JPS63222078A - Manufacture of carbon fiber porous body - Google Patents
Manufacture of carbon fiber porous bodyInfo
- Publication number
- JPS63222078A JPS63222078A JP62054587A JP5458787A JPS63222078A JP S63222078 A JPS63222078 A JP S63222078A JP 62054587 A JP62054587 A JP 62054587A JP 5458787 A JP5458787 A JP 5458787A JP S63222078 A JPS63222078 A JP S63222078A
- Authority
- JP
- Japan
- Prior art keywords
- fibers
- short
- short fibers
- carbon fiber
- carbon
- 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
- 229920000049 Carbon (fiber) Polymers 0.000 title claims description 42
- 239000004917 carbon fiber Substances 0.000 title claims description 42
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000000835 fiber Substances 0.000 claims description 84
- 239000000126 substance Substances 0.000 claims description 29
- 239000002243 precursor Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000000463 material Substances 0.000 description 15
- 239000002609 medium Substances 0.000 description 10
- 239000005011 phenolic resin Substances 0.000 description 10
- 239000011295 pitch Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000003763 carbonization Methods 0.000 description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 6
- 229920001568 phenolic resin Polymers 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229920006282 Phenolic fiber Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- Paper (AREA)
- Inert Electrodes (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Filtering Materials (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
- Inorganic Fibers (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
産業上の利用分野
この発明は、燃料電池用電極、特開昭６０−１４７２０
８号公報や同６０−１４７２０９号公報に記載される電
気浸透脱水機用電極、フィルタなどとして好適な炭素繊
維多孔体を製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application This invention is directed to electrodes for fuel cells,
The present invention relates to a method of manufacturing a carbon fiber porous body suitable for use as an electrode for an electroosmotic dehydrator, a filter, etc., as described in Publication No. 8 and Publication No. 60-147209.
従来の技術
炭素繊維の短繊維を炭素で結着してなる炭素繊維多孔体
は、比強度が高く、また耐蝕性等の化学的性質にも優れ
ているため、燃料電池用電極などとして注目されている
。Conventional technology Carbon fiber porous bodies made by binding short carbon fibers with carbon have high specific strength and excellent chemical properties such as corrosion resistance, so they are attracting attention as electrodes for fuel cells. ing.
そのような炭素繊維多孔体を製造する方法はいろいろあ
るが、たとえば特開昭５７−１２９８１４号公報に記載
されているように、バインダたるポリビニルアルコール
などの溶液と、炭素繊維の短繊維とを混合、抄造し、乾
燥して短繊維同士を互いに結着せしめた１麦、フェノー
ル樹脂などの炭素化可能物質の溶液を含浸し、加熱して
炭素化可催物質を炭素化することによるのか普通である
。There are various methods for manufacturing such carbon fiber porous bodies, but for example, as described in JP-A-57-129814, a solution of polyvinyl alcohol as a binder and short carbon fibers are mixed. It is common practice to make paper, dry it, bind short fibers together, impregnate it with a solution of a carbonizable substance such as phenol resin, and heat it to carbonize the carbonizable substance. be.
バインダ溶液と短繊維とを混合、抄造する代わりに、短
繊維を、たとえば渦噴気流等で解繊しながら堆積せしめ
た後、バインダ溶液を噴霧して短繊維同士を結着する場
合もめる。しかしながら、これらの方法は、いずれも、
短繊維同士の結着と炭素化可能物質の溶液の含浸とを全
く別の工程で行うため、工程が長くなり、製造コストが
高くなるという問題がある。また、内部や短繊維同士の
接点等に炭素化可能物質の溶液が十分に含浸されないこ
とがあり、その場合、機械的強度が低下したり、気孔の
大きさや分イ５にむらができたり、導電性が低下する。Instead of mixing the binder solution and short fibers and forming the paper, the short fibers may be deposited while being defibrated by, for example, a vortex jet flow, and then the binder solution may be sprayed to bind the short fibers together. However, all of these methods
Since binding of the short fibers to each other and impregnation with a solution of a carbonizable substance are performed in completely different steps, there is a problem that the steps are longer and the manufacturing cost is higher. In addition, the interior or contact points between short fibers may not be sufficiently impregnated with a solution of carbonizable substances, in which case mechanical strength may decrease, pore size or separation may become uneven, Conductivity decreases.
