JP2003208905A - Carbonaceous material for fuel cell and dispersion liquid containing the same - Google Patents
Carbonaceous material for fuel cell and dispersion liquid containing the sameInfo
- Publication number
- JP2003208905A JP2003208905A JP2002005381A JP2002005381A JP2003208905A JP 2003208905 A JP2003208905 A JP 2003208905A JP 2002005381 A JP2002005381 A JP 2002005381A JP 2002005381 A JP2002005381 A JP 2002005381A JP 2003208905 A JP2003208905 A JP 2003208905A
- Authority
- JP
- Japan
- Prior art keywords
- fuel cell
- carbonaceous material
- water
- repellent
- resin
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は導電性と撥水性を兼
ね備えた炭素質材料、並びにこれを用いた固体高分子
型、リン酸型などの燃料電池用電極のガス拡散層、触媒
層、セパレーター及びその製造に関するものである。TECHNICAL FIELD The present invention relates to a carbonaceous material having both conductivity and water repellency, and a gas diffusion layer, a catalyst layer, and a separator of a solid polymer type or phosphoric acid type fuel cell electrode using the same. And its manufacture.
【０００２】[0002]
【従来の技術】従来から、燃料の有する化学エネルギー
を直接電気エネルギーに変換する装置として、燃料電池
が知られている。この燃料電池は、一般的に、多孔質材
料を使用した一対の電極、すなわち燃料極（アノード
極）と酸化剤極（カソード極）との間に、電解質を保持
する電解質層を挟み、燃料極の背面に反応ガスとして燃
料ガスを接触させることにより、このときに生じる電気
化学的反応を利用して、上記各電極間から電気エネルギ
ーを取り出すように構成した装置である。2. Description of the Related Art Conventionally, a fuel cell has been known as an apparatus for directly converting chemical energy of fuel into electric energy. This fuel cell generally includes a pair of electrodes using a porous material, that is, a fuel electrode (anode electrode) and an oxidant electrode (cathode electrode), and an electrolyte layer for holding an electrolyte interposed between the electrodes. By bringing a fuel gas as a reaction gas into contact with the back surface of the device, the electrochemical reaction generated at this time is utilized to take out electric energy from between the electrodes.
【０００３】燃料極は、水素から電子を引き抜く触媒
と、燃料である水素のガス拡散層と、集電体としてのセ
パレータが積層された構造である。また酸化剤極は、プ
ロトンと酸素の反応触媒と、空気の拡散層と、セパレー
タが積層された構造である。電解質としてスルホン酸系
のプロトン伝導性の固体高分子膜（電解質膜）を用いた
固体高分子型の燃料電池が、低温での使用について実用
化が有望視されている。The fuel electrode has a structure in which a catalyst for extracting electrons from hydrogen, a gas diffusion layer for hydrogen as a fuel, and a separator as a current collector are laminated. The oxidizer electrode has a structure in which a reaction catalyst of protons and oxygen, an air diffusion layer, and a separator are laminated. A solid polymer type fuel cell using a sulfonic acid-based proton conductive solid polymer membrane (electrolyte membrane) as an electrolyte is expected to be put to practical use at low temperatures.
【０００４】ここで、カソード極での、1/2Ｏ２＋２Ｈ
＋＋２ｅ−→Ｈ２Ｏ の反応で発生した水分を速やかに
除去するために、電極部材には導電性のみならず撥水性
をも付与する必要がある。例えばガス拡散層の製法とし
ては、カーボンペーパーまたはカーボン繊維体から成る
多孔質の材料に、カーボンブラックや黒鉛などの導電材
料と、バインダー兼撥水剤としてのフッ素樹脂とを混合
して塗布することで導電性と撥水性を両立させた層を形
成する方法が知られている（特開平１０−２６１，４２
１号公報、特開２００１−４３，８６５号公報等）。触
媒層は、カーボン粒子等の炭素質材料に白金、ルテニウ
ム等の触媒物質を担持し、バインダー樹脂と混合して電
解質膜上に塗布して形成するか、ガス拡散層上に形成し
た後に電解質膜とホットプレスする等の方法で形成され
る（特開平７−２１１，３２４号公報、特開平８−１３
８，６８３号公報等）。Here, 1 / 2O 2 + 2H at the cathode electrode
In order to quickly remove the water generated by the reaction of + + 2e − → H 2 O, it is necessary to impart not only conductivity but also water repellency to the electrode member. For example, as a method of manufacturing the gas diffusion layer, a conductive material such as carbon black or graphite and a fluororesin serving as a binder and a water repellent are mixed and applied to a porous material made of carbon paper or a carbon fiber body. A method of forming a layer having both conductivity and water repellency is known (Japanese Patent Laid-Open No. 10-261,42).
No. 1, JP 2001-43,865, etc.). The catalyst layer is formed by supporting a catalyst substance such as platinum or ruthenium on a carbonaceous material such as carbon particles and mixing it with a binder resin and coating it on the electrolyte membrane, or after forming it on the gas diffusion layer and then forming the electrolyte membrane. And hot pressing, etc. (Japanese Patent Application Laid-Open Nos. 7-211,324 and 8-13
No. 8,683).
【０００５】また、導電性粒子と、テトラフルオロエチ
レンのような撥水性の材料とから成る層上に触媒担持カ
ーボンブラックからなる層を形成しこれと高分子固体電
解質とで接合体を形成する方法も知られている（特開平
７−２９６，８１８号公報等）。セパレータとしては黒
鉛シートのプレス成形によるもの、炭素焼結体に樹脂を
含浸させた樹脂含浸材、ガラス状カーボン、エポキシ樹
脂等の熱硬化性樹脂に、カーボンブラックや黒鉛等の炭
素質材料を配合してなるもの等が知られている（特開昭
５８−５３，１６７号公報、特開昭６０−３７，６７０
号公報、特開昭６０−２４６，５６８号公報、特開２０
００−２３９，４８８号公報等）。A method of forming a layer of catalyst-supporting carbon black on a layer of conductive particles and a water-repellent material such as tetrafluoroethylene, and forming a bonded body with the solid polymer electrolyte Is also known (Japanese Patent Laid-Open No. 7-296,818, etc.). The separator is made by press molding of a graphite sheet, resin impregnated material in which a carbon sintered body is impregnated with resin, glassy carbon, thermosetting resin such as epoxy resin, and carbonaceous material such as carbon black or graphite is blended. And the like are known (Japanese Patent Laid-Open No. 58-53,167 and Japanese Patent Laid-Open No. 60-37,670).
