JP2003213563A - Hydrophilic carbon fiber sheetlike material, carbon fiber electrode material and method for producing the same - Google Patents
Hydrophilic carbon fiber sheetlike material, carbon fiber electrode material and method for producing the sameInfo
- Publication number
- JP2003213563A JP2003213563A JP2002011190A JP2002011190A JP2003213563A JP 2003213563 A JP2003213563 A JP 2003213563A JP 2002011190 A JP2002011190 A JP 2002011190A JP 2002011190 A JP2002011190 A JP 2002011190A JP 2003213563 A JP2003213563 A JP 2003213563A
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- water
- hydrophilic
- fiber sheet
- electrode
- 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 abstract description 102
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 102
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000000463 material Substances 0.000 title claims abstract description 81
- 239000007772 electrode material Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 230000003647 oxidation Effects 0.000 claims abstract description 35
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 35
- 239000005871 repellent Substances 0.000 claims abstract description 26
- 239000010419 fine particle Substances 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 238000011282 treatment Methods 0.000 claims description 36
- 239000004745 nonwoven fabric Substances 0.000 claims description 24
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 239000012071 phase Substances 0.000 claims description 7
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 239000012808 vapor phase Substances 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 66
- 239000005518 polymer electrolyte Substances 0.000 description 25
- 239000012528 membrane Substances 0.000 description 21
- 239000000446 fuel Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 230000007423 decrease Effects 0.000 description 15
- 239000002243 precursor Substances 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 150000007524 organic acids Chemical class 0.000 description 9
- 230000002940 repellent Effects 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 239000002759 woven fabric Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 8
- 229920002239 polyacrylonitrile Polymers 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 230000005484 gravity Effects 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 238000003763 carbonization Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910002848 Pt–Ru Inorganic materials 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、炭素繊維シート状
物に関するものであり、さらに詳しくは、高分子電解質
型燃料電池の電極材料に好適に用いられる親水性炭素繊
維シート状物、炭素繊維電極材料およびその製造方法に
関する。TECHNICAL FIELD The present invention relates to a carbon fiber sheet material, and more specifically, to a hydrophilic carbon fiber sheet material and a carbon fiber electrode which are preferably used as an electrode material of a polymer electrolyte fuel cell. The present invention relates to a material and a manufacturing method thereof.
【０００２】[0002]
【従来の技術】高分子電解質型燃料電池は、排出は水だ
けという非常にクリーンな発電システムであり、昨今非
常に注目されてきている。そして燃料電池は水素を含む
燃料ガスと酸素を含む酸化ガスによる電気化学反応によ
って起電力を得ているが、このような反応が連続して進
行するためにはガス拡散能、導電性、耐熱性、耐薬品性
に優れた電極が必要である。炭素材料はそれらの特性に
優れるため、燃料電池の電極として最適なものである。2. Description of the Related Art A polymer electrolyte fuel cell is a very clean power generation system in which only water is discharged, and has recently been receiving much attention. Fuel cells obtain electromotive force by an electrochemical reaction between a fuel gas containing hydrogen and an oxidizing gas containing oxygen. In order for such a reaction to proceed continuously, gas diffusivity, conductivity, heat resistance , An electrode with excellent chemical resistance is required. Since carbon materials are excellent in their characteristics, they are optimal as electrodes for fuel cells.
【０００３】しかし、燃料電池の電気化学反応ではその
電極に水が生成するが、その水によって電極のガス拡散
能が低下し、電気化学反応が起こりにくくなるという問
題があった。However, in the electrochemical reaction of the fuel cell, water is generated at the electrode, but the water has a problem that the gas diffusing ability of the electrode is lowered and the electrochemical reaction is difficult to occur.
【０００４】その問題を解決するために、例えば特開平
１１−３１０４６０号公報では水との接触角が１０８度
以上の撥水性炭素繊維材料が提案されている。しかし、
燃料電池中の高分子電解質膜は充分に含水した状態での
み高いイオン伝導性を示す性質が有り、その高分子電解
質膜は電極に接しているので、撥水性の炭素繊維材料か
らなる電極では充分な水分が高分子電解質膜へ移動しな
い、という問題があった。また、電極や高分子電解質膜
に対しては、作動時には加湿したガスが供給されるが、
未使用時には供給されない。そのため、未使用時に水分
が蒸発すると再起動時の運転に時間がかかるばかりか、
高分子電解質膜が劣化し燃料電池自体の寿命が縮む、な
どの問題があった。In order to solve the problem, for example, Japanese Patent Application Laid-Open No. 11-310460 proposes a water-repellent carbon fiber material having a contact angle with water of 108 degrees or more. But,
The polymer electrolyte membrane in a fuel cell has the property of exhibiting high ionic conductivity only when it is sufficiently hydrated.Since the polymer electrolyte membrane is in contact with the electrode, an electrode made of a water repellent carbon fiber material is sufficient. However, there is a problem that various moisture does not move to the polymer electrolyte membrane. Also, humidified gas is supplied to the electrodes and the polymer electrolyte membrane during operation,
Not supplied when not in use. Therefore, if water evaporates when not in use, it not only takes time to restart,
There is a problem that the polymer electrolyte membrane is deteriorated and the life of the fuel cell itself is shortened.
【０００５】[0005]
【発明が解決しようとする課題】本発明は上記の問題点
を解決するためになされたものであり、その目的は長時
間の連続使用によっても電極のガス拡散能が低下せず、
高い電池性能を維持できる炭素繊維電極材料、および電
極材料に好適に用いられる親水性炭素シート状物、およ
びその製造方法を提供することにある。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and its purpose is to prevent the gas diffusing ability of the electrode from being deteriorated even after continuous use for a long time.
It is intended to provide a carbon fiber electrode material capable of maintaining high battery performance, a hydrophilic carbon sheet material suitably used for the electrode material, and a method for producing the same.
【０００６】[0006]
【課題を解決するための手段】本発明の親水性炭素繊維
シート状物は、断面を水に５分間浸漬したときの吸水度
が０．２〜１５ｇ／ｇであることを特徴とする。さらに
は、炭素繊維が不織布構造であることが、またはＮａ含
有量が３０ｐｐｍ以下、Ｋ含有量が３０ｐｐｍ以下、か
つＣａ含有量が１５０ｐｐｍ以下であることが好まし
い。The hydrophilic carbon fiber sheet material of the present invention is characterized by having a water absorption of 0.2 to 15 g / g when its cross section is immersed in water for 5 minutes. Further, it is preferable that the carbon fiber has a non-woven fabric structure, or that the Na content is 30 ppm or less, the K content is 30 ppm or less, and the Ca content is 150 ppm or less.
【０００７】また、本発明の親水性炭素繊維シート状物
の製造方法は、炭素繊維シート状物を液相酸化または気
相酸化により親水化することを特徴とする。さらに気相
酸化の条件が、７００〜１０００℃の水蒸気中で、３〜
４５分処理することであることが好ましい。The method for producing a hydrophilic carbon fiber sheet material of the present invention is characterized in that the carbon fiber sheet material is hydrophilized by liquid phase oxidation or gas phase oxidation. Furthermore, the conditions for vapor phase oxidation are 3 to 3 in water vapor at 700 to 1000 ° C.
Treatment for 45 minutes is preferable.
【０００８】さらにもう一つの本発明の炭素繊維電極材
料は、本発明の親水性炭素繊維シート状物の一方の表面
に、撥水性樹脂と導電性微粒子からなる層を有すること
を特徴とする。さらには、撥水性樹脂と導電性微粒子
の、炭素繊維全重量に対する付着量が０．０１〜３０重
量％であることや、撥水性を有する表面の水との接触角
が１０８度以上であることが好ましい。Still another carbon fiber electrode material of the present invention is characterized by having a layer comprising a water-repellent resin and conductive fine particles on one surface of the hydrophilic carbon fiber sheet material of the present invention. Further, the adhesion amount of the water-repellent resin and the conductive fine particles to the total weight of the carbon fibers is 0.01 to 30% by weight, and the contact angle of water on the water-repellent surface is 108 degrees or more. Is preferred.
【０００９】[0009]
【発明の実施の形態】本発明の親水性炭素繊維シート状
物は、断面を水に５分間浸漬したときの吸水度が０．２
〜１５ｇ／ｇであることが必要である。さらには４〜１
０ｇ／ｇであることがより好ましい。吸水度が０．２ｇ
／ｇ未満の場合、電極材料として用いた時に高分子電解
質膜に十分に水分が供給されず、逆に吸水度が１５ｇ／
ｇを超えると、生成した水分が過剰となりガス拡散が妨
げられる。BEST MODE FOR CARRYING OUT THE INVENTION The hydrophilic carbon fiber sheet material of the present invention has a water absorption of 0.2 when its cross section is immersed in water for 5 minutes.
