JPH04219370A - Cellular carbon plate and its production - Google Patents

Cellular carbon plate and its production

Info

Publication number
JPH04219370A
JPH04219370A JP2410644A JP41064490A JPH04219370A JP H04219370 A JPH04219370 A JP H04219370A JP 2410644 A JP2410644 A JP 2410644A JP 41064490 A JP41064490 A JP 41064490A JP H04219370 A JPH04219370 A JP H04219370A
Authority
JP
Japan
Prior art keywords
porous carbon
sheets
film
organic polymer
fiber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2410644A
Other languages
Japanese (ja)
Other versions
JP2674317B2 (en
Inventor
Shigeru Murakami
村上 繁
Takayuki Fukai
孝行 深井
Keigo Sasabayashi
笹林 敬吾
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Showa Denko KK filed Critical Showa Denko KK
Priority to JP2410644A priority Critical patent/JP2674317B2/en
Publication of JPH04219370A publication Critical patent/JPH04219370A/en
Application granted granted Critical
Publication of JP2674317B2 publication Critical patent/JP2674317B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Landscapes

  • Inert Electrodes (AREA)
  • Ceramic Products (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

PURPOSE:To remarkably improve electric and thermal conductivities in the thin plate thickness direction of a cellular carbon thin plate of a large area required as an electrode material in a phosphoric acid type fuel cell. CONSTITUTION:Sheets of prepreg prepared by impregnating sheets of paper made of carbonizable organic polymer fiber with a thermosetting resin are subjected to laminate molding. In the process, thermoplastic sheets are interposed between the sheets of the prepreg to increase bonding force between the sheets. The resultant laminate is carbonized, then impregnated with pitch and subjected to reheating treatment. As a result, electric and thermal conductivities are improved.

Description

【発明の詳細な説明】[Detailed description of the invention]

【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 a method for manufacturing 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 Porous carbon plates for fuel cells are often manufactured by impregnating a carbon fiber sheet or its precursor sheet with a thermosetting resin, 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, with the demand for higher performance and lower costs for fuel cells themselves, demands for improving the physical properties of porous carbon electrodes, reducing variations in quality, reviewing manufacturing methods, etc. have also increased, and various improvement proposals have been made. is being 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。
[0004] For example, a method of obtaining a porous carbon plate with a uniform in-plane surface and high bulk by using various techniques in the papermaking process (Japanese Patent Application Laid-Open No. 1983-1982)
-12681, 60-122711), a manufacturing method that uses carbon powder in combination to improve thermal conductivity (JP-A-6
0-42213, 61-236664), etc.

【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。
[Problems to be Solved by the Invention] In order to improve the performance of fuel cells, porous carbon plates used as electrode materials must not only have high gas permeability in the direction perpendicular to the surface, but also have high electrical conductivity. It is also required to have excellent physical properties such as elasticity 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。
[0006] In the general manufacturing method, that is, a method in which a sheet after papermaking is impregnated with a thermosetting resin and the dried sheet (hereinafter referred to as a prepreg sheet) is laminated and crimped, various improvements have been made in the resin impregnation and lamination crimping steps. 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。
[0007] In order to obtain a bulky product, it is necessary to mold without applying large molding pressure during lamination and pressure bonding, and for this reason, if the amount of resin impregnated is reduced, the adhesion between the sheets will decrease and product defects will occur. On the other hand, when the impregnated amount is increased, the adhesion between the sheets is improved, but the impregnated resin tends to form a film between the sheet layers, reducing 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, conventional techniques have been to use spacers to maintain gas permeability by laminating the laminate (to control the thickness of the laminate), and to improve thermal conductivity by adding fine graphite powder to the impregnating liquid. Efforts have been made to find ways to add it.

【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 efforts have not been very effective in improving productivity or significantly improving 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
[0010] An object of the present invention is to provide a porous carbon plate and a method for producing the same which greatly improves productivity and gas permeability, electrical conductivity, and thermal conductivity in the direction perpendicular to the surface of the product.

