JP2000021415A - Conductive porous body and metallic porous body using the same, and electrode plate for battery - Google Patents
Conductive porous body and metallic porous body using the same, and electrode plate for batteryInfo
- Publication number
- JP2000021415A JP2000021415A JP10189281A JP18928198A JP2000021415A JP 2000021415 A JP2000021415 A JP 2000021415A JP 10189281 A JP10189281 A JP 10189281A JP 18928198 A JP18928198 A JP 18928198A JP 2000021415 A JP2000021415 A JP 2000021415A
- Authority
- JP
- Japan
- Prior art keywords
- porous body
- conductive
- metal
- silver
- fine particles
- 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.)
- Pending
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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、連続気孔構造を有
する合成樹脂製の多孔質体の表面を導電化した導電性多
孔質体と、かかる導電性多孔質体を中間材料として製造
される、とくにアルカリ２次電池などの電池用の極板に
好適に使用される金属多孔質体と、そして、かかる金属
多孔質体を用いた電池用の極板とに関するものである。[0001] The present invention relates to a conductive porous body made of a synthetic resin porous body having a continuous pore structure, the surface of which is made conductive, and the conductive porous body manufactured using the conductive porous body as an intermediate material. In particular, the present invention relates to a metal porous body suitably used for a battery electrode plate such as an alkaline secondary battery, and a battery electrode plate using such a metal porous body.
【０００２】[0002]
【従来の技術】アルカリ２次電池は、高信頼性でかつ小
型化、軽量化が可能であるため、ポータブル機器用の小
型のものから産業用、大形設備用の大形のものまで、各
種装置の電源として多用されている。2. Description of the Related Art Alkaline secondary batteries are highly reliable and can be reduced in size and weight. Therefore, various types of alkaline secondary batteries are available, from small ones for portable equipment to large ones for industrial and large equipment. It is often used as a power source for equipment.
【０００３】上記アルカリ２次電池には、正負両極の組
み合わせによって多数の種類があるが、ほとんどの場
合、正極としてはニッケル電極が使用される。また負極
としては、カドミウム電極、亜鉛電極、鉄電極、水素電
極などがあり、これらのうちカドミウム電極が最も一般
的であるが、活物質として水素吸蔵合金を使用した水素
電極も、高容量化と低公害化が可能であるために注目さ
れている。There are many types of alkaline secondary batteries depending on the combination of positive and negative electrodes. In most cases, a nickel electrode is used as a positive electrode. As the negative electrode, there are a cadmium electrode, a zinc electrode, an iron electrode, a hydrogen electrode, and the like. Among these, a cadmium electrode is the most common, but a hydrogen electrode using a hydrogen storage alloy as an active material also has a high capacity. Attention has been paid to low pollution.
【０００４】上記のうちニッケル電極としては最初、い
わゆるポケット式のものが用いられていたが、現在は、
ニッケルなどの導電性材料からなり、かつ多孔質である
集電用の極板の空げき中に、水酸化ニッケルなどの正極
用の活物質粒子を多数、充てんしたものが、電池の密閉
化が可能で、しかもポケット式のものよりも電池の特性
を向上できるために一般化している。また、カドミウム
電極や水素電極としても、上記と同様に多孔質の極板の
空げき中に、カドミウムや水素吸蔵合金などの負極用の
活物質粒子を多数、充てんしたものが用いられる。At first, the so-called pocket type was used as the nickel electrode.
A battery filled with a large number of active material particles for the positive electrode, such as nickel hydroxide, in the gap of the current-collecting electrode plate made of a conductive material such as nickel and porous It is generalized because it is possible and can improve the characteristics of the battery as compared with the pocket type. Also, as the cadmium electrode and the hydrogen electrode, a material in which a large number of negative electrode active material particles such as cadmium and a hydrogen storage alloy are filled in the space of the porous electrode plate as described above is used.
【０００５】かかる多孔質の極板としては従来、ニッケ
ル粉末を焼結した焼結体が用いられてきたが、近時、上
記焼結体よりも活物質粒子の充てん量を多くできるため
に電池の高容量化に適したものとして、連続気孔構造を
有する多孔率の大きな合成樹脂の多孔質体（ポリウレタ
ンフォームなど）を芯材として製造された金属多孔質体
が実用化されつつある。Conventionally, a sintered body obtained by sintering nickel powder has been used as such a porous electrode plate. However, recently, since the amount of active material particles to be filled can be larger than that of the sintered body, a battery is required. As a material suitable for increasing the capacity, a metal porous body manufactured by using a porous body of a synthetic resin having a continuous pore structure and a large porosity (such as polyurethane foam) as a core material is being put to practical use.
【０００６】上記金属多孔質体は一般に、芯材の表面
を、 塩化パラジウムなどの触媒で処理し、ついで無電解
ニッケルめっきなどの無電解めっきを行うことによっ
て、あるいは 黒鉛などのカーボンの微粒子を含むバインダー樹脂
の溶液を塗布して乾燥させることによって導電化したの
ち、かかる導電化された多孔質体（導電性多孔質体）を
陰極として金属、とくにニッケルなどを電気めっきし
て、その表面に、連続した金属めっき層（ニッケルめっ
き層など）を形成し、さらに必要に応じて熱処理して芯
材を除去することによって製造される。[0006] Generally, the above-mentioned porous metal material is obtained by treating the surface of a core material with a catalyst such as palladium chloride and then performing electroless plating such as electroless nickel plating, or containing carbon fine particles such as graphite. After applying a binder resin solution and drying it to make it conductive, the conductive porous body (conductive porous body) is used as a cathode to electroplate a metal, particularly nickel, and the like, It is manufactured by forming a continuous metal plating layer (such as a nickel plating layer) and, if necessary, performing a heat treatment to remove the core material.
【０００７】[0007]
【発明が解決しようとする課題】ところが、上記のよ
うに無電解めっきによって多孔質体の表面を導電化した
導電性多孔質体は、その取り扱いが容易でなく、たとえ
ば(1) 連続的な生産設備を用いて、前記芯材から導電性
多孔質体を経て金属多孔質体を連続的に製造する際に、
次工程である電気めっき工程への送りなどにおいて導電
性多孔質体に加えられる、曲げや、張力による長さ方向
への延伸、(2) 製造された導電性多孔質体の所定量を、
次工程で一度に電気めっき処理すべく、ロール状、フー
プ状などの形状とするための捲回、(3) あらかじめロー
ル状、フープ状などの形状に捲回された所定量の芯材を
一度に導電化処理した後、製造された導電性多孔質体を
次工程で連続的に電気めっき処理すべく、上記ロールや
フープから巻き戻す際の繰り出し、などの変形を受ける
と、その電気抵抗値が大きく上昇して、電気めっき工程
におけるニッケルなどの金属めっき層の成長速度が低下
し、その結果として金属多孔質体の生産性や生産効率な
どが低下するおそれがあった。However, as described above, the conductive porous body in which the surface of the porous body is made conductive by electroless plating is not easy to handle. For example, (1) continuous production Using equipment, when continuously producing a metal porous body through the conductive porous body from the core material,
Bending or stretching in the length direction by tension, which is added to the conductive porous body in sending to the next step of the electroplating step, (2) a predetermined amount of the manufactured conductive porous body,
In order to perform electroplating at one time in the next process, winding to form a roll, hoop, etc., (3) A predetermined amount of core material previously wound into a roll, hoop, etc. In order to continuously electroplate the produced conductive porous body in the next step after conducting treatment, the unwinding process when unwinding from the roll or hoop is performed. , And the growth rate of the metal plating layer such as nickel in the electroplating step is reduced, and as a result, the productivity and production efficiency of the porous metal body may be reduced.
【０００８】すなわち無電解めっきにて芯材の表面に形
成される導電層は、たとえば無電解ニッケルめっきの場
合０．１μｍ程度というごく薄い、しかも連続した金属
膜であるため、上記のように導電性多孔質体に曲げ、延
伸、捲回、繰り出しなどの変形が加えられた際に割れた
り折れたりしやすく、かかる割れや折れなどが発生する
と導電性多孔質体の導電性が低下して、上記のように電
気抵抗値が大きく上昇し、その結果として電気めっき工
程における、ニッケルなどの金属めっき層の成長速度が
低下するのである。That is, the conductive layer formed on the surface of the core material by electroless plating is a very thin and continuous metal film of about 0.1 μm in the case of electroless nickel plating, for example. When the porous body is bent, stretched, wound, deformed such as unreeling, it is easily broken or broken, and when such cracks or breaks occur, the conductivity of the conductive porous body decreases, As described above, the electric resistance value greatly increases, and as a result, the growth rate of the metal plating layer of nickel or the like in the electroplating step decreases.
【０００９】そこで、たとえば導電性多孔質体に加わる
張力を抑制すべく送り速度を遅くしたり、あるいは曲げ
や捲回の曲率を大きくしたりすることが検討されたが、
その場合には、(a) 金属多孔質体の生産性や生産効率が
低下する、(b) 生産設備や運搬、貯蔵のための設備にこ
れまでよりも大きなスペースが必要になる、といった新
たな問題を生じることが明らかとなった。Therefore, for example, it has been studied to reduce the feed rate or to increase the curvature of the bend or winding in order to suppress the tension applied to the conductive porous body.
In such a case, it is necessary to (a) reduce the productivity and production efficiency of the porous metal body, and (b) require more space for production equipment, transportation and storage equipment. It turned out to be problematic.