It should be ~ 15 g / g. Furthermore, 4-1
It is more preferably 0 g / g. Water absorption is 0.2g
If it is less than / g, water is not sufficiently supplied to the polymer electrolyte membrane when it is used as an electrode material, and conversely the water absorption is 15 g /
If it exceeds g, the generated water becomes excessive and gas diffusion is hindered.
【００１０】さらに、本発明の親水性炭素繊維シート状
物は、その炭素繊維が不織布構造体であることが好まし
い。炭素繊維が不織布構造である場合には、表面平滑性
が高く、例えば燃料電池内で高分子電解質膜と接合した
状態で数ＭＰａの圧力をかけた場合、凹凸が少ないため
に高分子電解質膜が損傷しにくい。また、炭素繊維不織
布では、炭素繊維軸方向が厚さ方向に向いているものが
多く、厚さ方向の電気抵抗値が低い傾向にある。Further, in the hydrophilic carbon fiber sheet material of the present invention, it is preferable that the carbon fiber is a non-woven fabric structure. When the carbon fiber has a non-woven fabric structure, the surface smoothness is high, and for example, when a pressure of several MPa is applied in a state where the carbon fiber is bonded to the polymer electrolyte membrane in the fuel cell, the polymer electrolyte membrane has a small unevenness and Hard to damage. In many carbon fiber nonwoven fabrics, the carbon fiber axial direction is oriented in the thickness direction, and the electric resistance value in the thickness direction tends to be low.
【００１１】また、本発明の親水性炭素繊維シート状物
は、Ｎａ含有量が３０ｐｐｍ以下、Ｋ含有量が３０ｐｐ
ｍ以下、かつＣａ含有量が１５０ｐｐｍ以下であること
が好ましい。さらにはＮａ含有量が１０ｐｐｍ以下、Ｋ
含有量が１０ｐｐｍ以下、Ｃａ含有量が５０ｐｐｍ以下
であることが好ましい。これら金属含有量が上記範囲の
場合、本発明の親水性炭素繊維シート状物を用いた電極
材料において、電極から高分子電解質膜への金属の移動
が少なく、高分子電解質膜の劣化が生じにくく、燃料電
池の耐久性をより高めることができる。The hydrophilic carbon fiber sheet of the present invention has a Na content of 30 ppm or less and a K content of 30 pp.
It is preferable that m or less and the Ca content be 150 ppm or less. Furthermore, Na content is 10 ppm or less, K
It is preferable that the content is 10 ppm or less and the Ca content is 50 ppm or less. When the content of these metals is in the above range, in the electrode material using the hydrophilic carbon fiber sheet-like material of the present invention, migration of metal from the electrode to the polymer electrolyte membrane is small, and deterioration of the polymer electrolyte membrane is unlikely to occur. The durability of the fuel cell can be further increased.
【００１２】このような本発明の親水性炭素繊維シート
状物は、炭素繊維から構成されるものである。ここで用
いられる炭素繊維としては、ポリアクリロニトリル（Ｐ
ＡＮ）系、ピッチ系、フェノール樹脂系、アラミド系、
セルロース系等があり特に限定される物ではないが、し
かし、強力の高いシート状物とするためには、強伸度の
高いＰＡＮ系の炭素繊維であることが好ましい。The hydrophilic carbon fiber sheet material of the present invention is composed of carbon fibers. The carbon fiber used here is polyacrylonitrile (P
AN) series, pitch series, phenol resin series, aramid series,
There are cellulose-based materials and the like, and the materials are not particularly limited. However, in order to obtain a sheet-like material having high strength, PAN-based carbon fibers having high strength and elongation are preferable.
【００１３】本発明の炭素繊維シート状物の目付は３０
〜２２０ｇ／ｍ2であることが好ましい。炭素繊維シー
ト状物の目付が３０ｇ／ｍ2未満の場合には、シート状
物の強度が低下する、電極とした場合、ガス拡散速度が
速すぎ、電池性能が低下するなど傾向にある。また、シ
ート状物の目付が２２０ｇ／ｍ2を超える場合は、厚さ
方向の電気抵抗値が増加する傾向にある。The unit weight of the carbon fiber sheet material of the present invention is 30.
It is preferably ˜220 g / m 2 . When the basis weight of the carbon fiber sheet material is less than 30 g / m 2 , the strength of the sheet material tends to decrease, and when it is used as an electrode, the gas diffusion rate tends to be too fast and the battery performance tends to decrease. When the basis weight of the sheet material exceeds 220 g / m 2 , the electric resistance value in the thickness direction tends to increase.
【００１４】シート状物のかさ密度は０．０８〜０．５
０ｇ／ｃｍ3であることが好ましい。かさ密度が０．０
８ｇ／ｃｍ3未満の場合、電極とした場合、シート状物
の内部抵抗が増大することから電気抵抗値が高くなる傾
向にある。かさ密度が０．５０ｇ／ｃｍ3を超える場
合、ガス拡散性が低下する傾向にある。The bulk density of the sheet material is 0.08 to 0.5.
It is preferably 0 g / cm 3 . Bulk density is 0.0
When it is less than 8 g / cm 3 , when it is used as an electrode, the internal resistance of the sheet-like material increases, so that the electric resistance value tends to increase. When the bulk density exceeds 0.50 g / cm 3 , gas diffusibility tends to decrease.
【００１５】シート状物の厚さは、０．１５〜１．０ｍ
ｍであることが好ましい。シート状物の厚さが０．１５
ｍｍ未満の場合には、シート状物の強度が低下したり、
加工時に切断しやすくなる、伸びが発生しやすくなるな
どの傾向にある。シート状物の厚さが１．０ｍｍを超え
る場合には、電極とした時に厚さ方向の電気抵抗値が増
加する、電池のコンパクト化が難しい、寸法の制御が難
しいなどの不具合が生じる傾向にある。The sheet material has a thickness of 0.15 to 1.0 m.
It is preferably m. The thickness of the sheet is 0.15
If it is less than mm, the strength of the sheet-like material may decrease,
It tends to be easily cut during processing, and tends to cause elongation. When the thickness of the sheet-like material exceeds 1.0 mm, electric resistance in the thickness direction increases when it is used as an electrode, it is difficult to make the battery compact, and it is difficult to control the dimensions. is there.
【００１６】シート状物の強度は２Ｎ／ｃｍ以上である
ことが好ましく、５Ｎ／ｃｍ以上であることがより好ま
しい。一般に上限は、不織布の場合で３０Ｎ／ｃｍ、織
物の場合で１００Ｎ／ｃｍ程度である。強度が２Ｎ／ｃ
ｍ未満の場合、連続的に加工する工程でシート状物に張
力がかかった場合に破断する場合がある。The strength of the sheet material is preferably 2 N / cm or more, more preferably 5 N / cm or more. Generally, the upper limit is about 30 N / cm for a nonwoven fabric and about 100 N / cm for a woven fabric. Strength is 2N / c
If it is less than m, the sheet may be broken when tension is applied to the sheet in the continuous processing step.
【００１７】本発明で用いる炭素繊維のＸ線結晶子サイ
ズは、１．３〜３．５ｎｍであることが好ましい。Ｘ線
結晶子サイズが１．３ｎｍ未満の場合は、電気伝導性が
低く、電極とした時の電池性能が低下するなどの傾向に
ある。Ｘ線結晶子サイズが３．５ｎｍを超える場合は、
繊維が脆くなる傾向にある。The carbon fiber used in the present invention preferably has an X-ray crystallite size of 1.3 to 3.5 nm. When the X-ray crystallite size is less than 1.3 nm, the electrical conductivity is low, and the battery performance when used as an electrode tends to deteriorate. When the X-ray crystallite size exceeds 3.5 nm,
The fibers tend to be brittle.
【００１８】本発明の親水性炭素繊維シート状物は、比
抵抗値（通電性）が１０Ωｃｍ以下であることが好まし
く、さらには０．０１〜６Ωｃｍであることが好まし
い。シート状物を電極材とした場合、親水性炭素繊維シ
ート状物の比抵抗値が高いと通電性が低下し、電池性能
が低下する傾向にある。さらには発熱し炭素繊維が脆化
する傾向にある。The hydrophilic carbon fiber sheet material of the present invention preferably has a specific resistance value (conductivity) of 10 Ωcm or less, more preferably 0.01 to 6 Ωcm. When the sheet-shaped material is used as an electrode material, if the specific resistance value of the hydrophilic carbon fiber sheet-shaped material is high, the electrical conductivity is lowered, and the battery performance tends to be lowered. Furthermore, heat is generated and the carbon fibers tend to become brittle.
