JPS63312989A - Fine powder for producing gas diffusion electrode - Google Patents
Fine powder for producing gas diffusion electrodeInfo
- Publication number
- JPS63312989A JPS63312989A JP62149733A JP14973387A JPS63312989A JP S63312989 A JPS63312989 A JP S63312989A JP 62149733 A JP62149733 A JP 62149733A JP 14973387 A JP14973387 A JP 14973387A JP S63312989 A JPS63312989 A JP S63312989A
- Authority
- JP
- Japan
- Prior art keywords
- fine powder
- gas diffusion
- water
- fine
- diffusion 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.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 44
- 238000009792 diffusion process Methods 0.000 title claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 17
- 239000005871 repellent Substances 0.000 claims abstract description 17
- 239000010419 fine particle Substances 0.000 claims abstract description 13
- 239000006229 carbon black Substances 0.000 claims abstract description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 4
- 229920001577 copolymer Polymers 0.000 claims abstract 2
- 229920013653 perfluoroalkoxyethylene Polymers 0.000 claims abstract 2
- 238000004519 manufacturing process Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 230000002940 repellent Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 33
- 239000003054 catalyst Substances 0.000 description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Inert Electrodes (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、撥水性に優れかつガス供給能が従来のものよ
りも格段に優れたガス拡散電極製造用微粉末に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a fine powder for manufacturing gas diffusion electrodes that has excellent water repellency and gas supply ability that is significantly superior to conventional powders.
（従来技術とその問題点）
触媒層と該触媒層に接するガス供給層から成る燃料電池
等のガス拡散電極の前記ガス供給層は、例えばカーボン
ブラック等と撥水性のポリテトラフルオロエチレン（以
下ＰＴＦＥという）の微粉体の混合物を塗布又は圧着す
るなどした後、使用されている。しかし該ガス供給層は
、長時間に亘ってガス供給能を維持するためには、多量
のＰＴＦＨの添加を必要とし、その結果カーボンブラン
ク粒子間の細孔が前記ＰＴＦＥにより閉塞されガス供給
能の低下を招き、その結果電池などに使用したとき性能
の低下をきたす欠点がある。(Prior art and its problems) The gas supply layer of a gas diffusion electrode for a fuel cell or the like, which is composed of a catalyst layer and a gas supply layer in contact with the catalyst layer, is made of, for example, carbon black or the like and water-repellent polytetrafluoroethylene (hereinafter referred to as PTFE). It is used after applying or compressing a mixture of fine powders. However, in order to maintain the gas supply capacity for a long time, this gas supply layer requires the addition of a large amount of PTFH, and as a result, the pores between the carbon blank particles are blocked by the PTFE, and the gas supply capacity is reduced. This has the drawback of causing deterioration in performance when used in batteries, etc.
他方、前記触媒層はガス流通路と電解液流通路とを有し
、前記ガス供給層から供給された反応ガスは前記触媒層
中のガス流通路中を拡散し、これと接する電解液中に溶
解して該電解液中の触媒上で電極反応を行うようになっ
ている。On the other hand, the catalyst layer has a gas flow path and an electrolyte flow path, and the reaction gas supplied from the gas supply layer diffuses through the gas flow path in the catalyst layer, and enters the electrolyte in contact with the gas flow path. After being dissolved, an electrode reaction is carried out on the catalyst in the electrolyte.
しかしながら該触媒層中においても、例えばリン酸型燃
料電池等で見られるように、長時間運転により前記ガス
流通路中に電解液が浸入しガス供給能が低下して、これ
により電池性能の極端な低下を招来する。この欠点を回
避すべく撥水剤の量を増加させると触媒層中に電解液が
入り難くなり、触媒が反応の関与できなくなり、やはり
電池性能の低下を来してしまうという欠点がある。However, even in the catalyst layer, as seen in, for example, phosphoric acid fuel cells, electrolyte enters into the gas flow path due to long-term operation, reducing the gas supply ability, resulting in extreme cell performance. resulting in a significant decline. If the amount of water repellent is increased in order to avoid this drawback, it will become difficult for the electrolyte to enter the catalyst layer, and the catalyst will no longer be able to participate in the reaction, resulting in a decrease in battery performance.
