JPS6353855A - Carbon electrode - Google Patents
Carbon electrodeInfo
- Publication number
- JPS6353855A JPS6353855A JP61197360A JP19736086A JPS6353855A JP S6353855 A JPS6353855 A JP S6353855A JP 61197360 A JP61197360 A JP 61197360A JP 19736086 A JP19736086 A JP 19736086A JP S6353855 A JPS6353855 A JP S6353855A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- dimensional accuracy
- addition
- carbon electrode
- corrosion resistance
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 229920000620 organic polymer Polymers 0.000 claims description 5
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003575 carbonaceous material Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052786 argon Inorganic materials 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract 2
- 229920002554 vinyl polymer Polymers 0.000 abstract 2
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000004227 thermal cracking Methods 0.000 abstract 1
- 238000010304 firing Methods 0.000 description 10
- 239000011148 porous material Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 206010049040 Weight fluctuation Diseases 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 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
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、例えば燃料電池に用いられる炭素電極に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to carbon electrodes used, for example, in fuel cells.
従来の燃料電池に用いられている炭素電極はグラファイ
トあるいは炭素の粉末や繊維をバインダーと混練し、こ
の混合物を加熱成形した後燃成炭化したものが主であっ
た（例えば、特開昭６１−８３６１１．６１−８６４１
１号公＠）。The carbon electrodes used in conventional fuel cells have mainly been made by kneading graphite or carbon powder or fibers with a binder, heating the mixture, and then combusting it to carbonize it. 83611.61-8641
Public No. 1 @).
・Ａｔ
しかしながら、このような混合物釉結体からなる炭素電
極は細孔径にばらつきがあるため電気車こるため、電極
の寸法精度も十分ではなかった。- At However, the carbon electrode made of such a mixture glazed body has a variation in pore diameter, which causes an electric car to break, and the dimensional accuracy of the electrode is also not sufficient.
本発明は上記のよつな欠点のない炭素電極を提供するこ
とを目的とする。The object of the present invention is to provide a carbon electrode that does not have the above-mentioned disadvantages.
発明者らは検討を重ねた結果、炭素成形体の表面にがラ
ス状の炭素を被覆したものが上記のような欠点のない優
れた炭素′４極となりうろことを見出した。すなわち、
本発明は、炭素成形体の表面に有機高分子の熱分解生成
物からなる被膜を設けた炭素電極である。As a result of repeated studies, the inventors have found that a carbon molded body whose surface is coated with carbon laths can form an excellent carbon quadrupole without the above-mentioned drawbacks. That is,
The present invention is a carbon electrode in which a coating made of a thermal decomposition product of an organic polymer is provided on the surface of a carbon molded body.
以下、本発明の詳細な説明する。本発明において炭素成
形体とは炭素材料を必要とする電極の形状に合わせて成
形加工したものである。炭素材料は常温での引張り強さ
が５０Ｋｇ／α２以上のものであり、開気孔率は５〜７
０チのものが好ましく、より好ましくは６０〜６０％で
ある。The present invention will be explained in detail below. In the present invention, a carbon molded body is one formed by molding a carbon material to match the shape of a required electrode. The carbon material has a tensile strength of 50 kg/α2 or more at room temperature and an open porosity of 5 to 7.
It is preferably 0%, more preferably 60 to 60%.
有機高分子は特に限定はないが、炭素含有量が３０ｕ量
チ以上のものが好ましく、特にポリ塩化ビニル、ポリビ
ニルアルコール、ポリ酢酸ビニルおよびアルキルフェノ
ールｍ脂は炭素収率の点で好ましい。The organic polymer is not particularly limited, but those having a carbon content of 30 μl or more are preferred, and polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, and alkylphenol resins are particularly preferred from the viewpoint of carbon yield.