【００１９】このような親水性炭素繊維シート状物は、
別の本発明である親水性炭素繊維シート状物の製造方
法、すなわち炭素繊維シート状物を液相酸化または気相
酸化により親水化することによって得ることができる。
この方法は炭素繊維シート状物を酸化し、炭素繊維表面
の親水性の官能基を増加させる製造方法である。本発明
の製造方法による親水性シート状物では、親水化処理剤
等を使用しないため、使用時に不純物が発生せず、連続
使用時の性能の低下が少ない。Such a hydrophilic carbon fiber sheet material is
It can be obtained by another method for producing a hydrophilic carbon fiber sheet material of the present invention, that is, by hydrophilizing a carbon fiber sheet material by liquid phase oxidation or gas phase oxidation.
This method is a production method in which a carbon fiber sheet material is oxidized to increase hydrophilic functional groups on the surface of the carbon fiber. In the hydrophilic sheet material according to the production method of the present invention, since no hydrophilic treatment agent or the like is used, impurities are not generated during use, and the performance is not significantly deteriorated during continuous use.
【００２０】親水化処理の方法としての液相酸化方法と
しては、過酸化水素水や次亜塩素酸ソーダでの高温酸化
処理(５０〜８０℃)や、電解質（硫酸、苛性ソーダ、硫
酸アンモニウム、食塩等）での電解酸化処理方法が挙げ
られる。The liquid phase oxidation method as the hydrophilic treatment method includes high temperature oxidation treatment with hydrogen peroxide solution or sodium hypochlorite (50 to 80 ° C.) and electrolytes (sulfuric acid, caustic soda, ammonium sulfate, salt, etc.). ).
【００２１】親水化処理の気相酸化方法としては、空気
酸化（３００〜６００℃）、オゾン酸化（２５〜４００
℃）や水蒸気や二酸化炭素による酸化（５００〜１２０
０℃）方法等が用いられる。As the gas phase oxidation method for the hydrophilic treatment, air oxidation (300 to 600 ° C.) and ozone oxidation (25 to 400) are used.
℃) and oxidation by steam and carbon dioxide (500-120
0 ° C.) method or the like is used.
【００２２】特にこれらの親水化方法のうち、液相酸化
方法では危険性の少ない電解質を用いた電解酸化処理が
好ましい。気相酸化方法では、金属等の混入が少ない水
蒸気や二酸化炭素による酸化処理が好ましい。Of these hydrophilic methods, the electrolytic oxidation treatment using an electrolyte, which is less dangerous in the liquid phase oxidation method, is preferable. In the gas-phase oxidation method, it is preferable to carry out an oxidation treatment with water vapor or carbon dioxide in which a metal or the like is less mixed.
【００２３】特に気相酸化方法の中でも、炭素繊維シー
ト状物を、７００〜１０００℃の水蒸気中で、３〜４５
分処理することが、より好ましくは５〜３０分処理する
ことが最も好ましい。親水化時間が３分未満の時は、十
分な親水性を得ることができない。親水化時間が４５分
を超えると過処理により酸化劣化が起こり、黒粉が発生
する傾向にある。Among the vapor phase oxidation methods, in particular, the carbon fiber sheet-like material is steamed at 700 to 1000 ° C. for 3 to 45 minutes.
It is most preferable that the treatment is carried out for a minute, more preferably for 5 to 30 minutes. If the hydrophilization time is less than 3 minutes, sufficient hydrophilicity cannot be obtained. If the hydrophilization time exceeds 45 minutes, oxidative deterioration occurs due to overtreatment, and black powder tends to be generated.
【００２４】本発明で用いられる親水化処理前の炭素繊
維シート状物は、例えば次のようにして得ることができ
る。The carbon fiber sheet material before the hydrophilic treatment used in the present invention can be obtained, for example, as follows.
【００２５】炭素繊維シート状物の原料となるプリカー
サ繊維はポリアクリロニトリル（ＰＡＮ）系、ピッチ
系、フェノール樹脂系、アラミド系、セルロース系等が
あり特に限定される物ではないが、本発明においては、
前述のようにＰＡＮ系プリカーサ繊維を用いることが最
も好ましい。The precursor fiber, which is a raw material for the carbon fiber sheet material, includes polyacrylonitrile (PAN) type, pitch type, phenol resin type, aramid type, cellulose type and the like and is not particularly limited, but in the present invention. ,
As mentioned above, it is most preferable to use the PAN-based precursor fiber.
【００２６】特に好ましいプリカーサ繊維となるＰＡＮ
系繊維としては、アクリロニトリルモノマー単位を９０
〜９８質量％、コモノマー単位を２〜１０質量％含有す
るものが最も好ましく、コモノマーとしては、アクリル
酸メチルエステル、アクリルアミド、イタコン酸等のビ
ニルモノマーが例示できる。PAN as a particularly preferred precursor fiber
As the system fiber, 90 acrylonitrile monomer units are used.
It is most preferable that the content of the comonomers is from about 98% by mass to about 2% to 10% by mass, and examples of the comonomer include vinyl monomers such as methyl acrylate, acrylamide, and itaconic acid.
【００２７】プリカーサ繊維の繊度は、０．６〜２．４
ｄｔｅｘが好ましく、特に０．７〜２．４ｄｔｅｘが好
ましい。繊度が０．６ｄｔｅｘ未満の場合は，酸化処理
時に蓄熱切断が生じ易く、繊度が２．４ｄｔｅｘを超え
る場合は、酸化処理に長時間を要し、酸化繊維強度が低
下する。The fineness of the precursor fiber is 0.6 to 2.4.
dtex is preferable, and 0.7 to 2.4 dtex is particularly preferable. When the fineness is less than 0.6 dtex, heat storage cutting is likely to occur during the oxidation treatment, and when the fineness exceeds 2.4 dtex, the oxidation treatment requires a long time and the strength of the oxidized fiber is lowered.
【００２８】得られたプリカーサ繊維は空気中での酸化
処理により酸化繊維とする。酸化繊維はさらに紡績糸織
物加工または不織布加工し、最後に炭素化処理し、炭素
繊維シート状物とする。The obtained precursor fiber is oxidized in air to be an oxidized fiber. The oxidized fiber is further processed into a spun yarn woven fabric or a non-woven fabric, and finally carbonized to obtain a carbon fiber sheet.
【００２９】本発明に用いられる炭素繊維シート状物
は、工程の途中で例えばプリカーサ繊維の延伸工程や炭
素繊維シート状物とした後の工程にて、有機酸処理によ
り金属（Ｎａ、Ｋ、Ｃａ）含有量を低減することが好ま
しい。有機酸処理に用いる有機酸としては、いずれのも
のでも使用できるが、安価で塩の除去も容易である塩酸
を用いることが最も好ましい。硫酸では塩の除去が困難
であり、シュウ酸等の他の有機酸は高価であったり、使
用時にプリカーサ繊維が着色される、塩の除去が困難で
あるなどの若干の問題点がある。The carbon fiber sheet-like material used in the present invention is treated with an organic acid in the course of, for example, a step of stretching precursor fibers or a step after the carbon fiber sheet-like material is formed in the middle of the process. ) It is preferable to reduce the content. As the organic acid used for the organic acid treatment, any one can be used, but it is most preferable to use hydrochloric acid, which is inexpensive and easy to remove salts. It is difficult to remove salts with sulfuric acid, and other organic acids such as oxalic acid are expensive, the precursor fibers are colored during use, and it is difficult to remove salts.
【００３０】有機酸処理における酸濃度はｐＨ＝０．１
〜２．０の範囲が好ましく、０．２〜１．０の範囲がさ
らに好ましい。処理温度は２５〜９０℃の範囲が好まし
い。酸が強すぎたり、処理温度が高すぎたりする場合、
プリカーサ繊維中の二トリル基等が加水分解され、コモ
ノマーの増加、収率の低下等の傾向がある。逆にｐＨが
２を超える場合、２５℃より低い処理温度の場合には、
金属含有量を充分に取り除けない傾向にある。塩酸を用
いた場合には、例えば塩酸１．０質量％、８０℃で洗浄
を行うことが好ましい条件である。The acid concentration in the organic acid treatment is pH = 0.1.
The range of -2.0 is preferable, and the range of 0.2-1.0 is more preferable. The treatment temperature is preferably in the range of 25 to 90 ° C. If the acid is too strong or the processing temperature is too high,
The nitrile group in the precursor fiber is hydrolyzed, so that the amount of comonomer increases and the yield tends to decrease. On the contrary, if the pH exceeds 2, and if the treatment temperature is lower than 25 ° C,
There is a tendency that the metal content cannot be sufficiently removed. When hydrochloric acid is used, it is preferable to perform washing at 80 ° C. at 1.0% by mass of hydrochloric acid.
