JP3177653B2 - Method for producing hydrogen storage electrode - Google Patents
Method for producing hydrogen storage electrodeInfo
- Publication number
- JP3177653B2 JP3177653B2 JP05544889A JP5544889A JP3177653B2 JP 3177653 B2 JP3177653 B2 JP 3177653B2 JP 05544889 A JP05544889 A JP 05544889A JP 5544889 A JP5544889 A JP 5544889A JP 3177653 B2 JP3177653 B2 JP 3177653B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- electrode
- paste
- storage alloy
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/242—Hydrogen storage electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、アルカリ電池に用いる水素吸蔵電極の製造
方法に関するものである。Description: TECHNICAL FIELD The present invention relates to a method for producing a hydrogen storage electrode used for an alkaline battery.
従来の技術とその課題 水素吸蔵電極は、水素を可逆的に吸蔵し放出する水素
吸蔵合金を電極に用いたものである。2. Description of the Related Art A conventional hydrogen storage electrode uses a hydrogen storage alloy that reversibly stores and releases hydrogen as an electrode.
水素吸蔵電極は、その作動電位がカドミウム電極とほ
ぼ等しく、しかも単位体積当りの放電容量がカドミウム
電極よりも著しく大きい。したがって、この電極をアル
カリ蓄電池の負極に用いる場合には、カドミウムを負極
に用いる場合とほぼ同じ電圧で作動し、しかも放電容量
がカドミウムを負極に用いる場合よりも著しく大きいア
ルカリ蓄電池が得られることが知られている。The working potential of the hydrogen storage electrode is almost equal to that of the cadmium electrode, and the discharge capacity per unit volume is significantly larger than that of the cadmium electrode. Therefore, when this electrode is used for the negative electrode of an alkaline storage battery, it is possible to obtain an alkaline storage battery that operates at substantially the same voltage as when cadmium is used for the negative electrode, and has a discharge capacity that is significantly larger than that when cadmium is used for the negative electrode. Are known.
この水素吸蔵電極は、従来は主として水素吸蔵合金と
金属とを焼結する方法および水素吸蔵合金と高分子結着
剤とを含むペーストを用いる方法で製作されていた。前
者の方法で製作された電極は、水素吸蔵合金と金属とが
強固に結合しているので、電極の強度が高いという点で
有利であるが、電極を製作する際に高温で長時間の焼結
を必要とする欠点がある。一方、ペーストを用いる後者
の方法（以下では、この方法を「ペースト式」と呼ぶ）
は、前者の方法と比較して短時間で電極を製作できる点
で有利である。Conventionally, this hydrogen storage electrode has been manufactured mainly by a method of sintering a hydrogen storage alloy and a metal and a method of using a paste containing a hydrogen storage alloy and a polymer binder. The electrode manufactured by the former method is advantageous in that the strength of the electrode is high because the hydrogen storage alloy and the metal are firmly bonded. There are drawbacks that require knotting. On the other hand, the latter method using a paste (hereinafter, this method is referred to as “paste method”)
Is advantageous in that an electrode can be manufactured in a short time as compared with the former method.
ペースト式の水素吸蔵電極の製造方法には次のものが
ある。There are the following methods for producing a paste-type hydrogen storage electrode.
すなわち、実公昭57−34678号公報に記載されるよう
に、水素吸蔵合金の粉末と耐アルカリ性の高分子結着剤
とを含むペースト状混合物を発泡メタルに充填する方法
である。この方法では、高分子結着剤として分散液の状
態のフッ素樹脂や溶液の状態のメチルセルロースを用い
ている。そして、ペーストを乾燥させて、これらの高分
子の結着力を発現させている。That is, as described in Japanese Utility Model Publication No. 57-34678, a foamed metal is filled with a paste-like mixture containing a powder of a hydrogen storage alloy and an alkali-resistant polymer binder. In this method, a fluororesin in a dispersion state or methylcellulose in a solution state is used as a polymer binder. Then, the paste is dried to express the binding force of these polymers.
発明者は、この方法で水素吸蔵合金の製作を試みた結
果、次のような欠点を見出だした。The inventor has attempted to produce a hydrogen storage alloy by this method, and as a result, has found the following disadvantages.
すなわち、フッ素樹脂を結着剤に用いる場合には、こ
のフッ素樹脂が混練によって繊維状に変形しやすいの
で、ペーストを混練している間にこの繊維がからみあっ
てペースト全体の粘度が高くなり、ペーストの粘度を調
節することが困難になってペーストの塗着量が不均一に
なるという不都合がある。さらにフッ素樹脂の繊維は、
ペーストを発泡ニッケルに充填する際に、発泡ニッケル
の多孔体を形成している骨格にからみつくので、発泡ニ
ッケルにペーストを充填することが困難になるという不
都合も生ずる。That is, when a fluororesin is used as the binder, the fluororesin is easily deformed into a fibrous shape by kneading, so that the fibers are entangled during kneading of the paste, and the viscosity of the entire paste increases, and the paste becomes It is difficult to adjust the viscosity of the paste, and there is an inconvenience that the amount of paste applied becomes uneven. In addition, fluororesin fibers
When the paste is filled in the foamed nickel, the skeleton forming the porous body of the foamed nickel is entangled with the paste, so that it becomes difficult to fill the foamed nickel with the paste.
また、メチルセルロースなどの水溶性高分子を結着剤
に用いる場合には、ペーストを乾燥する際に、この高分
子の被膜が水素吸蔵合金の表面に形成されて、水素吸蔵
合金とアルカリ電解液との接触が阻害される。その結
果、電極の充放電反応に関与しない水素吸蔵合金の量が
増加し、水素吸蔵電極の放電容量が減少するという不都
合がある。When a water-soluble polymer such as methylcellulose is used as the binder, when the paste is dried, a film of this polymer is formed on the surface of the hydrogen storage alloy, and the hydrogen storage alloy and the alkaline electrolyte are mixed together. Contact is inhibited. As a result, the amount of the hydrogen storage alloy that does not participate in the charge / discharge reaction of the electrode increases, and the discharge capacity of the hydrogen storage electrode decreases.