【００１０】また、上記の無電解めっきとして最も一
般的な無電解ニッケルめっきによって芯材の表面に形成
される導電層は、めっき浴に含まれるリン（Ｐ）を含有
するために、その上にニッケルなどの金属めっき層を電
気めっきした後、熱処理して芯材を除去する際などに、
上記リンが金属めっき層に拡散する結果、製造された金
属多孔質体の電気抵抗値が高くなって、たとえば電池用
の極板として使用した場合にはその充放電の効率が低下
するという問題もあった。The conductive layer formed on the surface of the core material by the most common electroless nickel plating as the above-mentioned electroless plating contains phosphorus (P) contained in the plating bath. After electroplating a metal plating layer such as nickel, heat treatment to remove the core material, etc.
As a result of the diffusion of the phosphorus into the metal plating layer, the electric resistance value of the manufactured porous metal body increases, and for example, when used as an electrode plate for a battery, the charge / discharge efficiency decreases. there were.
【００１１】また、前記のうちのようにカーボンの微
粒子によって表面を導電化した導電性多孔質体もやは
り、とくに延伸されることによってバインダー樹脂の割
れなどを生じて、上記のものと同様に、その電気抵抗
値が大きく上昇してしまう他、かかる導電性多孔質体
は、そもそもカーボン自体の電気抵抗値が金属に比べて
大幅に高いために、電気めっきにおける金属めっき層の
成長速度が著しく低く、金属多孔質体の生産性や生産効
率が低いという問題もあった。[0011] Further, the conductive porous body whose surface is made conductive by carbon fine particles as described above also causes a crack or the like of the binder resin by being particularly stretched. In addition to the large increase in the electric resistance value, such a conductive porous body has a very low growth rate of the metal plating layer in the electroplating because the electric resistance value of the carbon itself is much higher than the metal in the first place. In addition, there is a problem that productivity and production efficiency of the porous metal body are low.
【００１２】本発明の主たる目的は、電気めっきにおけ
る金属めっき層の成長速度が高く、かつ取り扱いが容易
で、大きな変形が加えられても上記成長速度がほとんど
低下しないために、金属多孔質体の生産性や生産効率に
すぐれており、しかも電気抵抗値の低いすぐれた金属多
孔質体を製造し得る、新規な導電性多孔質体を提供する
ことにある。[0012] The main object of the present invention is to provide a metal porous layer having a high growth rate in electroplating, being easy to handle, and hardly reducing the growth rate even when a large deformation is applied. An object of the present invention is to provide a novel conductive porous body which is excellent in productivity and production efficiency and can produce an excellent metal porous body having a low electric resistance value.
【００１３】また、本発明の他の目的は、かかる導電性
多孔質体から製造されるために電気抵抗値が低く、たと
えば電池用の極板として使用した際にその充放電の効率
を向上しうる、新規な金属多孔質体を提供することにあ
る。Another object of the present invention is to improve the charge / discharge efficiency when used as an electrode plate for a battery, for example, because it is manufactured from such a conductive porous body and has a low electric resistance. To provide a novel metal porous body.
【００１４】また本発明のさらに他の目的は、かかる金
属多孔質体にて形成されるために充放電の効率にすぐれ
た、新規な電池用の極板を提供することにある。Still another object of the present invention is to provide a novel battery electrode plate which is formed of such a porous metal body and has excellent charge / discharge efficiency.
【００１５】[0015]
【課題を解決するための手段】上記課題を解決すべく、
発明者らは、合成樹脂製の芯材の表面を導電化するため
の導電材料について種々、検討を行った。Means for Solving the Problems In order to solve the above problems,
The present inventors have conducted various studies on conductive materials for making the surface of a synthetic resin core material conductive.
【００１６】その結果、無電解銀めっきによって形成さ
れる銀の導電層の一部は、乾燥状態での電気抵抗値こそ
高いものの、次工程である電気めっき工程においては金
属めっき層の成長速度が高く、しかも驚くべきことにこ
の成長速度は、導電性多孔質体に前記のような種々の変
形が加えられた後もあまり変化しないために、金属多孔
質体を生産性よく、高い生産効率でもって製造できると
いう、これまで知られていなかったすぐれた特性を有す
ることが判明した。As a result, although a part of the silver conductive layer formed by the electroless silver plating has a high electric resistance value in a dry state, the growth rate of the metal plating layer in the next electroplating step is low. Highly and surprisingly, this growth rate does not change much after the above-mentioned various deformations are applied to the conductive porous body, so that the metal porous body can be produced with high productivity and high production efficiency. It has been found that it has excellent properties which were previously unknown and which can be manufactured.
【００１７】そこで、銀の導電層のミクロな構造に着目
してさらに検討を行った結果、導電層が銀の微粒子の集
合体からなる場合に、上記のようなすぐれた特性を発揮
し得ることを見出し、本発明を完成するに至った。Therefore, as a result of further study focusing on the microstructure of the silver conductive layer, it was found that the above-described excellent characteristics can be exhibited when the conductive layer is made of an aggregate of silver fine particles. And completed the present invention.
【００１８】すなわち本発明の導電性多孔質体は、連続
気孔構造を有する合成樹脂製の多孔質体を芯材として、
その表面に、銀の微粒子の集合体からなる導電層が形成
されたことを特徴とするものである。That is, the conductive porous body of the present invention comprises, as a core material, a porous body made of synthetic resin having a continuous pore structure.
On the surface thereof, a conductive layer composed of an aggregate of silver fine particles is formed.
【００１９】また、本発明の金属多孔質体は、上記本発
明の導電性多孔質体を陰極とする電気めっきにより、当
該導電性多孔質体の表面に、連続した金属めっき層が形
成されたことを特徴とするものである。In the metal porous body of the present invention, a continuous metal plating layer is formed on the surface of the conductive porous body by electroplating using the conductive porous body of the present invention as a cathode. It is characterized by the following.
【００２０】なお上記金属多孔質体は、金属めっき層を
形成後に熱処理して、合成樹脂製の芯材を除去してもよ
い。The metal porous body may be heat-treated after forming the metal plating layer to remove the synthetic resin core.
【００２１】さらに本発明の電池用の極板は、上記本発
明の金属多孔質体を主体とすることを特徴とするもので
ある。Further, an electrode plate for a battery according to the present invention is characterized by being mainly composed of the porous metal body of the present invention.
【００２２】かかる本発明において、導電層を構成する
銀の微粒子は、銀自体の持つ特性として水および酸素に
対して安定で、その表面がほとんど酸化されないため
に、常に高導電率でかつ低抵抗の状態を維持している。In the present invention, the silver fine particles constituting the conductive layer are stable to water and oxygen as characteristics of silver itself, and the surface thereof is hardly oxidized. The state is maintained.
【００２３】それゆえ、かかる銀の微粒子の集合体から
なる導電層は、乾燥状態では、微粒子間の電気伝導が悪
いために電気抵抗値が高くなるが、電気めっき工程で電
気めっき浴に浸漬されると、微粒子間の細かな隙間に浸
透しためっき液を介して微粒子間の電気伝導が維持され
て電気抵抗値が低くなるためか、前記のように金属めっ
き層の成長速度が高い。Therefore, the conductive layer made of the aggregate of silver fine particles has a high electric resistance in a dry state due to poor electric conduction between the fine particles, but is immersed in an electroplating bath in the electroplating step. Then, the growth rate of the metal plating layer is high as described above, probably because the electric resistance between the fine particles is maintained through the plating solution penetrating into the fine gaps between the fine particles and the electric resistance value decreases.
【００２４】しかも導電性多孔質体が変形されても、上
記の、導電層の構造と、電気めっき浴への浸漬状態での
電気伝導の機構にはほとんど影響がないため、電気めっ
き工程での金属めっき層の成長速度はほとんど低下せ
ず、金属多孔質体を生産性よく、高い生産効率でもって
製造することができる。Moreover, even if the conductive porous body is deformed, the structure of the conductive layer and the mechanism of electric conduction in the state of being immersed in the electroplating bath are hardly affected. The growth rate of the metal plating layer hardly decreases, and the metal porous body can be manufactured with high productivity and high production efficiency.
【００２５】しかも製造された金属多孔質体は、たとえ
ば熱処理して芯材を除去する際などに、上述した銀の微
粒子の導電層を起源とする銀が、ごく少量ながら、不純
物として金属めっき層中に拡散するため、純粋な金属単
体（たとえばニッケル単体）に比べて僅かに電気抵抗値
が上昇するものの、その度合いは、前述した無電解ニッ
ケルめっき層からのリンの拡散による電気抵抗値の上昇
に比べれば著しく小さいため、金属多孔質体の全体的な
電気抵抗値にはほとんど影響しない。In addition, in the produced porous metal body, for example, when the core material is removed by heat treatment, a small amount of silver originating from the conductive layer of the silver fine particles described above is contained as a metal plating layer as an impurity. Although the electric resistance slightly increases in comparison with a pure metal simple substance (for example, nickel simple substance) due to the diffusion into the inside, the degree of the increase is due to the increase in the electric resistance value due to the diffusion of phosphorus from the electroless nickel plating layer. Since it is significantly smaller than the above, it hardly affects the overall electric resistance value of the porous metal body.
【００２６】そしてその結果として本発明によれば、金
属多孔質体の生産性や生産効率にすぐれるとともに、電
気抵抗値の低いすぐれた金属多孔質体を製造しうる導電
性多孔質体と、かかる導電性多孔質体から製造されるた
めに電気抵抗値が低く、たとえば電池用の極板として使
用した際にその充放電の効率を向上しうる金属多孔質体
と、そしてかかる金属多孔質体にて形成されるために充
放電の効率にすぐれた電池用の極板とが得られる。As a result, according to the present invention, a conductive porous body which is excellent in productivity and production efficiency of a porous metal body and can produce an excellent porous metal body having a low electric resistance value; A metal porous body which has a low electric resistance value because it is manufactured from such a conductive porous body and which can improve the charge / discharge efficiency thereof when used as an electrode plate for a battery, and a metal porous body such as this Thus, an electrode plate for a battery having excellent charge / discharge efficiency can be obtained.
