
一に分散させた水溶液とを含有することを特徴とするフ
ッ素樹脂分散液。1. A fluororesin dispersion added to impart water repellency to a hydrogen storage alloy electrode, wherein the fluororesin powder is uniformly dispersed in an organic solvent, and the fluororesin powder is uniformly dispersed. An aqueous solution in which the organic solvent is uniformly dispersed.
を特徴とする請求項１に記載のフッ素樹脂分散液。2. The fluororesin dispersion according to claim 1, wherein the aqueous solution contains a surfactant.
とを特徴とする請求項１または請求項２に記載のフッ素
樹脂分散液。3. The fluororesin dispersion according to claim 1, wherein the aqueous solution contains a water-soluble binder.
めに添加するフッ素樹脂分散液の製造方法であって、 有機溶剤中にフッ素樹脂粉末を分散させる工程と、 前記フッ素樹脂粉末を分散させた有機溶剤を水溶液に分
散させる工程とを備え、前記フッ素樹脂粉末を前記水溶
液に均一に分散させてフッ素樹脂分散液とすることを特
徴とするフッ素樹脂分散液の製造方法。4. A method for producing a fluororesin dispersion to be added for imparting water repellency to a hydrogen storage alloy electrode, comprising the steps of: dispersing a fluororesin powder in an organic solvent; Dispersing the organic solvent in an aqueous solution, wherein the fluororesin powder is uniformly dispersed in the aqueous solution to obtain a fluororesin dispersion.
を特徴とする請求項４に記載のフッ素樹脂分散液の製造
方法。5. The method according to claim 4, wherein a surfactant is added to the aqueous solution.
とを特徴とする請求項４または請求項５に記載のフッ素
樹脂分散液の製造方法。6. The process for producing a fluororesin dispersion according to claim 4, wherein a water-soluble binder is added to the aqueous solution.
混合して水素吸蔵合金電極に撥水性を付与する水素吸蔵
合金電極の製造方法であって、 フッ素樹脂粉末を均一に分散させた有機溶剤を水溶液に
均一に分散させてフッ素樹脂分散液とする分散工程と、 前記分散工程により得られたフッ素樹脂分散液と水素吸
蔵合金粉末と水溶性結着剤とを混練してスラリーとする
スラリー工程と、 前記スラリー工程により得られたスラリーを集電体に塗
着する塗着工程と、 前記塗着工程により集電体に塗着されたスラリーを乾燥
する乾燥工程と、 前記乾燥工程により乾燥された水素吸蔵電極を圧延する
圧延工程とを備えたことを特徴とする水素吸蔵合金電極
の製造方法。7. A method for producing a hydrogen-absorbing alloy electrode for imparting water repellency to a hydrogen-absorbing alloy electrode by mixing a fluororesin dispersion liquid with the hydrogen-absorbing alloy powder, comprising: an organic solvent in which the fluororesin powder is uniformly dispersed. Dispersing uniformly in an aqueous solution to obtain a fluororesin dispersion, and a slurry process of kneading the fluororesin dispersion obtained in the dispersion step, a hydrogen storage alloy powder, and a water-soluble binder to form a slurry An application step of applying the slurry obtained in the slurry step to the current collector; a drying step of drying the slurry applied to the current collector in the application step; and a drying step of drying in the drying step. And a rolling step of rolling the hydrogen storage electrode.
塗布して同水素吸蔵合金電極に撥水性を付与する水素吸
蔵合金電極の製造方法であって、 フッ素樹脂粉末を均一に分散させた有機溶剤を水溶液に
均一に分散させてフッ素樹脂分散液とする分散工程と、 水素吸蔵合金粉末と水溶性結着剤とを混練してスラリー
とするスラリー工程と、 前記スラリー工程により得られたスラリーを集電体に塗
着する塗着工程と、 前記塗着工程により集電体に塗着されたスラリー上に前
記分散工程により得られたフッ素樹脂分散液を塗着する
分散液塗着工程と、 前記スラリーおよび同スラリー上に塗着された前記フッ
素樹脂分散液を乾燥する乾燥工程と、 前記乾燥工程により乾燥された水素吸蔵電極を圧延する
圧延工程とを備えたことを特徴とする水素吸蔵合金電極
の製造方法。8. A method for producing a hydrogen storage alloy electrode in which a fluororesin dispersion liquid is applied to a hydrogen storage alloy electrode to impart water repellency to the hydrogen storage alloy electrode, the method comprising uniformly dispersing a fluororesin powder. A dispersion step of uniformly dispersing the solvent in the aqueous solution to obtain a fluororesin dispersion liquid; a slurry step of kneading the hydrogen storage alloy powder and the water-soluble binder to form a slurry; and a slurry obtained by the slurry step. A coating step of coating the current collector, and a dispersion liquid coating step of coating the fluororesin dispersion obtained in the dispersion step on the slurry coated on the current collector in the coating step, A hydrogen storage step, comprising: a drying step of drying the slurry and the fluororesin dispersion applied on the slurry; and a rolling step of rolling the hydrogen storage electrode dried in the drying step. Manufacturing method of alloy electrode.
添加したことを特徴とする請求項７または請求項８に記
載の水素吸蔵合金電極の製造方法。9. The method for producing a hydrogen storage alloy electrode according to claim 7, wherein a gas absorption catalyst is added to the fluororesin dispersion.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18285697A JP4179648B2 (en) | 1997-07-08 | 1997-07-08 | Polytetrafluoroethylene dispersion, method for producing the same, and method for producing a hydrogen storage alloy electrode using the dispersion |
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| Publication Number | Publication Date |
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Cited By (2)
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|---|---|---|---|---|
| JP2004327387A (en) * | 2003-04-28 | 2004-11-18 | Matsushita Electric Ind Co Ltd | Nickel-hydrogen storage battery and method for manufacturing negative electrode plate |
| JP2019175616A (en) * | 2018-03-27 | 2019-10-10 | Fdk株式会社 | Negative electrode for nickel hydrogen secondary battery, and nickel hydrogen secondary battery |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220158150A1 (en) * | 2020-11-13 | 2022-05-19 | Licap Technologies, Inc. | Dry electrode manufacture with composite binder |
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| JPH04249067A (en) * | 1991-01-31 | 1992-09-04 | Furukawa Battery Co Ltd:The | Manufacture of hydrogen storage electrode |
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| JPS62139255A (en) * | 1985-12-11 | 1987-06-22 | Matsushita Electric Ind Co Ltd | Manufacture of hydrogen absorbing electrode |
| JPS63195960A (en) * | 1987-02-09 | 1988-08-15 | Matsushita Electric Ind Co Ltd | Sealed alkaline storage battery |
| JPH04249067A (en) * | 1991-01-31 | 1992-09-04 | Furukawa Battery Co Ltd:The | Manufacture of hydrogen storage electrode |
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| JP2004327387A (en) * | 2003-04-28 | 2004-11-18 | Matsushita Electric Ind Co Ltd | Nickel-hydrogen storage battery and method for manufacturing negative electrode plate |
| JP4524998B2 (en) * | 2003-04-28 | 2010-08-18 | パナソニック株式会社 | Nickel-hydrogen storage battery |
| JP2019175616A (en) * | 2018-03-27 | 2019-10-10 | Fdk株式会社 | Negative electrode for nickel hydrogen secondary battery, and nickel hydrogen secondary battery |
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| Publication number | Publication date |
|---|---|
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