前記触媒層中のガス供給能と触媒反応の能力を両立させ
るための手段として、撥水性微粒子と触媒を含まないカ
ーボンブランク微粉末の混合物等と、ｔａ水剤を含まな
い触媒微粉末を混合し、これにより触媒層を形成する方
法も提案されている（特願昭６０−１６２６１４号）。As a means for achieving both gas supply ability and catalytic reaction ability in the catalyst layer, a mixture of water-repellent fine particles and carbon blank fine powder not containing a catalyst, etc., and a catalyst fine powder not containing a TA water agent are mixed. A method of forming a catalyst layer using this method has also been proposed (Japanese Patent Application No. 162614/1982).
しかしこの場合でも長時間ガス供給能を維持するために
は、前記混合物中のｔθ水性微粒子の組成比を高くする
ことが必要であり必然的にガス供給能の低下を招いてい
る。However, even in this case, in order to maintain the gas supply ability for a long time, it is necessary to increase the composition ratio of the tθ aqueous fine particles in the mixture, which inevitably leads to a decrease in the gas supply ability.
（発明の目的）
本発明は、従来技術では解決できなかった優れたガス供
給能と触媒能との両者を併せ持つガス拡散電極製造用微
粉末を提供することを目的とする。(Objective of the Invention) An object of the present invention is to provide a fine powder for producing a gas diffusion electrode that has both excellent gas supply ability and catalytic ability, which have not been achieved using conventional techniques.
（問題点を解決するための手段）
本発明は、微粉末のほぼ全表面上に、その粒径が該微粉
末の粒径以下である多数の（８水性微粒子を被覆して成
ることを特徴とするガス拡散電極製造用微粉末である。(Means for Solving the Problems) The present invention is characterized in that almost the entire surface of a fine powder is coated with a large number of (8) aqueous fine particles whose particle size is equal to or less than the particle size of the fine powder. This is a fine powder for manufacturing gas diffusion electrodes.
以下本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の特徴は、触媒作用を有するあるいは有しない微
粉末の粒径を比較的大径とし、該微粉末上に被覆される
ＰＴＦＢ等の１８水性粒子の粒径を比較的小径として前
記微粉末のほぼ全表面が前記撥水性粒子で被覆されるよ
うにした点にあり、これにより長時間使用しても電解液
が（θ水性粒子の被覆されていない部分を通して浸入す
ることがなく、前記微粉末により形成されるガス流通路
が閉塞されてガス供給能が低下することが防止される。The feature of the present invention is that the particle size of the fine powder with or without catalytic action is made relatively large, and the particle size of the 18 aqueous particles such as PTFB coated on the fine powder is made relatively small. Almost the entire surface of the water-repellent particles is coated with the water-repellent particles, so that even if the electrolyte is used for a long time, the electrolyte (θ) will not penetrate through the uncovered part of the water-based particles, and the water-repellent particles will not infiltrate. This prevents the gas flow path formed by the powder from being blocked and the gas supply ability from decreasing.
従ってガス拡散電極のガス供給層あるいは触媒層のいず
れの層の１８水性原料粉末として本発明の微粉末を使用
しても撥水性に優れガス供給能が劣化することのないガ
ス拡散電極を提供することが可能になる。Therefore, to provide a gas diffusion electrode which has excellent water repellency and does not deteriorate its gas supply ability even when the fine powder of the present invention is used as the 18 aqueous raw material powder in either the gas supply layer or the catalyst layer of the gas diffusion electrode. becomes possible.
本発明における微粉末としてはカーボンブラックを使用
することが好ましく、この他にも従来から使用されてい
る微粉末をそのまま使用することができる。It is preferable to use carbon black as the fine powder in the present invention, and other fine powders conventionally used can be used as they are.