JP, JP-A-60-246,568, JP, 20
No. 00-239,488).
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、上記の
ような公知の方法でガス拡散層を形成した場合、撥水剤
量が多いと電気的な抵抗値が上がり充分な導電性を保て
ない。逆に、撥水剤量が少ないと、十分な撥水性を得る
事ができずに、ガスの透過の妨げとなり、結果として電
池性能の低下を引き起こしていた。However, when the gas diffusion layer is formed by the known method as described above, if the amount of the water repellent is large, the electrical resistance value increases and sufficient conductivity cannot be maintained. On the contrary, when the amount of the water repellent is small, sufficient water repellency cannot be obtained, which hinders gas permeation, resulting in deterioration of battery performance.
【０００７】触媒層、セパレーターにしても同様の事が
いえる。触媒層は多量の水分が触媒の周りを覆う事によ
り、触媒機能が低下する。また、セパレーターは通常は
ガスを通過させるための溝を形成させるが、セパレータ
ー溝の撥水性が悪いと、水が付着してガス流路が閉鎖す
るとともに、空気極と電解質との境界にできる水分を除
去しなければ、この水分が邪魔をした部分で空気極の反
応が進まなくなり、結果として電池性能の低下を引き起
こしていた。The same applies to the catalyst layer and the separator. In the catalyst layer, a large amount of water covers the periphery of the catalyst, so that the catalytic function is deteriorated. Further, the separator usually forms a groove for passing gas, but when the water repellency of the separator groove is poor, water adheres and the gas flow path is closed, and moisture formed at the boundary between the air electrode and the electrolyte is formed. If the water was not removed, the reaction of the air electrode did not proceed at the portion where this water interfered, resulting in a decrease in battery performance.
【０００８】燃料電池用の導電材料として用いるため
に、炭素質材料のような導電性の材料に撥水化処理を施
す試みは従来より行われている。例えば、特開２０００
−２３９，７０４号公報には、カーボンブラック、カー
ボンペーパー、グラファイト、ニッケル粉末、スポンジ
状チタンといった導電性の材料を、エタノールの存在下
に、各種のシランカップリング剤と混合したり、環状シ
リコーンオイルに分散した上で各種のシランカップリン
グ剤と混合し、撥水化処理を行っている。そして、得ら
れた被処理物の重量変化、拡散反射法による赤外吸収ス
ペクトルから撥水膜が微粒子表面に化学結合した化学吸
着単分子膜である、としている。[0008] For use as a conductive material for fuel cells, attempts have been made so far to subject a conductive material such as a carbonaceous material to a water repellent treatment. For example, JP 2000
-239,704, conductive materials such as carbon black, carbon paper, graphite, nickel powder, and titanium sponge are mixed with various silane coupling agents in the presence of ethanol, or cyclic silicone oil is used. And then mixed with various silane coupling agents for water repellent treatment. Then, from the obtained weight change of the object to be treated and the infrared absorption spectrum by the diffuse reflection method, the water repellent film is a chemical adsorption monomolecular film chemically bonded to the surface of the fine particles.
【０００９】また、特開平６−２５６，００８号公報で
は、カーボン粒子を３５０〜６００℃で１分〜６時間フ
ッ素と反応させることによりフッ化カーボン粒子を得る
こと、これを燃料電池等の電池材料として用いることが
記載されている。Further, in Japanese Unexamined Patent Publication (Kokai) No. 6-256,008, carbon particles are reacted with fluorine at 350 to 600 ° C. for 1 minute to 6 hours to obtain fluorinated carbon particles, which are used in a battery such as a fuel cell. It is described to be used as a material.
【００１０】しかしながら、特開２０００−２３９，７
０４号公報記載の方法の場合、カーボンブラック等の炭
素質材料をアルコールや液状シリコーンに分散して撥水
処理を行っているが、カーボンブラックは極めて凝集し
やすい材料であり、カーボンブラック粒子の一粒一粒を
撥水処理することは勿論、比較的微細な分散状態で処理
すること自体が非常に困難である。たとえフッ化シラン
化合物の膜が単分子膜の状態で被覆していたとしても、
カーボンブラック自体が凝集した状態では、均一な処理
を行うことができない。また、この方法では、撥水性の
物質としては、カーボンブラックの表面の官能基と結合
し得る、アルコキシ基等の官能基を有するシランカップ
リング剤のような特定の物質に限定されてしまう。However, JP-A-2000-239,7
In the method described in Japanese Patent Publication No. 04, a carbonaceous material such as carbon black is dispersed in alcohol or liquid silicone for water repellent treatment. It is very difficult to perform water repellent treatment on a single grain and to treat it in a relatively finely dispersed state. Even if the fluorinated silane compound film is coated as a monomolecular film,
If the carbon black itself is agglomerated, uniform treatment cannot be performed. Further, in this method, the water-repellent substance is limited to a specific substance such as a silane coupling agent having a functional group such as an alkoxy group capable of binding to a functional group on the surface of carbon black.
【００１１】一方、特開平６−２５６，００８号公報記
載の方法では、メソカーボン、マイクロビーズ、サーマ
ルブラック等のカーボン粒子とフッ素との接触は、反応
器内でニッケル製のボートにカーボン粒子を入れた状態
で行われているものであるが、やはり、撥水化剤として
用いることのできる物質は反応器に流通させてボート内
のカーボン粒子と接触し得る、気体あるいは比較的低温
で気化し得る物質に限定されてしまい、極めて狭い選択
肢となってしまう。On the other hand, in the method described in JP-A-6-256,008, when carbon particles such as mesocarbon, microbeads and thermal black are brought into contact with fluorine, the carbon particles are placed in a nickel boat in the reactor. Although it is carried out in a state that it is put in, the substance that can be used as a water repellent agent can be passed through the reactor and contact with the carbon particles in the boat, vaporized at a relatively low temperature. It is limited to the substances that can be obtained, making it an extremely narrow option.
【００１２】本発明は、できる限り少量の撥水剤量にて
十分でかつ長期間にわたる撥水性能と導電性能を両立さ
せる燃料電池用導電材料を提供することを目的とするも
のである。An object of the present invention is to provide a conductive material for a fuel cell in which the water repellent amount is as small as possible and the water repellent performance and the conductive performance are compatible for a long period of time.