発明が解決しようとする問題点
この発明は、従来の方法の上述した問題点を解決し、均
質な炭素繊維多孔体を低コストで製造することかできる
方法を提供することを目的としている。Problems to be Solved by the Invention It is an object of the present invention to solve the above-mentioned problems of the conventional methods and to provide a method capable of producing a homogeneous carbon fiber porous body at low cost.
問題点を解決するだめの手段
上）ホした目的を達成するために、この発明においては
、炭素化可能物質を含む抄造媒体と、炭素繊維の短繊維
とを混合、抄造し、乾燥して短繊維同士を互いに結着せ
しめた後、加熱して炭素化可能物質を炭素化することを
特徴とする炭素繊維多孔体の製造方法か提供される。も
っとも、この発明においては、炭素繊維の短繊維を使用
する代わりにその前駆体繊維の短繊維を使用し、加熱に
よって炭素化可能物質を炭素化するのと同時に前駆体繊
維の短繊維をも炭素化し、炭素繊維の短繊維とすること
ができるものである。また、炭素繊維の短繊維と、炭素
繊維の前駆体繊維の短繊維とを併用することもてきるも
のである。Means for Solving the Problems In order to achieve the above object, in this invention, a paper-making medium containing a carbonizable substance and short carbon fibers are mixed, paper-formed, dried and shortened. A method for producing a porous carbon fiber body is provided, which comprises binding fibers together and then heating to carbonize a carbonizable substance. However, in this invention, short fibers of its precursor fibers are used instead of short fibers of carbon fibers, and at the same time as the carbonizable substance is carbonized by heating, the short fibers of the precursor fibers are also carbonized. It can be converted into short carbon fibers. It is also possible to use short carbon fibers and short fibers of carbon fiber precursor fibers together.
この発明をさらに詳細に説明するに、この発明において
は、まず、炭素化可能物質を含む抄造媒体と、炭素繊維
の短繊維および／または炭素繊維の前駆体繊維の短繊維
との混合物を調製する。To explain this invention in more detail, in this invention, first, a mixture of a papermaking medium containing a carbonizable substance and short fibers of carbon fibers and/or short fibers of precursor fibers of carbon fibers is prepared. .
炭素化可能物質は、抄造時に短繊維間に入り込み、後の
乾燥、炭素化を経て短繊維同士を互いに結着するもので
ある。そのような炭素化可能物質としては、たとえば、
フェノール樹脂、フラン樹脂、アクリル樹脂、エポキシ
樹脂、不飽和ポリエステル樹脂、ポリイミド樹脂などの
熱硬化性樹脂や、塩化ビニル樹脂、ナイロン樹脂、ポリ
エステル樹脂、ＡＢＳ樹脂、ポリカーボネー１〜樹脂、
ポリアセタール樹脂、ポリプロピレン樹脂、ポリフェニ
レン（）−ルファイト樹脂、ポリスルホン樹脂などの熱
可塑性樹脂を使用することができる。また、ピッチやタ
ール、セルロース等を使用することができる。なかでも
、炭素化収率が比較的高いフェノール樹脂やピッチであ
るのが好ましい。The carbonizable substance enters between the short fibers during papermaking and binds the short fibers together through subsequent drying and carbonization. Examples of such carbonizable substances include:
Thermosetting resins such as phenol resin, furan resin, acrylic resin, epoxy resin, unsaturated polyester resin, polyimide resin, vinyl chloride resin, nylon resin, polyester resin, ABS resin, polycarbonate resin,
Thermoplastic resins such as polyacetal resin, polypropylene resin, polyphenylene()-ruphite resin, polysulfone resin, etc. can be used. Further, pitch, tar, cellulose, etc. can be used. Among these, phenol resins and pitches, which have relatively high carbonization yields, are preferred.