【００２７】[0027]
【発明の実施の形態】以下に、本発明を説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below.
【００２８】まず本発明の導電性多孔質体について説明
する。First, the conductive porous body of the present invention will be described.
【００２９】かかる導電性多孔質体は、前記のように、
連続気孔構造を有する合成樹脂製の多孔質体を芯材とし
て、その表面に、銀の微粒子の集合体からなる導電層が
形成されたものである。[0029] Such a conductive porous body is, as described above,
A porous body made of a synthetic resin having a continuous pore structure is used as a core material, and a conductive layer made of an aggregate of silver fine particles is formed on the surface thereof.
【００３０】このうち芯材としては、合成樹脂にて形成
された、連続気孔構造を有する従来公知の種々の多孔質
体が、いずれも使用可能である。As the core material, any of various conventionally known porous bodies having a continuous pore structure formed of a synthetic resin can be used.
【００３１】すなわち、 内部に連続気孔構造を有する、それ自体は３次元網
目状構造を備えた発泡体、 合成樹脂製の繊維からなる不織布 合成樹脂製の繊維を織成した織布などがあげられ
る。That is, a foam having a continuous pore structure therein and itself having a three-dimensional network structure, a nonwoven fabric made of synthetic resin fibers, and a woven fabric woven of synthetic resin fibers are exemplified.
【００３２】このうちの発泡体の具体例としては、前
述したポリウレタンフォームや、あるいはポリスチレ
ン、ポリエチレン、ポリプロピレン、ポリ塩化ビニルな
どの熱可塑性樹脂の発泡体などがあげられる。Specific examples of the foam include the above-mentioned polyurethane foam and foams of a thermoplastic resin such as polystyrene, polyethylene, polypropylene, and polyvinyl chloride.
【００３３】また、の不織布およびの織布を構成す
る合成樹脂製の繊維としては、たとえばポリエチレン、
ポリエステル、ポリプロピレン、ナイロンなどの、従来
公知の種々の合成樹脂の繊維があげられる。The synthetic resin fibers constituting the nonwoven fabric and the woven fabric are, for example, polyethylene,
Various known synthetic resin fibers such as polyester, polypropylene, and nylon can be used.
【００３４】なお、本発明の導電性多孔質体から製造さ
れる金属多孔質体が、後述するように芯材を除去せずに
残したままのものであって、それがアルカリ２次電池用
の極板として使用される場合には、かかる芯材が、アル
カリ電解液の強アルカリに対する耐性、すなわち耐アル
カリ性にすぐれている必要がある。The metal porous body produced from the conductive porous body of the present invention is a metal porous body which remains without removing a core material as described later, and is used for an alkaline secondary battery. When used as an electrode plate, it is necessary that such a core material has excellent resistance to the strong alkali of the alkaline electrolyte, that is, excellent alkali resistance.
【００３５】具体的にはたとえば、アメリカ試験材料協
会（ＡＳＴＭ）が定めた規格ＡＳＴＭ Ｄ５４３−６３
Ｔ中の耐薬品性試験において、アルカリ電解液に相当す
るｐＨ１１以上の強アルカリ液に対してＧ（良好）以
上、とくにＥ（優秀）の評価がえられるものが好まし
い。Specifically, for example, the standard ASTM D543-63 defined by the American Society for Testing and Materials (ASTM).
In the chemical resistance test during T, those which can be evaluated as G (good) or more, particularly E (excellent), with respect to a strong alkaline solution having a pH of 11 or more corresponding to an alkaline electrolyte are preferable.
【００３６】かかる耐アルカリ性にすぐれた芯材として
は、たとえばポリエチレン、ポリプロピレンなどのポリ
オレフィンにて形成された多孔質体が好ましい。As such a core material having excellent alkali resistance, a porous body formed of a polyolefin such as polyethylene or polypropylene is preferable.
【００３７】その具体例としては、これに限定されない
がたとえば、直径およそ１０〜４０μｍ程度のポリオレ
フィン製の単繊維を、平均孔径およそ０．６ｍｍ以下程
度の不織布状となるように、単繊維の交差部分で結合
し、さらにそれを１方向に引き延ばしたような形状を有
する多孔質体〔たとえば日立化成（株）製の商品名ＲＦ
−３０など〕があげられる。Specific examples thereof include, but are not limited to, cross-linking of single fibers made of polyolefin having a diameter of about 10 to 40 μm into a nonwoven fabric having an average pore diameter of about 0.6 mm or less. A porous body having such a shape as to be joined at a portion and further extended in one direction [for example, trade name RF manufactured by Hitachi Chemical Co., Ltd.
-30].
【００３８】なお、本発明の導電性多孔質体から製造さ
れる金属多孔質体が、これも後述するように芯材を除去
したものである場合、あるいは芯材を除去せずに残した
ものであっても、アルカリ２次電池用の極板以外の、他
の用途に使用される場合には、芯材は、上記のように高
い耐アルカリ性を有している必要はなく、むしろ熱処理
による除去の容易さや、あるいはコスト面などを考慮す
ると、ポリウレタンフォームなどの汎用の多孔質体を芯
材として使用するのが好ましい。The metal porous body produced from the conductive porous body of the present invention has a core material removed as described later, or a metal porous body left without removing the core material. However, when used for other purposes other than the electrode plate for an alkaline secondary battery, the core material does not need to have high alkali resistance as described above, but rather is subjected to heat treatment. Considering ease of removal, cost, etc., it is preferable to use a general-purpose porous body such as polyurethane foam as the core material.
【００３９】芯材の厚み、平均孔径、空隙率などは、金
属多孔質体の用途に応じて適宜、設定すればよい。The thickness, average pore diameter, porosity, etc. of the core material may be appropriately set according to the use of the porous metal body.
【００４０】上記芯材の表面に形成される導電層は、前
記のように、銀の微粒子の集合体にて形成されている必
要がある。The conductive layer formed on the surface of the core material needs to be formed of an aggregate of silver fine particles as described above.
【００４１】かかる銀の微粒子の大きさはとくに限定さ
れないが、前述したように、電気めっき工程における金
属めっき層の成長速度を向上する効果を考慮すると、そ
の粒径は小さいほど好ましい。これは、銀の微粒子の粒
径が小さいほど、先に述べた微粒子間の隙間が小さくな
って、当該隙間に浸透しためっき液による、微粒子間の
電気伝導を維持する働きが向上するためと考えられる。Although the size of the silver fine particles is not particularly limited, as described above, in consideration of the effect of improving the growth rate of the metal plating layer in the electroplating step, the smaller the particle size, the better. This is because the smaller the particle size of the silver fine particles, the smaller the gap between the fine particles described above, and the better the function of maintaining the electric conduction between the fine particles by the plating solution penetrating the gap. Can be
【００４２】銀の微粒子の、具体的な粒径の範囲につい
てはとくに限定されないが、平均粒径で表しておよそ
０．５μｍ以下であるのが好ましい。The specific range of the particle size of the silver fine particles is not particularly limited, but is preferably about 0.5 μm or less in terms of average particle diameter.
【００４３】銀の微粒子の平均粒径が０．５μｍ以下で
あれば、後述する実施例１、２の結果からも明らかなよ
うに、電気めっき工程における金属めっき層の成長速度
を向上することができる。 なお、上記平均粒径の範囲
の下限値についてはとくに限定されないが、およそ０．
０１μｍ程度であるのが好ましい。When the average particle size of the silver fine particles is 0.5 μm or less, as is clear from the results of Examples 1 and 2 described later, the growth rate of the metal plating layer in the electroplating step can be improved. it can. The lower limit of the range of the average particle diameter is not particularly limited, but may be about 0.
It is preferably about 01 μm.
【００４４】銀の微粒子の平均粒径が上記０．０１μｍ
未満では、導電層が、銀の微粒子の集合体としてよりも
むしろ、連続した銀の層と類似したものとしての挙動を
示すようになり、導電性多孔質体が変形を受けることに
よって導電層に、銀の微粒子の隙間よりも大きな割れや
折れが生じて、電気めっき工程における金属めっき層の
成長速度が大きく低下するおそれがある。The average particle diameter of the silver fine particles is 0.01 μm.
Below, the conductive layer behaves more like a continuous silver layer, rather than as an aggregate of silver fine particles, and the conductive porous body is deformed by the deformation of the conductive porous body. Further, cracks or breaks larger than the gaps between the silver fine particles may occur, and the growth rate of the metal plating layer in the electroplating step may be significantly reduced.
【００４５】なお銀の微粒子の平均粒径は、上述した、
銀の微粒子の集合体からなる導電層に特有の特性を考慮
すると、上記の範囲内でもとくに０．０５〜０．２μｍ
程度であるのが好ましく、０．０７〜０．２μｍ程度で
あるのがさらに好ましい。The average particle size of the silver fine particles is as described above.
Taking into account the characteristics specific to the conductive layer made of an aggregate of silver fine particles, 0.05 to 0.2 μm
It is preferably about 0.07 to 0.2 μm.
【００４６】また、上記導電層の厚みについても、本発
明ではとくに限定されないが、芯材１ｍ2あたりの銀の
付着量（ｇ）を示す目付け量（ｇ／ｍ2）で表して、お
よそ１〜７ｇ／ｍ2程度であるのが好ましい。Although the thickness of the conductive layer is not particularly limited in the present invention, it is expressed as a basis weight (g / m 2 ) indicating the amount of silver (g) deposited per m 2 of the core material. It is preferably about 7 g / m 2 .
【００４７】導電層の目付け量が上記の範囲未満では、
芯材に十分な導電性を付与することができないために、
電気めっき工程における金属めっき層の成長速度が低下
するおそれがある。When the basis weight of the conductive layer is less than the above range,
Because sufficient conductivity cannot be given to the core material,
The growth rate of the metal plating layer in the electroplating step may be reduced.