熱分解は真空中または不活性雰囲気中でユ度２００〜５
００°Ｃで行なうが、炭素含有量が５０〜９８重量％の
範囲、好ましくは９０〜９５重量％になるように熱分解
の温度、時間を定める。得られたピッチ状の炭素前駆体
（以下、これをＰＣと略する）を溶媒に解解して溶液と
し、これを前記炭素成形体狭面に塗布する。Thermal decomposition is carried out in vacuum or in an inert atmosphere at a temperature of 200 to 5 degrees
The temperature and time of thermal decomposition are determined so that the carbon content is in the range of 50 to 98% by weight, preferably 90 to 95% by weight. The obtained pitch-like carbon precursor (hereinafter abbreviated as PC) is dissolved in a solvent to form a solution, which is applied to the narrow surface of the carbon molded body.
前記溶媒はトリクレン、クロロセン等の脂肪族塩素系の
もの、あるいはベンゼン、トルエン等の芳香族系のもの
が溶解性の点で好ましい。溶解濃度は１００〜１０００
Ｉ！／Ｊが適当である。とくに、炭素電極の強度を高め
たい場合には、前記溶液にＰＣを８００°Ｃ程度で不活
性雰囲気中で炭化したものを平均粒径が０．１〜５０μ
ｍになるように粉砕した炭素粉末を添加してもよい。The solvent is preferably an aliphatic chlorine solvent such as tricrene or chlorocene, or an aromatic solvent such as benzene or toluene from the viewpoint of solubility. Dissolution concentration is 100-1000
I! /J is appropriate. In particular, if you want to increase the strength of the carbon electrode, add PC to the above solution and carbonize it at about 800°C in an inert atmosphere, and add it to the solution with an average particle size of 0.1 to 50μ.
Carbon powder pulverized to a particle size of m may be added.
このようにｐｃの被膜を設けた炭素成形体を不活性がス
または真空中で加熱することによってＰＣを炭化する。The carbon molded body provided with the PC film is heated in an inert gas or vacuum to carbonize the PC.
炭化する際の昇温速度は６００〜５５０°Ｃを特に注意
して１℃／ ｍｉｎ ＠度にするが、それ以外の領域は
１５℃／ ｍｉｎ程度でよい。The temperature increase rate during carbonization is set to 1°C/min with special care in the range of 600 to 550°C, but in other regions it may be about 15°C/min.
最終焼成温度は、６００℃以上であればよいが、炭素電
極の使用温度より約１００°Ｃ以上高くすることが好ま
しい。最終焼成温度で１〜１０時間維持することによっ
て炭素成極が完成する。The final firing temperature may be at least 600°C, but is preferably about 100°C or more higher than the temperature at which the carbon electrode is used. Carbon polarization is completed by maintaining the final firing temperature for 1 to 10 hours.
なお、前記炭化処理を行なう前に、空気中で１００〜６
５０℃の温度で１０時間程度加熱すると、ＰＣが適度に
酸化されて架橋化が起って緻密になるため、炭化処理中
の炭素分の揮散損失がなくなり、また、完成した炭素電
極にクラックが入るおそれも少なくなる。In addition, before carrying out the carbonization treatment, 100 to 6
When heated at a temperature of 50°C for about 10 hours, PC is moderately oxidized and crosslinked to become dense, eliminating volatilization loss of carbon content during carbonization and preventing cracks in the completed carbon electrode. There is less chance of it getting in.
以下、実施例により本発明を具体的に説明する。Hereinafter, the present invention will be specifically explained with reference to Examples.
〔実施例〕゛
実施例１〜３
炭素成形体は、気孔率５５％、４５％および６５％の６
種類の炭素材を長さ６０ｍｘ、幅１５ｍｇ。[Example] [Examples 1 to 3] Carbon molded bodies had porosity of 55%, 45%, and 65%.
Different types of carbon material 60m long and 15mg wide.
厚さ４．０ｍに切出したものを用いた。A piece cut out to a thickness of 4.0 m was used.