さらにこの方法では、ペースト状混合物を発泡メタル
に充填する際に、ペーストをゴムベラで練り込む必要が
あるので、電極の製作に煩雑な操作を必要とするという
欠点もある。Further, in this method, when the paste-like mixture is filled in the foamed metal, it is necessary to knead the paste with a rubber spatula.
課題を解決するための手段 本発明は、従来のペースト式水素吸蔵電極よりも簡単
な操作で製作できて、しかも水素吸蔵合金の重量の分布
が均一であり、さらに合金中の水素の放電が容易で放電
容量が大きいペースト式の水素吸蔵電極を得て、上述の
課題を解決しようとするものである。Means for Solving the Problems The present invention can be manufactured by a simpler operation than the conventional paste-type hydrogen storage electrode, and furthermore, the weight distribution of the hydrogen storage alloy is uniform, and the discharge of hydrogen in the alloy is easy. Thus, a paste-type hydrogen storage electrode having a large discharge capacity is obtained to solve the above-mentioned problem.
具体的に、本発明は、水素吸蔵合金の粉末と、混練時
に球状を保つ耐アルカリ性高分子の粒子を分散した高分
子ラテックスを含むペースト状混合物を導電性芯体に塗
布してから、塗布されたペースト状混合物を乾燥する水
素吸蔵電極の製造方法を提供する。Specifically, the present invention applies a paste-like mixture containing a powder of a hydrogen storage alloy and a polymer latex in which particles of an alkali-resistant polymer that maintains a spherical shape during kneading are applied to a conductive core, and then applied. To provide a method for producing a hydrogen storage electrode for drying a paste-like mixture.
また、本発明は、前記ペースト状混合物が、前記水素
吸蔵合金の粉末と前記高分子ラテックスのほかに、金属
または炭素質の耐アルカリ性導電性粉末を含む水素吸蔵
電極の製造方法を提供するものである。Further, the present invention provides a method for producing a hydrogen storage electrode, wherein the paste-like mixture contains, in addition to the powder of the hydrogen storage alloy and the polymer latex, a metal or carbonaceous alkali-resistant conductive powder. is there.
さらに、本発明は、前記塗布されたペースト状混合物
を乾燥する温度が、該ラテックスに含まれる耐アルカリ
性高分子の融点よりも低いことを特徴とする水素吸蔵電
極の製造方法を提供する。Further, the present invention provides a method for producing a hydrogen storage electrode, wherein a temperature at which the applied paste-like mixture is dried is lower than a melting point of an alkali-resistant polymer contained in the latex.
作用 高分子ラテックスとは、界面活性剤等を作用させてモ
ノマを水中に分散させ、このモノマを重合させて（この
反応は乳化重合と呼ばれる）得たもので、高分子の微粒
子が水に分散しているものである。乳化重合で得られる
高分子には、ポリエチレン，ポリ塩化ビニリデン，ポリ
塩化ビニル，ポリ酢酸ビニル，ポリエチレン，ポリプロ
ピレン，ポリメチルメタクリレート，ポリウレタン，ク
ロロプレン，ポリテトラフロロエチレン等のポリマや、
スチレン−ブタジエン共重合体，塩化ビニリデン−塩化
ビニル共重合体，アクリルニトリル−ブタンジエン共重
合体，アクリロニトリル−スチレン共重合体，塩化ビニ
ル−酢酸ビニル共重合体等のコポリマ等、きわめて多く
の種類がある。そして、これらの高分子ラテックスを構
成する粒子は、その粒径がサブミクロンというきわめて
小さいものを含んでいる。本発明は、以下に述べるよう
に、この高分子ラテックスの特徴を利用するものであ
る。Action Polymer latex is obtained by dispersing a monomer in water by the action of a surfactant or the like and polymerizing this monomer (this reaction is called emulsion polymerization). Is what you are doing. Polymers obtained by emulsion polymerization include polymers such as polyethylene, polyvinylidene chloride, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polymethyl methacrylate, polyurethane, chloroprene, and polytetrafluoroethylene.
There are very many types such as copolymers such as styrene-butadiene copolymer, vinylidene chloride-vinyl chloride copolymer, acrylonitrile-butanediene copolymer, acrylonitrile-styrene copolymer, and vinyl chloride-vinyl acetate copolymer. . The particles constituting these polymer latexes include those having an extremely small particle diameter of submicron. The present invention utilizes the characteristics of the polymer latex as described below.
発明者は、この高分子ラテックスについて次のことを
見出した。すなわち、この高分子ラテックスを水素吸蔵
合金の粉末と混合してペースト状混合物を作り、これを
乾燥すると、乾燥の進行にともなって、水素吸蔵合金と
ラテックス粒子との間隙の水が失われていく。この乾燥
過程の途中でラテックスを構成する粒子や水素吸蔵合金
の粒子の間隙に水が残留している状態では、この水の大
きい毛管力が作用する。したがって、水素吸蔵合金の粒
子間に介在するラテックス粒子は、乾燥温度がラテック
スの高分子の融点よりもはるかに低い場合にも著しく圧
縮されて変形する。その結果、ラテックス粒子は、水素
吸蔵合金粒子間の強固な結着剤としての作用が発現す
る。The inventor has found the following about this polymer latex. That is, the polymer latex is mixed with the powder of the hydrogen storage alloy to form a paste-like mixture, and when this is dried, water in the gap between the hydrogen storage alloy and the latex particles is lost as the drying proceeds. . If water remains in the gaps between the particles constituting the latex and the particles of the hydrogen storage alloy during the drying process, a large capillary force of the water acts. Therefore, the latex particles interposed between the particles of the hydrogen storage alloy are significantly compressed and deformed even when the drying temperature is much lower than the melting point of the polymer of the latex. As a result, the latex particles exhibit a function as a strong binder between the hydrogen storage alloy particles.