【００１３】[0013]
【課題を解決するための手段】本発明者らは上記の課題
に鑑みて鋭意検討を行った。その結果、炭素質材料に特
定の方法で撥水化処理を施して得られた材料は、燃料電
池用材料として撥水性、導電性の要求特性を兼ね備える
という優れた特定を有することを見出して本発明に到達
した。すなわち、本発明は、Means for Solving the Problems The present inventors have made extensive studies in view of the above problems. As a result, it was found that the material obtained by subjecting the carbonaceous material to the water-repellent treatment by a specific method has an excellent specification that it has both required properties of water repellency and conductivity as a fuel cell material. The invention was reached. That is, the present invention is
【００１４】（１）炭素質材料の水分散液に、撥水性物
質を有機溶剤に溶解した溶液を滴下して撥水処理を施し
て成る燃料電池用炭素質材料、（２）炭素質材料がカー
ボンブラック、黒鉛、炭素繊維のうち一種以上である上
記（１）記載の燃料電池用炭素質材料、（３）撥水性物
質がフッ素樹脂、ケイ素樹脂、シランカップリング剤、
及びワックスのうち一種以上である上記（１）又は
（２）に記載の燃料電池用炭素質材料、(1) A carbonaceous material for a fuel cell, which is obtained by adding a solution of a water-repellent substance dissolved in an organic solvent to an aqueous dispersion of a carbonaceous material to perform a water-repellent treatment, and (2) a carbonaceous material. (1) The carbonaceous material for a fuel cell according to (1) above, which is one or more of carbon black, graphite and carbon fiber, (3) the water repellent substance is a fluororesin, a silicone resin, a silane coupling agent,
And a carbonaceous material for a fuel cell according to (1) or (2), which is one or more of waxes,
【００１５】（４）上記（１）〜（３）のいずれかに記
載の燃料電池用炭素質材料を含有する分散液、（５）上
記（１）〜（３）のいずれかに記載の燃料電池用炭素質
材料に触媒成分を担持してなる燃料電池用電極用材料、
（６）上記（５）記載の燃料電池用電極用材料を含有す
る燃料電池用電極、(4) A dispersion containing the carbonaceous material for a fuel cell according to any one of (1) to (3) above, (5) a fuel according to any one of (1) to (3) above. A material for a fuel cell electrode, which comprises a carbonaceous material for a cell carrying a catalyst component,
(6) A fuel cell electrode containing the fuel cell electrode material according to (5) above,
【００１６】（７）上記（１）〜（３）のいずれかに記
載の燃料電池用炭素質材料をバインダー樹脂と配合して
多孔質材料に含浸してなる燃料電池用ガス拡散層、
（８）上記（１）〜（３）のいずれかに記載の燃料電池
用炭素質材料を、熱硬化性樹脂と配合して成形してなる
燃料電池用セパレーター、（９）上記（４）記載の分散
液をバインダー樹脂と配合し、多孔質材料に含浸するこ
とを特徴とする燃料電池用ガス拡散層の製造方法、(7) A gas diffusion layer for a fuel cell obtained by blending the carbonaceous material for a fuel cell according to any one of (1) to (3) above with a binder resin and impregnating the porous material.
(8) A fuel cell separator formed by blending the carbonaceous material for fuel cell according to any one of (1) to (3) above with a thermosetting resin, and molding (9) above (4). A method for producing a gas diffusion layer for a fuel cell, which comprises blending the dispersion liquid with a binder resin and impregnating the porous material,
【００１７】（１０）上記（４）記載の分散液を熱硬化
性樹脂と配合して成形することを特徴とする燃料電池用
セパレーター、に存する。(10) A separator for a fuel cell, characterized in that the dispersion according to (4) above is blended with a thermosetting resin and molded.
【００１８】[0018]
【発明の実施の形態】以下、本発明を詳細に説明する。
〔炭素質材料〕本発明で用いる炭素質材料としては、導
電性を有する炭素質材料であれば特に制限されない。好
ましくは、耐蝕性及び導電性の高い材料、例えばアセチ
レンブラック、ファーネスブラック、チャンネルブラッ
ク、ケッチェンブラックなどのカーボンブラック、黒
鉛、活性炭、カーボン繊維、カーボンナノチューブなど
が挙げられる。これらの炭素質材料を一種、又は二種以
上使用してもよい。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. [Carbonaceous Material] The carbonaceous material used in the present invention is not particularly limited as long as it is a carbonaceous material having conductivity. Preferably, a material having high corrosion resistance and high conductivity, for example, carbon black such as acetylene black, furnace black, channel black, and Ketjen black, graphite, activated carbon, carbon fiber, carbon nanotube and the like can be mentioned. You may use these carbonaceous materials 1 type (s) or 2 or more types.
【００１９】これらの炭素質材料のうち、特に好ましく
は高比表面積や高ストラクチャーを有した導電性カーボ
ンブラックを用いる。これは、特に高い導電性を有し、
且つ十分に微細な粒子であることから他の成分例えばバ
インダー樹脂等に微分散して均一な物性を付与できるこ
と、またカーボンペーパー等の多孔質材料の微細な空隙
を充填するために好都合なためである。導電性カーボン
ブラックの中でも特に、熱処理して結晶子を発達させた
黒鉛化カーボンブラックを用いることにより、より一層
の高い導電性と、バインダー樹脂等のマトリクス成分へ
の優れた分散性を得ることができる。Of these carbonaceous materials, conductive carbon black having a high specific surface area and a high structure is particularly preferably used. It has a particularly high conductivity,
And since it is sufficiently fine particles, it is possible to finely disperse it in other components such as a binder resin to provide uniform physical properties, and it is convenient for filling fine voids of a porous material such as carbon paper. is there. Among the conductive carbon blacks, it is possible to obtain higher conductivity and excellent dispersibility in the matrix component such as the binder resin by using the graphitized carbon black in which the crystallite is developed by heat treatment. it can.
【００２０】炭素質材料の比表面積は限定されないが、
通常、１０〜１５００ｍ２／ｇ、好ましくは１０〜５０
０ｍ２／ｇの範囲から選択することにより微細な空隙へ
の充填、導電面積の確保を図ることができる。炭素質材
料の粒径も限定されないが、一般的には平均一次粒子径
として０．０１〜１μｍ、好ましくは０．０１〜０．２
μｍ程度である。Although the specific surface area of the carbonaceous material is not limited,
Usually 10 to 1500 m 2 / g, preferably 10 to 50
By selecting from the range of 0 m 2 / g, it is possible to fill the minute voids and secure the conductive area. The particle size of the carbonaceous material is not limited, but generally the average primary particle size is 0.01 to 1 μm, preferably 0.01 to 0.2.