【００４８】一方、導電層を、たとえば以下に述べる無
電解銀めっき法にて形成した場合には、当該導電層の目
付け量と、導電層を構成する銀の微粒子の粒径とがほぼ
比例関係となるため、導電層の目付け量が上記の範囲を
超えた場合には、銀の微粒子が、前述した平均粒径０．
５μｍ以下の好適範囲を超える大きなものとなってしま
って、やはり電気めっき工程における金属めっき層の成
長速度が低下するおそれがある。On the other hand, when the conductive layer is formed by, for example, the electroless silver plating method described below, the basis weight of the conductive layer and the particle size of the silver fine particles constituting the conductive layer are substantially proportional to each other. Therefore, when the basis weight of the conductive layer exceeds the above range, the silver fine particles have a mean particle size of 0.1 to 0.3.
There is a possibility that the growth rate of the metal plating layer in the electroplating step may be reduced because the thickness is larger than the preferable range of 5 μm or less.
【００４９】なお導電層の目付け量は、上記の各特性の
バランスを考慮すると、上記の範囲内でもとくに２〜５
ｇ／ｍ2程度であるのが好ましい。The weight per unit area of the conductive layer should be within the above range, especially 2-5
It is preferably about g / m 2 .
【００５０】芯材の表面に、上記の、銀の微粒子の集合
体からなる導電層を形成するには、前記のように無電解
銀めっき法が採用される。In order to form a conductive layer composed of an aggregate of silver fine particles on the surface of the core material, the electroless silver plating method is employed as described above.
【００５１】無電解銀めっき法とは、硝酸銀のアンモニ
ア性溶液（銀液）を、ホルマリンなどのアルデヒド類、
ブドウ糖の水溶液、ロッシェル塩、ロッシェル塩と硝酸
銀の反応生成物、グリオキザール、硫酸ヒドラジン、ロ
ッシェル塩と氷砂糖の混合液を煮沸したもの、砂糖を少
量の硝酸で転化した溶液などの還元剤と混合して銀を還
元析出させる、いわゆる銀鏡反応を基本とするものであ
る。The electroless silver plating method means that an ammoniacal solution of silver nitrate (silver solution) is treated with an aldehyde such as formalin,
Aqueous glucose solution, Rochelle salt, reaction product of Rochelle salt and silver nitrate, glyoxal, hydrazine sulfate, boiled mixture of Rochelle salt and ice sugar, mixed with reducing agents such as a solution of sugar converted with a small amount of nitric acid It is based on a so-called silver mirror reaction for reducing and depositing silver.
【００５２】ただし通常の、一般的な銀鏡反応では、上
記銀液と還元剤とを混合した瞬間から反応が進行して、
その反応温度にもよるが、およそ数十秒の後には反応が
完結し、そのようにして得られる導電層の多くは、本発
明において必要とする、銀の微粒子の集合体ではなく、
単なる連続した膜状になってしまう。However, in a general silver mirror reaction, the reaction proceeds from the moment the silver solution and the reducing agent are mixed, and
Depending on the reaction temperature, the reaction is completed after about several tens of seconds, and many of the conductive layers thus obtained are not aggregates of silver fine particles required in the present invention,
It simply becomes a continuous film.
【００５３】浴の構成と、反応の条件とを慎重に選定す
れば、通常の銀鏡反応でも、たとえば後述する実施例３
にみるように、銀の微粒子の集合体からなる導電層を形
成することはでき、かかる導電層も本発明の範囲に含ま
れる。If the composition of the bath and the conditions of the reaction are carefully selected, even a normal silver mirror reaction can be performed, for example, in Example 3 described later.
As shown in the above, a conductive layer composed of an aggregate of silver fine particles can be formed, and such a conductive layer is also included in the scope of the present invention.
【００５４】しかし、この実施例３の結果からも明らか
なように、そのようにして形成される導電層は、銀の微
粒子の平均粒径が、前述した好適な範囲（０．５μｍ以
下）を超える比較的大きなものとなってしまい、電気め
っき工程における金属めっき層の成長速度が僅かに低下
する傾向を示す。However, as is evident from the results of Example 3, the conductive layer thus formed has an average particle diameter of the silver fine particles within the above-mentioned preferred range (0.5 μm or less). Therefore, the growth rate of the metal plating layer in the electroplating step tends to slightly decrease.
【００５５】また上記通常の銀鏡反応では、先に述べた
ように銀液と還元剤とを混合した瞬間から反応が進行し
て、およそ数十秒の後には反応が完結してしまうため、
たとえばシート状の芯材を、前述したように連続的に送
りながら、あるいはロール状やフープ状に捲回した状態
で、その全体に均一な導電層を形成するのは容易でな
く、工業的な実施が難しいという問題もある。In the ordinary silver mirror reaction, as described above, the reaction proceeds from the moment the silver liquid and the reducing agent are mixed, and the reaction is completed after about several tens of seconds.
For example, it is not easy to form a uniform conductive layer on the entire surface of a sheet-shaped core material while continuously feeding it as described above, or in a state of being wound in a roll or hoop shape. There is also a problem that implementation is difficult.
【００５６】そこで発明者らは、銀の微粒子の平均粒径
が０．５μｍ以下であるような導電層を、たとえばシー
ト状の芯材の表面に均一かつ連続的に形成しうる、新た
な無電解銀めっき浴の組成について、種々検討を行っ
た。Accordingly, the present inventors have developed a new non-conductive layer capable of uniformly and continuously forming a conductive layer in which the average particle diameter of silver fine particles is 0.5 μm or less, for example, on the surface of a sheet-shaped core material. Various studies were made on the composition of the electrolytic silver plating bath.
【００５７】その結果、芳香族ヨウ素化合物とアミノ酸
とを安定化剤として添加してやると、銀液が安定化し
て、還元剤を混合した後も常温では数週間以上にわたっ
て銀が析出せず、しかもかかる無電解銀めっき浴は、感
応化処理としてすずを吸着した芯材の表面と接触するこ
とによって初めて、徐々に、微粒子状に銀を析出させる
機能を有するものとなるという、これまで知られていな
かった新たな事実を見出した。As a result, when the aromatic iodine compound and the amino acid are added as stabilizers, the silver solution is stabilized, and even after mixing with the reducing agent, silver does not precipitate for several weeks or more at room temperature even after mixing with the reducing agent. The electroless silver plating bath has a function of gradually depositing silver in fine particles only when it comes into contact with the surface of the core material to which tin is adsorbed as a sensitizing treatment, which has not been known until now. Have found a new fact.
【００５８】そして、上記の無電解銀めっき浴を用いる
ことによって、後述する実施例１、２にみるように、銀
の微粒子の平均粒径が０．５μｍ以下であるような導電
層を、シート状の芯材の表面に均一かつ連続的に形成す
ることに成功した。Then, by using the above electroless silver plating bath, as shown in Examples 1 and 2 described below, a conductive layer having an average particle diameter of silver fine particles of 0.5 μm or less was formed on a sheet. Successfully and uniformly formed on the surface of the core material.
【００５９】かかる銀めっき浴に添加される安定化剤の
うち芳香族ヨウ素化合物としては、たとえばヨードベン
ゼン、ジヨードサリチルなどがあげられ、アミノ酸とし
ては、たとえばグリシン、アラニン、アミノ酢酸などが
あげられる。芳香族ヨウ素化合物とアミノ酸は、モル比
で１：１の割合で使用するのが好ましい。Among the stabilizers added to the silver plating bath, examples of the aromatic iodine compound include iodobenzene and diiodosalicyl, and examples of the amino acid include glycine, alanine and aminoacetic acid. . The aromatic iodine compound and the amino acid are preferably used in a molar ratio of 1: 1.
【００６０】上記安定化剤とともに浴を構成する銀液お
よび還元剤としては、従来と同様のものが使用される。
すなわち銀液としては、硝酸銀のアンモニア性溶液があ
げられ、還元剤としては、ホルマリンなどのアルデヒド
類、ブドウ糖の水溶液、ロッシェル塩、ロッシェル塩と
硝酸銀の反応生成物、グリオキザール、硫酸ヒドラジ
ン、ロッシェル塩と氷砂糖の混合液を煮沸したもの、砂
糖を少量の硝酸で転化した溶液などがあげられる。As the silver liquor and the reducing agent constituting the bath together with the above-mentioned stabilizer, the same ones as in the prior art can be used.
That is, as the silver liquid, an ammoniacal solution of silver nitrate can be mentioned, and as the reducing agent, aldehydes such as formalin, an aqueous solution of glucose, Rochelle salt, a reaction product of Rochelle salt and silver nitrate, glyoxal, hydrazine sulfate, Rochelle salt Examples thereof include a mixture obtained by boiling a mixture of ice sugar and a solution obtained by converting sugar with a small amount of nitric acid.
【００６１】上記の銀めっき浴を使用した無電解銀めっ
きにおいては、形成される銀の微粒子の粒径が、めっき
の反応速度、つまり銀の微粒子の析出速度、および時間
と比例し、このうち析出速度を制御するには、浴のｐＨ
と液温を変化させればよいことが、発明者らの検討によ
って明らかとなっている。すなわち浴のｐＨを高くする
（浴をアルカリ性にする）ほど、また液温を高くするほ
ど、析出速度が高くなることが確認されている。In the electroless silver plating using the above silver plating bath, the particle size of the silver fine particles formed is proportional to the plating reaction rate, that is, the deposition rate of silver fine particles, and time. To control the deposition rate, the pH of the bath
It is clear from the investigations of the inventors that the liquid temperature may be changed. That is, it has been confirmed that the higher the pH of the bath (the bath is made alkaline) and the higher the liquid temperature, the higher the deposition rate.