本発明では、この現象を利用して水素吸蔵電極を得て
いる。すなわち、水素吸蔵合金の粉末と、耐アルカリ性
高分子の微粒子を分散した高分子ラテックスとを含むペ
ースト状混合物を、ニッケルメッキを施した穿孔を有す
る鋼板や、金属ニッケル製のエクスパンデッドメタルや
三次元多孔体等のような耐アルカリ性導電性芯体に塗着
し、その塗着物を乾燥する。このようにすると、単にペ
ースト状混合物を導電性芯体に塗着して乾燥するという
きわめて簡単な操作で、強度が高い水素吸蔵電極が得ら
れるのである。したがって、本発明によれば、従来のペ
ースト式の電極のように発泡ニッケルの三次元的な骨格
によって活物質を支持することもなく、強度が高い電極
が得られる。もちろん、本発明において、三次元的な骨
格を導電性芯体とする場合には、電極の強度が一層高く
なる。In the present invention, a hydrogen storage electrode is obtained by utilizing this phenomenon. That is, a paste-like mixture containing a powder of a hydrogen storage alloy and a polymer latex in which fine particles of an alkali-resistant polymer are dispersed is applied to a steel plate having perforations plated with nickel, an expanded metal made of nickel metal, or a tertiary metal. It is applied to an alkali-resistant conductive core such as an original porous body, and the applied material is dried. By doing so, a highly-stable hydrogen storage electrode can be obtained by a very simple operation of simply applying the paste-like mixture to the conductive core and drying. Therefore, according to the present invention, an electrode having high strength can be obtained without supporting an active material by a three-dimensional skeleton of foamed nickel unlike a conventional paste-type electrode. Of course, in the present invention, when the three-dimensional skeleton is a conductive core, the strength of the electrode is further increased.
さらに、本発明では、ペースト状混合物を高分子の融
点よりも低い温度で乾燥する。その理由は次の通りであ
る。すなわち、温度が高分子の融点よりも高くなると、
高分子が流動して、高分子の被膜が水素吸蔵合金の表面
に形成され、水素吸蔵合金とアルカリ電解液との接触が
阻害されて、充放電に関与する水素吸蔵合金の量が減少
し、電極の放電容量が減少するという不都合が生ずるこ
とがある。しかし、該高分子の融点よりも低い温度で乾
燥するという本発明の手段を採用すると、高分子の被膜
が形成されにくくなるので、このような不都合が取り除
かれるという作用がある。Furthermore, in the present invention, the paste mixture is dried at a temperature lower than the melting point of the polymer. The reason is as follows. That is, when the temperature is higher than the melting point of the polymer,
The polymer flows, a polymer film is formed on the surface of the hydrogen storage alloy, the contact between the hydrogen storage alloy and the alkaline electrolyte is inhibited, and the amount of the hydrogen storage alloy involved in charge and discharge decreases, In some cases, the discharge capacity of the electrode may be reduced. However, when the means of the present invention of drying at a temperature lower than the melting point of the polymer is employed, it is difficult to form a polymer film, so that such an inconvenience is eliminated.
また、本発明では、高分子ラテックスとしてポリエチ
レン，ポリ塩化ビニリデン，ポリ塩化ビニル，ポリ酢酸
ビニル，ポリエチレン，ポリプロピレン，ポリメチルメ
タクリレート，クロロプレン等のポリマや、スチレン−
ブタジエン共重合体，塩化ビニリデン−塩化ビニル共重
合体，アクリルニトリル−ブタジエン共重合体，アクリ
ロニトリル−スチレン共重合体等のコポリマのように、
ペーストを混練してこれを調製する際に、球状を保って
繊維化しにくい耐アルカリ性高分子を分散したものを用
いる。そして、ポリテトラフロロエチレン等のフッ素樹
脂のように混練によって容易に繊維化する高分子を分散
したラテックスを、ペーストの粘度が安定しないほど多
量には用いない。したがって、本発明では、ペーストを
混練する際にラテックス粒子が繊維化することがなく、
安定したペーストの粘度が得られるので、前述の不都合
が生ずることがなくなり、安定した作業条件が得られる
点で有利である。In the present invention, polymers such as polyethylene, polyvinylidene chloride, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polymethyl methacrylate, and chloroprene, and styrene-
Like copolymers such as butadiene copolymer, vinylidene chloride-vinyl chloride copolymer, acrylonitrile-butadiene copolymer, and acrylonitrile-styrene copolymer,
When preparing the paste by kneading the paste, a paste in which an alkali-resistant polymer which maintains a spherical shape and is hard to fibrillate is dispersed is used. Then, a latex in which a polymer that easily becomes a fiber by kneading such as a fluororesin such as polytetrafluoroethylene is dispersed is not used in such a large amount that the viscosity of the paste becomes unstable. Therefore, in the present invention, when kneading the paste, latex particles do not fibrillate,
Since a stable viscosity of the paste is obtained, the above-described disadvantages do not occur, which is advantageous in that stable working conditions can be obtained.
さらに本発明では、ペースト状混合物に金属または炭
素質の耐アルカリ性導電性粉末を添加する。その目的
は、電極の水素吸蔵合金粉末と導電性芯体との導電性を
良好にして、水素吸蔵合金の水素化物の放電を容易にす
ることにある。すなわち、発明者は、耐アルカリ性の導
電性粉末の添加量を変えて、水素吸蔵電極を本発明の方
法で製作し、この電極をアルカリ電解液中で充放電した
結果、導電性粉末を添加しない場合には、この電極を充
電することは容易であるが、放電することは極めて困難
な場合があることを見出した。Further, in the present invention, a metal or carbonaceous alkali-resistant conductive powder is added to the paste mixture. It is an object of the present invention to improve the conductivity between the hydrogen storage alloy powder of the electrode and the conductive core, thereby facilitating the discharge of the hydride of the hydrogen storage alloy. That is, the inventor changed the addition amount of the alkali-resistant conductive powder, produced a hydrogen storage electrode by the method of the present invention, and charged and discharged this electrode in an alkaline electrolyte. In this case, it has been found that it is easy to charge this electrode, but it is extremely difficult to discharge it.
