JPS6237482B2 - - Google Patents
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- Publication number
- JPS6237482B2 JPS6237482B2 JP55025538A JP2553880A JPS6237482B2 JP S6237482 B2 JPS6237482 B2 JP S6237482B2 JP 55025538 A JP55025538 A JP 55025538A JP 2553880 A JP2553880 A JP 2553880A JP S6237482 B2 JPS6237482 B2 JP S6237482B2
- Authority
- JP
- Japan
- Prior art keywords
- conductive
- porous
- base material
- porous body
- electrically insulating
- 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
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
- Inert Electrodes (AREA)
Description
【発明の詳細な説明】
本発明は導電性多孔質体に関し、更に詳しくは
多孔性空間内に導電性物質を保持した多孔質体に
関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrically conductive porous body, and more particularly to a porous body that retains an electrically conductive substance within a porous space.
導電性を有する多孔質体として知られている最
も典型的なものは、燃料電池の電極材料として用
いられているものである。これは導電性物質が樹
脂中に混合された構造となつており、従つて導電
性物質添加の効果はその添加量に比較して小さく
なつている。また従来のものでは多孔質とするた
めに溶出可能な粒子を導電性物質と同時に混入し
て成形した後粒子を溶出除去する方法をとること
が一般的であるため、得られる多孔質体の気孔率
を大きくすることは困難であり、また強度の大き
なものも得られないという欠点がある。 The most typical porous material known to have electrical conductivity is one used as an electrode material for fuel cells. This has a structure in which a conductive substance is mixed into the resin, and therefore the effect of adding the conductive substance is small compared to the amount added. Furthermore, in order to make the porous material porous, it is common practice to mix elutable particles with a conductive material, mold the material, and then elute and remove the particles. It is difficult to increase the ratio, and it also has the disadvantage that high strength cannot be obtained.
本発明は特定のミクロ構造を有し、かつ0.1mm
以下の孔径を有する電気絶縁性多孔質基材の多孔
性空間内に導電性物質を保持した構造の導電性多
孔質体を提出するものであり、従来の導電性多孔
質体とは全く異なる構造を有するものである。本
発明の導電性多孔質体は、その多孔性空間内に導
電性物質を保持しているため、導電性物質はほと
んど電気絶縁性基材に覆われることがなく、その
導電性が有効に生かされることになる。また、導
電性物質を添加することによる多孔質体強度の低
下もなく、多孔質体の気孔率を大きくすることも
可能であるため、従来にない特性を備えた導電性
多孔質体であると言える。 The present invention has a specific microstructure and 0.1mm
We are submitting a conductive porous body with a structure in which a conductive substance is held within the porous space of an electrically insulating porous base material having the following pore diameter, and the structure is completely different from that of conventional conductive porous bodies. It has the following. Since the conductive porous body of the present invention holds a conductive substance within its porous space, the conductive substance is hardly covered with the electrically insulating base material, and its conductivity is effectively utilized. It will be. In addition, it is possible to increase the porosity of the porous material without reducing the strength of the porous material by adding a conductive substance, so it is said to be a conductive porous material with unprecedented properties. I can say it.