It is about μm.
【００２１】〔撥水化処理〕上述した炭素質材料を、撥
水性物質で表面処理して撥水性を付与する。撥水処理
は、まず炭素質材料の水分散液を用意し、撥水性物質の
有機溶媒溶液をここに滴下して炭素質材料を有機溶媒相
に移行させる、いわゆるフラッシングを利用する方法で
処理を行う。この方法によれば、微細な分散が困難な小
粒子径の炭素質材料を予め水中で微分散しているため撥
水性物質での処理が均一に行える。また、有機溶媒を適
宜選択することにより、ここに溶解又は均一分散可能な
撥水性物質であればいずれも使用可能であることから、
撥水性物質の選択肢が大きく広がる。このため、例え
ば、ポリテトラフルオロエチレン（ＰＴＦＥ）のよう
な、炭素質材料と反応し得る官能基を有さない物質を用
いて撥水処理を行うこともでき、少量でも撥水効果の高
い物質を選択することで導電性を維持しつつ撥水性を付
与した導電材料を提供できる。[Water repellent treatment] The carbonaceous material described above is surface-treated with a water repellent substance to impart water repellency. For the water repellent treatment, first, an aqueous dispersion liquid of a carbonaceous material is prepared, and a solution of a water repellent substance in an organic solvent is dropped here to transfer the carbonaceous material to an organic solvent phase. To do. According to this method, since the carbonaceous material having a small particle size, which is difficult to be finely dispersed, is finely dispersed in water in advance, the treatment with the water-repellent substance can be performed uniformly. Further, by appropriately selecting the organic solvent, any water-repellent substance that can be dissolved or uniformly dispersed therein can be used,
The choice of water repellent materials will be greatly expanded. Therefore, the water repellent treatment can be performed using a substance having no functional group capable of reacting with the carbonaceous material, such as polytetrafluoroethylene (PTFE), and a substance having a high water repellent effect even in a small amount. By selecting, it is possible to provide a conductive material having water repellency while maintaining conductivity.
【００２２】〔撥水性物質〕撥水性物質としては、撥水
性の高い材料、例えばＰＴＦＥ（ポリテトラフルオロエ
チレン）、ＦＥＰ（フッ化エチレンポリプロピレンコポ
リマー）、ＰＦＡ（テトラフルオロエチレン−パーフル
オロアルキルビニルエーテルコポリマー）、ＥＴＦＥ
（エチレン・テトラフルオロエチレン共重合体）、ＰＣ
ＴＦＥ（ポリクロロトリフルオロエチレン）、ＰＶＤＦ
（ポリフッ化ビニリデン）、Ｅ−ＣＴＦＥ（三フッ化塩
化エチレン−エチレンコポリマー）などのフッ素樹脂、
ケイ素樹脂、シランカップリング剤、ワックスが挙げら
れるが、特に撥水効果が高いＰＴＦＥが好ましい。[Water-Repellent Substance] As the water-repellent substance, a highly water-repellent material such as PTFE (polytetrafluoroethylene), FEP (fluorinated ethylene polypropylene copolymer), PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) , ETFE
(Ethylene / tetrafluoroethylene copolymer), PC
TFE (polychlorotrifluoroethylene), PVDF
(Polyvinylidene fluoride), E-CTFE (trifluorochloroethylene-ethylene copolymer) and other fluororesins,
Silicon resin, a silane coupling agent, and a wax may be mentioned, and PTFE having a particularly high water repellency is particularly preferable.
【００２３】好ましくは、処理後に除去が容易な有機溶
媒を用い、ここに溶解又は均一に分散可能な撥水性物質
を選択すれば良い。有機溶媒としては例えば、トルエ
ン、キシレン、テトラハイドロフラン、ｎ−ヘキサノン
など、水に難可溶なものが挙げられる。また、これらの
有機溶媒に溶解又は均一に分散可能な撥水性物質として
は、フッ素樹脂、シリコン樹脂等が挙げられる。It is preferable to use an organic solvent that can be easily removed after the treatment and select a water-repellent substance that can be dissolved or uniformly dispersed therein. Examples of the organic solvent include those which are hardly soluble in water, such as toluene, xylene, tetrahydrofuran, and n-hexanone. Further, examples of the water-repellent substance which can be dissolved or uniformly dispersed in these organic solvents include fluororesins and silicone resins.
【００２４】炭素質材料と撥水性物質との量比は、所望
する撥水性の程度に応じて適宜選択すれば良いが、一般
には、炭素質材料１００重量部に対して撥水性物質０．
５重量部〜１５重量部の範囲、特に好ましくは炭素質材
料１００重量部に対して撥水性物質１重量部〜１０重量
部の範囲である。この範囲で特に撥水性と導電性のバラ
ンスに優れている。炭素質材料１００重量部に対して撥
水性物質が０．５部未満では撥水性が十分でない傾向に
ある。一方、１５重量部を超えると導電性が十分でない
ことがある。The amount ratio of the carbonaceous material and the water-repellent substance may be appropriately selected according to the desired degree of water repellency, but generally, the water-repellent substance 0.
It is in the range of 5 parts by weight to 15 parts by weight, and particularly preferably in the range of 1 part by weight to 10 parts by weight of the water-repellent substance with respect to 100 parts by weight of the carbonaceous material. Within this range, the balance between water repellency and conductivity is excellent. If the water-repellent substance is less than 0.5 parts by weight with respect to 100 parts by weight of the carbonaceous material, the water repellency tends to be insufficient. On the other hand, if it exceeds 15 parts by weight, the conductivity may be insufficient.