又ｔａ水性粒子としてもＰＴＦＥ等従来から使用されて
いる材料を使用することができる。Furthermore, conventionally used materials such as PTFE can be used as the ta aqueous particles.
前記微粉末及び微粒子から本発明のガス拡散電極製造用
微粉末を製造するには、比較的大径の前記微粉末の周囲
にディスパージョンとして市販されている比較的小径の
前記微粒子をそのまま付着させる等してもよいが、この
他にテトラフロロエチレンモノマー等の↑θ水性微粒子
を重合させ成長せながら、前記微粉末の周囲に付着させ
るようにすることも可能である。In order to produce the fine powder for producing a gas diffusion electrode of the present invention from the fine powder and fine particles, the relatively small diameter fine particles commercially available as a dispersion are directly attached around the relatively large diameter fine powder. Alternatively, it is also possible to polymerize and grow ↑θ aqueous fine particles such as tetrafluoroethylene monomer and attach them around the fine powder.
本発明に係わるガス拡散電極製造用微粉末は、導電性微
粉末だけでなく、撥水性ガス透過多孔質体等各種のガス
拡散膜の合成原料を対象とするものである。The fine powder for manufacturing gas diffusion electrodes according to the present invention is intended not only as a conductive fine powder but also as a raw material for synthesizing various gas diffusion membranes such as water-repellent gas-permeable porous bodies.
以下本発明に係わるガス拡散電極製造用微粉末の製造方
法の一例につき説明するが、本発明のガス拡散電極製造
用微粉末の製法は本例の製造方法に限定されるものでは
ない。An example of the method for manufacturing a fine powder for manufacturing a gas diffusion electrode according to the present invention will be described below, but the method for manufacturing a fine powder for manufacturing a gas diffusion electrode according to the present invention is not limited to the manufacturing method of this example.
１遺■
攪拌羽根を有するオートクレーブ（１１）に蒸留水５０
０ ｍｌ、パラフィン１０ｇ１パーフロロオクタル酸ア
ンモニウム０．３５ｇ、ジコハク酸パーオキサイド０．
３ｇ、過硫酸アンモニウム１０ｍｇ、カーボンブラック
２００ｇを充填し、６ｋｇ／−のテトラフロロエチレン
モノマーを注意深く導入しながら、約５０℃で重合を行
わせ、反応時間を調節することにより重合物の粒径をカ
ーボンブランクの粒径より小さくするようにし、ｔθ水
性微粒子であるＰＴＦＥの被覆量を加減した。1. Add 50 ml of distilled water to an autoclave (11) equipped with a stirring blade.
0 ml, 10 g of paraffin, 0.35 g of ammonium perfluorooctate, 0.0 g of disuccinic acid peroxide.
3g of ammonium persulfate, and 200g of carbon black, and while carefully introducing 6kg/- of tetrafluoroethylene monomer, polymerization was carried out at about 50°C. By adjusting the reaction time, the particle size of the polymerized product was adjusted to carbon. The particle size was made smaller than that of the blank, and the amount of coating of PTFE, which is the tθ aqueous fine particles, was adjusted.
このように撥水化処理を行ったカーボンブラック粉末（
ＰＴＦＥ１５重量％含有）を基材上に単位平方センナメ
ートル当たり２０■塗布した後、３６０℃、５０ ｋｇ
／ａｎ！、 ３秒の条件でホットプレスを行い目的とす
る電極基材を得た。Carbon black powder treated with water repellency in this way (
After applying 20 μg of PTFE (containing 15% by weight) on the base material per unit square meter, 50 kg was applied at 360°C.
/an! , Hot pressing was performed for 3 seconds to obtain the desired electrode base material.