本発明の電気絶縁性多孔質基材としては、樹脂
の延伸により微細孔を生成させたものが特に有効
であつた。この多孔質基材は気孔率を大きくする
ことができ、しかも機械的強度にも優れ、導電性
物質保特性に於ても良好で、本発明に最適のもの
であることがわかつた。その材料としては、ポリ
テトラフルオロエチレン、ポリエチレン、ポリプ
ロピレンが最適であり、これらを延伸することに
より、繊維と該繊維によつて互に連結された結節
とから成るミクロ構造を有する多光質基材が得ら
れる。その製造方法は公知であるが、ポリテトラ
フルオロエチレンを例にとり説明する。ポリテト
ラフルオロエチレン多孔質基材を延伸法により製
造するには、特公昭42−13560に記載の方法を基
本的に用いることができる。先ずポリテトラフル
オロエチレン未焼結粉末に液状潤滑剤を混和し、
押出し、圧延等により所望の形状に成形する。こ
の成形物から液状潤滑剤を抽出、加熱蒸発等によ
り除去し、あるいは除去せずして成形物を少なく
とも一軸方向に延伸する。熱収縮防止状態にて焼
結温度の約327℃以上に加熱して延伸した構造を
焼結固定すると強度の向上したポリテトラフルオ
ロエチレン多孔質基材が得られる。ここで熱収縮
防止状態とは収縮を完全に防止した状態だけでな
く、一部収縮を許す状態をも含むものとする。こ
のポリテトラフルオロエチレン多孔質体は非常に
細い繊維とその繊維により互に連結された結節と
から成るミクロ構造を有しており、その繊維径と
長さ、結節の大きさやそれらの数は延伸と焼結の
条件により変化させ得るため、得られる多孔質基
材の孔径と気孔率も自由に決定し得る。このよう
なミクロ構造を有する多孔質基材を用いると導電
性物質はそのミクロ構造中に保持されるため、本
発明の目的には非常に好適なものである。 As the electrically insulating porous base material of the present invention, one in which fine pores were generated by stretching a resin was particularly effective. It was found that this porous base material can have a large porosity, has excellent mechanical strength, and has good conductive substance retention properties, and is optimal for the present invention. The most suitable materials are polytetrafluoroethylene, polyethylene, and polypropylene, and by stretching these materials, a multi-optic substrate with a microstructure consisting of fibers and nodes interconnected by the fibers can be created. is obtained. Although the manufacturing method thereof is known, it will be explained using polytetrafluoroethylene as an example. In order to produce a polytetrafluoroethylene porous base material by a stretching method, the method described in Japanese Patent Publication No. 13560/1983 can basically be used. First, a liquid lubricant is mixed with unsintered polytetrafluoroethylene powder,
It is formed into a desired shape by extrusion, rolling, etc. The liquid lubricant is removed from the molded product by extraction, heat evaporation, etc., or the molded product is stretched in at least one axial direction without being removed. A polytetrafluoroethylene porous base material with improved strength can be obtained by sintering and fixing the stretched structure by heating it to a sintering temperature of about 327° C. or higher while preventing heat shrinkage. Here, the state of preventing heat shrinkage includes not only a state where shrinkage is completely prevented, but also a state where some shrinkage is allowed. This polytetrafluoroethylene porous material has a microstructure consisting of very thin fibers and nodes interconnected by the fibers, and the fiber diameter and length, the size of the nodes, and their number vary depending on the stretching. The pore size and porosity of the resulting porous base material can also be freely determined because they can be changed depending on the sintering conditions and sintering conditions. When a porous base material having such a microstructure is used, the conductive substance is retained in the microstructure, so it is very suitable for the purpose of the present invention.
この電気絶縁性多孔質基材の多孔性空間内に保
持させる導電性物質としては、炭素、金属等がそ
の例として挙げられる。これらの導電性物質は通
常微粉末の形で用いられ、電気絶縁性多孔質基材
の多孔性空間内に保持させるには、分散液の形で
含浸する方法が最も有用な方法であつた。またこ
の導電性物質の分散液を含浸するには超音波を作
用させるのが最も効果的であつた。分散液の分散
媒としては電気絶縁性多孔質基材に対して濡れ性
を示し、かつ導電性物質をよく分散させる液体が
用いられる。電気絶縁性多孔質基材が例えばポリ
テトラフルオロエチレンから成る場合、分散媒と
しては、エタノール、イソプロピルアルコール、
アセトン、メチルエチルケトン、界面活性剤水溶
液等が有効であつた。導電性物質をより多く電気
絶縁性多孔質基材の多孔性空間内に保持させるに
は、多孔質基材の孔径より小さな粒径の導電性物
質を含む分散液の含浸と乾燥を繰返せばよいこと
がわかつた。導電性物質が炭素の場合を例にとる
と、黒鉛、カーボンブラツク、活性炭等いずれも
0.1mm以下の粒径の微細粉末が市販されており、
それらの分散液が利用し得るが、本発明の目的に
は導電性の高いものを用いることは言うまでもな
い。 Examples of the conductive substance held within the porous space of this electrically insulating porous base material include carbon, metal, and the like. These conductive substances are usually used in the form of fine powder, and impregnating them in the form of a dispersion has been the most effective method for retaining them within the porous spaces of electrically insulating porous substrates. Furthermore, the most effective method for impregnating the conductive material dispersion was to apply ultrasonic waves. As the dispersion medium of the dispersion liquid, a liquid is used which shows wettability to the electrically insulating porous substrate and which disperses the conductive substance well. When the electrically insulating porous substrate is made of polytetrafluoroethylene, for example, the dispersion medium may be ethanol, isopropyl alcohol,
Acetone, methyl ethyl ketone, surfactant aqueous solution, etc. were effective. In order to retain more of the conductive substance in the porous spaces of the electrically insulating porous base material, it is possible to repeatedly impregnate and dry a dispersion containing the conductive substance with a particle size smaller than the pore size of the porous base material. I found out something good. For example, if the conductive substance is carbon, graphite, carbon black, activated carbon, etc.