炭素化可能物質を含む抄造媒体は、上述した炭素化可能
物質の溶液または分散液として用意される。すなわち、
炭素化可能物質は、溶解していてもよく、また懸濁状態
で含まれていてもよいものである。溶媒または分散媒と
しては、たとえば水、メタノール、テ１へラヒドロフラ
ン、ピリジン、キノリン、ベンゼン、トルエン、ジメチ
ルスルホキシドなどを使用することができる。抄造媒体
中にお（プる炭素化可能物質の濃度は、炭素化可能物質
の種類、溶媒または分散媒の種類、抄造媒体と混合され
る短繊維の種類や平均繊維長、得たい多孔体の用途、気
孔率、機械的特性等によって好適な範囲があるものの、
通常、５〜５０重量％、好ましくは２０〜４０重量％と
される。The papermaking medium containing the carbonizable material is prepared as a solution or dispersion of the carbonizable material described above. That is,
The carbonizable substance may be dissolved or contained in a suspended state. As the solvent or dispersion medium, for example, water, methanol, tetrahydrofuran, pyridine, quinoline, benzene, toluene, dimethyl sulfoxide, etc. can be used. The concentration of the carbonizable substance in the papermaking medium depends on the type of carbonizable substance, the type of solvent or dispersion medium, the type and average fiber length of the short fibers mixed with the papermaking medium, and the desired porous material. Although there is a suitable range depending on the application, porosity, mechanical properties, etc.
It is usually 5 to 50% by weight, preferably 20 to 40% by weight.
抄造媒体と混合される短繊維は、上述したように、炭素
繊維および／または炭素繊維の前駆体繊維からなるもの
である。炭素繊維は、従来周知の、ポリアクリロニ１〜
リル系炭素繊維、ピッチ系炭素繊維、セルロース系炭素
繊維など、いずれてあってもよい。前駆体繊維は、加熱
すると炭素化して炭素繊維になるもので、ポリアクリロ
ニｉ〜リル繊維、ピッチ繊維、タール繊維や、それらの
耐炎化繊維のようなものである。ノボロイド繊維を硬化
させた、いわゆる硬化ノボロイド繊維などを使用するこ
ともできる。これらの短繊維の直径は、多孔体の機械的
強度や気孔の大きざ等に影響を及ばず。炭素繊維である
か前駆体繊維でおるかといったことや、多孔体の用途等
によって異なるものの、通常、１〜５０μｍ、好ましく
は５〜２０ｕ、ｍの直径をもつものを使用する。また、
その平均繊維長は、短繊維の種類や抄造媒体の種類等に
よっても異なるものの、抄造の容易さなどを考慮すると
、２〜５０ｍｍであるのか好ましい。さらに好ましい平
均繊維長は、５〜２０ｍｍである。The short fibers mixed with the papermaking medium are composed of carbon fibers and/or carbon fiber precursor fibers, as described above. The carbon fiber is a conventionally well-known polyacryloni 1~
Any of rill-based carbon fibers, pitch-based carbon fibers, cellulose-based carbon fibers, etc. may be used. The precursor fibers are carbonized to become carbon fibers when heated, and include polyacrylonyl fibers, pitch fibers, tar fibers, and flame-resistant fibers thereof. It is also possible to use so-called hardened novoloid fibers obtained by hardening novoloid fibers. The diameter of these short fibers does not affect the mechanical strength of the porous body or the size of the pores. Although it differs depending on whether it is carbon fiber or precursor fiber and the purpose of the porous body, it usually has a diameter of 1 to 50 μm, preferably 5 to 20 μm. Also,
Although the average fiber length varies depending on the type of short fibers and the type of papermaking medium, it is preferably 2 to 50 mm in consideration of ease of papermaking. A more preferable average fiber length is 5 to 20 mm.