このような現象が生ずる理由は定かではないが、次の
ように考えられる。すなわち、水素吸蔵合金は放電状態
では金属であるので、電子伝導性がきわめて良好である
から、導電性の粉末を用いなくとも容易に充電できる。
しかし重電が進行すると、電子伝導性に劣る金属水酸化
物のような腐食生成物が生成する。次に、放電する場合
には、導電性粉末を用いない場合には、充電生成物であ
る金属水素化物粉末間の金属水酸化物のような腐食生成
物の電気抵抗が大きいので、導電性芯体から遠い位置に
ある金属水素化物の集電が困難になって、電極の放電が
困難になる。一方、導電性粉末を用いる場合には、金属
水素化物の集電性が良好になって、電極の放電が容易に
なる。本発明の方法では、３次元のネットワークを形成
しないパンチングメタルやエキスパンデッドメタルを導
電性芯体に用いるので、耐アルカリ性の導電性粉末を用
いることによって、電極の放電が可能になる。なお、発
泡ニッケルに水素吸蔵合金を充填する従来の電極の場合
には、その骨格は３次元の集電体ネットワークとして作
用するので、導電性粉末は必ずしも用いる必要はない
が、前述のような電極の制作に煩雑な操作を必要とする
という問題が解決しない。The reason why such a phenomenon occurs is not clear, but is considered as follows. That is, since the hydrogen storage alloy is a metal in a discharged state, it has very good electron conductivity, and can be easily charged without using a conductive powder.
However, as heavy electricity progresses, corrosion products such as metal hydroxides with poor electron conductivity are generated. Next, in the case of discharging, when the conductive powder is not used, since the electric resistance of a corrosion product such as a metal hydroxide between metal hydride powders as a charge product is large, the conductive core is not used. It becomes difficult to collect the metal hydride located far from the body, and it becomes difficult to discharge the electrode. On the other hand, when the conductive powder is used, the current collecting property of the metal hydride is improved, and the discharge of the electrode is facilitated. In the method of the present invention, since a punching metal or an expanded metal that does not form a three-dimensional network is used for the conductive core, the electrode can be discharged by using an alkali-resistant conductive powder. In the case of a conventional electrode in which foamed nickel is filled with a hydrogen storage alloy, since the skeleton acts as a three-dimensional current collector network, it is not necessary to use conductive powder. The problem that complicated operations are required for the production of an image cannot be solved.
実施例 以下、本発明を好適な実施例を用いて詳細に説明す
る。Examples Hereinafter, the present invention will be described in detail using preferred examples.
〈実験１〉 まず、ペーストを混練する際に球状を保つ耐アルカリ
性高分子の粒子を分散した高分子ラテックスを用いる本
発明の水素吸蔵電極と、混練時に球状を保つことなく繊
維化する高分子の粒子を分散した高分子ラテックスを用
いる比較例の水素吸蔵電極および水溶性高分子を結着剤
に用いる比較例の水素吸蔵電極を製作した例を示して、
本発明による水素吸蔵電極の優位性を具体的に説明す
る。<Experiment 1> First, a hydrogen storage electrode of the present invention using a polymer latex in which particles of an alkali-resistant polymer that maintains a spherical shape during kneading of a paste and a polymer that forms fibers without maintaining a spherical shape during kneading. Examples of producing a hydrogen storage electrode of a comparative example using a polymer latex in which particles are dispersed and a hydrogen storage electrode of a comparative example using a water-soluble polymer as a binder are shown.
The superiority of the hydrogen storage electrode according to the present invention will be specifically described.
［水素吸蔵電極Ａ］（本発明実施例） 本発明による水素吸蔵電極Ａを次のようにして製作し
た。[Hydrogen storage electrode A] (Example of the present invention) A hydrogen storage electrode A according to the present invention was manufactured as follows.
水素吸蔵合金は、金属チタン粉末および金属ニッケル
粉末を原子比で2:1の割合で混合し、アルゴ雰囲気のア
ーク溶解炉を用いてこの混合物を溶解して製作した。溶
解して得た合金塊は、その組成を均一にするために、冷
却した後に裏返して再度溶解するという操作を３回繰り
返した。次に、このようにして得られた金属間化合物Ti
2Niの合金塊を、超硬合金製の乳鉢で粉砕した。そし
て、100メッシュの篩を通過したこの水素吸蔵合金粉末1
00重量部と人造黒鉛粉末（LONZA社製，商品名:LN50−20
0）20重量部とを混合し、この混合物に水を加えてよく
混練した。そして混練時に球状を保つ耐アルカリ性高分
子の粉末を分散した高分子ラテックスとしてポリエチレ
ン樹脂（融点110℃）の微粒子が分散した高分子ラテッ
クス（三洋化成（株）製，商品名：パーマリンPN）を用
い、このラテックス20重量部を加えて混練し、ペースト
状の混練物を得た。そして、この混合物を、穿孔を有す
る厚さ0.09mmの鋼板に厚さ20ミクロンのニッケルメッキ
を施した導電性芯体に塗着し、ドクターブレードで塗着
物の厚さを調節した。次に、75℃の熱風を用いてこの塗
着物を乾燥した。そして、室温でロールでプレスして電
極の厚さを約0.7mmに調節し、40mm×40mmの大きさに切
断して水素吸蔵電極を得た。The hydrogen storage alloy was produced by mixing metal titanium powder and metal nickel powder at an atomic ratio of 2: 1 and melting the mixture using an arc melting furnace in an algo atmosphere. The operation of cooling, turning over, and re-melting the alloy ingot obtained by melting was repeated three times in order to make the composition uniform. Next, the thus obtained intermetallic compound Ti
A 2Ni alloy lump was pulverized with a cemented carbide mortar. Then, this hydrogen storage alloy powder 1 passed through a 100 mesh sieve
00 parts by weight and artificial graphite powder (manufactured by LONZA, trade name: LN50-20
0) and 20 parts by weight, and water was added to the mixture and kneaded well. A polymer latex (trade name: Permarine PN, manufactured by Sanyo Chemical Co., Ltd.) in which fine particles of a polyethylene resin (melting point: 110 ° C.) are dispersed as a polymer latex in which alkali-resistant polymer powder that maintains a spherical shape during kneading is dispersed. Then, 20 parts by weight of this latex was added and kneaded to obtain a paste-like kneaded product. Then, this mixture was applied to a 20 μm-thick nickel-plated conductive core having a perforated steel plate having a thickness of 0.09 mm, and the thickness of the applied material was adjusted with a doctor blade. Next, the coated product was dried using hot air at 75 ° C. Then, the thickness of the electrode was adjusted to about 0.7 mm by pressing with a roll at room temperature, and the electrode was cut into a size of 40 mm × 40 mm to obtain a hydrogen storage electrode.