この電極基材を１９０℃のリン酸に浸漬したところ、時
間とともにリン酸を吸収し約５０時間後に飽和に達した
。このときのカーボンブランク微粉末角たりのリン酸吸
収量はＯ，Ｉｇ／ｇ程度であり、電極基材の中の気孔の
全体積に占めるリン酸の割合は２％程度に過ぎず、ガス
の供給が阻害されることは殆どない。When this electrode base material was immersed in phosphoric acid at 190°C, it absorbed phosphoric acid over time and reached saturation after about 50 hours. At this time, the amount of phosphoric acid absorbed per square inch of carbon blank fine powder is about O.Ig/g, and the proportion of phosphoric acid in the total volume of pores in the electrode base material is only about 2%, and the Supply is rarely disrupted.
比較のためにカーボンブランクに撥水化処理を施すこと
なく撥水性高分子微粉末（ＰＴＦ２３０重量％含を重量
％台して上記条件でホットプレスを行ったところ、得ら
れた電極基材はカーボンブランク１ｇ当たり３ｇ程度リ
ン酸の浸透が起こる。For comparison, a carbon blank was hot-pressed under the above conditions using water-repellent polymer fine powder (including 30% by weight of PTF) without water-repellent treatment, and the electrode base material obtained was carbon. Penetration of about 3 g of phosphoric acid occurs per 1 g of blank.
換言すると撥水剤が倍量台まれるにもかかわらず、全気
孔体積の７５％までリン酸が浸透することが実験的に明
らかになった。In other words, it has been experimentally revealed that phosphoric acid penetrates up to 75% of the total pore volume even though the amount of water repellent is doubled.
前記した本発明に係わるガス拡散電極製造用微粉末を塗
布した電極基村上に、カーボンブランク微粉末に白金を
担持した触媒７０重量％とＰＴＦＥｌ粉末３０重量％か
ら成る触媒層をホットプレスで形成した。A catalyst layer consisting of 70% by weight of a catalyst in which platinum was supported on carbon blank fine powder and 30% by weight of PTFEL powder was formed by hot pressing on the electrode substrate coated with the above-mentioned fine powder for producing gas diffusion electrodes according to the present invention. .
該電極の電極性能を測定したところ、９００ｍＡ ／
ｃｄまで濃度分極に基づく性能低下がなく、従来の電極
が２００ ｍＡ／ｃｔＪ以上で濃度分極による特性低下
が生ずるのと比較して格段に性能が向上することが確認
された。When the electrode performance of the electrode was measured, it was 900mA/
It was confirmed that there was no performance deterioration due to concentration polarization up to cd, and the performance was significantly improved compared to conventional electrodes whose characteristics deteriorate due to concentration polarization at 200 mA/ctJ or higher.
更に前記電極基村上に、本発明によるカーボンブラック
微粉末５０重量％と、撥水剤を含まない白金を担持した
カーボンブラック微粉末５０重量％を混合した触媒層を
ホットプレスで形成した。Further, on the electrode base layer, a catalyst layer was formed by hot pressing, which was a mixture of 50% by weight of the fine carbon black powder according to the present invention and 50% by weight of the fine carbon black powder supporting platinum and not containing a water repellent.
この電極の電極性能を測定したところ、１０００ｍ Ａ
／ ｃ４まで濃度分極に基づく性能低下が生じないこ
とが確認された。When the electrode performance of this electrode was measured, it was found that 1000mA
It was confirmed that no performance deterioration due to concentration polarization occurred up to /c4.
（発明の効果）
本発明によると、比較的少量の撥水性微粒子のみで電解
液吸収の殆んどない電極基材を得ることができ、該電極
基材を使用して大電流密度でも濃度分極が少なく、更に
長時間高いガス供給能を維持できる高性能電極を製造す
ることが可能になる。(Effects of the Invention) According to the present invention, it is possible to obtain an electrode base material with almost no electrolyte absorption using only a relatively small amount of water-repellent fine particles, and by using the electrode base material, concentration polarization can be achieved even at high current density. This makes it possible to manufacture high-performance electrodes that can maintain high gas supply performance for a longer period of time.