【００３１】プリカーサ繊維の酸化処理は、例えば、空
気中、初期酸化温度２１５〜２４５℃で酸化処理後、更
に２５０〜２８０℃まで昇温し、酸化処理する。初期酸
化温度が２４５℃を超えると、繊維と繊維表面間の融着
が生じ、これが繊維表面の欠陥となり繊維強度が低下す
る傾向にある。また初期酸化温度が２１５℃未満の場
合、酸化繊維が所定の比重に到達するまでに長時間を要
し、生産性が低下する傾向にある。For the oxidation treatment of the precursor fiber, for example, after the oxidation treatment at an initial oxidation temperature of 215 to 245 ° C. in air, the temperature is further raised to 250 to 280 ° C. to perform the oxidation treatment. When the initial oxidation temperature exceeds 245 ° C., fusion between the fibers and the fiber surface occurs, which causes defects on the fiber surface and tends to reduce the fiber strength. When the initial oxidation temperature is lower than 215 ° C, it takes a long time for the oxidized fiber to reach a predetermined specific gravity, and the productivity tends to be lowered.
【００３２】酸化した後の酸化繊維の繊度は０．８〜
３．２ｄｔｅｘが好ましく、より好ましくは１．０〜
２．５ｔｅｘである。酸化繊維の繊度が０．８ｄｔｅｘ
未満の場合、単繊維の糸強力が低く、織物加工や不織布
加工及び、炭素化時に糸切れが生じ易く、繊維の収束
（分散性低下）により加工性が低下するなどの不具合が
生じる傾向にある。酸化繊維の繊度が３．２ｄｔｅｘを
超える場合は、酸化時間が長時間となり生産性が低下の
傾向にあり、後の工程の炭素化時に繊維強度が低下し、
炭素繊維微粉末の発生量が増加する傾向にある。酸化繊
維の繊度は製造原料のプリカーサ繊維の繊度、酸化時の
リラックス条件等により調節することができる。The fineness of the oxidized fiber after oxidation is 0.8 to
3.2 dtex is preferable, and more preferably 1.0 to
It is 2.5 tex. Oxidation fiber fineness is 0.8 dtex
When it is less than 1, the yarn strength of the single fiber is low, yarn breakage is likely to occur during woven or non-woven fabric processing and carbonization, and there is a tendency that the processability decreases due to fiber convergence (dispersion decrease). . When the fineness of the oxidized fiber exceeds 3.2 dtex, the oxidation time becomes long and the productivity tends to decrease, and the fiber strength decreases during carbonization in the subsequent step,
The amount of carbon fiber fine powder generated tends to increase. The fineness of the oxidized fiber can be adjusted by the fineness of the precursor fiber as a raw material for production, the relaxation condition at the time of oxidation, and the like.
【００３３】このとき酸化繊維の好ましい強度（標準状
態）は、１．５ｇ／ｄｔｅｘ以上であり、伸度（標準状
態）は１２％以上である。酸化繊維の強度が、１．５ｇ
／ｄｔｅｘ未満の場合、あるいは伸度が１２％未満の場
合には、構造材への加工性が低下する傾向にある。At this time, the preferable strength (standard state) of the oxidized fiber is 1.5 g / dtex or more, and the elongation (standard state) is 12% or more. The strength of the oxidized fiber is 1.5g
If it is less than / dtex, or if the elongation is less than 12%, the workability into a structural material tends to decrease.
【００３４】酸化繊維の好ましい結節強度は、０．６ｇ
／ｄｔｅｘ以上であり、結節伸度は、４％以上である。
酸化繊維の結節強度が０．６ｇ／ｄｔｅｘ未満の場合、
あるいは結節伸度が４％未満の場合には、紡績加工性低
下及び炭素繊維構造材強度低下などが生じる傾向にあ
る。The preferred knot strength of the oxidized fiber is 0.6 g.
/ Dtex or more and the nodule elongation is 4% or more.
When the knot strength of the oxidized fiber is less than 0.6 g / dtex,
Alternatively, if the knot elongation is less than 4%, spinning processability and carbon fiber structural material strength tend to decrease.
【００３５】酸化繊維比重は、１．３０〜１．４２であ
ることが好ましい。酸化繊維比重が１．３０未満の場
合、炭素繊維微粉末が生じ易く、また、得られる炭素繊
維紡績糸織物・不織布の強度も低下する傾向しある。酸
化繊維比重が１．４２を超える場合、酸化繊維の単繊維
強度及び伸度が低下し、酸化繊維を用いて酸化繊維紡績
糸織物、酸化繊維不織布を製造する際の加工性が低下す
る傾向にある。The specific gravity of the oxidized fiber is preferably 1.30 to 1.42. When the specific gravity of the oxidized fiber is less than 1.30, carbon fiber fine powder is likely to be produced, and the strength of the obtained carbon fiber spun yarn woven fabric / nonwoven fabric tends to be lowered. When the specific gravity of the oxidized fiber exceeds 1.42, the single fiber strength and the elongation of the oxidized fiber decrease, and the processability when producing the oxidized fiber spun yarn fabric and the oxidized fiber nonwoven fabric tends to decrease. is there.
【００３６】上記酸化繊維は、定長カットまたは、トウ
リアクターでバイアスカットをして短繊維にし、この繊
維を用いて酸化繊維シート状物を製造する。単繊維の平
均カット長は２５〜６５ｍｍであることが好ましく、こ
の範囲外の場合においては、酸化繊維構造材への加工時
に糸切れを生ずるので好ましくない。The above-mentioned oxidized fiber is cut to a fixed length or bias-cut with a tow reactor to make a short fiber, and an oxidized fiber sheet-like material is produced using this fiber. The average cut length of the single fiber is preferably 25 to 65 mm, and when it is out of this range, yarn breakage occurs during processing into an oxidized fiber structure material, which is not preferable.
【００３７】酸化繊維ステープルのクリンプ率は８〜１
６％であることが好ましい。クリンプ率が８％未満の場
合には、繊維同士の絡み合いが少なく、構造材への加工
時に糸切れが生じ易い傾向にある。酸化繊維構造材のク
リンプ率が１６％より高い場合には酸化繊維構造材を構
成する単繊維の強度が低下し、構造材加工時に糸切れを
生じる傾向にある。The crimp ratio of the oxidized fiber staple is 8 to 1
It is preferably 6%. When the crimping rate is less than 8%, the fibers are less entangled with each other and the yarn tends to be broken during processing into the structural material. When the crimp rate of the oxidized fiber structural material is higher than 16%, the strength of the single fiber constituting the oxidized fiber structural material is lowered, and the yarn breakage tends to occur during the processing of the structural material.
【００３８】このようにして得られた酸化繊維を用い
て、酸化繊維シート状物を作成する。シート状物として
は、紡績糸に精紡することにより、酸化繊維紡績糸を作
成し、酸化繊維紡績糸織物とすることもできるが、不織
布とすることが最も好ましい。織物から、電極を作成し
た場合、燃料電池内で高分子電解質膜と電極が接合した
状態で、数ＭＰａの圧力がかかるために、織物表面の凹
凸により高分子電解質膜が損傷する場合がある。また、
織物を裁断した場合、織物端部から紡績糸がほつれ、形
状を保持しにくい傾向にある。さらにほつれた紡績糸は
燃料電池接合時に各部材の間に入り込む場合が有る。An oxidized fiber sheet is prepared using the oxidized fiber thus obtained. As the sheet-like material, an oxidized fiber spun yarn can be prepared by spinning a spun yarn to give an oxidized fiber spun yarn woven fabric, but a nonwoven fabric is most preferable. When an electrode is formed from a woven fabric, a pressure of several MPa is applied in a state where the polymer electrolyte membrane and the electrode are joined in the fuel cell, so that the unevenness of the woven fabric surface may damage the polymer electrolyte membrane. Also,
When the woven fabric is cut, the spun yarn is frayed from the end of the woven fabric, and it tends to be difficult to maintain the shape. Further, the loosened spun yarn may enter between the respective members at the time of joining the fuel cell.
【００３９】不織布から電極を作成した場合には、燃料
電池内で高分子電解質膜と電極が接合した状態で、数Ｍ
Ｐａの圧力がかかる時にも繊維が均一に分散されている
ため高分子電解質の損傷が少ない。また、製造工程が単
純で、複雑な工程を経ないので繊維自体の損傷が少なく
なり、炭素繊維微粉末の発生量が極めて少なくなり、コ
ストを低減できる効果がある。When the electrode is made of a non-woven fabric, the polymer electrolyte membrane and the electrode are bonded together in the fuel cell, and the number of M
Even when a pressure of Pa is applied, the fibers are uniformly dispersed, so that the polymer electrolyte is less damaged. Further, since the manufacturing process is simple and the complicated process is not performed, the damage of the fiber itself is reduced, the amount of carbon fiber fine powder generated is extremely reduced, and the cost can be reduced.
