JP2674317B2 - Porous carbon plate and method for producing the same - Google Patents
Porous carbon plate and method for producing the sameInfo
- Publication number
- JP2674317B2 JP2674317B2 JP2410644A JP41064490A JP2674317B2 JP 2674317 B2 JP2674317 B2 JP 2674317B2 JP 2410644 A JP2410644 A JP 2410644A JP 41064490 A JP41064490 A JP 41064490A JP 2674317 B2 JP2674317 B2 JP 2674317B2
- Authority
- JP
- Japan
- Prior art keywords
- porous carbon
- producing
- film
- fiber
- organic 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
-
- 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
Description
【０００１】[0001]
【産業上の利用分野】本発明は燃料電池用電極等に使用
される多孔質炭素板及びその製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a porous carbon plate used for fuel cell electrodes and the like and a method for producing the same.
【０００２】[0002]
【従来の技術】燃料電池用多孔質炭素板は、炭素繊維シ
ートあるいは、その前駆体シート等に熱硬化性樹脂を含
浸し、硬化、焼成することによって製造される事が多
い。2. Description of the Related Art A porous carbon plate for a fuel cell is often manufactured by impregnating a carbon fiber sheet, a precursor sheet thereof or the like with a thermosetting resin, followed by curing and firing.
【０００３】しかし、燃料電池自体の高性能化、低コス
ト化要求に伴なって、多孔質炭素電極の物性改善、品質
のバラツキの低減化、製法の見直し等に対する要求も高
まり、種々の改良提案がなされている。However, along with the demand for higher performance and lower cost of the fuel cell itself, there are increasing demands for improving the physical properties of the porous carbon electrode, reducing the variation in quality, reviewing the manufacturing method, etc., and proposing various improvements. Has been done.
【０００４】例えば抄紙工程で様々な工夫をなし、面内
が均一でカサ高な多孔質炭素板を得る方法（特開昭６２
−１２６８１、同６０−１２２７１１）、熱伝導率を向
上させる為にカーボン粉末を併用する製造法（特開昭６
０−４２２１３、同６１−２３６６６４）等がある。For example, a method for obtaining a porous carbon plate having a uniform in-plane and a high dryness by making various measures in a papermaking process (Japanese Patent Laid-Open No. 62-62160).
-12681, 60-122711), a production method in which carbon powder is used in combination to improve the thermal conductivity (Japanese Patent Laid-Open No. Sho 6-62)
0-42213 and 61-236664).
【０００５】[0005]
【発明が解決しようとする課題】燃料電池の高性能化の
為には、電極材として用いられる多孔質炭素板は、面に
垂直な方向のガス透過性の高いことのみならず、更に電
気伝導性、熱伝導性等の物性も優れていることが要求さ
れる。In order to improve the performance of the fuel cell, the porous carbon plate used as the electrode material is not only high in gas permeability in the direction perpendicular to the plane, but also has a high electric conductivity. It is required to have excellent physical properties such as properties and thermal conductivity.
【０００６】一般的な製法、すなわち抄紙後のシートを
熱硬化性樹脂に含浸し、乾燥したシート（以降プリプレ
グシートと称する）を積層圧着する方法においては樹脂
含浸、積層圧着工程で様々な工夫が必要である。In a general manufacturing method, that is, a method in which a sheet after paper making is impregnated with a thermosetting resin and a dried sheet (hereinafter referred to as a prepreg sheet) is laminated and pressure-bonded, various measures are taken in the resin impregnation and the lamination pressure-bonding step. is necessary.
【０００７】カサ高な製品を得るには、積層圧着時に大
きな成形圧力をかけないで成形しなければならず、この
為、樹脂含浸量を少なくするとシート間の接着性が低下
して製品不良発生率が高くなり、一方、含浸量を多くす
ると、シート間の接着性は良くなるが、含浸樹脂がシー
ト層間に膜を形成し易くなり、製品のガス透過性を低下
させる。In order to obtain a product with a high dryness, it is necessary to carry out molding without applying a large molding pressure at the time of laminating and crimping. Therefore, if the resin impregnation amount is reduced, the adhesiveness between the sheets is deteriorated and product defects occur. On the other hand, when the impregnation amount is increased, on the other hand, when the impregnated amount is increased, the adhesiveness between the sheets is improved, but the impregnated resin easily forms a film between the sheet layers, which lowers the gas permeability of the product.