出願人 田中貴金属工業株式会社 渡辺政廣Applicant: Tanaka Kikinzoku Kogyo Co., Ltd. Masahiro Watanabe
Claims (3)
粒径以下である多数の撥水性微粒子を被覆して成ること
を特徴とするガス拡散電極製造用微粉末。(1) A fine powder for producing a gas diffusion electrode, characterized in that substantially the entire surface of the fine powder is coated with a large number of water-repellent fine particles whose particle size is equal to or less than the particle size of the fine powder.
第１項に記載のガス拡散電極製造用微粉末。(2) The fine powder for producing a gas diffusion electrode according to claim 1, wherein the fine powder is carbon black.
トラフルオロエチレン−パーフロロアルコキシエチレン
共重合体、テトラフルオロエチレン−ヘキサフルオロプ
ロピレン共重合体である特許請求の範囲第１項又は第２
項に記載のガス拡散電極製造用微粉末。(3) Claim 1 or 2, wherein the water-repellent fine particles are polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkoxyethylene copolymer, or tetrafluoroethylene-hexafluoropropylene copolymer.
Fine powder for manufacturing gas diffusion electrodes as described in .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62149733A JP2555360B2 (en) | 1987-06-16 | 1987-06-16 | Fine powder for gas diffusion electrode production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62149733A JP2555360B2 (en) | 1987-06-16 | 1987-06-16 | Fine powder for gas diffusion electrode production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63312989A true JPS63312989A (en) | 1988-12-21 |
| JP2555360B2 JP2555360B2 (en) | 1996-11-20 |
Family
ID=15481624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62149733A Expired - Lifetime JP2555360B2 (en) | 1987-06-16 | 1987-06-16 | Fine powder for gas diffusion electrode production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2555360B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0447735A1 (en) * | 1988-09-16 | 1991-09-25 | Tanaka Kikinzoku Kogyo K.K. | Fine powdery body for gas diffusion electrode and water repellent treatment thereof |
| EP0665274A3 (en) * | 1994-01-26 | 1996-08-14 | Central Glass Co Ltd | Water-repellent composite grains, method for producing same, and water-repellent article using same. |
| WO2003059812A1 (en) * | 2002-01-11 | 2003-07-24 | Mikuni Shikiso Kabushiki Kaisha | Carbonaceous material and dispersion containing the same |
| JP2013075775A (en) * | 2011-09-29 | 2013-04-25 | Neos Co Ltd | Method for modifying surface of carbon material and carbon material with modified surface |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6229069A (en) * | 1985-07-30 | 1987-02-07 | Masahiro Watanabe | Bfe-type electrode for fuel cell or the like |
-
1987
- 1987-06-16 JP JP62149733A patent/JP2555360B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6229069A (en) * | 1985-07-30 | 1987-02-07 | Masahiro Watanabe | Bfe-type electrode for fuel cell or the like |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0447735A1 (en) * | 1988-09-16 | 1991-09-25 | Tanaka Kikinzoku Kogyo K.K. | Fine powdery body for gas diffusion electrode and water repellent treatment thereof |
| EP0665274A3 (en) * | 1994-01-26 | 1996-08-14 | Central Glass Co Ltd | Water-repellent composite grains, method for producing same, and water-repellent article using same. |
| WO2003059812A1 (en) * | 2002-01-11 | 2003-07-24 | Mikuni Shikiso Kabushiki Kaisha | Carbonaceous material and dispersion containing the same |
| CN1302985C (en) * | 2002-01-11 | 2007-03-07 | 御国色素株式会社 | Carbonaceous material and dispersion containing the same |
| JP2013075775A (en) * | 2011-09-29 | 2013-04-25 | Neos Co Ltd | Method for modifying surface of carbon material and carbon material with modified surface |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2555360B2 (en) | 1996-11-20 |
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