［水素吸蔵電極Ｂ］（比較例） 本発明による水素吸蔵電極Ａにおけるポリエチレン樹
脂の微粒子が分散している高分子ラテックスの代わり
に、混練時に繊維化する高分子であるポリテトラフロロ
エチレンの微粒子が分散している高分子ラテックス（ダ
イキン（株）製，商品名：ポリフロンディスパージョン
Ｄ−１）を用いたほかは、本発明による水素吸蔵電極Ａ
と同様の条件で比較例の水素吸蔵電極Ｂを製作した。[Hydrogen Storage Electrode B] (Comparative Example) In place of the polymer latex in which the fine particles of the polyethylene resin are dispersed in the hydrogen storage electrode A according to the present invention, the fine particles of polytetrafluoroethylene, which is a polymer that becomes a fiber during kneading, are used. A hydrogen storage electrode A according to the present invention was used, except that a dispersed polymer latex (trade name: Polyflon Dispersion D-1 manufactured by Daikin Co., Ltd.) was used.
The hydrogen storage electrode B of the comparative example was manufactured under the same conditions as described above.
［水素吸蔵電極Ｃ］（比較例） 本発明による水素吸蔵電極Ａにおいてポリエチレン樹
脂の微粒子が分散している高分子ラテックス20重量部を
加えて混練する代りに、水溶性高分子であるメチルセル
ロース（信越化学（株）製，商品名：メトロースSM−40
00）10重量部を加え、これを混合して分散させてから、
70℃に昇温してメチルセルロースを溶解させた後に室温
に冷却して、ペースト状混合物を得た。そして、そのほ
かの条件を本発明による水素吸蔵電極Ａと同様にして比
較例の水素吸蔵電極Ｃを製作した。[Hydrogen Storage Electrode C] (Comparative Example) Instead of adding and kneading 20 parts by weight of a polymer latex in which fine particles of a polyethylene resin are dispersed in the hydrogen storage electrode A according to the present invention, methyl cellulose (Shin-Etsu) which is a water-soluble polymer is used. Chemical name: Metroose SM-40
00) Add 10 parts by weight, mix and disperse,
After the temperature was raised to 70 ° C. to dissolve methyl cellulose, the mixture was cooled to room temperature to obtain a paste-like mixture. Then, a hydrogen storage electrode C of a comparative example was manufactured under the same conditions as those of the hydrogen storage electrode A according to the present invention.
これらの電極１枚に含まれる水素吸蔵合金の平均値お
よび標準偏差を第１表に示す。Table 1 shows the average value and standard deviation of the hydrogen storage alloy contained in one of these electrodes.
第１表から、本発明による水素吸蔵電極Ａおよび比較
例の水素吸蔵電極Ｃに含まれる水素吸蔵合 金の重量の標準偏差は、比較例の水素吸蔵電極Ｂよりも
著しく小さいので、これらの電極ＡおよびＣに含まれる
水素吸蔵合金の重量の分布は、電極Ｂよりも均一である
ことがわかる。Table 1 shows that the hydrogen storage electrodes included in the hydrogen storage electrode A according to the present invention and the hydrogen storage electrode C of the comparative example are included. Since the standard deviation of the weight of gold is significantly smaller than that of the hydrogen storage electrode B of the comparative example, it can be seen that the distribution of the weight of the hydrogen storage alloy contained in these electrodes A and C is more uniform than that of the electrode B.
次に、上述の水素吸蔵電極A,BおよびＣのそれぞれ１
枚を負極に用い、焼結式の水酸化ニッケル電極２枚を正
極に用いて、電池の放電が負極の容量で制限される３種
類のアルカリ蓄電池を製作した。そして、水素吸蔵電極
に用いる結着剤の種類が、電池を構成した状態における
負極の放電性能に及ぼす影響を調べた。Next, each of the hydrogen storage electrodes A, B, and C
Three types of alkaline storage batteries in which the discharge of the battery was limited by the capacity of the negative electrode were manufactured using the negative electrode as the negative electrode and two sintered nickel hydroxide electrodes as the positive electrode. Then, the effect of the type of the binder used for the hydrogen storage electrode on the discharge performance of the negative electrode in a state where the battery was configured was examined.
負極には、上述の３種類のどの電極の場合にも、約5.
2gの水素吸蔵合金を含む電極を選んだ。For the negative electrode, about 5.
An electrode containing 2 g of hydrogen storage alloy was selected.
正極の水酸化ニッケル電極は、次のようにして製作し
た。The nickel hydroxide electrode of the positive electrode was manufactured as follows.
すなわち、多孔度が約85％の焼結ニッケル基板を用
い、通常の減圧含浸法で減圧含浸を６回繰り返して、水
酸化ニッケルと水酸化コバルトとをこの焼結基板の細孔
中に共沈させて、焼結式水酸化ニッケル電極を製作し
た。この電極の大きさは、40mm×40mm×0.85mmであり、
この電極１枚に充填されている水酸化ニッケルおよび水
酸化コバルトの合計の量は、2.4gであった。また水酸化
コバルトの含有量は、水酸化ニッケルと水酸化コバルト
との合計の量に対するモル比で約95％であった。That is, using a sintered nickel substrate having a porosity of about 85%, vacuum impregnation is repeated six times by a normal vacuum impregnation method, and nickel hydroxide and cobalt hydroxide are coprecipitated in the pores of the sintered substrate. Thus, a sintered nickel hydroxide electrode was manufactured. The size of this electrode is 40mm x 40mm x 0.85mm,
The total amount of nickel hydroxide and cobalt hydroxide filled in one electrode was 2.4 g. Further, the content of cobalt hydroxide was about 95% by a molar ratio to the total amount of nickel hydroxide and cobalt hydroxide.