【００２５】以上説明したように炭素質材料を特定の方
法で撥水性物質で処理して撥水性を付与することによ
り、導電性と撥水性のバランスの取れた導電性炭素材料
を得ることができる。この、本発明の炭素質材料に、バ
インダー的役割を持たせるための撥水剤、水又は有機溶
剤と任意の割合で混合し、カーボンペーパー、カーボン
繊維体等から成る多孔質材料に含浸する事で燃料電池用
電極のガス拡散層を得る事ができる。As described above, by treating the carbonaceous material with a water-repellent substance by a specific method to impart water repellency, it is possible to obtain a conductive carbon material having a well-balanced conductivity and water repellency. . The carbonaceous material of the present invention may be mixed with a water repellent agent for having a role of a binder, water or an organic solvent at an arbitrary ratio, and then impregnated into a porous material such as carbon paper or carbon fiber body. Thus, the gas diffusion layer of the fuel cell electrode can be obtained.
【００２６】ここで用いることのできる有機溶剤、撥水
剤は特に限定されず、従来より燃料電池用ガス拡散層を
形成する際に用いられているものを適宜、使用すれば良
い。具体的には、バインダー的役割を持たせるための撥
水剤としては例えば、その撥水性、結着性の優れている
点からフッ素樹脂が好ましく、より具体的にはＦＥＰ、
ＰＴＦＥ、ＥＴＦＥ、パーフルオロスルホン酸樹脂の
他、カルボキシル基や水酸基を付与したりグラフト処理
して有機溶剤への溶解性を付与した溶剤可溶型フッ素樹
脂（旭硝子（株）製「ルミフロンＬＦ１００」、「ルミ
フロンＬＦ２００」、「ルミフロンＬＦ３０２」、「ル
ミフロンＬＦ４００」、「ルミフロンＬＦ５５４」、
「ルミフロンＬＦ６００」、セントラル硝子（株）製
「セフラルコートＡ１０１Ｅ」、「セフラルコートＡ２
０２Ｂ」、「セフラルコートＡ４０２Ｂ」、「セフラル
コートＡ６１０Ｘ」、「セフラルコートＡ６７０Ｘ」、
「セフラルコートＡ６８０ＸＳ」、「セフラルコートＷ
Ｓ２５０」（水系）、「セフラルコートＦＧ７００Ｘ」
（グラフト処理品））等の溶剤可溶型フッ素樹脂等が挙
げられる。また、本発明の炭素質材料、撥水剤、水又は
有機溶剤の割合も特に限定されず、含浸作業に適した物
性に調整すれば良い。The organic solvent and water repellent that can be used here are not particularly limited, and those conventionally used when forming the gas diffusion layer for a fuel cell may be appropriately used. Specifically, as the water repellent for giving a role as a binder, for example, a fluororesin is preferable from the viewpoint of its excellent water repellency and binding property, and more specifically, FEP,
In addition to PTFE, ETFE, and perfluorosulfonic acid resins, solvent-soluble fluororesins (“Lumiflon LF100” manufactured by Asahi Glass Co., Ltd.) to which a carboxyl group or a hydroxyl group has been added or graft treatment has been performed to impart solubility to organic solvents. "Lumiflon LF200", "Lumiflon LF302", "Lumiflon LF400", "Lumiflon LF554",
"Lumiflon LF600", "Cefural Coat A101E" manufactured by Central Glass Co., Ltd., "Cefural Coat A2"
02B ”,“ Sephralcoat A402B ”,“ Sephralcoat A610X ”,“ Sephralcoat A670X ”,
"Cefural coat A680XS", "Cefural coat W
S250 "(water system)," Sephral coat FG700X "
(Graft-treated product) and the like. Solvent-soluble fluororesins and the like. Further, the proportions of the carbonaceous material, the water repellent, the water or the organic solvent of the present invention are not particularly limited, and may be adjusted to physical properties suitable for the impregnation work.
【００２７】この際、必要に応じて適宜、界面活性剤、
樹脂などを分散剤として使用しても良い。カーボンペー
パー、カーボン繊維体は空隙部が多く、面方向の導電性
は高いが厚み方向の導電性は面方向に比べて低いもので
あるため、空隙部に本発明の炭素質材料を充填させるこ
とで、導電性を安定させる目的も達成できる。また、本
発明の燃料電池用炭素材料を、予め有機溶媒あるいは水
性媒体（乾燥により除去できるものが望ましく、例えば
見ず、エタノール、プロピルアルコールなどのアルコー
ル類、ベンゼン、トルエンなどのハイドロカーボン、ア
セテート、エーテル、ラクトン、アミン、アミド、ハロ
ゲン化アルキルなどが挙げられる）に分散した分散液と
しておき、これをバインダー樹脂と配合して多孔質材料
に含浸する方法を採ることもできる。このようにすれ
ば、炭素質材料のバインダー樹脂への微分散が比較的容
易に可能である。At this time, if necessary, a surfactant,
You may use resin etc. as a dispersing agent. Since carbon paper and carbon fiber bodies have many voids and have high conductivity in the plane direction, but conductivity in the thickness direction is lower than that in the plane direction, it is necessary to fill the voids with the carbonaceous material of the present invention. Thus, the purpose of stabilizing the conductivity can also be achieved. Further, the carbon material for a fuel cell of the present invention, an organic solvent or an aqueous medium (which can be removed by drying in advance is desirable, for example, ethanol, alcohols such as propyl alcohol, benzene, hydrocarbons such as toluene, acetate, It is also possible to employ a method in which a dispersion liquid is dispersed in ether, lactone, amine, amide, alkyl halide, etc.), and this is mixed with a binder resin to impregnate the porous material. By doing so, fine dispersion of the carbonaceous material in the binder resin is relatively easy.
【００２８】本発明の導電性と撥水性を兼ね備えた燃料
電池用炭素質材料は単独使用しても撥水効果を発揮でき
るため、さらに別個に撥水剤を添加しなくとも良く、本
発明の炭素質材料と、撥水効果を有さないバインダー樹
脂とを、水又は有機溶剤と任意の割合で混合し、カーボ
ンペーパー、カーボン繊維体等の多孔質材料に含浸して
燃料電池用電極のガス拡散層を得る事ができる。Since the carbonaceous material for fuel cells having both conductivity and water repellency of the present invention can exhibit the water repellency effect even when used alone, it is not necessary to add a water repellent agent separately. A carbonaceous material and a binder resin having no water repellent effect are mixed with water or an organic solvent at an arbitrary ratio and impregnated into a porous material such as carbon paper or a carbon fiber body to form a gas for a fuel cell electrode. A diffusion layer can be obtained.