さて、この発明においては、次に、上述した抄造媒体と
短繊維とを混合、抄造し、乾燥して溶媒または分散媒を
除去し、短繊維同士が炭素化可能物質で互いに結着され
た、紙状、シート状、板状等の中間素材を得る。このと
き、溶媒または分散媒に、短繊維の分散性を向上させる
ための分散剤や、短繊維同士の結着をより強固に行うた
めのバインダ等を必要に応じて少量添７ＪＨることもで
きる。これらは、後の炭素化工程で分解し、残存しない
ものであるのか好ましい。乾燥は、自然乾燥でも加熱乾
燥でもにいか、炭素化可能物質が熱硬化性樹脂である場
合には、それを乾燥するとともに完全に硬化せしめてあ
くほうか、中間素材の形態保持の面から好ましい。抄造
は、通常の抄紙機等を用いて行えばよい。Now, in this invention, next, the above-mentioned paper-making medium and short fibers are mixed, paper-formed, dried to remove the solvent or dispersion medium, and the short fibers are bonded to each other with a carbonizable substance. Obtain intermediate materials such as paper, sheet, and plate shapes. At this time, a small amount of a dispersant to improve the dispersibility of the short fibers, a binder to more firmly bind the short fibers, etc. can be added to the solvent or dispersion medium as necessary. . It is preferable that these are decomposed in the subsequent carbonization step and do not remain. Drying can be done by natural drying or heat drying.If the carbonizable substance is a thermosetting resin, it is preferable to dry it and completely cure it from the viewpoint of maintaining the shape of the intermediate material. . Paper making may be performed using a normal paper machine or the like.
次に、抄造により得た中間素材を不活性雰囲気中で加熱
し、炭素化可能物質を炭化する。短＋１１ｉ紐が前駆体
繊維である場合には、その炭素化、つまり炭素繊維化も
同時に行われる。これにより炭素繊維多孔体が得られる
。加熱温度は、９００〜３５００’Ｃ１好ましくは１２
００〜３０００’Ｃである。なお、この炭素化処理に先
立って、短繊維同士の結着をにり強固に行ったり、多孔
体の気孔率や密度を調整する目的で、中間素材を加圧処
理覆ることがある。また、短繊維が前駆体繊維からなる
ものでおる場合で、それが加熱にＪ：り溶融するような
ものである場合、たとえばピッチ繊維からなるものであ
る場合には、その繊維形態を保持する目的で酸化による
耐炎化処理などの不融化処理を施しておく。ポリアクリ
ロニトリル繊維の場合は、不融化処理を行わなくても炭
素化できるが、不融化処理を行うと収率や強度が向上す
るので好ましい。また、炭素化可能物質においても、炭
素化時の収率を高める目的で、不融化処理を施すほうが
好ましいものがある。たとえば、フェノール樹脂やピッ
チなどがそうである。Next, the intermediate material obtained by papermaking is heated in an inert atmosphere to carbonize the carbonizable material. When the short +11i string is a precursor fiber, its carbonization, that is, carbon fiber formation, is also performed at the same time. A carbon fiber porous body is thereby obtained. The heating temperature is 900 to 3500'C1, preferably 12
00-3000'C. Note that, prior to this carbonization treatment, the intermediate material may be subjected to pressure treatment for the purpose of strongly binding the short fibers together or adjusting the porosity and density of the porous body. In addition, if the short fibers are made of precursor fibers that melt when heated, for example, if they are made of pitch fibers, the fiber form must be maintained. For this purpose, it is subjected to infusibility treatment such as flame-retardant treatment by oxidation. In the case of polyacrylonitrile fibers, carbonization can be performed without infusibility treatment, but infusibility treatment is preferable because it improves yield and strength. Furthermore, some carbonizable substances are preferably subjected to infusibility treatment for the purpose of increasing the yield during carbonization. Examples include phenolic resin and pitch.
実施例１
フェノール樹脂の１５重量％メタノール溶液と、直径が
１０μｍで、平均繊維長が６ｍｍでおる石炭質ピッチ系
炭素繊維短繊維とを、短繊維が１５重量％になるように
混合、攪拌し、抄造した後、８０′Ｃの熱風で乾燥して
メタノールを除去し、厚みか０．２ｍｍて必る中間素材
を得た。Example 1 A 15% by weight methanol solution of phenolic resin and short carbon fibers having a diameter of 10 μm and an average fiber length of 6 mm were mixed and stirred so that the short fibers were 15% by weight. After papermaking, methanol was removed by drying with hot air at 80'C to obtain an intermediate material with a thickness of about 0.2 mm.