【０００８】これらの問題を回避する為、従来、ガス透
過性を維持する為にスペーサーを用いた積層圧着（積層
品厚さ制御）、熱伝導率等の改善の為に含浸液に黒鉛微
粉を添加させる方法等の工夫がなされてきた。In order to avoid these problems, conventionally, graphite fine powder was added to the impregnating liquid for the purpose of lamination pressure bonding (controlling the thickness of laminated products) using spacers to maintain gas permeability and improvement of thermal conductivity. Ingenuity such as the method of adding has been made.
【０００９】しかし、これらの工夫は、生産性の改善お
よび大幅な物性改良等に対しては余り効果がなかった。However, these measures have not been very effective in improving the productivity and greatly improving the physical properties.
【００１０】本発明の目的は生産性および製品面垂直方
向のガス透過性、電気伝導性、熱伝導性を大幅に改善し
た多孔質炭素板およびその製造法を提供することにあ
る。It is an object of the present invention to provide a porous carbon plate which is remarkably improved in productivity, gas permeability in the direction perpendicular to the product surface, electrical conductivity and thermal conductivity, and a method for producing the same.
【００１１】[0011]
【課題を解決するための手段】本発明者は前記状況に鑑
み、鋭意研究努力した結果、下記製法を用いることによ
り、前記問題を解決できることを見出した。DISCLOSURE OF THE INVENTION In view of the above situation, the present inventor has made earnest research efforts and found that the above problems can be solved by using the following production method.
【００１２】１）プリプレグシートを積層圧着させる際
に、各シート間に、炭素化可能で且つ、熱可塑性を有す
るフイルムを挿入し、交互積層する。1) When laminating and press-bonding prepreg sheets, a carbonizable and thermoplastic film is inserted between the sheets and laminated alternately.
【００１３】シートに多量の樹脂が含浸されていると、
製品のガス透過性能を低下させるので、プリプレグシー
トの樹脂含浸量は３０％以下にするのが望ましい。If the sheet is impregnated with a large amount of resin,
It is desirable that the resin impregnation amount of the prepreg sheet is 30% or less because it lowers the gas permeability of the product.
【００１４】上記熱可塑性フイルムとしては、ポリ塩化
ビニリデンフイルム、塩化ビニールフイルム、ポリテト
ラフルオロエチレンフイルム等のいずれかが用いられ
る。As the thermoplastic film, any one of polyvinylidene chloride film, vinyl chloride film, polytetrafluoroethylene film and the like can be used.
【００１５】これら熱可塑性フイルムは、プリプレグシ
ート相互を接着する機能を持つと同時に、炭素化時の昇
温過程で、ガスの透過性を阻害する熱硬化性樹脂炭化膜
を形成し難くするものと推定される。These thermoplastic films have a function of adhering the prepreg sheets to each other and, at the same time, make it difficult to form a carbonized thermosetting resin film which inhibits gas permeability during the temperature rising process during carbonization. Presumed.
【００１６】プリプレグシート基材にアクリル繊維のよ
うな熱可塑性物質が用いられている場合には、これらフ
イルムは炭素化加熱時にシート基材を不融化する機能を
併せ持っている。When a thermoplastic material such as acrylic fiber is used for the prepreg sheet base material, these films also have a function of making the sheet base material infusible during carbonization heating.
【００１７】２）次いで炭化焼成後の多孔質炭素板にピ
ッチ含浸処理を行なった後、再度、８００℃以上の温度
に加熱し含浸ピッチを炭化させる。2) Next, the porous carbon plate after carbonization and firing is subjected to pitch impregnation treatment, and then heated again to a temperature of 800 ° C. or higher to carbonize the impregnated pitch.