【００２９】この場合には、バインダー樹脂としては撥
水剤としても用いられるもの以外の、固着力の強いアク
リル系、ウレタン系、エポキシ系、ポリエステル系など
公知のバインダー樹脂を少量使用すれば良いことから、
多孔質材料に強固に固着させる事も可能であり、導電材
料としての炭素質材料の充填率を増加させることが可能
である。この場合も必要に応じて界面活性剤、樹脂など
を分散剤として使用しても良く、カーボンペーパー、カ
ーボン繊維体等の多孔質材料の空隙部に本発明の炭素質
材料を充填させることで、導電性を安定させる目的も達
成できる。In this case, as the binder resin, a small amount of a known binder resin such as acrylic, urethane, epoxy, or polyester resin having a strong adhesive strength may be used in addition to the binder resin which is also used as the water repellent. From
It is also possible to firmly adhere to the porous material, and it is possible to increase the filling rate of the carbonaceous material as the conductive material. Also in this case, if necessary, a surfactant, a resin or the like may be used as a dispersant, and carbon paper, by filling the carbonaceous material of the present invention into the voids of a porous material such as a carbon fiber body, The purpose of stabilizing the conductivity can also be achieved.
【００３０】本発明の導電性と撥水性を兼ね備えた炭素
質材料を公知の方法にて、白金、ルテニウム等の触媒物
質を担持させることにより撥水性触媒として使用するこ
とができる。白金等の触媒物質を担持させた本発明の燃
料電池用炭素質材料に、バインダー樹脂、水又は有機溶
剤を任意の割合で混合し、カーボンペーパー、カーボン
繊維体等の多孔質材料に含浸塗布する事で燃料電池用触
媒層を得る事ができる。必要に応じて界面活性剤、樹脂
などを分散剤として使用しても良い。本発明の燃料電池
用炭素質材料は単独使用でも撥水効果を有するため、バ
インダー樹脂としては撥水効果を有するもの以外にも、
アクリル系などの公知のバインダー樹脂を使用すること
ができる。The carbonaceous material having both conductivity and water repellency of the present invention can be used as a water repellent catalyst by supporting a catalyst substance such as platinum or ruthenium by a known method. The carbonaceous material for fuel cells of the present invention supporting a catalyst substance such as platinum is mixed with a binder resin, water or an organic solvent at an arbitrary ratio, and impregnated and applied to a porous material such as carbon paper or carbon fiber body. By doing so, a catalyst layer for a fuel cell can be obtained. If necessary, a surfactant, a resin or the like may be used as a dispersant. The carbonaceous material for a fuel cell of the present invention has a water-repellent effect even when used alone. Therefore, in addition to a binder resin having a water-repellent effect,
A known binder resin such as an acrylic resin can be used.
【００３１】本発明の燃料電池用炭素質材料を、例えば
特開２０００−２３９，４８８号公報に記載されている
ように、熱硬化性樹脂と配合して成形することにより、
撥水性を備えた燃料電池用セパレーターを得る事ができ
る。By blending the carbonaceous material for fuel cells of the present invention with a thermosetting resin and molding as described in, for example, Japanese Patent Application Laid-Open No. 2000-239,488,
A fuel cell separator having water repellency can be obtained.
【００３２】[0032]
【実施例】（実施例１〜４）炭素質材料として、表−１
に物性を示す市販のカーボンブラックＡを用い、撥水性
物質として、溶剤可溶型フッ素樹脂（「ルミフロンLF20
0」、旭硝子（株）製）をトルエンに分散した分散液
（以下「フッ素樹脂分散液」という）を用い、表−２に
示す配合比率（炭素質材料と溶解性フッ素樹脂との固形
分換算）で、以下の操作を行った。Examples (Examples 1 to 4) As a carbonaceous material, Table-1
As a water-repellent substance, a solvent-soluble fluororesin (“Lumiflon LF20
0 ", manufactured by Asahi Glass Co., Ltd., in a dispersion liquid (hereinafter referred to as" fluororesin dispersion liquid ") dispersed in toluene, and blending ratios shown in Table 2 (solid content conversion of carbonaceous material and soluble fluororesin) ), The following operations were performed.
【００３３】カーボンブラックＡをイオン交換水に２．
５重量％となるよう添加し、ホモミキサーで９０００ｒ
ｐｍ、３０分、分散した。この液を攪拌しながら「フッ
素樹脂分散液」を滴下して撥水処理した。トルエン溶液
滴下後数分攪拌してから２００メッシュでメッシュ濾過
した。メッシュ濾過後、一晩常温乾燥した後８０℃の真
空乾燥機で乾燥し、撥水化炭素質材料を得た。1. Carbon black A in ion-exchanged water
Add 5% by weight and use a homomixer for 9000r.
pm, dispersed for 30 minutes. While stirring this liquid, the "fluorine resin dispersion liquid" was added dropwise for water repellent treatment. After the toluene solution was added dropwise, the mixture was stirred for several minutes and then filtered with a mesh of 200 mesh. After filtering the mesh, it was dried at room temperature overnight and then dried in a vacuum dryer at 80 ° C. to obtain a water repellent carbonaceous material.
【００３４】[0034]
【表１】 [Table 1]
【００３５】表−１中、５μｍ以上粗粒分（５μｍフィ
ルター残）は、ノニオン系分散剤（例えば、ニッサン
（株）製「ＮＳ２２０」）を５％溶解した純水４００ｍ
ｌ中にカーボンブラック２０ｇをホモジナイザー４００
０ｒｐｍで３０分間分散させる。この分散液をまず、孔
径５μｍのナイロン製フィルターで同様に濾過し、フィ
ルター上の残渣を秤量して算出した。In Table 1, 5 μm or more of coarse particles (5 μm filter residue) is 400 m of pure water in which 5% of a nonionic dispersant (for example, “NS220” manufactured by Nissan Co., Ltd.) is dissolved.
20 g of carbon black in 1 l of homogenizer 400
Disperse for 30 minutes at 0 rpm. This dispersion was first filtered with a nylon filter having a pore size of 5 μm in the same manner, and the residue on the filter was weighed and calculated.
【００３６】１５００℃のＨ２量は、１０５℃で１時間
乾燥したカーボンブラック０．１〜０．５ｇを耐熱製の
磁製サンプル管に入れ、１０−５トール以下まで減圧し
た後、１５００℃に昇温してある電気炉で３０分間加熱
し、脱離してきたガスをクロマトグラフィーで分析して
Ｈ２量を定量した。The amount of H 2 at 1500 ° C. is such that 0.1 to 0.5 g of carbon black dried at 105 ° C. for 1 hour is put into a heat-resistant porcelain sample tube and the pressure is reduced to 10 −5 Torr or less, then 1500 ° C. After heating for 30 minutes in an electric furnace whose temperature was raised to 1, the desorbed gas was analyzed by chromatography to determine the amount of H 2 .