【００４０】酸化繊維不織布は、例えば、定長カットし
た酸化繊維の綿をカード加工し、更に目付１０〜５０ｇ
／ｍ2のウェッブを作成し、重ね合わせた後、ウォータ
ジェット法により、連続的に水流によりパンチングする
ことにより作成することができる。The oxidized fiber non-woven fabric is formed by, for example, processing cotton of oxidized fiber, which is cut to a fixed length, into a card, and further has a basis weight of 10 to 50 g.
It can be prepared by forming webs of / m 2 and superposing them, and then continuously punching with a water stream by the water jet method.
【００４１】次いで上記のようにして得た酸化繊維シー
ト状物を炭素化し、炭素繊維シート状物とする。Next, the oxidized fiber sheet material obtained as described above is carbonized to obtain a carbon fiber sheet material.
【００４２】炭素繊維シート状物は、例えば上記酸化繊
維シート状物を連続的に、不活性雰囲気下、１３００〜
２０００℃で１〜１０分間炭素化を行うことで得ること
ができる。不活性ガスとしては、窒素、ヘリウム、アル
ゴン等が用いられる。炭素化温度が１３００℃未満の時
には、電気抵抗値が高くなったり、Ｎａ、Ｋが昇華せず
残留する傾向にある。また炭素化温度が２０００℃を超
える場合、電気抵抗値は低下し、Ｎａ、Ｋも低減できる
ものの、Ｃａの含有量がやや増加し、繊維が脆くなる傾
向にあり、炭素繊維構造材の強度低下や、炭素微粉末の
発生量が増加する傾向にある。The carbon fiber sheet-like material is, for example, 1300 to 1300 continuously obtained by oxidizing the above-mentioned oxidized fiber sheet-like material in an inert atmosphere.
It can be obtained by carrying out carbonization at 2000 ° C. for 1 to 10 minutes. As the inert gas, nitrogen, helium, argon or the like is used. When the carbonization temperature is lower than 1300 ° C., the electric resistance value tends to be high, and Na and K tend to remain without sublimation. When the carbonization temperature exceeds 2000 ° C., the electric resistance value decreases and Na and K can also be reduced, but the Ca content tends to increase slightly and the fiber tends to become brittle, which reduces the strength of the carbon fiber structural material. Alternatively, the amount of carbon fine powder generated tends to increase.
【００４３】この段階で、前述したように金属（Ｎａ、
Ｋ、Ｃａ）含有量を低減化するために、炭素繊維シート
状物を塩酸等による有機酸処理することも好ましい。At this stage, as described above, metal (Na,
In order to reduce the (K, Ca) content, it is also preferable to treat the carbon fiber sheet material with an organic acid such as hydrochloric acid.
【００４４】得られた炭素繊維シート状物は、有機酸処
理または未処理のまま、親水化処理することにより、本
発明の親水性炭素繊維シート状物となる。この本発明の
親水性炭素繊維シート状物を用いることにより、容易に
高性能の炭素繊維電極材料を得ることができる。The obtained carbon fiber sheet-like material is treated with an organic acid or untreated to be hydrophilized to be the hydrophilic carbon fiber sheet-like material of the present invention. By using this hydrophilic carbon fiber sheet material of the present invention, a high performance carbon fiber electrode material can be easily obtained.
【００４５】もう一つの本発明の炭素繊維電極材料は、
本発明の親水性炭素繊維シート状物の一方の表面に、撥
水性樹脂と導電性微粒子からなる層を有するシート状物
である。Another carbon fiber electrode material of the present invention is
The hydrophilic carbon fiber sheet material of the present invention is a sheet material having a layer comprising a water-repellent resin and conductive fine particles on one surface.
【００４６】撥水性樹脂としては、例えばテトラフルオ
ロエチレン／ヘキサフルオロプロピレン共重合体（ＦＥ
Ｐ）、テトラフルオロエチレン／パーフルオロアルキル
ビニルエーテル共重合体（ＰＦＡ）、ポリテトラフルオ
ロエチレン（ＰＴＦＥ）等のフッ素系樹脂が燃料電池に
要求される撥水性や耐酸化性の点から好ましく、中でも
ＰＴＦＥは電気抵抗値を低減化する効果があるのでより
好ましい。As the water-repellent resin, for example, tetrafluoroethylene / hexafluoropropylene copolymer (FE
P), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), polytetrafluoroethylene (PTFE), and other fluorine-based resins are preferable from the viewpoint of water repellency and oxidation resistance required for fuel cells, and among them PTFE Is more preferable because it has the effect of reducing the electric resistance value.
【００４７】導電性微粒子としては、例えばカーボンブ
ラック、粉末活性炭、活性炭素繊維のミルト゛ファイバー
が用いられる。粒径としては０．１〜１０μｍ以下であ
ることが好ましい。導電性微粒子を付着させることによ
り、親水性処理により表面の平滑性が低下した炭素繊維
シート状物の表面平滑性が向上し、電気抵抗値（比抵
抗）の値を小さくすることができる。As the conductive fine particles, for example, carbon black, powdered activated carbon, and milled fiber of activated carbon fiber are used. The particle size is preferably 0.1 to 10 μm or less. By attaching the conductive fine particles, the surface smoothness of the carbon fiber sheet material whose surface smoothness is lowered by the hydrophilic treatment is improved, and the electric resistance value (specific resistance) can be reduced.
【００４８】付着量としては、シート状物の重量に対し
て０．０１〜３０質量％であることが好ましい。０．０
１質量％未満の場合には充分な撥水性が得られない傾向
にある。３０質量％を超える場合には、ガス拡散電極層
が厚くなりすぎ、スタックの小型化が困難になる傾向に
ある。The amount of adhesion is preferably 0.01 to 30% by mass with respect to the weight of the sheet material. 0.0
If it is less than 1% by mass, sufficient water repellency tends not to be obtained. When it exceeds 30% by mass, the gas diffusion electrode layer becomes too thick, and it tends to be difficult to reduce the size of the stack.
【００４９】撥水性樹脂と導電性微粒子の比率は質量比
で、撥水性樹脂：導電性微粒子が、０．０５：０．９５
から０．９５：０．０５であることが好ましい。撥水性
樹脂の比率が少ないと充分な撥水性が得られない傾向に
あり、導電性微粒子の比率が少ないと充分な平面平滑性
が得られず、接触抵抗が大きくなる傾向がある。設ける
一方の表面が撥水性を有するシート状物である。The ratio of the water-repellent resin and the conductive fine particles is a mass ratio, and the ratio of water-repellent resin: conductive fine particles is 0.05: 0.95.
To 0.95: 0.05 is preferable. If the ratio of the water-repellent resin is low, sufficient water repellency tends to be unobtainable, and if the ratio of the conductive fine particles is low, sufficient planar smoothness cannot be obtained and the contact resistance tends to increase. The one surface provided is a sheet-like material having water repellency.
【００５０】そして撥水性の面の水との接触角が１０８
度以上であることが必要である。さらには１２０度以上
であることが好ましい。このような撥水性を有している
ために、燃料電池の電極で生成する水による、電極のガ
ス拡散能の低下を防止することができる。The contact angle of the water-repellent surface with water is 108.
It must be at least a degree. Further, it is preferably 120 degrees or more. Due to such water repellency, it is possible to prevent a decrease in the gas diffusing ability of the electrode due to water generated in the electrode of the fuel cell.
【００５１】また本発明の炭素繊維電極材料は、親水性
炭素繊維シートを用いているため、裏面および断面にお
いては吸水性を有する。また断面を水に５分間浸漬した
ときの吸水度が０．２〜１５ｇ／ｇであることが好まし
く、さらには４〜１０ｇ／ｇであることがより好まし
い。このように裏面や内部が吸水性を有することによ
り、燃料電池の電解質膜表面で発生した水分を撥水相か
ら速やかに排水できる。Further, since the carbon fiber electrode material of the present invention uses the hydrophilic carbon fiber sheet, it has water absorption on the back surface and the cross section. The water absorption when the cross section is immersed in water for 5 minutes is preferably 0.2 to 15 g / g, and more preferably 4 to 10 g / g. Since the back surface and the inside have water absorbing properties in this way, water generated on the surface of the electrolyte membrane of the fuel cell can be quickly drained from the water repellent phase.
【００５２】このような本発明の炭素繊維電極は、前述
の本発明の親水性炭素繊維シート状物を用い、その一方
の表面に撥水性樹脂と導電性微粒子を付着させる処理を
おこなうことにより得ることができる。撥水処理・導電
性微粒子処理は、撥水性樹脂に導電性微粒子を混合し、
炭素繊維シート状物の片面のみにコートし付着させ、３
００〜４００℃の空気中、より好ましくは不活性ガス中
にて処理する。Such a carbon fiber electrode of the present invention is obtained by using the hydrophilic carbon fiber sheet material of the present invention described above and applying a treatment for adhering a water-repellent resin and conductive fine particles on one surface thereof. be able to. Water repellent treatment / conductive fine particle treatment mixes conductive fine particles with water repellent resin,
Coat only one side of the carbon fiber sheet and attach it to
The treatment is carried out in air at 00 to 400 ° C., more preferably in an inert gas.