有機高分子は塩化ビニル樹脂（４気化学工業（株）商品
名５ｓ−１１０）を用いた。前記塩化ビニル樹脂をアル
ゴンがス中、３９０ ’Ｃの温度で９０分加熱焼成する
ことによりＰＣを得た。As the organic polymer, vinyl chloride resin (trade name 5s-110, manufactured by Shikki Kagaku Kogyo Co., Ltd.) was used. PC was obtained by heating and baking the vinyl chloride resin at a temperature of 390'C for 90 minutes in an argon atmosphere.
つぎに、ｐｃをトリクレンに５００ ！！／ｌの濃度で
溶解し、この溶液中に上記炭素成形体を浸漬し、超片波
含没することによりｐｃを塗布した。Next, 500 for the PC! ! PC was applied by dipping the above-mentioned carbon molded body into this solution and ultrasonic wave impregnation.
これらｐｃを塗布された成形体を焼成炉に入れ、空気雰
囲気中２５０℃で１０時間の不融化処理を行なったのち
、アルゴンがスで置換し、３００’Ｃまでは５℃／ ｍ
ｉｎ 、 ６００〜５５０℃は１℃／ｍｉｎ、 ５５０
〜１ ［） ［１０’Ｃは１０℃／ ｍｉｎで昇温し、
１０００℃で２時間保持して炭化させ、炭素な極の試験
片を得た。These molded bodies coated with PC were placed in a firing furnace and subjected to infusibility treatment for 10 hours at 250°C in an air atmosphere, then argon was replaced with gas and heated at 5°C/m up to 300'C.
in, 600-550℃, 1℃/min, 550
~1 [) [10'C is a temperature increase of 10°C/min,
It was held at 1000° C. for 2 hours to carbonize, and a carbon electrode test piece was obtained.
得られた試験片の平均細孔径、細孔径の標準偏差、・４
気抵抗および焼成前後の厚み変化を下記の方法で測定し
た。また、下記の方法で耐薬品性試験を行なった。Average pore diameter of the obtained test piece, standard deviation of pore diameter, ・4
Air resistance and thickness change before and after firing were measured using the following methods. In addition, a chemical resistance test was conducted using the method described below.
平均細孔径、細孔径の標準ｔｍ＝の測定・・・ｃａｒｌ
。Measurement of average pore diameter, standard tm= of pore diameter...carl
.
Ｂｒｂａ 製水銀ポロシメーターを用いて測定した。Measurements were made using a mercury porosimeter manufactured by Brba.
成気抵抗測定・・・Ｊ工ｓ Ｒ７２０２に準じて四探針
法で測定した。Measurement of atmospheric resistance: Measured using the four-probe method according to J Engineering S R7202.
焼成前後の厚み変化の測定・・・焼成前と焼成後に炭素
電極の厚さをノギスを用いて０．［］５ｍの精度で測定
し、焼成前の厚さ／焼成後の厚さの比を厚み比とした。Measurement of thickness change before and after firing: Measure the thickness of the carbon electrode before and after firing using calipers. [ ] Measured with an accuracy of 5 m, and the ratio of thickness before firing/thickness after firing was taken as the thickness ratio.
耐薬品性試験・・・表に示した薬品中に２４０時間浸し
、試料の重量変化を測定した。Chemical resistance test: The sample was immersed in the chemicals shown in the table for 240 hours, and the change in weight of the sample was measured.
上記測定結果は表１および表２に示すとおりである。こ
れらの値は炭素電極として優れた特性のものである。The above measurement results are shown in Tables 1 and 2. These values are excellent characteristics for a carbon electrode.