【００３７】吸着水分量は、単位比表面積当たりの相対
圧（Ｐ／Ｐｏ）０．４における値であり、コールター・
クォリティー・カウンター社製の「オムニソープ１００
ＣＸ」を用い「コールター・オムニソープ・オペレータ
ーズ・ガイド（１９９１年２月発行）」に記載されてい
る条件で測定した。ただし、カーボンブラックの前処理
は、１０−５トール以下の真空状態で３００℃で３時間
実施した。平均粒子径は電子顕微鏡による算術平均径、
比表面積は低温窒素吸着法（ＪＩＳＫ６２１７による）
による値、ＤＢＰ吸油量はＡＳＴＭ Ｄ−３４９３−８
８による値である。The amount of adsorbed water is a value at a relative pressure (P / Po) per unit specific surface area of 0.4, and
"Omni soap 100" manufactured by Quality Counter
It was measured under the conditions described in "Coulter Omnithorpe Operator's Guide (issued in February 1991)" using "CX". However, the pretreatment of carbon black was performed at 300 ° C. for 3 hours in a vacuum state of 10 −5 Torr or less. The average particle diameter is the arithmetic average diameter by an electron microscope,
Specific surface area is low temperature nitrogen adsorption method (according to JISK6217)
Value, DBP oil absorption is ASTM D-3493-8
The value is 8.
【００３８】得られた撥水化炭素質材料について、以下
の評価試験を行った。
（撥水性試験）試料０．１ｇとイオン交換水１０ｇをサ
ンプル瓶に入れ、ふたをして良く振った後の状態を、以
下の基準により目視で判断して評価する。The water-repellent carbonaceous material obtained was subjected to the following evaluation tests. (Water repellency test) 0.1 g of the sample and 10 g of ion-exchanged water are put in a sample bottle, and the state after the lid is shaken well is evaluated visually by the following criteria.
【００３９】＜撥水性の基準＞
第１段階：試料の浮遊状態…大部分浮遊しているもの
を、撥水性が高いものと判断する。
第２段階：液のにごり…にごりなしのものを、撥水性が
高いものと判断する。この２点で撥水性を○△×で評価
する。結果を表−３に示す。<Water Repellent Criteria> First Stage: Floating State of Sample ... Most floating samples are judged to have high water repellency. Second stage: Liquid turbidity: No turbidity is judged to have high water repellency. Water repellency is evaluated by ◯ Δx at these two points. The results are shown in Table-3.
【００４０】（導電性試験）試料の粉体抵抗を三菱化学
（株）製「ロレスタPA」を用いて測定した。温度は常
温、加重１６ｋｇ／ｃｍ２で行った。結果を表−３に示
す。フッ素樹脂で撥水処理しても粉体抵抗は処理前と同
じオーダーの数値にとどまっていることがわかる。(Conductivity test) The powder resistance of the sample was measured using "Loresta PA" manufactured by Mitsubishi Chemical Corporation. The temperature was room temperature and the load was 16 kg / cm 2 . The results are shown in Table-3. It can be seen that even if the water repellent treatment is performed with the fluororesin, the powder resistance remains on the same order as before the treatment.
【００４１】（実施例５、６）炭素質材料としてカーボ
ンブラックＡに代えて市販のカーボンブラックＢ（表−
１に物性を示す）を用いた以外は、実施例１〜４と同様
の操作を行い、撥水化炭素質材料を得た。評価試験結果
を、表−３に示す。(Examples 5 and 6) Commercially available carbon black B (Table-
The same operation as in Examples 1 to 4 was performed, except that the water-repellent carbonaceous material was obtained. The evaluation test results are shown in Table-3.
【００４２】（実施例７、８）炭素質材料としてカーボ
ンブラックＡに代えて市販のカーボンブラックＣ（表−
１に物性を示す）を用いた以外は、実施例１〜４と同様
の操作を行い、撥水化炭素質材料を得た。評価試験結果
を、表−３に示す。Examples 7 and 8 Commercially available carbon black C (Table-
The same operation as in Examples 1 to 4 was performed, except that the water-repellent carbonaceous material was obtained. The evaluation test results are shown in Table-3.
【００４３】（比較例１）撥水処理をしていないカーボ
ンブラックＡについての評価試験結果を表−３に示す。(Comparative Example 1) Table 3 shows the evaluation test results for the carbon black A not subjected to the water repellent treatment.
【００４４】（比較例２）撥水処理をしていないカーボ
ンブラックＢについての評価試験結果を表−３に示す。(Comparative Example 2) Table 3 shows the evaluation test results for carbon black B not subjected to the water repellent treatment.
【００４５】（比較例３）撥水処理をしていないカーボ
ンブラックＣについての評価試験結果を表−３に示す。(Comparative Example 3) Table 3 shows the evaluation test results for the carbon black C not subjected to the water repellent treatment.
【００４６】[0046]
【表２】 [Table 2]
【００４７】[0047]
【表３】 [Table 3]
【００４８】本発明の撥水化処理した炭素質材料は、極
微細な粒子状態に分散した炭素質材料の表面に撥水処理
を施していることから、撥水性物質の寄与する表面積が
大きく、少量で撥水効果を発揮していると考えられる。
また、フラッシング処理を用いることにより、幅広い選
択肢の撥水性物質の使用が可能であり、少量で高い撥水
効果を有する物質を用いることで撥水性を付与しつつ高
い導電性を保つことが可能である。The water-repellent treated carbonaceous material of the present invention has a large surface area contributed by the water-repellent substance because the surface of the carbonaceous material dispersed in the state of extremely fine particles is subjected to the water-repellent treatment. It is believed that a small amount of water repellent effect is exhibited.
Further, by using the flushing treatment, a wide variety of water repellent substances can be used, and by using a substance having a high water repellent effect in a small amount, it is possible to impart water repellency and maintain high conductivity. is there.