次に、水素吸蔵電極１枚を負極とし、水酸化ニッケル
電極２枚を正極とし、ナイロン製の不織布をセパレータ
として、5.8M KOH電解液を大量に用いて開放形に構成し
たいゆるフラッデッドタイプの試験用電池を製作した。
この電池に用いている正極の放電容量は、放電が１電子
反応過程に従う場合に、1.39Ahである。電槽は、寸法が
45×45×3mmのアクリル樹脂製のものを用いた。Next, a flooding type of open type using a large amount of 5.8M KOH electrolyte, using one hydrogen storage electrode as a negative electrode, two nickel hydroxide electrodes as a positive electrode, a nonwoven fabric made of nylon as a separator, and a large amount of 5.8M KOH electrolyte. A test battery was manufactured.
The discharge capacity of the positive electrode used in this battery is 1.39 Ah when the discharge follows a one-electron reaction process. The battery case has dimensions
A 45 × 45 × 3 mm acrylic resin was used.
このようにして本発明による水素吸蔵電極A,比較例の
水素吸蔵電極ＢおよびＣを用いて製作した電池を、それ
ぞれ電池A,B,Cと呼ぶ。The batteries manufactured using the hydrogen storage electrode A according to the present invention and the hydrogen storage electrodes B and C of the comparative examples are referred to as batteries A, B, and C, respectively.
これらの電池を25℃において、0.085Aの電流で20時間
充電し、0.085Aの電流で1.0Vまで放電するという条件で
充放電試験を行なった場合の３サイクル目の放電容量を
第２表に示す。Table 2 shows the discharge capacity at the third cycle when these batteries were charged at 25 ° C with a current of 0.085 A for 20 hours and discharged at a current of 0.085 A to 1.0 V under the condition that they were discharged. Show.
第２表から、電池Ａおよび電池Ｂの放電容量は、電池
Ｃよりも著しく大きいことがわかる。 From Table 2, it can be seen that the discharge capacities of Battery A and Battery B are significantly larger than Battery C.
これらの試験結果から、混練時に球状を保つ耐アルカ
リ性高分子の粒子を分散した高分子ラテックスを用いる
本発明の場合には、混練時に繊維化する高分子の粒子を
分散した高分子ラテックスを用いる場合や水溶性高分子
を用いる場合と比較して、電極に含まれる水素吸蔵合金
の重量分布が均一で、しかも放電容量が大きいという２
つの特徴を兼ね備える水素吸蔵電極が得られることが明
らかである。From these test results, in the case of the present invention using a polymer latex in which particles of an alkali-resistant polymer that maintains a spherical shape during kneading are used, in the case of using a polymer latex in which particles of a polymer that forms fibers during kneading are used. In comparison with the case where a water-soluble polymer is used, the weight distribution of the hydrogen storage alloy contained in the electrode is uniform and the discharge capacity is large.
It is clear that a hydrogen storage electrode having both features can be obtained.
〈実験２〉 次に、金属または炭素質の耐アルカリ性の導電性粉末
の添加量を変えて試験した結果を示して、これらの導電
性粉末を添加することが、水素吸蔵合金粉末の種類によ
っては本発明の効果を一層発揮させるための構成要件と
なることを説明する。<Experiment 2> Next, the results of tests conducted by changing the amount of addition of the metal or carbonaceous alkali-resistant conductive powder are shown. The addition of these conductive powders depends on the type of the hydrogen storage alloy powder. The fact that the present invention is a component for further exerting the effects of the present invention will be described.
水素吸蔵電極は次のようにして製作した。すなわち、
水素吸蔵合金として、実験１におけるTi2Niの代りにLaN
i2.5Co2.5を用いた。そして、耐アルカリ性の導電性粉
末として、カーボニルニッケル粉末（INCO社製，商品
名:Type255）または人造黒鉛粉末（LONZA社製，商品名:
LN50−200）を用い、水素吸蔵合金と耐アルカリ性の導
電性粉末との合計を110重量部の一定値にしながら、水
素吸蔵合金粉末と導電性粉末との混合比を広い範囲で変
えた。そして、混練時に球状を保つ耐アルカリ性高分子
の粒子を分散した高分子ラテックスとして、アクリルニ
トリル−スチレン共重合体の微粒子が分散している高分
子ラテックス（旭化成（株）性，商品名：ポリトロンＡ
−65）を用いた。そのほかの条件は、実験１における本
発明の水素吸蔵電極Ａと同じにした。ここで、導電性粉
末としてカーボニルニッケル粉末および人造黒鉛粉末を
用いる電極をそれぞれ電極Ｄおよび電極Ｅと呼ぶ。The hydrogen storage electrode was manufactured as follows. That is,
As a hydrogen storage alloy, LaN was used instead of Ti 2 Ni in Experiment 1.
i 2.5 Co 2.5 was used. And, as the alkali-resistant conductive powder, carbonyl nickel powder (manufactured by INCO, trade name: Type 255) or artificial graphite powder (manufactured by LONZA, trade name:
Using LN50-200), the mixing ratio of the hydrogen storage alloy powder and the conductive powder was varied over a wide range while the total amount of the hydrogen storage alloy and the alkali-resistant conductive powder was kept at a constant value of 110 parts by weight. As a polymer latex in which alkali-resistant polymer particles that maintain a spherical shape during kneading are dispersed, a polymer latex in which fine particles of an acrylonitrile-styrene copolymer are dispersed (Asahi Kasei Corporation, trade name: Polytron A)
−65) was used. Other conditions were the same as those of the hydrogen storage electrode A of the present invention in Experiment 1. Here, electrodes using carbonyl nickel powder and artificial graphite powder as the conductive powder are referred to as electrodes D and E, respectively.
そして、これらの電極を負極として用いる他は、実験
１における電池Ａと同じ構成にして、試験用の電池を製
作した。電極Ｄを用いた電池を電池Ｄ、電極Ｅを用いた
電池を電池Ｅと呼ぶ。Then, a test battery was manufactured in the same configuration as the battery A in Experiment 1 except that these electrodes were used as the negative electrodes. A battery using the electrode D is called a battery D, and a battery using the electrode E is called a battery E.
これらの電池を用いて、実験１と同じ通電条件の充放
電サイクル試験を行ない、10サイクル目の放電容量を測
定した。また、10サイクル目の放電されることなく水素
吸蔵合金に残留している水素の量を測定した。その結果
を第１図に示す。Using these batteries, a charge / discharge cycle test under the same energizing conditions as in Experiment 1 was performed, and the discharge capacity at the 10th cycle was measured. Further, the amount of hydrogen remaining in the hydrogen storage alloy without being discharged in the tenth cycle was measured. The result is shown in FIG.