次に、上記中間素材を窒素雰囲気中にて１５００′Ｃに
加熱し、フェノール樹脂を炭素化して厚みが０．１８ｍ
ｍである多孔体を１ｑた。この多孔体は、密度が０．２
ｇ／ｃｍ３で、かつ厚み方向の抵抗率か０．２５０・ｃ
ｍであった。Next, the above intermediate material was heated to 1500'C in a nitrogen atmosphere to carbonize the phenolic resin and reduce the thickness to 0.18 m.
1 q of porous body of m. This porous body has a density of 0.2
g/cm3, and the resistivity in the thickness direction is 0.250・c
It was m.
実施例２
実施例１において、中間素材を１６０°Ｃの温度下に８
Ｋｇ／ｃｍ２の圧力で押圧し、厚みを０．１ｍｍにした
。以下、実施例１と全く同様にして、厚みが０．０９ｍ
ｍである多孔体を得た。この多孔体は、密度が０．４ｇ
／ｃｍ３で、かつ厚み方向の抵抗率が０．１Ω・ｃｍで
必り、燃料電池用集電電極として好適なものであった。Example 2 In Example 1, the intermediate material was heated to 160°C for 8
It was pressed with a pressure of Kg/cm2 to a thickness of 0.1 mm. Hereinafter, in exactly the same manner as in Example 1, the thickness was 0.09 m.
A porous body having a diameter of m was obtained. This porous body has a density of 0.4g
/cm3 and the resistivity in the thickness direction was 0.1 Ω·cm, making it suitable as a current collecting electrode for fuel cells.
＝ ９ 一
実施例３
フェノール樹脂の１５重量％メタノール溶液と、直径が
１０μｍで、平均繊維長が６ｍｍである、ポリアクリロ
ニトリル繊維の短繊維とを、短繊維が３０重量％になる
ように混合、攪拌し、抄造した後、８０’Ｃの熱風で乾
燥してメタノールを除去し、厚みか０．２ｍｍである中
間索イＪを得た。= 9 Example 3 A 15% by weight methanol solution of phenolic resin and short fibers of polyacrylonitrile fibers having a diameter of 10 μm and an average fiber length of 6 mm were mixed so that the short fibers were 30% by weight. After stirring and paper-forming, the mixture was dried with hot air at 80'C to remove methanol, and an intermediate cord J having a thickness of about 0.2 mm was obtained.
次に、上記中間素材を１６０’Ｃの温度下に８Ｋｑ／Ｃ
ｍ２の圧力で押圧し、厚みを０．１ｍｍにした。Next, the above intermediate material was heated to 8 Kq/C at a temperature of 160'C.
It was pressed with a pressure of m2 to a thickness of 0.1 mm.
次に、加圧処理後の中間素材を、空気中にて５’Ｃ／分
の速度で２８０°Ｃまで加熱し、短繊維を耐炎化すると
ともに短繊維同士の結着をより強固なものとした。Next, the intermediate material after pressure treatment is heated to 280°C in air at a rate of 5'C/min to make the short fibers flame resistant and to strengthen the bond between the short fibers. did.
次に、実施例１と全く同様にして、厚みがＯ０Ｑ９ｍｍ
である多孔体を得た。この多孔体は、密度か０．４ｃ＋
／ｃｍ３て、かつ厚み方向の抵抗率か０゜１２Ω・ｃｍ
であった。Next, in exactly the same manner as in Example 1, the thickness was O0Q9mm.
A porous body was obtained. This porous body has a density of 0.4c+
/cm3 and the resistivity in the thickness direction is 0°12Ω・cm
Met.