【００６２】それゆえ、目的とする銀の微粒子の平均粒
径にあわせて、また浴の、とくに還元剤の種類や濃度な
どにあわせて、上記浴のｐＨおよび温度と、芯材の浴へ
の浸漬時間とを設定するのが好ましい。Therefore, the pH and temperature of the above-mentioned bath and the core material to the bath are adjusted in accordance with the average particle size of the target silver fine particles and in accordance with the type of bath, particularly the type and concentration of the reducing agent. It is preferable to set the immersion time.
【００６３】その具体的な数値範囲はとくに限定され
ず、とくに上記のように還元剤の種類や濃度などによっ
て最適値は異なるものの、通常は、浴のｐＨがおよそ９
〜１１程度、温度が３０〜５０℃程度、浸漬時間が２〜
１５分程度であるのが好ましい。The specific numerical range is not particularly limited, and although the optimum value varies depending on the type and concentration of the reducing agent as described above, the pH of the bath is usually about 9%.
~ 11, temperature about 30 ~ 50 ° C, immersion time 2 ~
Preferably, it is about 15 minutes.
【００６４】上記の、銀の微粒子の集合体からなる導電
層を備えた本発明の導電性多孔質体は、前述したように
乾燥状態での電気抵抗値こそ高いものの、次工程である
電気めっき工程における金属めっき層の成長速度が高
く、しかもこの成長速度は、導電性多孔質体に前記のよ
うな種々の変形が加えられた後もあまり変化しないため
に、金属多孔質体を、効率よく、高い生産性で持って製
造できるという、すぐれた特性を有するものである。As described above, the conductive porous body of the present invention provided with the conductive layer composed of the aggregate of silver fine particles has a high electric resistance in a dry state as described above. The growth rate of the metal plating layer in the process is high, and since this growth rate does not change much after the above-described various deformations are applied to the conductive porous body, the metal porous body can be efficiently formed. It has excellent characteristics that it can be manufactured with high productivity.
【００６５】また、かかる本発明の導電性多孔質体によ
れば、上記のように導電層が銀の微粒子にて形成され、
次工程である電気めっき工程において形成される金属め
っき層の電気抵抗値を著しく向上させるおそれがないの
で、電気抵抗値の低い、すぐれた金属多孔質体を製造で
きるという利点もある。According to the conductive porous body of the present invention, the conductive layer is formed of silver fine particles as described above.
Since there is no possibility that the electric resistance value of the metal plating layer formed in the subsequent electroplating step is significantly improved, there is also an advantage that an excellent metal porous body having a low electric resistance value can be manufactured.
【００６６】つぎに、本発明の金属多孔質体について説
明する。Next, the metal porous body of the present invention will be described.
【００６７】かかる金属多孔質体は、先に述べたよう
に、上記本発明の導電性多孔質体を陰極とする電気めっ
きにより、当該導電性多孔質体の表面に、連続した、１
種または２種以上の金属からなる、単層または２層以上
の複層の金属めっき層を形成することによって構成され
る。As described above, such a metal porous body is continuously plated on the surface of the conductive porous body by electroplating using the conductive porous body of the present invention as a cathode.
It is constituted by forming a single layer or a multilayer metal plating layer of two or more layers made of a kind or two or more kinds of metals.
【００６８】たとえばニッケル製の単層構造の金属めっ
き層は、上記導電性多孔質体を陰極として、これをニッ
ケル板などの適当な陽極とともにニッケルの電気めっき
浴に浸漬した状態で、両極間に電圧を印可して電気めっ
きすることによって形成される。For example, a nickel-plated metal plating layer having a single-layer structure is formed between the two electrodes by dipping the conductive porous body in a nickel electroplating bath together with a suitable anode such as a nickel plate. It is formed by applying a voltage and electroplating.
【００６９】また金属めっき層は、少なくともその表面
が、極板として必要な金属（たとえばニッケル）にて形
成されていればよいので、下地としてより安価な、ある
いは形成が容易な金属などの下地めっき層を１層または
２層以上、形成して、その最表層に、上記ニッケルなど
の表面めっき層を積層した複層構造としてもよい。The metal plating layer may be formed of a metal (for example, nickel) required for an electrode plate at least on the surface thereof. One or more layers may be formed, and a multi-layer structure in which a surface plating layer of nickel or the like is stacked on the outermost layer may be used.
【００７０】金属めっき層の厚みは、本発明ではとくに
限定されないが、当該金属めっき層の強度や抵抗値など
を考慮すると、５〜３０μｍ程度が好ましく、５〜１０
μｍ程度がさらに好ましい。かかる金属めっき層の厚み
は、前述した単層構造の金属めっき層の場合は、いうま
でもなくそれ自体の厚みであるが、２層以上の積層構造
の金属めっき層の場合は、各層の厚みの合計値である。The thickness of the metal plating layer is not particularly limited in the present invention, but is preferably about 5 to 30 μm, and more preferably 5 to 10 μm, in consideration of the strength and resistance value of the metal plating layer.
More preferably, it is about μm. The thickness of such a metal plating layer is, of course, its own thickness in the case of the above-described metal plating layer having a single-layer structure, but in the case of a metal plating layer having a multilayer structure of two or more layers, the thickness of each layer is Is the sum of
【００７１】また本発明の金属多孔質体においては、こ
れも前述したように金属めっき層の形成後に、その全体
を、まず合成樹脂を酸化して熱分解させるための空気中
で、つぎに酸化、不導体化した金属めっき層を還元する
ための、水素ガスなどの非酸化性雰囲気中で、それぞれ
およそ１０００℃近い高温で熱処理して、芯材を完全
に、つまり芯材を構成する合成樹脂が起源のカーボンが
全く検出されなくなるまで除去してやってもよい。Also, in the porous metal body of the present invention, as described above, after the formation of the metal plating layer, the whole is firstly oxidized in the air for oxidizing and thermally decomposing the synthetic resin, and then oxidized. A heat treatment at a high temperature of about 1000 ° C. in a non-oxidizing atmosphere such as hydrogen gas to reduce the nonconductive metal plating layer, thereby completely reducing the core material, that is, the synthetic resin constituting the core material. May be removed until no carbon originating from is detected.
【００７２】この際、前述したように従来の、無電解ニ
ッケルめっき層では、当該層中に含まれるリンが金属め
っき層に拡散して、金属多孔質体の電気抵抗値が上昇す
るという問題を生じる。At this time, as described above, in the conventional electroless nickel plating layer, there is a problem that phosphorus contained in the layer diffuses into the metal plating layer and the electric resistance value of the porous metal body increases. Occurs.
【００７３】これに対し、本発明の金属多孔質体は、前
記のように本発明の導電性多孔質体を中間材料として製
造されるために電気抵抗値が低く、たとえば電池用の極
板として使用した際に、その充放電の効率を向上できる
という、すぐれた特性を有するものである。On the other hand, the metal porous body of the present invention has a low electric resistance because it is manufactured using the conductive porous body of the present invention as an intermediate material as described above. It has excellent characteristics that, when used, its charge / discharge efficiency can be improved.
【００７４】つぎに、本発明の電池用の極板について説
明する。Next, the battery electrode plate of the present invention will be described.
【００７５】かかる極板は、上記本発明の金属多孔質体
を主体とするものである。すなわち、本発明の導電性多
孔質体を陰極とする電気めっきにより製造された金属多
孔質体がそのままで、あるいは前記のように熱処理して
芯材を除去した状態で、電池用の極板として使用され
る。Such an electrode plate is mainly composed of the porous metal body of the present invention. That is, the metal porous body produced by electroplating using the conductive porous body of the present invention as a cathode, as it is, or with the core material removed by heat treatment as described above, as a battery electrode plate used.
【００７６】かかる極板としての金属多孔質体において
は、その多孔率が、およそ５０％以上であるのが好まし
い。It is preferable that the metal porous body as the electrode plate has a porosity of about 50% or more.
【００７７】多孔率が上記の範囲未満では、連続気孔構
造の空げき中に保持しうる活物質の充てん量が小さくな
って、電池を高容量化できないおそれがある。If the porosity is less than the above range, the amount of the active material that can be held in the pores having the continuous pore structure becomes small, and the battery may not be able to have a high capacity.
【００７８】なお多孔率は、上記の範囲内でもとくに９
９％以下であるのが好ましい。The porosity is preferably 9 within the above range.
It is preferably at most 9%.
【００７９】多孔率がこの範囲を超えた場合には、金属
多孔質体の全体としての強度が著しく低下して、極板と
して使用できなくなるおそれがある。If the porosity exceeds this range, the overall strength of the porous metal body may be significantly reduced, making it impossible to use it as an electrode plate.
【００８０】なお多孔率は、上記の各特性の兼ね合いを
考慮すると、上記の範囲内でもとくに９０〜９３％程度
であるのがさらに好ましい。The porosity is more preferably within a range from 90 to 93%, especially in the above range, in consideration of the balance between the above-mentioned properties.
【００８１】かかる本発明の極板は、上記のように本発
明の金属多孔質体を主体として構成されるために、充放
電の効率にすぐれており、たとえば前述したアルカリ２
次電池などに好適に使用される。とくに単１型乾電池の
大きさで、およそ１００Ａ程度の大容量の電流を流す必
要のある、ハイブリッド自動車、電気自動車などの電源
用の電池として開発が進められている、アルカリ−水素
２次電池用の極板などとして好適である。Since the electrode plate of the present invention is mainly composed of the porous metal body of the present invention as described above, it has excellent charge / discharge efficiency.
It is suitably used for secondary batteries and the like. Especially for alkaline-hydrogen secondary batteries, which are being developed as power supply batteries for hybrid vehicles, electric vehicles, etc., which need to carry a large current of about 100 A in the size of a single type dry battery. And the like.