第１図において、曲線（ア）および（イ）は、それぞ
れ水素吸蔵合金粉末と導電性粉末との混合比を変えた場
合の電池ＤおよびＥの放電容量と負極の水素吸蔵合金の
重量との比と、水素吸蔵合金と導電性粉末との合計に対
する導電性粉末の重量比との関係を表す。そして曲線
（ウ）および（エ）は、それぞれ電池ＤおよびＥの負極
の水素吸蔵合金に含まれる未放電の水素の量を放電容量
に換算した値と負極の水素吸蔵合金の重量との比と、水
素吸蔵合金と導電性粉末との合計に対する導電性粉末の
重量比との関係を表す。In FIG. 1, curves (A) and (A) show the relationship between the discharge capacities of the batteries D and E and the weight of the hydrogen storage alloy of the negative electrode when the mixing ratio of the hydrogen storage alloy powder and the conductive powder was changed, respectively. It shows the relationship between the ratio and the weight ratio of the conductive powder to the total of the hydrogen storage alloy and the conductive powder. Curves (c) and (d) show the ratio between the value obtained by converting the amount of undischarged hydrogen contained in the hydrogen storage alloy of the negative electrode of batteries D and E into the discharge capacity and the weight of the hydrogen storage alloy of the negative electrode, respectively. And the weight ratio of the conductive powder to the total of the hydrogen storage alloy and the conductive powder.
第１図の曲線（ア）および（イ）から、電池Ｄおよび
Ｅのいずれにおいても、導電性粉末を添加しない場合に
は、電池がほとんど放電できないことがわかる。そし
て、電池の放電容量と水素吸蔵合金の重量との比は、導
電性粉末の添加量が少ない場合には、添加量の増加にと
もなって大きくなり、導電性粉末の添加量が水素吸蔵合
金の量と同程度よりも大きくなると、ほぼ一定になるこ
とがわかる。From the curves (A) and (A) in FIG. 1, it can be seen that in each of the batteries D and E, the battery can hardly be discharged when the conductive powder is not added. When the amount of the conductive powder is small, the ratio between the discharge capacity of the battery and the weight of the hydrogen storage alloy increases with an increase in the amount of the conductive powder. It can be seen that when the amount is larger than the same amount, it becomes almost constant.
そして曲線（ア），（イ），（ウ）および（エ）を合
わせて考えると、導電性粉末を添加しない場合に水素吸
蔵合金が放電できない現象および導電性粉末の添加量が
少ない場合に水素吸蔵合金の放電容量が小さい現象の主
たる原因は、放電が困難な水素が水素吸蔵合金に残留し
ていることにあることがわかる。Considering the curves (a), (a), (c) and (d) together, the phenomenon that the hydrogen storage alloy cannot be discharged when the conductive powder is not added, and that the hydrogen storage alloy does not discharge when the conductive powder is added in a small amount. It can be understood that the main cause of the phenomenon that the discharge capacity of the storage alloy is small is that hydrogen that is difficult to discharge remains in the hydrogen storage alloy.
したがって、本発明においては、ニッケルや黒鉛のよ
うに金属または炭素質の耐アルカリ性導電性粉末を添加
すると、高い放電容量が得られることが明らかである。Therefore, in the present invention, it is clear that a high discharge capacity can be obtained by adding a metal or carbonaceous alkali-resistant conductive powder such as nickel or graphite.
〈実験３〉 最後に、ペースト状混合物の乾燥温度を変えた場合の
水素吸蔵電極の放電性能を示して、ペースト状混合物の
乾燥温度を耐アルカリ性高分子の融点よりも低くするこ
とが、水素吸蔵合金粉末の種類によっては本発明の効果
を一層高めるための構成要件となることを説明する。<Experiment 3> Finally, the discharge performance of the hydrogen storage electrode when the drying temperature of the paste-like mixture was changed was shown, and it was found that the drying temperature of the paste-like mixture was lower than the melting point of the alkali-resistant polymer. It will be explained that depending on the type of the alloy powder, it is a constituent element for further enhancing the effect of the present invention.
負極板は、実験２における電極Ｄにおいて、混合時に
球状を保つ耐アルカリ性高分子としてポリエチレン（融
点110℃）の粒子を分散した前述の高分子ラテックス
（三洋化成（株）性，商品名：パーマリンPN）を用い、
水素吸蔵合金100重量部を用い、カーボニルニッケル粉
末40重量部を用いて、乾燥の温度を60℃から160℃の範
囲で変えたほかは、条件を電極Ｄと同様にした水素吸蔵
電極Ｆを製作した。The negative electrode plate was the same as the electrode latex in Experiment 2 except that particles of polyethylene (melting point: 110 ° C.) were dispersed as an alkali-resistant polymer that maintains a spherical shape during mixing (Sanyo Chemical Co., Ltd., trade name: Permarin PN) )
Using hydrogen storage alloy 100 parts by weight and carbonyl nickel powder 40 parts by weight, the hydrogen storage electrode F was manufactured under the same conditions as the electrode D except that the drying temperature was changed in the range of 60 ° C to 160 ° C. did.
次に、電極Ｆを用いるほかは、条件を実験１の電池Ａ
と同じにした電池Ｆを製作した。そして、実験１と同じ
通電条件で充放電サイクル試験を行ない、10サイクル目
の放電容量を調べた。Next, except that the electrode F was used, the conditions of the battery
Battery F was manufactured in the same manner as described above. Then, a charge / discharge cycle test was performed under the same energizing conditions as in Experiment 1, and the discharge capacity at the 10th cycle was examined.
この場合の放電容量とペースト状混合物の乾燥温度と
の関係を第２図に示す。第２図から、乾燥温度がラテッ
クスに含まれる高分子の融点110℃よりも低い場合に放
電容量が低下しないという特徴があることがわかる。FIG. 2 shows the relationship between the discharge capacity and the drying temperature of the paste mixture in this case. FIG. 2 shows that the discharge capacity does not decrease when the drying temperature is lower than the melting point of the polymer contained in the latex, 110 ° C.