【００１８】ピッチ含浸再焼成により、当然、多孔質炭
素板のガス透過量は低下する（１０〜５０％低下）の
で、製品のガス透過量を確保する為にはピッチ含浸前の
多孔質炭素板の段階で、３０００ｍｌ・mm／hr・ｃｍ2
・mmAq以上のガス透過性を保持していることが望まし
い。Since the gas impregnation amount of the porous carbon plate naturally decreases (10 to 50% decrease) by the pitch impregnation and re-baking, in order to secure the gas permeation amount of the product, the porous carbon plate before pitch impregnation is secured. At the stage of 3000 ml ・ mm / hr ・ cm 2
・ It is desirable to maintain gas permeability of mmAq or more.
【００１９】ガス透過性の低下防止および製品の面内で
のバラツキ発生防止のため、含浸用ピッチはタール等で
適宜、濃度調整することが望ましい。It is desirable that the impregnating pitch is appropriately adjusted with tar or the like in order to prevent the deterioration of gas permeability and the occurrence of variations within the surface of the product.
【００２０】[0020]
【作用】プリプレグシート間に挿入された熱可塑性フイ
ルムは、シート、フイルム複合積層体の焼成炭化時に軟
化溶融してプリプレグを構成している有機高分子繊維の
間に拡がり、シート間の接合を強固なものとする。同時
に、熱分解時に発生する活性ガスにより、プリプレグを
構成している有機高分子繊維をも不融化するものと推定
される。[Function] The thermoplastic film inserted between the prepreg sheets spreads between the organic polymer fibers constituting the prepreg by softening and melting at the time of firing and carbonization of the sheet and film composite laminate, to firmly bond the sheets. It should be At the same time, it is presumed that the organic polymer fibers constituting the prepreg are also made infusible by the active gas generated during the thermal decomposition.
【００２１】こうして構成された強固な一次構造体にピ
ッチ含浸して組織内部表面まで含めた全体を黒鉛結晶性
の良いソフトカーボンで覆うことにより、熱的、電気的
特性が大幅に改善される。By thermally impregnating the thus constructed strong primary structure with pitch and covering the entire surface including the internal surface of the tissue with soft carbon having good graphite crystallinity, thermal and electrical characteristics are significantly improved.
【００２２】[0022]
【実施例】実験条件を一覧表にして、表１に、結果を表
２に示した。EXAMPLES Experimental conditions are listed in Table 1, and the results are shown in Table 2.
【００２３】 [0023]
【００２４】本実験において使用した抄紙シート、フェ
ノール樹脂、ピッチは下記のとおりである。The papermaking sheet, phenolic resin and pitch used in this experiment are as follows.
【００２５】 レーヨン・シート：リンテック（株）製 レーヨン繊維５デニール×５mm長をパルプと混合抄紙Rayon sheet: Lintec Co., Ltd. Rayon fiber 5 denier × 5 mm length mixed with pulp papermaking
【００２６】 米坪１００ｇ／ｍ2 不融化アクリルシート：リンテック（株）製 東邦レーヨン製不融化アクリル２デニール×３mm長をパ ルプと混合抄紙100 g / m 2 tsubo infusible acrylic sheet: Lintec Co., Ltd. Toho Rayon infusible acrylic 2 denier x 3 mm length mixed with pulp
【００２７】 [0027]
【００２８】 [0028]
【００２９】 タール ：新日鉄化学（株）製 人造黒鉛製品含浸用ピッチ濃度調整用Tar: manufactured by Nippon Steel Chemical Co., Ltd. For impregnating artificial graphite products For adjusting pitch concentration
【００３０】なお、本実験は原料シート材を３０cm角に
切断し、常温常圧下、フェノール樹脂液に浸漬してプリ
プレグとなし、ピッチ含浸は人造黒鉛製造用含浸装置を
用いることにより行なった。In this experiment, the raw material sheet material was cut into 30 cm square pieces and immersed in a phenol resin solution at room temperature under normal pressure to form a prepreg, and pitch impregnation was carried out by using an impregnation apparatus for producing artificial graphite.