【００８２】なお本発明の極板は、アルカリ２次電池以
外の電池用の極板としても使用できる。また本発明の金
属多孔質体は、上記電池用の極板以外にも、たとえば各
種触媒用の担体、各種暖房機器用部材（灯油の気化、霧
化用部材や、ガスの炎口板など）、エンジンや空気機器
の消音用サイレンサー、オイルミスト分離器、ディーゼ
ルエンジンなどの排ガス中のスス捕集部材、電磁波遮蔽
部材、各種フィルター、ディーゼルエンジンなどのピス
トンや、油圧機器の耐磨耗部品などの、種々の用途にも
使用することができる。The electrode plate of the present invention can be used as an electrode plate for batteries other than the alkaline secondary battery. Further, the metal porous body of the present invention may be, for example, a carrier for various catalysts, a member for various heating devices (a member for vaporizing or atomizing kerosene, a gas flame plate, etc.) in addition to the electrode plate for the battery. Such as silencers for noise reduction of engines and air equipment, oil mist separators, soot collection members in exhaust gas from diesel engines, electromagnetic wave shielding members, various filters, pistons for diesel engines, etc., and wear-resistant parts for hydraulic equipment, etc. Can be used for various applications.
【００８３】[0083]
【実施例】以下に本発明を、実施例、比較例に基づいて
説明する。The present invention will be described below based on examples and comparative examples.
【００８４】実施例１ 厚み１ｍｍ、平均孔径０．４５ｍｍ、空隙率９８％の、
連続気孔構造を有するポリウレタンフォームを芯材とし
て使用し、まずこの芯材を、液温３０℃の塩化すず水溶
液［塩化すず濃度２０ｇ／リットル、濃塩酸濃度１０ｍ
ｌ／リットル］に５分間、浸漬して、その表面を感応化
処理した。Example 1 A sample having a thickness of 1 mm, an average pore diameter of 0.45 mm, and a porosity of 98% was prepared.
A polyurethane foam having a continuous pore structure is used as a core material. First, this core material is treated with a tin chloride aqueous solution at a liquid temperature of 30 ° C. [tin chloride concentration 20 g / liter, concentrated hydrochloric acid concentration 10 m
1 / liter] for 5 minutes to sensitize the surface.
【００８５】つぎに、上記芯材を水、温水および脱イオ
ン水でこの順に洗浄した後、下記の各成分を１リットル
の水に添加するとともに、希硝酸を加えてｐＨを９．９
に調整した、液温３５℃の無電解銀めっき浴に１０分
間、浸漬して、目付け量２ｇ／ｍ2の導電層を形成し、
水洗して、導電性多孔質体を製造した。Next, after washing the above core material with water, warm water and deionized water in this order, the following components are added to 1 liter of water, and diluted nitric acid is added to adjust the pH to 9.9.
Immersed in an electroless silver plating bath at a liquid temperature of 35 ° C. for 10 minutes to form a conductive layer having a basis weight of 2 g / m 2 ,
After washing with water, a conductive porous body was produced.
【００８６】 （成 分） （ミリモル） ＊硝酸銀 ８．８（銀濃度０．９３ｇ／リットル） ＊エチレンジアミン ５４ ＊ロッシェル塩 ３５ ＊３，５−ジヨードサリチル酸 ０．０４ ＊グリシン ０．０４ 製造された導電性多孔質体を、走査型電子顕微鏡を用い
て観察したところ、芯材の表面に、銀の微粒子の集合体
からなる導電層が形成されているのが確認された。ま
た、上記導電層を構成する銀の微粒子の平均粒径を、走
査型電子顕微鏡を用いて撮影した写真からの実測値より
算出したところ、０．０８μｍであった。また上記写真
に撮影された銀の微粒子の、実際の粒径の分布は、０．
５μｍ以下であった。(Ingredient) (mmol) * Silver nitrate 8.8 (silver concentration 0.93 g / l) * Ethylenediamine 54 * Rochelle salt 35 * 3,5-Diiodosalicylic acid 0.04 * Glycine 0.04 Manufactured When the conductive porous body was observed using a scanning electron microscope, it was confirmed that a conductive layer composed of an aggregate of silver fine particles was formed on the surface of the core material. The average particle size of the silver fine particles constituting the conductive layer was calculated from an actually measured value from a photograph taken using a scanning electron microscope, and was found to be 0.08 μm. Further, the distribution of the actual particle diameter of the silver fine particles photographed in the above-mentioned photograph is 0.
It was 5 μm or less.
【００８７】実施例２ 下記の各成分を１リットルの水に添加するとともに、硝
酸と水酸化ナトリウムを加えてｐＨを１０．２に調整し
た、液温４０℃の無電解銀めっき浴を使用したこと以外
は実施例１と同様にして、目付け量５ｇ／ｍ2の導電層
を有する導電性多孔質体を製造した。Example 2 An electroless silver plating bath having a solution temperature of 40 ° C. was used, in which the following components were added to 1 liter of water and the pH was adjusted to 10.2 by adding nitric acid and sodium hydroxide. Except that, in the same manner as in Example 1, a conductive porous body having a conductive layer with a basis weight of 5 g / m 2 was produced.
【００８８】 （成 分） （ミリモル） ＊硝酸銀 ８．８（銀濃度０．９３ｇ／リットル） ＊エチレンジアミン ５４ ＊ロッシェル塩 ３５ ＊３，５−ジヨードサリチル酸 ０．０４ ＊グルタミン酸 ０．０４ 製造された導電性多孔質体を、走査型電子顕微鏡を用い
て観察したところ、芯材の表面に、銀の微粒子の集合体
からなる導電層が形成されているのが確認された。ま
た、上記導電層を構成する銀の微粒子の平均粒径を、走
査型電子顕微鏡を用いて撮影した写真からの実測値より
算出したところ、０．２μｍであった。また上記写真に
撮影された銀の微粒子の、実際の粒径の分布は、０．５
μｍ以下であった。(Ingredient) (mmol) * Silver nitrate 8.8 (silver concentration 0.93 g / liter) * Ethylenediamine 54 * Rochelle salt 35 * 3,5-Diiodosalicylic acid 0.04 * Glutamic acid 0.04 When the conductive porous body was observed using a scanning electron microscope, it was confirmed that a conductive layer composed of an aggregate of silver fine particles was formed on the surface of the core material. Further, the average particle size of the silver fine particles constituting the conductive layer was calculated from an actually measured value from a photograph taken using a scanning electron microscope, and was 0.2 μm. The distribution of the actual particle size of the silver fine particles photographed in the above photograph is 0.5%.
μm or less.
【００８９】実施例３ 下記の製造方法によって製造した無電解銀めっき浴を用
いたこと以外は実施例１と同様にして、目付け量８ｇ／
ｍ2の導電層を有する導電性多孔質体を製造した。なお
無電解銀めっきの条件は室温で１分間とした。製造され
た導電性多孔質体を、走査型電子顕微鏡を用いて観察し
たところ、芯材の表面に、銀の微粒子の集合体からなる
導電層が形成されているのが確認された。また、上記導
電層を構成する銀の微粒子の平均粒径を、走査型電子顕
微鏡を用いて撮影した写真からの実測値より算出したと
ころ、０．７μｍであった。また上記写真に撮影された
銀の微粒子の、実際の粒径のおよその分布は、０．６〜
１．０μｍであった。またごく少数ではあるが、粒径が
数μｍにおよぶ大径の銀の粒子も確認された。 （無電解銀めっき浴の製造）濃度１０ｇ／リットルの硝
酸銀水溶液に、溶液の色が褐色から透明になる兆しが見
えるまでアンモニア水を滴下したのち、硫酸ヒドラジン
−水酸化ナトリウム混合水溶液［硫酸ヒドラジン濃度２
０ｇ／リットル、水酸化ナトリウム濃度５ｇ／リット
ル］を等量、加えて無電解銀めっき浴を製造した。Example 3 The same procedure was followed as in Example 1 except that the electroless silver plating bath produced by the following production method was used, and the basis weight was 8 g / g.
A conductive porous body having an m 2 conductive layer was produced. The conditions of the electroless silver plating were 1 minute at room temperature. When the manufactured conductive porous body was observed using a scanning electron microscope, it was confirmed that a conductive layer formed of an aggregate of silver fine particles was formed on the surface of the core material. Further, the average particle size of the silver fine particles constituting the conductive layer was calculated from an actually measured value from a photograph taken using a scanning electron microscope, and it was 0.7 μm. The approximate distribution of the actual particle size of the silver fine particles taken in the above photograph is 0.6 to
It was 1.0 μm. Although very small, large-sized silver particles having a particle size of several μm were also confirmed. (Manufacture of electroless silver plating bath) Ammonia water is added dropwise to an aqueous solution of silver nitrate having a concentration of 10 g / liter until the color of the solution turns brown to transparent, and then a mixed aqueous solution of hydrazine sulfate and sodium hydroxide [hydrazine sulfate concentration] 2
0 g / liter and a sodium hydroxide concentration of 5 g / liter] to prepare an electroless silver plating bath.
【００９０】比較例１ 実施例１で使用したのと同じポリウレタンフォームを芯
材として使用し、まずこの芯材を、１０％の硫酸水溶液
に１ｇ／リットルの割合で界面活性剤を添加した処理液
（液温６０℃）に浸漬して酸洗浄した。Comparative Example 1 The same polyurethane foam as used in Example 1 was used as a core material, and this core material was first treated with a 10% aqueous sulfuric acid solution at a rate of 1 g / liter of a surfactant. (Liquid temperature 60 ° C.) for acid cleaning.