【００５３】[0053]
【作用】高分子電解質型燃料電池の高分子電解質膜は、
十分に含水した状態でのみ高いイオン伝導性を示す。本
発明の炭素繊維電極材料は吸水性を有するため、たとえ
燃料電池の電極に、加湿したガスの供給が少ない場合で
あっても、高分子電解質に本発明の電極材料から水分を
供給し、乾燥を防止することができる。そのため高分子
電解質の劣化を防止し燃料電池自体の寿命を延ばすこと
ができる。さらには、加湿ガスの供給が停止される未使
用状態からの再起動時の運転開始時間が短時間で可能と
なる。[Function] The polymer electrolyte membrane of the polymer electrolyte fuel cell is
It exhibits high ionic conductivity only when it is fully hydrated. Since the carbon fiber electrode material of the present invention has water absorbency, even if the supply of humidified gas to the electrode of the fuel cell is small, water is supplied from the electrode material of the present invention to the polymer electrolyte and dried. Can be prevented. Therefore, deterioration of the polymer electrolyte can be prevented and the life of the fuel cell itself can be extended. Furthermore, the operation start time at the time of restarting from the unused state where the supply of the humidifying gas is stopped becomes possible in a short time.
【００５４】また、使用時には電極表面の高分子電解質
膜に接する部分に反応水が発生し、その水によるガスの
拡散が阻害される、いわゆるフラッティング現象が起こ
るが、本発明の炭素繊維電極材料は高分子電解質膜に接
する表面が撥水性を有するので、そのフラッティング現
象を防ぐことができる。Further, when used, a so-called flatting phenomenon occurs in which reaction water is generated in a portion of the electrode surface which is in contact with the polymer electrolyte membrane and the diffusion of gas by the water is hindered. However, the carbon fiber electrode material of the present invention Since the surface in contact with the polymer electrolyte membrane has water repellency, the flatting phenomenon can be prevented.
【００５５】[0055]
【実施例】以下、実施例により本発明を更に具体的に説
明するが、本発明はこれら実施例に限定されるものでは
ない。なお、各物性の測定は次の方法によった。The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In addition, each physical property was measured by the following methods.
【００５６】（１）電池特性
炭素繊維電極材料を５０ｍｍ角にカットし、陽極側及び
負極側の電極材として触媒を担持後、下記の構成で高分
子電解質膜（デュポン社製：ナフィオン膜１１７）と熱
圧着により接合し、セパレータと組み合わせ、温度８０
℃条件下、電流密度１．６Ａ／ｃｍ2の時のセル電圧を
測定した。撥水性を有する面は三層目の高分子電解質膜
に接する側である。
一層目：溝付セパレータ
二層目：炭素繊維電極材料（陽極側）
（触媒 Ｐｔ−Ｒｕ：０．３ｍｇ／ｃｍ2）
三層目：高分子電解質膜
四層目：炭素繊維電極材料（陰極側）
（触媒 Ｐｔ：０．３ｍｇ／ｃｍ2）
五層目：溝付セパレータ
水素：１０００ｍｌ／分、酸素：１０００ｍｌ／分(1) Battery characteristics A carbon fiber electrode material was cut into 50 mm square, and after supporting a catalyst as an electrode material on the anode side and the anode side, a polymer electrolyte membrane (Nafion membrane 117 manufactured by DuPont) was constructed as follows. By thermocompression bonding, combined with a separator, temperature 80
The cell voltage was measured at a current density of 1.6 A / cm 2 under the condition of ° C. The surface having water repellency is the side in contact with the third-layer polymer electrolyte membrane. First layer: grooved separator Second layer: carbon fiber electrode material (anode side) (catalyst Pt-Ru: 0.3 mg / cm 2 ) Third layer: polymer electrolyte membrane Fourth layer: carbon fiber electrode material (cathode side) ) (Catalyst Pt: 0.3 mg / cm 2 ) Fifth layer: grooved separator Hydrogen: 1000 ml / min, oxygen: 1000 ml / min
【００５７】（２）比抵抗値（通電性）
サンプルの炭素線にシートの両面を、２枚の５０ｍｍ角
（厚さ１０ｍｍ）の金メッキした電極で、０．０１ＭＰ
ａの圧力ではさみ、両電極間の電気抵抗値（Ｒ）を測定
し、厚さ（Ｔ）と接触面積（Ｓ）より下記式にて算出し
た。(2) Specific resistance value (conductivity) 0.01MP was applied to the carbon wire of the sample with two 50 mm square (10 mm thick) gold-plated electrodes on both sides of the sheet.
The electric resistance value (R) between both electrodes was measured with the pressure of a, and calculated from the thickness (T) and the contact area (S) by the following formula.
【００５８】[0058]
【数１】 [Equation 1]
【００５９】（３）撥水性
サンプルを１２０℃、１時間乾燥後、デシケータ内で室
温まで放冷する。サンプルの平面上に水を１滴（１０μ
ｍ）滴下する。次いでマイクロスコープを用い、液滴を
モニターテレビに拡大し、画像処理により液滴高さｈ、
液滴の頂点と水平面との直交点と、液滴と平面との交点
との距離ａを測定し、次式により接触角θを求める。(3) The water-repellent sample is dried at 120 ° C. for 1 hour and then left to cool to room temperature in a desiccator. A drop of water (10μ
m) Drop. Then, using a microscope, the droplet was enlarged to the monitor TV, and the droplet height h, and
The distance a between the orthogonal point between the apex of the droplet and the horizontal plane and the intersection of the droplet and the plane is measured, and the contact angle θ is determined by the following equation.
【００６０】[0060]
【数２】 [Equation 2]
【００６１】（４）金属分析
サンプルを７５０℃で灰化し、王水処理する。それをフ
レーム原子吸光によって、金属（Ｃａ、Ｎａ、Ｋ）量を
測定した。(4) The metal analysis sample is ashed at 750 ° C. and treated with aqua regia. The amount of metal (Ca, Na, K) was measured by flame atomic absorption.
【００６２】（５）吸水度（親水性評価方法）
親水化処理したサンプル（２０ｍｍ×５０ｍｍ）を１２
０℃、１時間乾燥後、デシケータ中で放冷し、室温まで
降温した後に重量を測定する(サンプル重量)。次にサン
プルを長手方向の断面が下になるようにつるし、その断
面から５ｍｍまでを水に浸漬した状態で５分間放置す
る。水から出した後の重量を測定し、得られた付着水分
量とサンプル重量から吸水度（付着水分量／サンプル重
量）を評価した。単位はｇ／ｇとした。(5) Water Absorption (Evaluation Method for Hydrophilicity) 12 samples (20 mm × 50 mm) subjected to hydrophilic treatment were used.
After drying at 0 ° C. for 1 hour, the sample is allowed to cool in a desiccator, cooled to room temperature, and then weighed (sample weight). Next, the sample is hung so that the cross section in the longitudinal direction is downward, and 5 mm from the cross section is left for 5 minutes while being immersed in water. The weight after removing from water was measured, and the water absorption (amount of attached water / weight of sample) was evaluated from the obtained amount of attached water and sample weight. The unit was g / g.
【００６３】（６）強度、伸度、結節強度、結節伸度 ＪＩＳ Ｌ１０１５により測定した。(6) Strength, elongation, knot strength, knot elongation It was measured according to JIS L1015.
【００６４】（７）目付
シート状物を120℃で1時間乾燥した後の単位面積当りの
質量として算出した。(7) The weighted sheet material was calculated as the mass per unit area after drying at 120 ° C. for 1 hour.
【００６５】（８）厚さ
直径３０ｍｍの円形圧板で２．８ｋＰａ（２００ｇの荷
重）時の厚さを測定した。(8) Thickness A circular pressure plate having a diameter of 30 mm was used to measure the thickness at 2.8 kPa (load of 200 g).
【００６６】（９）比重
液置換法（ＪＩＳ Ｒ７６０１、置換液：エチルアルコ
ール）により測定した。(9) It was measured by the specific gravity liquid replacement method (JIS R7601, replacement liquid: ethyl alcohol).
【００６７】（１０）引張強度
不織布幅５０ｍｍ、長さ１２０ｍｍ以上のシート状物
を、チャック間距離１００ｍｍの冶具に固定し、速度３
０ｍｍ／分で引っ張った時の破断強度を１０ｍｍ幅に換
算した。(10) Tensile strength A sheet-like material having a width of 50 mm and a length of 120 mm or more is fixed to a jig having a chuck distance of 100 mm, and a speed of 3 is set.