【００４９】本発明の導電性と撥水性を兼ね備えた炭素
質材料を燃料電池用ガス拡散層に使用した場合には、バ
インダー兼撥水剤として使用していた撥水剤の使用量を
大幅に低減させることが可能である。このためにガス拡
散層の電気的な抵抗値を大幅に下げる事が可能となり、
電池性能を向上させることが期待できる。When the carbonaceous material having both conductivity and water repellency of the present invention is used in the gas diffusion layer for a fuel cell, the amount of the water repellent used as the binder and the water repellent is greatly increased. It is possible to reduce. For this reason, it is possible to significantly reduce the electrical resistance value of the gas diffusion layer,
It can be expected to improve battery performance.
【００５０】また、本発明の導電性と撥水性を兼ね備え
た炭素質材料に白金等の触媒物質を担持させて触媒成分
として使用した場合、バインダー兼撥水剤として使用し
ていた撥水剤の使用量を大幅に低減させる事が可能とな
り、電気的な抵抗値を大幅に下げる事が可能となり、電
池性能を向上させることが期待できる。When a carbonaceous material having both conductivity and water repellency according to the present invention is used as a catalyst component by supporting a catalyst substance such as platinum, the water repellent agent used as a binder and a water repellent agent is used. It is possible to greatly reduce the amount used, it is possible to greatly reduce the electrical resistance value, and it can be expected that the battery performance will be improved.
【００５１】また、本発明の導電性と撥水性を兼ね備え
た炭素質材料は単独使用においても撥水性を持ち合わせ
ていることより、撥水剤以外のバインダー樹脂で固着さ
せてガス拡散層を得ることができる。Since the carbonaceous material of the present invention having both conductivity and water repellency has water repellency even when used alone, it can be fixed with a binder resin other than a water repellent to obtain a gas diffusion layer. You can
【００５２】また、セパレーター用途に使用した場合、
熱硬化性樹脂等のセパレーター材料樹脂と混合し、導電
性と撥水性とを両立して発揮させる事が可能である。When used for a separator,
It is possible to achieve both conductivity and water repellency by mixing with a separator material resin such as a thermosetting resin.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 5H018 AA04 AA06 AS01 BB01 BB05 BB06 BB08 BB12 DD05 DD06 EE03 EE06 EE08 EE16 EE17 EE18 5H026 AA04 AA06 BB03 CX02 CX03 CX07 EE05 EE06 EE17 EE18 ─────────────────────────────────────────────────── ─── Continued front page F-term (reference) 5H018 AA04 AA06 AS01 BB01 BB05 BB06 BB08 BB12 DD05 DD06 EE03 EE06 EE08 EE16 EE17 EE18 5H026 AA04 AA06 BB03 CX02 CX03 CX07 EE05 EE06 EE17 EE18
Claims (10)
機溶剤に溶解した溶液を滴下して撥水処理を施して成る
燃料電池用炭素質材料。1. A carbonaceous material for a fuel cell, which is obtained by adding a solution of a water-repellent substance dissolved in an organic solvent to an aqueous dispersion of a carbonaceous material to perform water-repellent treatment.
素繊維のうち一種以上である請求項２記載の燃料電池用
炭素質材料。2. The carbonaceous material for a fuel cell according to claim 2, wherein the carbonaceous material is one or more of carbon black, graphite and carbon fiber.
ランカップリング剤、及びワックスのうち一種以上であ
る請求項１又は２に記載の燃料電池用炭素質材料。3. The carbonaceous material for a fuel cell according to claim 1, wherein the water-repellent substance is one or more of a fluororesin, a silicon resin, a silane coupling agent, and a wax.
用炭素質材料を含有する分散液。4. A dispersion liquid containing the carbonaceous material for a fuel cell according to claim 1.
用炭素質材料に触媒成分を担持してなる燃料電池用電極
用材料。5. A material for an electrode for a fuel cell, which comprises the carbonaceous material for a fuel cell according to claim 1 carrying a catalyst component.
有する燃料電池用電極。6. A fuel cell electrode containing the fuel cell electrode material according to claim 5.
用炭素質材料をバインダー樹脂と配合して多孔質材料に
含浸してなる燃料電池用ガス拡散層。7. A gas diffusion layer for a fuel cell, which is obtained by blending the carbonaceous material for a fuel cell according to claim 1 with a binder resin and impregnating the porous material.
用炭素質材料を、熱硬化性樹脂と配合して成形してなる
燃料電池用セパレーター。8. A fuel cell separator formed by blending the carbonaceous material for a fuel cell according to claim 1 with a thermosetting resin and molding.
配合し、多孔質材料に含浸することを特徴とする燃料電
池用ガス拡散層の製造方法。9. A method for producing a gas diffusion layer for a fuel cell, which comprises blending the dispersion according to claim 4 with a binder resin and impregnating the porous material.
配合して成形することを特徴とする燃料電池用セパレー
ター。10. A separator for a fuel cell, which is obtained by blending the dispersion according to claim 4 with a thermosetting resin and molding the mixture.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002005381A JP2003208905A (en) | 2002-01-11 | 2002-01-11 | Carbonaceous material for fuel cell and dispersion liquid containing the same |
| EP03701045A EP1464620A4 (en) | 2002-01-11 | 2003-01-09 | Carbonaceous material and dispersion containing the same |
| KR1020087018696A KR100913803B1 (en) | 2002-01-11 | 2003-01-09 | Carbonaceous material and dispersion containing the same |
| KR1020047009402A KR100878548B1 (en) | 2002-01-11 | 2003-01-09 | Carbonaceous material and dispersion containing the same |
| US10/500,916 US20050130025A1 (en) | 2002-01-11 | 2003-01-09 | Carbonaceous material and dispersion containing the same |
| PCT/JP2003/000133 WO2003059812A1 (en) | 2002-01-11 | 2003-01-09 | Carbonaceous material and dispersion containing the same |
| CNB038057379A CN1302985C (en) | 2002-01-11 | 2003-01-09 | Carbonaceous material and dispersion containing the same |
| CA002473221A CA2473221A1 (en) | 2002-01-11 | 2003-01-09 | Carbonaceous material and dispersion containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002005381A JP2003208905A (en) | 2002-01-11 | 2002-01-11 | Carbonaceous material for fuel cell and dispersion liquid containing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003208905A true JP2003208905A (en) | 2003-07-25 |
Family
ID=27644443
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002005381A Pending JP2003208905A (en) | 2002-01-11 | 2002-01-11 | Carbonaceous material for fuel cell and dispersion liquid containing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003208905A (en) |
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