実施例４
フェノール樹脂の１５重量％メタノール溶液と、直径が
９ｍｍで、平均繊維長が３ｍｍであるポリアクリロニト
リル系炭素繊維の短繊維と、直径が１２μｍで、平均繊
維長が６ｍｍである石炭質ピッチ繊維の短繊維とを、炭
素繊維短繊維が７１重量％、ピッチ繊維短繊維が８重量
％になるように混合、攪拌し、抄造した後、８０’Ｃの
熱風で乾燥してメタノールを除去し、厚みが０．２１ｍ
ｍでおる中間素材を得た。Example 4 A 15% by weight methanol solution of phenolic resin, short fibers of polyacrylonitrile carbon fibers with a diameter of 9 mm and an average fiber length of 3 mm, and carbonaceous pitch with a diameter of 12 μm and an average fiber length of 6 mm. The short fibers were mixed and stirred so that the carbon fiber short fibers were 71% by weight and the pitch fiber short fibers were 8% by weight, and after papermaking, the methanol was removed by drying with hot air at 80'C. , thickness is 0.21m
An intermediate material having a diameter of m was obtained.
次に、上記中間素材を１６０’Ｃの温度下に８ＫＩｌ］
／ｃｍ２の圧力で押圧し、厚みを０．１４．ｍｍにした
後、３°Ｃ／分の昇温速度で２８０’Ｃまで加熱し、ピ
ッチ繊維短繊維を不融化するとともにフェノール樹脂を
硬化させた。Next, the above intermediate material was heated to 160'C for 8Kil]
/cm2 pressure to make the thickness 0.14. mm, and then heated to 280'C at a heating rate of 3°C/min to infusible the short pitch fibers and harden the phenolic resin.
次に、上記中間素材を窒素雰囲気中にて１５００′Ｃに
加熱し、ピッチ繊維短繊維とフェノール樹脂とを炭素化
して厚みが０．１３ｍｍである多孔体を得た。この多孔
体は、密度が０．３８ｇ／Ｃｍ３で、かつ厚み方向の抵
抗率が０．０８０・吐であった。Next, the intermediate material was heated to 1500'C in a nitrogen atmosphere to carbonize the short pitch fibers and the phenol resin to obtain a porous body having a thickness of 0.13 mm. This porous body had a density of 0.38 g/Cm3 and a resistivity in the thickness direction of 0.080.
発明の効果
この発明は、炭素化可能物質を含む抄造媒体と、炭素繊
維短繊維および／または炭素繊維の前駆体繊維の短繊維
とを混合、抄造し、乾燥して短繊維同士を互いに結着せ
しめた後、加熱して炭素化可能物質または炭素化可能物
質と前駆体繊維の短繊維とを炭素化するものであり、上
述した従来の方法のように、短繊維同士の結着と炭素化
可能物質の溶液の含浸とを全く別の工程で行う必要がな
いので、工程が短縮され、製造コストが安くなる。Effects of the Invention This invention mixes a papermaking medium containing a carbonizable substance and short carbon fibers and/or short fibers of carbon fiber precursor fibers, forms the paper, and then dries the short fibers to bind them together. After that, the carbonizable substance or the carbonizable substance and the short fibers of the precursor fiber are carbonized by heating, and as in the conventional method described above, the short fibers are bound together and carbonized. Since impregnation with a solution of a possible substance does not need to be performed in a completely separate process, the process is shortened and manufacturing costs are reduced.
また、炭素化可能物質を含む抄造媒体と短繊維とを混合
、抄造するので、炭素化可能物質が短繊維間によく入り
込み、気孔の大きさや分布が一様になるばか°りか、機
械的強度や導電性にも優れた多孔体を得ることができる
ようになる。In addition, since the papermaking medium containing a carbonizable substance and short fibers are mixed and formed, the carbonizable substance is well penetrated between the short fibers, which not only makes the size and distribution of pores uniform, but also improves mechanical strength. It is now possible to obtain a porous body with excellent conductivity and electrical conductivity.
Claims (3)
繊維とを混合、抄造し、乾燥して前記短繊維同士を互い
に結着せしめた後、加熱して前記炭素化可能物質を炭素
化することを特徴とする炭素繊維多孔体の製造方法。(1) A papermaking medium containing a carbonizable substance and short carbon fibers are mixed and formed, dried to bind the short fibers to each other, and then heated to convert the carbonizable substance into carbon. 1. A method for producing a porous carbon fiber body, the method comprising:
駆体繊維の短繊維とを混合、抄造し、乾燥して前記短繊
維同士を互いに結着せしめた後、加熱して前記炭素化可
能物質と短繊維とを炭素化することを特徴とする炭素繊
維多孔体の製造方法。(2) Mixing a papermaking medium containing a carbonizable substance and short fibers of carbon fiber precursor fibers, forming the paper, drying to bind the short fibers to each other, and then heating to carbonize the fibers. A method for producing a porous carbon fiber body, which comprises carbonizing a carbon fiber and short fibers.