Fine powder with a particle size of 0.1 mm or less is commercially available.
Dispersions of these can be used, but it goes without saying that those with high conductivity are used for the purpose of the present invention.
導電性物質を多孔性空間内に保持して多孔質体
は、多孔質基材が圧延可能な樹脂等から成る場合
には、乾燥後更に圧延することによりその導電性
を飛躍的に高めることができた。このようにして
見掛けの体積固有電気抵抗値が105Ω−cm以下で
ある導電性多孔質体が容易に得られることがわか
つた。 When a porous body is made by holding a conductive substance in a porous space, and the porous base material is made of a resin that can be rolled, the conductivity can be dramatically increased by further rolling after drying. did it. It has been found that a conductive porous body having an apparent volume specific electrical resistance value of 10 5 Ω-cm or less can be easily obtained in this manner.
本発明の導電性多孔質体は、導電性物質をその
多孔性空間内に保持しているため、電気絶縁性多
孔質基材の多孔性空間内表面を導電性物質が覆つ
た構造となつている。従つて導電性物質の有する
導電性は有効に生かされることになり、その表面
特性も何ら損なわれることがない。例えば導電性
物質の比表面積が150m2／dl以上であるような場
合には、触媒担体としての機能も非常に優れたも
のとなる。特にポリテトラフルオロエチレンから
成る電気絶縁性多孔質基材の多孔性空間内に、導
電性が大きく、かつ比表面積も大きな炭素粉末を
保持した導電性多孔質体は、基材の有する撥水性
と通気性の特性に加え、導電性と触媒保持能を有
するため、燃料電池のガス拡散電極材料として非
常に優れたものであることが確認された。その他
本発明の導電性多孔質体は種々の電極材料、電線
被覆材料、静電気除去材料、面状発熱体として利
用し得るものである。 Since the conductive porous body of the present invention holds a conductive substance in its porous space, it has a structure in which the conductive substance covers the inner surface of the porous space of the electrically insulating porous base material. There is. Therefore, the conductivity of the conductive material can be effectively utilized, and its surface properties are not impaired in any way. For example, when the specific surface area of the conductive material is 150 m 2 /dl or more, it also functions as a catalyst carrier very well. In particular, a conductive porous body that holds carbon powder with high conductivity and a large specific surface area in the porous space of an electrically insulating porous base material made of polytetrafluoroethylene is characterized by the water repellency of the base material. It has been confirmed that it is an extremely excellent material for gas diffusion electrodes in fuel cells because it has good air permeability, electrical conductivity, and catalyst retention ability. In addition, the conductive porous body of the present invention can be used as various electrode materials, wire coating materials, static electricity removal materials, and planar heating elements.
以下に本発明の実施例を示す。 Examples of the present invention are shown below.
実施例 １
ポリテトラフルオロエチレンを材料とし、繊維
と該繊維によつて互に連結された結節とから成る
ミクロ構造を有する電気絶縁性多孔質基材として
平均孔径10.0μｍ、気孔率85％、厚み120μｍの
シート状多孔質体フロロポアFP−1000（住友電
工製）を準備した。一方、比表面積1000m2／ｇの
高導電性カーボンブラツクであるケツチエンブラ
ツクEC（ライオン アクゾ社製）20ｇをイソプ
ロピルアルコール１中に加えて分散混合した。
この分散液を金属容器に入れ、周波数28KHz、
出力1200Wの超音波振動子上に設置した。超音波
を作用させながら分散液中に、上記シート状多孔
質基材を５分間浸漬し、加熱乾燥した。Example 1 An electrically insulating porous base material made of polytetrafluoroethylene and having a microstructure consisting of fibers and nodes interconnected by the fibers, with an average pore diameter of 10.0 μm, a porosity of 85%, and a thickness. A 120 μm sheet-like porous material Fluoropore FP-1000 (manufactured by Sumitomo Electric Industries) was prepared. Separately, 20 g of Ketsuen Black EC (manufactured by Lion Akzo), which is a highly conductive carbon black with a specific surface area of 1000 m 2 /g, was added to 1 part of isopropyl alcohol and dispersed and mixed.