The breaking strength when pulled at 0 mm / min was converted to a 10 mm width.
【００６８】（１１）結晶子サイズ測定方法
結晶子サイズ（Ｌｃ）は、広角Ｘ線測定結果（２θ＝２
６°付近のピーク)より、以下に示すシェラーの式を用
いて求めた。(11) Crystallite size measuring method The crystallite size (Lc) is the wide angle X-ray measurement result (2θ = 2).
It was determined from the peak around 6 °) using the Scherrer's formula shown below.
【００６９】[0069]
【数３】 [Equation 3]
【００７０】ここで、ｋは装置定数（本発明においては
０．９）、λはＸ線波長（０．１５４ｎｍ）、βは２θ
=２６゜付近のピークの半価幅、θはピーク位置（゜）
である。
測定条件
設定管電圧：４０ｋＶ
設定管電流：３０ｍＡ
測定範囲：１０゜〜４０゜
サンプリング間隔：０．０２゜
スキャン速度：４゜／分
積算回数：１回
試料の形態：ベースライン補正処理後のピーク強度が５
０００ｃｐｓ以上となるように、試料を複数枚重ねる。Here, k is a device constant (0.9 in the present invention), λ is an X-ray wavelength (0.154 nm), and β is 2θ.
Half-width of peak around = 26 °, θ is peak position (°)
Is. Measurement condition setting Tube voltage: 40 kV Setting tube current: 30 mA Measuring range: 10 ° to 40 ° Sampling interval: 0.02 ° Scanning speed: 4 ° / min Integration frequency: 1 time Sample form: Peak after baseline correction Strength is 5
A plurality of samples are stacked so that the rate becomes 000 cps or more.
【００７１】［実施例１〜４］ＰＡＮ系のプリカーサ
（ＡＮ:アクリロニトリル９６％、ＭＡ:メタクリル酸４
％、繊度１．７ｄｔｅｘ）を酸（ＨＣｌ 1％、８０
℃）で洗浄しプリカーサ繊維を作成した。このものの金
属成分含有量はＮａ:５ｐｐｍ、Ｋ：５ｐｐｍ、Ｃａ：
５ｐｐｍ、灰分:０．０２％であった。[Examples 1 to 4] PAN type precursor (AN: acrylonitrile 96%, MA: methacrylic acid 4)
%, Fineness 1.7 dtex) acid (HCl 1%, 80
(° C) to prepare a precursor fiber. The metal content of this product is Na: 5 ppm, K: 5 ppm, Ca:
It was 5 ppm and the ash content was 0.02%.
【００７２】このプリカーサを２３５℃×１時間＋２５
５℃×１．５時間、空気中で酸化処理を行い、繊度２．
３ｄｔｅｘ、伸度（標準状態）２７％、結節強度１．４
ｇ／ｄｔｅｘ、結節伸度１０％、比重１．３９の酸化繊
維を得た。This precursor is put at 235 ° C. for 1 hour + 25
Oxidation treatment in air at 5 ° C for 1.5 hours, and fineness 2.
3dtex, elongation (standard condition) 27%, knot strength 1.4
Oxidized fiber having g / dtex, knot elongation of 10% and specific gravity of 1.39 was obtained.
【００７３】更に、温水（純水、８０℃、バイブロウォ
ッシャー）により酸化繊維を洗浄した後、クリンプ加工
を行い、クリンプ数４．４ケ／ｃｍ、クリンプ率１２％
の酸化繊維を得、５１ｍｍにカットした。この酸化繊維
からなる５０ｇ／ｍ2のウェブを３枚重ね、ウォータジ
ェット法（使用水：純水）により不織布加工を行い、酸
化繊維不織布（目付１５０ｇ／ｍ2、厚さ０．８ｍｍ、
Ｘ線結晶サイズ３．０ｎｍ）を作成した。Further, after the oxidized fiber was washed with warm water (pure water, 80 ° C., vibro washer), crimping was performed to obtain a crimp number of 4.4 / cm and a crimp rate of 12%.
Oxidized fiber of was obtained and cut into 51 mm. Three 50 g / m 2 webs of this oxidized fiber are stacked and processed into a non-woven fabric by the water jet method (water used: pure water), and an oxidized fibrous non-woven fabric (Basis weight 150 g / m 2 , thickness 0.8 mm,
An X-ray crystal size of 3.0 nm) was prepared.
【００７４】得られた不織布を１９００℃、チッソガス
中で1分間処理することにより炭素繊維不織布（目付９
０ｇ／ｍ2、厚さ０．８ｍｍ）を得た。この炭素繊維不
織布を有機酸処理（ＨＣｌ 1％、８０℃、使用水：純
水）により金属成分の少ない炭素繊維不織布を得ること
ができた。この不織布を９００℃、スチーム中で５、１
０、３０、４５分間親水化処理をし、親水性炭素繊維シ
ート状物を得た。The obtained non-woven fabric was treated at 1900 ° C. in nitrogen gas for 1 minute to give a carbon fiber non-woven fabric (with a fabric weight of 9
0 g / m 2 , thickness 0.8 mm) was obtained. By subjecting this carbon fiber nonwoven fabric to an organic acid treatment (HCl 1%, 80 ° C., water used: pure water), a carbon fiber nonwoven fabric with a small amount of metal components could be obtained. This non-woven fabric is steamed at 900 ℃ for 5,1
Hydrophilization treatment was performed for 0, 30, and 45 minutes to obtain a hydrophilic carbon fiber sheet.
【００７５】これらの親水化処理後の炭素繊維不織布
（親水性炭素繊維シート状物）の片面のみに、ＰＴＦＥ
とカーボンブラック（平均粒径０．５μm）の質量比が
０．５:０．５の混合物を、炭素繊維全重量に対して５
質量％となるようにコートし、付着させ、３００℃、３
０分間処理をした。得られた電極材料の撥水処理側の表
面の接触角は１４０°であった。また裏面および断面は
吸水性を有し、接触角を測定することはできなかった。
その後、撥水処理面にＰｔ触媒塗布加工し、電池特性
（作動１時間後、および２００時間後）を評価した。こ
れらのものの物性を表１に示す。Only one side of the carbon fiber non-woven fabric (hydrophilic carbon fiber sheet-like material) after the hydrophilic treatment is treated with PTFE.
A mixture of carbon black and carbon black (average particle size 0.5 μm) in a mass ratio of 0.5: 0.5 was added to the total weight of the carbon fibers in 5
Coated so as to be mass%, adhered, 300 ℃, 3
It was treated for 0 minutes. The contact angle of the surface of the obtained electrode material on the water repellent treatment side was 140 °. Further, the back surface and the cross section had water absorbency, and the contact angle could not be measured.
Thereafter, the water-repellent treated surface was coated with Pt catalyst to evaluate the battery characteristics (1 hour after operation and 200 hours after operation). The physical properties of these are shown in Table 1.
【００７６】[0076]
【表１】 [Table 1]
【００７７】［比較例１］実施例１〜４の炭素繊維不織
布の親水化処理を省略した以外は、実施例１〜４と同様
の処理、および評価を行った。得られた電極材料の撥水
処理側の表面の接触角は１４０°であったが、２００時
間後の電池性能は低下する傾向が認められた。このもの
の物性を表２に示す。Comparative Example 1 The same treatments and evaluations as in Examples 1 to 4 were carried out except that the hydrophilic treatment of the carbon fiber nonwoven fabrics in Examples 1 to 4 was omitted. The contact angle of the surface of the obtained electrode material on the water repellent treatment side was 140 °, but it was recognized that the battery performance after 200 hours tended to deteriorate. The physical properties of this product are shown in Table 2.
【００７８】［比較例２］実施例１〜４の炭素繊維不織
布の親水化処理を、９００℃スチーム中で６０分間の条
件にした以外は、実施例１〜４と同様の処理、および評
価を行った。得られた電極材料の撥水処理側の表面の接
触角は１４０°であったが、２００時間後の電池性能は
低下する傾向が認められた。このものの物性を表２に併
せて示す。[Comparative Example 2] The same treatments and evaluations as in Examples 1 to 4 were carried out except that the carbon fiber nonwoven fabrics of Examples 1 to 4 were hydrophilized under conditions of 900 ° C. steam for 60 minutes. went. The contact angle of the surface of the obtained electrode material on the water repellent treatment side was 140 °, but it was recognized that the battery performance after 200 hours tended to deteriorate. The physical properties of this product are also shown in Table 2.
【００７９】［実施例５］実施例１〜４のプリカーサ時
と、炭素繊維時の２度の有機酸処理を行わなかった以外
は、実施例２（親水化処理９００℃スチーム中で１０分
間）と同様の処理、および評価を行った。[Example 5] Example 2 (hydrophilicizing treatment at 900 ° C for 10 minutes in steam) except that the precursor of Examples 1 to 4 and the carbon fiber were not treated twice with organic acid. The same treatment and evaluation were performed.