繊維と、炭素繊維の前駆体繊維の短繊維とを混合、抄造
し、乾燥して前記炭素繊維の短繊維および炭素繊維の前
駆体繊維の短繊維同士を互いに結着せしめた後、加熱し
て前記炭素化可能物質と炭素繊維の前駆体繊維の短繊維
とを炭素化することを特徴とする炭素繊維多孔体の製造
方法。(3) Mixing a papermaking medium containing a carbonizable substance, short carbon fibers, and short fibers of a precursor fiber of carbon fibers, forming the paper, and drying the short fibers of carbon fibers and the precursor of carbon fibers. 1. A method for producing a porous carbon fiber body, which comprises binding short fibers of the body fibers to each other, and then heating the carbonizable substance and the short fibers of the carbon fiber precursor fibers to carbonize the carbonizable substance and the short fibers of the carbon fiber precursor fibers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62054587A JPS63222078A (en) | 1987-03-10 | 1987-03-10 | Manufacture of carbon fiber porous body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62054587A JPS63222078A (en) | 1987-03-10 | 1987-03-10 | Manufacture of carbon fiber porous body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63222078A true JPS63222078A (en) | 1988-09-14 |
Family
ID=12974848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62054587A Pending JPS63222078A (en) | 1987-03-10 | 1987-03-10 | Manufacture of carbon fiber porous body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63222078A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010090164A1 (en) * | 2009-02-04 | 2010-08-12 | 三菱レイヨン株式会社 | Porous electrode substrate, method for producing the same, membrane-electrode assembly, and solid polymer-type fuel cell |
| WO2011065327A1 (en) * | 2009-11-24 | 2011-06-03 | 三菱レイヨン株式会社 | Porous electrode base material, process for production thereof, precursor sheet, film-electrode assembly, and solid polymer fuel cell |
-
1987
- 1987-03-10 JP JP62054587A patent/JPS63222078A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010090164A1 (en) * | 2009-02-04 | 2010-08-12 | 三菱レイヨン株式会社 | Porous electrode substrate, method for producing the same, membrane-electrode assembly, and solid polymer-type fuel cell |
| JP5404609B2 (en) * | 2009-02-04 | 2014-02-05 | 三菱レイヨン株式会社 | Porous electrode substrate, method for producing the same, membrane-electrode assembly, and polymer electrolyte fuel cell |
| US8927173B2 (en) | 2009-02-04 | 2015-01-06 | Mitsubishi Rayon Co., Ltd. | Porous electrode substrate, method for producing the same, membrane electrode assembly, and polymer electrolyte fuel cell |
| US8986907B2 (en) | 2009-02-04 | 2015-03-24 | Mitsubishi Rayon Co., Ltd. | Porous electrode substrate, method for producing the same, membrane electrode assembly, and polymer electrolyte fuel cell |
| WO2011065327A1 (en) * | 2009-11-24 | 2011-06-03 | 三菱レイヨン株式会社 | Porous electrode base material, process for production thereof, precursor sheet, film-electrode assembly, and solid polymer fuel cell |
| JPWO2011065327A1 (en) * | 2009-11-24 | 2013-04-11 | 三菱レイヨン株式会社 | Porous electrode substrate, process for producing the same, precursor sheet, membrane-electrode assembly, and polymer electrolyte fuel cell |
| JP5561171B2 (en) * | 2009-11-24 | 2014-07-30 | 三菱レイヨン株式会社 | Porous electrode substrate, process for producing the same, precursor sheet, membrane-electrode assembly, and polymer electrolyte fuel cell |
| US9343751B2 (en) | 2009-11-24 | 2016-05-17 | Mitsubishi Rayon Co., Ltd. | Porous electrode substrate, method for producing the same, precursor sheet, membrane electrode assembly, and polymer electrolyte fuel cell |
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