Put this dispersion liquid in a metal container, and set the frequency to 28KHz.
It was installed on an ultrasonic transducer with an output of 1200W. The sheet-like porous base material was immersed in the dispersion liquid for 5 minutes while applying ultrasonic waves, and then heated and dried.
次いでシートの上下面を逆にして再び上記と同
様の超音波の作用による含浸、乾燥の操作を繰返
した。得られたシート状多孔質体は多孔性空間内
にカーボンブラツクを重量で25％保持したもの
で、見掛けの（気孔率の補正なしの）体積固有電
気抵抗値は4.1×104Ω−cmであつた。 Next, the upper and lower surfaces of the sheet were turned over, and the same impregnation and drying operations using ultrasonic waves as described above were repeated. The obtained sheet-like porous material had 25% carbon black by weight held in the porous space, and the apparent volume specific electrical resistivity (without porosity correction) was 4.1 × 10 4 Ω-cm. It was hot.
次にこの多孔質体をロールで圧延して30μｍ厚
としたところ、見掛けの体積固有電気抵抗値８・
７×103Ω−cm（気孔率による補正後では5.2×
103Ω−cm）気孔率40％のシート状導電性多孔質
体が得られた。この多孔質体に常法により白金黒
を付着させこれを更に集電体に圧着し、リン酸水
溶液を電解質とした酸素一水素燃料電池のガス電
極として使用したところ、導電性、透気性、触媒
能のいずれも優れた性能を示し、また基材の撥水
性により漏液もなく、燃料電池の実用化を大きく
前進させるものであつた。 Next, when this porous body was rolled with a roll to a thickness of 30 μm, the apparent volume specific electrical resistance was 8.
7×10 3 Ω-cm (5.2× after correction for porosity)
10 3 Ω-cm) A sheet-like conductive porous material with a porosity of 40% was obtained. This porous material was coated with platinum black using a conventional method, and then pressed onto a current collector. When used as a gas electrode in an oxygen-hydrogen fuel cell using an aqueous phosphoric acid solution as an electrolyte, it was found to have good electrical conductivity, gas permeability, and catalytic properties. The material showed excellent performance in all cases, and due to the water repellency of the base material, there was no leakage, greatly advancing the practical application of fuel cells.
実施例 ２
実施例１と同様のポリテトラフルオロエチレン
多孔質基材として、二軸延伸法により製造した、
気孔率87％、厚み50μｍのシート状多孔質体を用
い、導電性物質として電池用黒鉛微粉末を用いて
実施例１と同様の超音波の作用による含浸、乾燥
の操作を行なつた。得られた導電性多孔質体は多
孔性空間内に黒鉛を重量で50％保持したもので見
掛けの体積固有電気抵抗値1.9×104Ω−cm（気孔
率による補正後では5.3×103Ω−cm）、気孔率72
％であつた。次にこの多孔質体をロールで圧延し
て20μｍ厚としたところ、見掛けの体積固有電気
抵抗値6.0×103Ω−cm（気孔率による補正後では
4.2×103Ω−cm）、気孔率30％のシート状導電性
多孔質体が得られた。Example 2 A polytetrafluoroethylene porous base material similar to Example 1 was produced by a biaxial stretching method.
A sheet-like porous body with a porosity of 87% and a thickness of 50 μm was used, and the same impregnation and drying operations as in Example 1 were performed using graphite fine powder for batteries as the conductive material. The obtained conductive porous material has 50% graphite by weight held in the porous space, and has an apparent volume specific electrical resistivity of 1.9×10 4 Ω-cm (5.3×10 3 Ω after correction for porosity) -cm), porosity 72
It was %. Next, when this porous body was rolled with a roll to a thickness of 20 μm, the apparent volume specific electrical resistance value was 6.0 × 10 3 Ω-cm (after correction for porosity).
4.2×10 3 Ω-cm) and a porosity of 30%.