【００８０】プリカーサ（ＡＮ:アクリロニトリル９６
％、ＭＡ:メタクリル酸４％、繊度１．７ｄｔｅｘ）時
の金属成分含有量はＮａ:５０ｐｐｍ、Ｋ：５０ｐｐ
ｍ、Ｃａ：２００ｐｐｍ、灰分:０．０２％であった。
また得られた電極材料の撥水処理側の表面の接触角は１
４０°であった。また裏面および断面は吸水性を有し、
接触角を測定することはできなかった。このものの物性
を表２に併せて示す。Precursor (AN: acrylonitrile 96
%, MA: methacrylic acid 4%, fineness 1.7 dtex), the metal component content is Na: 50 ppm, K: 50 pp
m, Ca: 200 ppm, ash content: 0.02%.
The contact angle of the surface of the obtained electrode material on the water repellent side is 1
It was 40 °. In addition, the back surface and cross section have water absorption,
It was not possible to measure the contact angle. The physical properties of this product are also shown in Table 2.
【００８１】［実施例６］炭素繊維不織布を、実施例１
〜４のように９００℃、スチーム中で親水化処理する代
わりに、硫酸アンモニア中で２０分間、電流密度１２Ｃ
／ｇで電解酸化処理することにより親水性の付与を行っ
た以外は、実施例１〜４と同様の処理、および評価を行
った。得られた電極材料の撥水処理側の表面の接触角は
１４０°であった。また裏面および断面は吸水性を有
し、接触角を測定することはできなかった。このものの
物性を表２に併せて示す。[Example 6] A carbon fiber non-woven fabric was used in Example 1.
Instead of hydrophilizing in steam at 900 ° C as in ~ 4, in ammonium sulfate for 20 minutes, current density 12C
The same treatments and evaluations as in Examples 1 to 4 were performed except that the hydrophilicity was imparted by electrolytically oxidizing the particles at a rate of / g. The contact angle of the surface of the obtained electrode material on the water repellent treatment side was 140 °. Further, the back surface and the cross section had water absorbency, and the contact angle could not be measured. The physical properties of this product are also shown in Table 2.
【００８２】[0082]
【表２】 [Table 2]
【００８３】[0083]
【発明の効果】本発明により、長時間の連続使用によっ
ても電極のガス拡散能が低下せず、高い電池性能を維持
できる炭素繊維電極材料、および電極材料に好適に用い
られる親水性炭素シート状物、およびその製造方法が提
供された。According to the present invention, a carbon fiber electrode material capable of maintaining high battery performance without deteriorating the gas diffusivity of the electrode even after continuous use for a long time, and a hydrophilic carbon sheet material suitably used for the electrode material An object and a manufacturing method thereof are provided.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０１Ｍ 4/96 Ｄ０６Ｍ 101:40 // Ｈ０１Ｍ 8/10 7/00 Ａ Ｄ０６Ｍ 101:40 11/00 Ｂ (72)発明者 島崎 賢司 静岡県駿東郡長泉町上土狩234番地 東邦 テナックス株式会社内 Ｆターム(参考） 4L031 AA27 AB34 BA08 CA02 CA08 DA00 DA08 DA15 4L033 AA09 AB07 AC03 AC07 CA17 DA06 4L047 AA03 BA04 CA02 CB10 DA00 5H018 AA06 BB17 DD06 EE02 EE05 EE19 HH03 HH05 HH08 5H026 AA06 BB00 BB10 CX03 EE02 EE05 EE19 HH03 HH05 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) H01M 4/96 D06M 101: 40 // H01M 8/10 7/00 A D06M 101: 40 11/00 B ( 72) Inventor Kenji Shimazaki 234, Uechikari, Nagaizumi-cho, Sunto-gun, Shizuoka F-term (reference) in Toho Tenax Co., Ltd. DD06 EE02 EE05 EE19 HH03 HH05 HH08 5H026 AA06 BB00 BB10 CX03 EE02 EE05 EE19 HH03 HH05
Claims (8)
が０．２〜１５ｇ／ｇであることを特徴とする親水性炭
素繊維シート状物。1. A hydrophilic carbon fiber sheet material having a water absorption of 0.2 to 15 g / g when its cross section is immersed in water for 5 minutes.
記載の親水性炭素繊維シート状物。2. The carbon fiber is a non-woven fabric structure.
The hydrophilic carbon fiber sheet material described.
が３０ｐｐｍ以下、かつＣａ含有量が１５０ｐｐｍ以下
である請求項１または２に記載の親水性炭素繊維シート
状物。3. The hydrophilic carbon fiber sheet material according to claim 1, which has a Na content of 30 ppm or less, a K content of 30 ppm or less, and a Ca content of 150 ppm or less.
相酸化により親水化することを特徴とする親水性炭素繊
維シート状物の製造方法。4. A method for producing a hydrophilic carbon fiber sheet material, which comprises hydrophilizing a carbon fiber sheet material by liquid phase oxidation or gas phase oxidation.
℃の水蒸気中で、３〜４５分処理することである請求項
４記載の親水性炭素繊維シート状物の製造方法。5. The gas phase oxidation condition is 700 to 1000.
The method for producing a hydrophilic carbon fiber sheet according to claim 4, wherein the treatment is carried out in water vapor at 0 ° C for 3 to 45 minutes.
水性炭素繊維シート状物の一方の表面に、撥水性樹脂と
導電性微粒子からなる層を有することを特徴とする炭素
繊維電極材料。6. A carbon fiber comprising a hydrophilic carbon fiber sheet-like material according to any one of claims 1 to 3 having a layer comprising a water-repellent resin and conductive fine particles on one surface thereof. Electrode material.
全重量に対する付着量が０．０１〜３０重量％である請
求項６記載の炭素繊維電極材料。7. The carbon fiber electrode material according to claim 6, wherein the adhesion amount of the water-repellent resin and the conductive fine particles is 0.01 to 30% by weight based on the total weight of the carbon fibers.
する表面の水との接触角が１０８度以上である請求項６
または７記載の炭素繊維電極材料。8. The contact angle between the water-repellent resin and the surface of the surface containing the conductive fine particles with water is 108 degrees or more.
Or the carbon fiber electrode material described in 7.
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| JP2002011190A JP2003213563A (en) | 2002-01-21 | 2002-01-21 | Hydrophilic carbon fiber sheetlike material, carbon fiber electrode material and method for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002011190A JP2003213563A (en) | 2002-01-21 | 2002-01-21 | Hydrophilic carbon fiber sheetlike material, carbon fiber electrode material and method for producing the same |
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| JP2008257928A (en) * | 2007-04-03 | 2008-10-23 | Hitachi Ltd | Fuel cell |
| WO2012026498A1 (en) * | 2010-08-27 | 2012-03-01 | 東邦テナックス株式会社 | Conductive sheet and production method for same |
| KR101609913B1 (en) * | 2014-02-14 | 2016-04-07 | 오씨아이 주식회사 | Carbon felt electrode for redox flow battery and method for preparing the same |
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| WO2012026498A1 (en) * | 2010-08-27 | 2012-03-01 | 東邦テナックス株式会社 | Conductive sheet and production method for same |
| CN103081194A (en) * | 2010-08-27 | 2013-05-01 | 东邦泰纳克丝株式会社 | Conductive sheet and production method for same |
| JPWO2012026498A1 (en) * | 2010-08-27 | 2013-10-28 | 東邦テナックス株式会社 | Conductive sheet and manufacturing method thereof |
| JP5537664B2 (en) * | 2010-08-27 | 2014-07-02 | 東邦テナックス株式会社 | Conductive sheet and manufacturing method thereof |
| US8916310B2 (en) | 2010-08-27 | 2014-12-23 | Toho Tenax Co., Ltd. | Conductive sheet and production method for same |
| US9825304B2 (en) | 2011-01-27 | 2017-11-21 | Mitsubishi Chemical Corporation | Porous electrode substrate, method for manufacturing same, precursor sheet, membrane electrode assembly, and polymer electrolyte fuel cell |
| US9705137B2 (en) | 2011-01-27 | 2017-07-11 | Mitsubishi Rayon Co., Ltd. | Porous electrode substrate, method for manufacturing same, precursor sheet, membrane electrode assembly, and polymer electrolyte fuel cell |
| US9716278B2 (en) | 2012-03-30 | 2017-07-25 | Mitsubishi Chemical Corporation | Porous electrode base material, method for manufacturing same, and precursor sheet |
| KR101609913B1 (en) * | 2014-02-14 | 2016-04-07 | 오씨아이 주식회사 | Carbon felt electrode for redox flow battery and method for preparing the same |
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