なお、融点が異なるそのほかの高分子を用いる場合に
も、同様にその高分子の融点よりも低い温度で乾燥する
ことが適していることがわかった。In addition, it has been found that when other polymers having different melting points are used, drying at a temperature lower than the melting point of the polymers is also suitable.
なお、以上の実施例における実験１〜３は、フラッデ
ッドタイプの試験用電池の場合について説明している
が、以上の説明から明らかなとおり、本発明によれば、
フラッデッドタイプだけではなく、電解液量を少なくし
た密閉形の電池においても、同様の作用効果が得られる
ものであり、本発明の範囲が、上記の具体的実施例に限
定されないことは言うまでもない。In Experiments 1 to 3 in the above examples, the case of a flooded type test battery was described. As is clear from the above description, according to the present invention,
Not only the flooded type but also a sealed battery having a reduced amount of electrolyte can provide the same function and effect, and it goes without saying that the scope of the present invention is not limited to the above specific examples. .
発明の効果 以上述べたように、本発明により、従来のペースト式
水素吸蔵電極よりも簡単な操作で製造でき、しかも水素
吸蔵合金の重量の分布が均一であり、さらに合金中の水
素の放電が容易で放電容量が大きいという効果を兼ね備
えた水素吸蔵電極を得ることができる。Effects of the Invention As described above, according to the present invention, it is possible to manufacture the electrode by a simpler operation than the conventional paste-type hydrogen storage electrode, and furthermore, the weight distribution of the hydrogen storage alloy is uniform, and the discharge of hydrogen in the alloy is reduced. It is possible to obtain a hydrogen storage electrode which has an effect of being easy and having a large discharge capacity.
第１図は、水素吸蔵電極を負極に用いるアルカリ電池の
放電容量および未放電の水素に対する容量と水素吸蔵合
金の重量との比と、水素吸蔵合金と導電性粉末との合計
に対する導電性粉末の重量比との関係を表す図である。
同図中（ア）および（イ）は、実際に放電した容量を表
し、（ウ）および（エ）は、未放電の水素の容量を表
す。 第２図は、水素吸蔵電極を負極に用いるアルカリ蓄電池
の放電容量と水素吸蔵合金の重量との比と、ペースト状
混合物の乾燥温度との関係を示した図である。FIG. 1 shows the discharge capacity of an alkaline battery using a hydrogen storage electrode as a negative electrode, the ratio of the capacity to undischarged hydrogen and the weight of the hydrogen storage alloy, and the ratio of the conductive powder to the total of the hydrogen storage alloy and the conductive powder. It is a figure showing the relationship with a weight ratio.
In the figure, (a) and (a) represent the actually discharged capacity, and (c) and (d) represent the capacity of undischarged hydrogen. FIG. 2 is a diagram showing the relationship between the ratio of the discharge capacity of an alkaline storage battery using a hydrogen storage electrode as a negative electrode to the weight of a hydrogen storage alloy, and the drying temperature of the paste mixture.
Claims (2)
つ耐アルカリ性高分子の粒子を分散した高分子ラテック
スと、金属または炭素質の耐アルカリ性導電性粉末とを
含むペースト状混合物を導電性芯体に塗布してから、塗
布されたペースト状混合物を乾燥することを特徴とする
水素吸蔵電極の製造方法。1. A paste-like mixture containing a powder of a hydrogen storage alloy, a polymer latex in which particles of an alkali-resistant polymer that maintains a spherical shape during kneading, and a metal or carbon-based alkali-resistant conductive powder is used. A method for producing a hydrogen storage electrode, comprising: applying a paste-like mixture to a core body; and drying the applied paste-like mixture.
る温度は、該ラテックスに含まれる耐アルカリ性高分子
の融点よりも低いことを特徴とする請求項１記載の水素
吸蔵電極の製造方法。2. The method for producing a hydrogen storage electrode according to claim 1, wherein the temperature at which the applied paste-like mixture is dried is lower than the melting point of the alkali-resistant polymer contained in the latex.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05544889A JP3177653B2 (en) | 1989-03-08 | 1989-03-08 | Method for producing hydrogen storage electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05544889A JP3177653B2 (en) | 1989-03-08 | 1989-03-08 | Method for producing hydrogen storage electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02234355A JPH02234355A (en) | 1990-09-17 |
| JP3177653B2 true JP3177653B2 (en) | 2001-06-18 |
Family
ID=12998884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05544889A Expired - Lifetime JP3177653B2 (en) | 1989-03-08 | 1989-03-08 | Method for producing hydrogen storage electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3177653B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006049149A (en) * | 2004-08-05 | 2006-02-16 | Sanyo Electric Co Ltd | Hydrogen storage alloy electrode for alkaline storage battery, alkaline storage battery using this electrode, and manufacturing method of this electrode |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2561200B2 (en) * | 1992-04-23 | 1996-12-04 | 古河電池株式会社 | Hydrogen storage electrode |
| JP2975790B2 (en) * | 1992-12-17 | 1999-11-10 | 三洋電機株式会社 | Surface treatment method for hydrogen storage alloy electrode |
| JP3573964B2 (en) | 1998-06-17 | 2004-10-06 | 三洋電機株式会社 | Method of manufacturing hydrogen storage alloy electrode for alkaline battery and hydrogen storage alloy electrode for alkaline storage battery |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5223636A (en) * | 1975-08-19 | 1977-02-22 | Tokyo Shibaura Electric Co | Secondary alkaline battery |
| JPS5271643A (en) * | 1975-12-11 | 1977-06-15 | Matsushita Electric Ind Co Ltd | Nickel electrode |
| JPH0810596B2 (en) * | 1986-05-13 | 1996-01-31 | 株式会社東芝 | Metal oxide / hydrogen battery |
-
1989
- 1989-03-08 JP JP05544889A patent/JP3177653B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006049149A (en) * | 2004-08-05 | 2006-02-16 | Sanyo Electric Co Ltd | Hydrogen storage alloy electrode for alkaline storage battery, alkaline storage battery using this electrode, and manufacturing method of this electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02234355A (en) | 1990-09-17 |
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