【００９１】ついでこの芯材を水洗したのち、液温４０
℃の塩化パラジウム−塩化すず混合水溶液［塩化パラジ
ウム濃度０．２ｇ／リットル、塩化すず濃度２０ｇ／リ
ットル、塩酸（３５体積％）濃度２００ｍｌ／リット
ル］に１分間、浸漬して、その表面を感応化処理した。Then, after washing the core material with water,
The surface was sensitized by immersing in a palladium chloride-tin chloride mixed aqueous solution at 0.2 ° C. [palladium chloride concentration 0.2 g / l, tin chloride concentration 20 g / l, hydrochloric acid (35% by volume) concentration 200 ml / l] for 1 minute. Processed.
【００９２】つぎに、上記芯材を水洗した後、下記の各
成分を水に添加した、液温６０℃の無電解ニッケルめっ
き浴に５分間、浸漬して、目付け量１０ｇ／ｍ2の導電
層を形成し、水洗して、導電性多孔質体を製造した。Next, after washing the above-mentioned core material with water, it was immersed for 5 minutes in an electroless nickel plating bath at a liquid temperature of 60 ° C., in which the following components were added to water, to give a conductive weight of 10 g / m 2 . A layer was formed and washed with water to produce a conductive porous body.
【００９３】 （成 分） （濃度） ＊硫酸ニッケル ２０ｇ／リットル ＊酢酸ナトリウム ５ｇ／リットル ＊次亜リン酸ナトリウム １０ｇ／リットル ＊クエン酸ナトリウム ５ｇ／リットル ＊乳酸 ３ｍｌ／リットル 製造された導電性多孔質体を、走査型電子顕微鏡を用い
て観察したところ、芯材の表面に、ニッケルの連続膜か
らなる導電層が形成されているのが確認された。(Component) (Concentration) * Nickel sulfate 20 g / L * Sodium acetate 5 g / L * Sodium hypophosphite 10 g / L * Sodium citrate 5 g / L * Lactic acid 3 mL / L Manufactured conductive porous material When the body was observed using a scanning electron microscope, it was confirmed that a conductive layer composed of a continuous nickel film was formed on the surface of the core material.
【００９４】比較例２ ポリビニルアルコールとフェノール樹脂とを、重量比で
７：３の割合でアルコールに溶解したアルコール溶液
に、平均粒径０．８μｍの黒鉛の微粒子を、濃度が１０
０ｇ／リットルとなるように分散して塗布液を作製し
た。Comparative Example 2 A fine particle of graphite having an average particle diameter of 0.8 μm was added to an alcohol solution in which polyvinyl alcohol and a phenol resin were dissolved at a weight ratio of 7: 3 to an alcohol solution having a concentration of 10 μm.
A coating solution was prepared by dispersing so as to be 0 g / liter.
【００９５】つぎにこの塗布液を、実施例１で使用した
のと同じポリウレタンフォームを芯材として、その両面
にスプレー塗布したのち、１００℃に加熱して乾燥させ
て、目付け量２０ｇ／ｍ2の導電層を有する導電性多孔
質体を製造した。Next, this coating solution was spray-coated on both sides of the same polyurethane foam used in Example 1 as a core material, and then heated to 100 ° C. and dried to give a basis weight of 20 g / m 2. Was produced.
【００９６】製造された導電性多孔質体を、走査型電子
顕微鏡を用いて観察したところ、芯材の表面に、黒鉛の
微粒子の集合体からなる導電層が形成されているのが確
認された。また、上記導電層を構成する黒鉛の微粒子の
平均粒径を、走査型電子顕微鏡を用いて撮影した写真か
らの実測値より算出したところ、原材料である黒鉛の微
粒子と同じ０．８μｍであった。また上記写真に撮影さ
れた黒鉛の微粒子の、実際の粒径の分布は、０．１〜
１．５μｍであった。When the manufactured conductive porous body was observed using a scanning electron microscope, it was confirmed that a conductive layer composed of an aggregate of graphite fine particles was formed on the surface of the core material. . Further, the average particle size of the graphite fine particles constituting the conductive layer was calculated from an actually measured value from a photograph taken using a scanning electron microscope, and found to be 0.8 μm, which was the same as the graphite fine particles as a raw material. . The actual particle size distribution of the graphite fine particles photographed in the above photograph is 0.1 to
It was 1.5 μm.
【００９７】上記各実施例、比較例で製造した導電性多
孔質体について、以下の各試験を行って、その特性を評
価した。The conductive porous bodies produced in the above Examples and Comparative Examples were subjected to the following tests to evaluate the characteristics.
【００９８】電気抵抗値の測定Ｉ（初期値） 各実施例、比較例の導電性多孔質体を幅１ｃｍ、長さ１
０ｃｍの矩形状に切り出し、その長さ方向の両端間の、
乾燥状態での電気抵抗値（Ω）を測定した。Measurement of Electric Resistance Value I (Initial Value) The conductive porous bodies of Examples and Comparative Examples were 1 cm wide and 1 cm long.
Cut out into a 0cm rectangular shape, and between the both ends in the length direction,
The electric resistance (Ω) in a dry state was measured.
【００９９】電気抵抗値の測定II（延伸後） 各実施例、比較例の導電性多孔質体を一方向に１０％延
伸したのち元に戻し、延伸した方向が長さ方向と一致す
るように、幅１ｃｍ、長さ１０ｃｍの矩形状に切り出し
て、その長さ方向の両端間の、乾燥状態での電気抵抗値
（Ω）を測定した。Measurement of Electric Resistance II (After Stretching) The conductive porous body of each of Examples and Comparative Examples was stretched by 10% in one direction and then returned to the original state, so that the stretched direction coincided with the length direction. , 1 cm wide and 10 cm long, and the electrical resistance (Ω) in the dry state between both ends in the length direction was measured.
【０１００】電気抵抗値の測定III（曲げ後） 各実施例、比較例の導電性多孔質体を幅１ｃｍ、長さ１
０ｃｍの矩形状に切り出し、半径６ｃｍの丸棒にあてが
って１８０°曲げ試験したのち元に戻し、その長さ方向
の両端間の、乾燥状態での電気抵抗値（Ω）を測定し
た。Measurement of Electric Resistance III (After Bending) Each of the conductive porous bodies of Examples and Comparative Examples was 1 cm wide and 1 cm long.
A 0 cm rectangular shape was cut out, applied to a round bar having a radius of 6 cm, subjected to a 180 ° bending test, returned to its original position, and the electrical resistance value (Ω) between both ends in the length direction in a dry state was measured.
【０１０１】金属めっき層成長試験 各実施例、比較例の導電性多孔質体を幅１０ｃｍ、長さ
３０ｃｍの矩形状に切り出し、その長さ方向の一端を、
導電性多孔質体の全幅にわたる一対の銅製の治具で挟む
とともに、他端に、ポリ塩化ビニル製の錘を取り付け
た。Metal Plating Layer Growth Test The conductive porous body of each of Examples and Comparative Examples was cut out into a rectangular shape having a width of 10 cm and a length of 30 cm.
The conductive porous body was sandwiched between a pair of jigs made of copper over the entire width, and a weight made of polyvinyl chloride was attached to the other end.
【０１０２】つぎに、銅製の治具のみ液面上に出るよう
に、錘を下にして、導電性多孔質体を垂直に吊り下げた
状態で、下記の両成分を１リットルの水に添加した、液
温４５℃のニッケルの電気めっき浴に浸漬した。 〈電気めっき浴〉 （成分） （濃度） ＊スルファミン酸ニッケル ４５０ｇ／リットル ＊ホウ酸 ３０ｇ／リットル また電気めっき浴の、錘よりさらに下方には、当該導電
性多孔質体と接触しないように、白金製の電極を配置し
た。Next, the following components were added to 1 liter of water while the conductive porous body was suspended vertically with the weight down so that only the copper jig emerged above the liquid surface. It was immersed in a nickel electroplating bath at a liquid temperature of 45 ° C. <Electroplating bath> (Component) (concentration) * Nickel sulfamate 450 g / liter * Boric acid 30 g / liter Further below the weight of the electroplating bath, platinum is used so as not to contact the conductive porous body. Electrodes were placed.
【０１０３】そして銅製の治具を電源の陰極に、白金製
の電極を電源の陽極に、それぞれ接続して、電流密度１
０Ａ／ｄｍ2の条件でニッケルめっきを行い、導電性多
孔質体の表面の、浴の液面側から下方、すなわち錘をつ
けた先端側へ成長するニッケルめっき層の成長速度（ｃ
ｍ／分）を目視により測定した。The copper jig was connected to the cathode of the power supply, and the platinum electrode was connected to the anode of the power supply.
Nickel plating is performed under the condition of 0 A / dm 2 , and the growth rate of the nickel plating layer that grows from the surface of the conductive porous body downward from the liquid surface side of the bath, that is, toward the tip end with a weight (c)
m / min) was measured visually.
【０１０４】なお試験は、各実施例、比較例の導電性多
孔質体についてそれぞれ、変形を加えない初期の状態
（初期）、前記の延伸を加えた状態（延伸後）、および
前記の曲げを加えた状態（曲げ後）の各サンプルを用意
して行った。In the tests, the conductive porous bodies of Examples and Comparative Examples were respectively subjected to the initial state where no deformation was applied (initial state), the state where the above-described stretching was applied (after stretching), and the bending. Each sample in the added state (after bending) was prepared and performed.