Claims (1)
性物質を保持して成る導電性多孔質体に於て、該
電気絶縁性多孔質基材が繊維と該繊維によつて互
いに連結された結節とから成るミクロ構造を有
し、かつ0.1mm以下の孔径を有することを特徴と
する導電性多孔質体。 ２ 電気絶縁性多孔質基材がポリテトラフルオロ
エチレンから成ることを特徴とする特許請求の範
囲第１項記載の導電性多孔質体。 ３ 電気絶縁性多孔質基材がポリエチレン又はポ
リプロピレンから成ることを特徴とする特許請求
の範囲第１項記載の導電性多孔質体。 ４ 導電性物質が炭素であることを特徴とする特
許請求の範囲第１項記載の導電性多孔質体。 ５ 導電性物質が金属であることを特徴とする特
許請求の範囲第１項記載の導電性多孔質体。 ６ 導電性多孔質体の見掛けの体積固有電気抵抗
値が105Ω−cm以下であることを特徴とする特許
請求の範囲第１項記載の導電性多孔質体。 ７ 導電性物質の比表面積が150m2／ｇ以上であ
ることを特徴とする特許請求の範囲第１項記載の
導電性多孔質体。[Scope of Claims] 1. In a conductive porous body comprising an electrically insulating porous base material holding a conductive substance in a porous space, the electrically insulating porous base material contains fibers and the fibers. 1. A conductive porous material having a microstructure consisting of nodules connected to each other by pores having a pore diameter of 0.1 mm or less. 2. The electrically conductive porous body according to claim 1, wherein the electrically insulating porous base material is made of polytetrafluoroethylene. 3. The electrically conductive porous body according to claim 1, wherein the electrically insulating porous base material is made of polyethylene or polypropylene. 4. The conductive porous body according to claim 1, wherein the conductive substance is carbon. 5. The conductive porous body according to claim 1, wherein the conductive substance is a metal. 6. The conductive porous body according to claim 1, wherein the conductive porous body has an apparent volume specific electrical resistance value of 10 5 Ω-cm or less. 7. The conductive porous body according to claim 1, wherein the conductive substance has a specific surface area of 150 m 2 /g or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2553880A JPS56121202A (en) | 1980-02-29 | 1980-02-29 | Conductive porous member and method of manufacturing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2553880A JPS56121202A (en) | 1980-02-29 | 1980-02-29 | Conductive porous member and method of manufacturing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56121202A JPS56121202A (en) | 1981-09-24 |
| JPS6237482B2 true JPS6237482B2 (en) | 1987-08-12 |
Family
ID=12168776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2553880A Granted JPS56121202A (en) | 1980-02-29 | 1980-02-29 | Conductive porous member and method of manufacturing same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56121202A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5940407A (en) * | 1982-08-28 | 1984-03-06 | ユニチカ株式会社 | Method of producing electrically conductive film |
| JPS61259406A (en) * | 1985-05-10 | 1986-11-17 | 日東電工株式会社 | Anisotropic conductive sheet and manufacture thereof |
| JPS6319708A (en) * | 1986-07-10 | 1988-01-27 | 東レ株式会社 | Transparent conducting film and manufacture thereof |
| EP0578755B1 (en) * | 1991-04-04 | 1995-09-06 | W.L. Gore & Associates, Inc. | Electrically conductive gasket materials |
| WO2004088795A1 (en) | 2003-03-31 | 2004-10-14 | Sumitomo Electric Industries, Ltd. | Anisotropic electrically conductive film and method of producing the same |
| EP2645373A1 (en) | 2012-03-26 | 2013-10-02 | Siemens Aktiengesellschaft | Material for isolation system, isolation system, outer corona protection and an electric machine |
| JP7010653B2 (en) | 2017-10-17 | 2022-01-26 | 三洋化成工業株式会社 | Resin current collectors, laminated current collectors, and lithium-ion batteries |
| DE102023212788A1 (en) * | 2023-12-15 | 2025-06-18 | Siemens Energy Global GmbH & Co. KG | External corona protection and an electrical machine |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS519466A (en) * | 1974-07-12 | 1976-01-26 | Sanshin Jitsugyo Kk | Ryutainyoru irooyobi kooryochoseisochi |
| US4091139A (en) * | 1975-09-17 | 1978-05-23 | Westinghouse Electric Corp. | Semiconductor binding tape and an electrical member wrapped therewith |
-
1980
- 1980-02-29 JP JP2553880A patent/JPS56121202A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56121202A (en) | 1981-09-24 |
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