比較例
フェノール・ホルムアルデヒド樹脂５０部（重量単位、
以下同じ）、黒鉛粉末２０部、セルロース２０部および
フェノール樹脂液５０部とを混練し、ロール圧延機を用
いて厚さ７朋の板を成形した。次いで、この圧延板を１
２０°Ｃで１０時間の加熱により硬化させたのち、アル
イン＃−気中５５０℃まで５℃／ ｈｒで、さらに１０
００’Ｏまで２℃／ ｍｉｎの昇温速度で加熱し、１０
００’Ｃで２時間保持して厚さ約４ ｍｘの多孔質炭素
板を得た。Comparative Example 50 parts of phenol-formaldehyde resin (weight unit,
20 parts of graphite powder, 20 parts of cellulose, and 50 parts of phenol resin liquid were kneaded and molded into a plate with a thickness of 7 mm using a roll mill. Next, this rolled plate was
After curing by heating at 20°C for 10 hours, it was further cured for 10 hours at 5°C/hr in Alyn #-air up to 550°C.
Heating at a temperature increase rate of 2°C/min to 00'O,
A porous carbon plate with a thickness of about 4 mx was obtained by holding at 00'C for 2 hours.
得られた炭素板より試験片を作成した。A test piece was prepared from the obtained carbon plate.
実施例１〜６と同じ方法で平均細孔径、細孔径の標準偏
差、１Ｌ気抵抗および焼成前後の厚み変化を測定した。The average pore diameter, standard deviation of pore diameter, 1L air resistance, and thickness change before and after firing were measured in the same manner as in Examples 1 to 6.
これらの結果は表１に示すとおり、実施例１〜乙に比べ
て、細孔径の標準偏差が大きく、電気抵抗が大きく、そ
して焼成前後の厚み比が大きかった。また表２に示すと
おり、耐薬品性試験の結果、実施例１〜６に比べて重量
の変動が大きかった。As shown in Table 1, these results showed that, compared to Examples 1 to B, the standard deviation of the pore diameter was large, the electrical resistance was large, and the thickness ratio before and after firing was large. Moreover, as shown in Table 2, as a result of the chemical resistance test, the weight fluctuation was large compared to Examples 1 to 6.
本発明の炭素成極は炭素成形体の表面に有機高分子の熱
分解生成物からなる被膜を設けてあり、均一な細孔径を
有し、Ｉ気抵抗が小さく、また、寸法精度が高く、さら
に耐食性が優れている。The carbon polarization of the present invention has a coating made of a thermal decomposition product of an organic polymer on the surface of a carbon molded body, has a uniform pore diameter, low I-air resistance, and high dimensional accuracy. Furthermore, it has excellent corrosion resistance.
Claims (1)
被膜を設けた炭素電極。A carbon electrode with a coating made of thermal decomposition products of organic polymers on the surface of a carbon molded body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61197360A JPH0810599B2 (en) | 1986-08-25 | 1986-08-25 | Method for manufacturing carbon electrode for fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61197360A JPH0810599B2 (en) | 1986-08-25 | 1986-08-25 | Method for manufacturing carbon electrode for fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6353855A true JPS6353855A (en) | 1988-03-08 |
| JPH0810599B2 JPH0810599B2 (en) | 1996-01-31 |
Family
ID=16373192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61197360A Expired - Lifetime JPH0810599B2 (en) | 1986-08-25 | 1986-08-25 | Method for manufacturing carbon electrode for fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0810599B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010150793A1 (en) * | 2009-06-26 | 2010-12-29 | 住友化学株式会社 | Method for producing electrode catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49104143A (en) * | 1973-01-22 | 1974-10-02 | ||
| JPS5521419A (en) * | 1978-07-29 | 1980-02-15 | Koa Sekiyu Kk | Pitch composition for impregnation |
-
1986
- 1986-08-25 JP JP61197360A patent/JPH0810599B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49104143A (en) * | 1973-01-22 | 1974-10-02 | ||
| JPS5521419A (en) * | 1978-07-29 | 1980-02-15 | Koa Sekiyu Kk | Pitch composition for impregnation |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010150793A1 (en) * | 2009-06-26 | 2010-12-29 | 住友化学株式会社 | Method for producing electrode catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0810599B2 (en) | 1996-01-31 |
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