【０１０５】金属多孔質体の製造とその電気抵抗値の測
定 変形を加えない初期の状態の、各実施例、比較例の導電
性多孔質体について、上記の、ニッケルめっき層の成長
速度を測定した後、さらに同じ条件でニッケルの電気め
っきを継続して行って、各導電性多孔質体の表面に、目
付け量６００ｇ／ｍ2のニッケルめっき層を形成したの
ち、９００℃の空気雰囲気中で５分間、ついで９００℃
の還元性雰囲気中で３０分間、熱処理して芯材を除去し
て、金属多孔質体を製造した。Production of Metallic Porous Body and Measurement of Its Electric Resistance Value The above-mentioned growth rate of the nickel plating layer was measured for the conductive porous bodies of Examples and Comparative Examples in an initial state without any deformation. After that, nickel electroplating is further continued under the same conditions to form a nickel plating layer having a basis weight of 600 g / m 2 on the surface of each conductive porous body. 5 minutes, then 900 ° C
The core material was removed by heat treatment in a reducing atmosphere for 30 minutes to produce a porous metal body.
【０１０６】そして各金属多孔質体を幅１ｃｍ、長さ１
０ｃｍの矩形状に切り出して、乾燥状態での、長さ方向
の両端間の電気抵抗値（Ω）を測定した。Then, each of the metal porous bodies was 1 cm wide and 1 cm long.
It was cut into a rectangular shape of 0 cm, and the electrical resistance value (Ω) between both ends in the length direction in a dry state was measured.
【０１０７】以上の結果を表１、２に示す。Tables 1 and 2 show the above results.
【０１０８】[0108]
【表１】 [Table 1]
【０１０９】[0109]
【表２】 両表より、芯材の表面を無電解ニッケルめっきの連続層
によって導電化した比較例１の導電性多孔質体は、延伸
および曲げによって電気抵抗値が著しく上昇し、とくに
延伸後は連続膜が破断して、電気抵抗値が無限大まで上
昇することがわかった。[Table 2] From both tables, the conductive porous body of Comparative Example 1 in which the surface of the core material was made conductive by a continuous layer of electroless nickel plating, the electric resistance value was significantly increased by stretching and bending. It was found that it broke, and the electric resistance increased to infinity.
【０１１０】また金属多孔質体を製造すべく、上記比較
例１の導電性多孔質体を陰極とするニッケルの電気めっ
きを行ったところ、変形を加えない初期の状態以外はニ
ッケルめっき層の成長速度が著しく低下し、とくに延伸
によって連続膜が破断して電気抵抗値が無限大まで上昇
したサンプルは、ニッケルめっき層を成長できないこと
がわかった。In order to produce a porous metal body, nickel electroplating was carried out using the conductive porous body of Comparative Example 1 as a cathode. It was found that the nickel plating layer could not be grown on the sample in which the speed was remarkably reduced, and especially the sample in which the continuous film was broken by stretching and the electric resistance value was increased to infinity.
【０１１１】さらに、ニッケルめっき層の成長速度が比
較的高かった、変形を加えない初期の状態のサンプルを
用いて金属多孔質体を製造したところ、前述した熱処理
時のリンの拡散によって、その電気抵抗値が著しく上昇
することがわかった。Further, a porous metal body was manufactured using a sample in an initial state in which the growth rate of the nickel plating layer was relatively high and no deformation was applied. It was found that the resistance value significantly increased.
【０１１２】また芯材の表面をカーボンの微粒子によっ
て導電化した比較例２の導電性多孔質体は、本来的に電
気抵抗値が著しく高い上、とくに延伸によってバインダ
ー樹脂の割れが生じて、その電気抵抗値がさらに上昇す
ることがわかった。Further, the conductive porous body of Comparative Example 2 in which the surface of the core material was made conductive by fine particles of carbon inherently has a remarkably high electric resistance value, and in particular, the binder resin is cracked by stretching. It was found that the electric resistance value further increased.
【０１１３】また金属多孔質体を製造すべく、上記比較
例２の導電性多孔質体を陰極とするニッケルの電気めっ
きを行ったところ、変形を加えない初期の状態から、そ
のめっき速度が著しく低い上、とくに上記のように延伸
によってその電気抵抗値が著しく上昇したサンプルは、
ニッケルめっき層を成長できないことがわかった。In order to produce a porous metal body, nickel was electroplated using the conductive porous body of Comparative Example 2 as a cathode. From the initial state where no deformation was applied, the plating rate was remarkably increased. In addition to the low, especially the sample whose electric resistance value has increased significantly by stretching as described above,
It was found that the nickel plating layer could not be grown.
【０１１４】なお、変形を加えない初期の状態の導電性
多孔質体を用いて金属多孔質体を製造したところ、その
電気抵抗値は各実施例よりも僅かに高い程度であった。When a metal porous body was manufactured using the conductive porous body in the initial state without any deformation, the electric resistance was slightly higher than in each of the examples.
【０１１５】これに対し、芯材の表面を銀の微粒子の集
合体からなる導電層によって導電化した実施例１〜３の
導電性多孔質体はいずれも、延伸および曲げによって電
気抵抗値があまり上昇しないことがわかった。とくに、
銀の微粒子の平均粒径が０．５μｍ以下である実施例
１、２の導電性多孔質体は、延伸および曲げによっても
その電気抵抗値がほとんど変化しなかった。On the other hand, all of the conductive porous bodies of Examples 1 to 3 in which the surface of the core material was made conductive by a conductive layer composed of an aggregate of silver fine particles, the electric resistance value was too small by stretching and bending. Turned out not to rise. In particular,
In the conductive porous bodies of Examples 1 and 2 in which the average particle diameter of the silver fine particles was 0.5 μm or less, the electric resistance value hardly changed even by stretching and bending.
【０１１６】また金属多孔質体を製造すべく、上記実施
例１〜３の導電性多孔質体を陰極とするニッケルの電気
めっきを行ったところ、それぞれ変形を加える前、およ
び延伸や曲げなどの変形を加えた後のいずれの状態にお
いても、ニッケルめっき層の成長速度に変化はなく、全
く同じであった。またとくに実施例１、２の導電性多孔
質体は、ニッケルめっき層の成長速度自体も、実施例３
や、あるいは比較例１の初期状態のものに比べて高い値
を示した。In order to produce a metal porous body, nickel was electroplated using the conductive porous bodies of Examples 1 to 3 as cathodes. In any state after the deformation, the growth rate of the nickel plating layer did not change and was completely the same. In particular, in the conductive porous bodies of Examples 1 and 2, the growth rate of the nickel plating layer itself was also lower than that of Example 3.
Or a higher value than the initial state of Comparative Example 1.
【０１１７】さらに、変形を加えない初期の状態の導電
性多孔質体を用いて金属多孔質体を製造したところ、そ
の電気抵抗値は、とくに比較例１に比べて著しく低い値
を示した。Further, when a metal porous body was manufactured using the conductive porous body in the initial state without deformation, the electric resistance value was remarkably lower than that of Comparative Example 1.
【０１１８】[0118]
【発明の効果】以上、詳述したように本発明によれば、
金属多孔質体の生産性や生産効率にすぐれるとともに、
電気抵抗値の低い金属多孔質体を製造しうる導電性多孔
質体と、かかる導電性多孔質体から製造されるために電
気抵抗値が低く、たとえば電池用の極板として使用した
際にその充放電の効率を向上しうる金属多孔質体と、そ
してかかる金属多孔質体にて形成されるために充放電の
効率にすぐれた電池用の極板とを提供できるという特有
の作用効果を奏する。As described in detail above, according to the present invention,
With excellent productivity and production efficiency of porous metal body,
A conductive porous body capable of producing a metal porous body having a low electric resistance value, and an electric resistance value which is low due to being produced from such a conductive porous body, for example, when used as an electrode plate for a battery. It has a specific function and effect that it is possible to provide a metal porous body capable of improving charge / discharge efficiency and an electrode plate for a battery formed of such a metal porous body and having excellent charge / discharge efficiency. .
───────────────────────────────────────────────────── フロントページの続き (72)発明者 假家 彩生 兵庫県伊丹市昆陽北一丁目１番１号 住友 電気工業株式会社伊丹製作所内 Ｆターム(参考） 5H017 AA02 BB01 BB16 CC28 DD05 DD06 EE01 EE04 HH03 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Akiyo Kariya 1-1-1 Kunyokita, Itami-shi, Itami-shi, Hyogo F-term in Sumitomo Electric Industries, Ltd. Itami Works (reference) 5H017 AA02 BB01 BB16 CC28 DD05 DD06 EE01 EE04 HH03
Claims (6)
体を芯材として、その表面に、銀の微粒子の集合体から
なる導電層が形成されたことを特徴とする導電性多孔質
体。1. A conductive porous body characterized in that a porous body made of synthetic resin having a continuous pore structure is used as a core material, and a conductive layer made of an aggregate of silver fine particles is formed on the surface thereof. .
０．５μｍ以下である請求項１記載の導電性多孔質体。2. The conductive porous body according to claim 1, wherein the silver fine particles forming the conductive layer have an average particle size of 0.5 μm or less.
る電気めっきにより、当該導電性多孔質体の表面に、連
続した金属めっき層が形成されたことを特徴とする金属
多孔質体。3. A continuous metal plating layer formed on the surface of the conductive porous body by electroplating using the conductive porous body according to claim 1 as a cathode. body.
求項３記載の金属多孔質体。4. The metal porous body according to claim 3, wherein the metal plating layer is a nickel plating layer.
て、合成樹脂製の芯材を除去したことを特徴とする金属
多孔質体。5. A porous metal body, wherein the porous metal body according to claim 3 is heat-treated to remove a synthetic resin core.
体とすることを特徴とする電池用の極板。6. An electrode plate for a battery, comprising the metal porous body according to claim 3 or 5 as a main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10189281A JP2000021415A (en) | 1998-07-03 | 1998-07-03 | Conductive porous body and metallic porous body using the same, and electrode plate for battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10189281A JP2000021415A (en) | 1998-07-03 | 1998-07-03 | Conductive porous body and metallic porous body using the same, and electrode plate for battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000021415A true JP2000021415A (en) | 2000-01-21 |
Family
ID=16238702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
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