【００３１】炭素化、黒鉛化等の熱処理は、試料を黒鉛
板にはさみ、非酸化性雰囲気下で加熱することにより行
なった。The heat treatment such as carbonization and graphitization was carried out by sandwiching the sample between graphite plates and heating them in a non-oxidizing atmosphere.
【００３２】 [0032]
【００３３】[0033]
【発明の効果】本発明に係る多孔質炭素板は製法が安易
であり、且つ、燃料電池用多孔質炭素電極板として優れ
た特性を有している。The porous carbon plate according to the present invention is easy to manufacture and has excellent properties as a porous carbon electrode plate for fuel cells.
【００３４】本発明は燐酸型燃料電池の市場導入に際
し、コスト、品質両面で貢献するところ大である。The present invention largely contributes to cost and quality when introducing a phosphoric acid fuel cell into the market.
Claims (5)
該抄紙原紙に熱硬化性樹脂を含浸し、積層圧着、炭素化
して得られる多孔質炭素の製法において、積層各含浸紙
間に、加熱圧着時に炭素化可能、且つ、熱可塑的性質を
有し、熱可塑性有機高分子繊維を不融化する機能を有す
るフイルムを介在させることを特徴とする多孔質炭素の
製造法。1. A papermaking machine for producing carbonizable organic polymer fibers,
In the method for producing porous carbon obtained by impregnating the papermaking base paper with a thermosetting resin, laminating pressure bonding, and carbonizing, it is possible to carbonize during thermocompression bonding between each laminated impregnated paper, and have a thermoplastic property. , A method for producing porous carbon, characterized by interposing a film having a function of making a thermoplastic organic polymer fiber infusible.
ス繊維、フェノール系繊維、アクリロニトリル繊維であ
る請求項（１）の多孔質炭素の製造法。2. The method for producing porous carbon according to claim 1, wherein the carbonizable organic polymer fiber is a cellulose fiber, a phenol fiber, or an acrylonitrile fiber.
ルムがポリ塩化ビニリデンフイルム、ポリ塩化ビニール
フイルム、ＰＴＦＥフイルムである請求項（１）の多孔
質炭素の製造法。3. The method for producing porous carbon according to claim 1, wherein the film interposed between the thermosetting resin-impregnated papers is polyvinylidene chloride film, polyvinyl chloride film, or PTFE film.
れる炭素化後の多孔質炭素にピッチ含浸した後、再度炭
素化して得られる多孔質炭素の製造法。4. A method for producing a porous carbon obtained by impregnating pitch of carbonized porous carbon obtained by the method according to any one of claims (1) and (2) and then carbonizing again.
質炭素において ガス透過量＝１５００ｍｌ・mm／hr・ｃｍ2 ・mmAq以上 厚さ方向熱伝導率＝３．０Kcal／ｍ・hr・℃以上 曲げ強さ＝１００Kg／ｃｍ2 以上 の特性を有する多孔質炭素。5. The porous carbon obtained by the method according to claim (4) has a gas permeation amount of 1500 ml · mm / hr · cm 2 · mmAq or more and a thermal conductivity in a thickness direction of 3.0 Kcal / m · hr · ° C. As described above, a porous carbon having characteristics of flexural strength = 100 kg / cm 2 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2410644A JP2674317B2 (en) | 1990-12-14 | 1990-12-14 | Porous carbon plate and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2410644A JP2674317B2 (en) | 1990-12-14 | 1990-12-14 | Porous carbon plate and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04219370A JPH04219370A (en) | 1992-08-10 |
| JP2674317B2 true JP2674317B2 (en) | 1997-11-12 |
Family
ID=18519769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2410644A Expired - Lifetime JP2674317B2 (en) | 1990-12-14 | 1990-12-14 | Porous carbon plate and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2674317B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115572183B (en) * | 2022-11-09 | 2023-05-05 | 航天特种材料及工艺技术研究所 | High-strength high-temperature-resistant heat insulation material and preparation method thereof |
-
1990
- 1990-12-14 JP JP2410644A patent/JP2674317B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04219370A (en) | 1992-08-10 |
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