【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。
[Means for Solving the Problems] In view of the above-mentioned situation, the inventors of the present invention made extensive research efforts and found that the above-mentioned problems could be solved by using the following manufacturing 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 prepreg sheets are laminated and pressure bonded, carbonizable and thermoplastic films are inserted between each sheet 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。
[0013] If the sheet is impregnated with a large amount of resin,
It is desirable that the amount of resin impregnated in the prepreg sheet is 30% or less, since this will reduce 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
[0014] As the thermoplastic film, any one of polyvinylidene chloride film, vinyl chloride film, polytetrafluoroethylene film, etc. is 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。
[0015] These thermoplastic films have the function of adhering the prepreg sheets to each other, and at the same time make it difficult to form a thermosetting resin carbonized film that 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。
[0016] When a thermoplastic material such as acrylic fiber is used for the prepreg sheet base material, these films also have the 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 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・cm
2 ・mmAq以上のガス透過性を保持していることが
望ましい。
[0018] Due to pitch impregnation and re-firing, the gas permeation rate of the porous carbon plate naturally decreases (10 to 50% decrease), so in order to ensure the gas permeation rate of the product, the porous carbon plate before pitch impregnation must be At the stage of 3000ml・mm/hr・cm
It is desirable to maintain gas permeability of 2.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。
[0019] In order to prevent a decrease in gas permeability and to prevent variations within the surface of the product, it is desirable to adjust the concentration of the pitch for impregnation as appropriate with tar or the like.

【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。
[Operation] The thermoplastic film inserted between the prepreg sheets softens and melts during firing and carbonization of the sheet and film composite laminate, and spreads between the organic polymer fibers that make up the prepreg, strengthening the bond between the sheets. make it a thing. At the same time, it is presumed that the active gas generated during thermal decomposition also renders the organic polymer fibers constituting the prepreg infusible.

【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 impregnating the strong primary structure thus constructed with pitch and covering the entire structure, including the internal surface of the structure, with soft carbon having good graphite crystallinity, the 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。
[Example] The 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 paper sheet, phenol 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×5m
m長をパルプと混合抄紙
Rayon sheet: manufactured by Lintec Corporation
Rayon fiber 5 denier x 5m
M-length paper mixed with pulp

【0026】                       米坪1
00g/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
[0026] Yonetsubo 1
00g/m2 Infusible acrylic sheet: Lintec Co., Ltd. Toho Rayon infusible acrylic 2 denier x 3mm length mixed with pulp to make paper

【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 adjusting pitch concentration for impregnating artificial graphite products

【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。
[0030] Furthermore,
In this experiment, the raw material sheet material was cut into 30 cm square pieces and immersed in a phenolic resin solution at room temperature and pressure to form a prepreg.Pitch impregnation was performed using an impregnation device 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。
Heat treatments such as carbonization and graphitization were carried out by sandwiching the sample between graphite plates and heating it 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。
[Effects of the Invention] 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 greatly contributes to the introduction of phosphoric acid fuel cells into the market in terms of both cost and quality.

Claims (5)

【特許請求の範囲】[Claims] 【請求項1】  炭素化可能な有機高分子繊維を抄紙後
、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。
Claim 1. In a method for producing porous carbon obtained by paper-making carbonizable organic polymer fibers, impregnating the paper base paper with a thermosetting resin, laminating and pressing, and carbonizing, there is a gap between each laminated impregnated paper. A method for producing porous carbon, which comprises interposing a film that can be carbonized during heat-pressing, has thermoplastic properties, and has a function of making thermoplastic organic polymer fibers infusible.
【請求項2】  炭素化可能な有機高分子繊維がセルロ
ース繊維、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 cellulose fiber, phenolic fiber, or acrylonitrile fiber.
【請求項3】  熱硬化性樹脂含浸紙間に介在させるフ
イ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 a polyvinylidene chloride film, a polyvinyl chloride film, or a PTFE film.
【請求項4】  請求項(1)、(2)の方法により得
ら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 porous carbon obtained by impregnating the carbonized porous carbon obtained by the method of claims (1) and (2) with pitch and then carbonizing it again.
【請求項5】  請求項(4)の方法により得られる多
孔質炭素において ガス透過量=1500ml・mm/hr・cm2 ・m
mAq以上厚さ方向熱伝導率=3.0Kcal/m・h
r・℃以上曲げ強さ=100Kg/cm2 以上 の特性を有する多孔質炭素。
[Claim 5] In the porous carbon obtained by the method of claim (4), gas permeation amount = 1500 ml·mm/hr·cm2·m
More than mAq Thickness direction thermal conductivity = 3.0Kcal/m・h
Porous carbon having a bending strength of 100 Kg/cm2 or higher at r.°C or higher.
JP2410644A 1990-12-14 1990-12-14 Porous carbon plate and method for producing the same Expired - Lifetime JP2674317B2 (en)

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 true JPH04219370A (en) 1992-08-10
JP2674317B2 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)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115572183A (en) * 2022-11-09 2023-01-06 航天特种材料及工艺技术研究所 High-strength high-temperature-resistant heat-insulating material and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115572183A (en) * 2022-11-09 2023-01-06 航天特种材料及工艺技术研究所 High-strength high-temperature-resistant heat-insulating material and preparation method thereof

Also Published As

Publication number Publication date
JP2674317B2 (en) 1997-11-12

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