JPH02170355A - Manufacturing method of electrode for fuel cell - Google Patents
Manufacturing method of electrode for fuel cellInfo
- Publication number
- JPH02170355A JPH02170355A JP63325167A JP32516788A JPH02170355A JP H02170355 A JPH02170355 A JP H02170355A JP 63325167 A JP63325167 A JP 63325167A JP 32516788 A JP32516788 A JP 32516788A JP H02170355 A JPH02170355 A JP H02170355A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- particles
- catalyst
- suspension
- fuel cell
- 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
- 239000000446 fuel Substances 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 35
- 239000000725 suspension Substances 0.000 claims abstract description 13
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 10
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 abstract description 5
- 239000000460 chlorine Substances 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000006229 carbon black Substances 0.000 abstract description 3
- 239000002923 metal particle Substances 0.000 abstract description 3
- -1 polytetrafluoroethylene Polymers 0.000 abstract description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 244000144992 flock Species 0.000 abstract 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 abstract 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- 239000002585 base Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001291 vacuum drying Methods 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
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
-
- 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
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8668—Binders
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inert Electrodes (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は燃料電池電極の製造方法に係り、特に電極触
媒層の製法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for manufacturing a fuel cell electrode, and particularly to a method for manufacturing an electrode catalyst layer.
燃料電池は燃料のもつ化学エネルギを直接電気玉名ルギ
に変換する装置であり、その構成は電解液層 （図示せ
ず）をはさんで第１図に示すようなカーボン基材４の上
に電極触媒層５を付着させた電極６を対向して配置し、
外部のガス供給系より前記各電極へ燃料ガスおよび酸化
剤ガスを供給し、各電極の触媒微粒子７の上で酸化剤ガ
スと燃料ガスを個別に電気化学的に反応させ、その結果
として系外に電気エネルギをとり出すことができる。A fuel cell is a device that directly converts the chemical energy of fuel into electricity, and its structure consists of electrodes placed on a carbon substrate 4 as shown in Figure 1, with an electrolyte layer (not shown) in between. Electrodes 6 to which catalyst layers 5 are attached are arranged facing each other,
A fuel gas and an oxidizing gas are supplied from an external gas supply system to each of the electrodes, and the oxidizing gas and the fuel gas are individually electrochemically reacted on the catalyst fine particles 7 of each electrode, and as a result, the gas is removed from the system. Electrical energy can be extracted.
電極触媒Ｎ５は触媒担体２に貴金属粒子１を担持した触
媒粒子７をフン素樹脂の粒子３により結着針して形成さ
れる。このような電極触媒層の製造方法としては例えば
触媒粒子とフッ素樹脂の粒子を溶媒に分散させて−様な
懸濁液とし、これに塩化アルミニウムを加えてｐＨａＪ
ｊ！整後水酸化アルミニウムの沈澱とともに触媒粒子と
フッ素樹脂の粒子を凝集させたフロックを形成し、この
フロックを電極基材上に塗布し、乾燥し、焼成する方法
が知られている。The electrode catalyst N5 is formed by binding catalyst particles 7 in which noble metal particles 1 are supported on a catalyst carrier 2 with particles 3 of fluorine resin. A method for producing such an electrode catalyst layer is, for example, by dispersing catalyst particles and fluororesin particles in a solvent to form a -like suspension, and adding aluminum chloride to the pH-like suspension.
j! A method is known in which flocs are formed by agglomerating catalyst particles and fluororesin particles together with precipitation of aluminum hydroxide after conditioning, and the flocs are applied onto an electrode base material, dried, and fired.
しかしながらこのような方法では、フロックの形成時に
塩化イオンも同時に吸着され、電極触媒層に塩素が混入
し、燃料電池運転時に白金が塩素と反応して溶出すると
いう問題があった。However, in such a method, chloride ions are also adsorbed at the same time when flocs are formed, chlorine is mixed into the electrode catalyst layer, and platinum reacts with chlorine and is eluted during fuel cell operation.
この発明は上述の点に鑑みなされ、その目的はフロック
形成時に塩素が混入しないようにして、信鎖性に優れる
燃料電池ｉ！橿を提供することにある。This invention was made in view of the above points, and its purpose is to prevent chlorine from being mixed in during floc formation, and to provide a fuel cell i! with excellent reliability. The purpose is to provide a framework.
上述の目的はこの発明によれば、
触媒粒子とフッ素樹脂の粒子からなる電極触媒層を電極
基材上に結着してなる燃料電池電極の製造方法において
、
触媒粒子とフッ素樹脂の粒子の懸濁液を形成し、この懸
濁液に硝酸アルミニウムまたは硫酸アルミニウムを添加
し、次いでｐＨ４ｒ−調整して触媒粒子とフッ素樹脂の
粒子のフロックを形成し、このフロックを電極基材上に
付着させる工程を備えることにより達成される。According to the present invention, the above-mentioned object is achieved by providing a method for manufacturing a fuel cell electrode in which an electrode catalyst layer made of catalyst particles and fluororesin particles is bonded on an electrode base material, in which suspension of catalyst particles and fluororesin particles is provided. A step of forming a suspension, adding aluminum nitrate or aluminum sulfate to this suspension, then adjusting the pH to 4r to form a floc of catalyst particles and fluororesin particles, and depositing this floc on an electrode base material. This is achieved by having the following.
硝酸アルミニウムまたは硫酸アルミニウムを用いてフロ
ックを形成するときは、塩化物イオンがフロックに吸着
されることがない。When forming flocs using aluminum nitrate or aluminum sulfate, chloride ions are not adsorbed to the flocs.
次にこの発明の詳細な説明する。 Next, this invention will be explained in detail.
実施例１
カーボンブラック上に１０重量％の貴金属粒子を担持し
た触媒粒子２ｇと純水３００ｇを混合し、さらに、ポリ
テトラフルオロエチレンの分散溶液を、カーボンブラッ
クに対して１００重量部となるように加え、混合し懸濁
液とした。これに、硝酸アルミニウムを添加し、次いで
アンモニアを加えて水酸化アルミニウム沈澱上に触媒粒
子とポリテトラフルオロエチレンの粒子の凝集したフロ
ックを形成した。このフロックをカーボンペーパー上に
０．５ｍｇ ／−の触媒金属密度となるように塗布し、
凍結真空乾燥法により乾燥した。この後、界面活性剤を
除去するため、約３００℃で加熱し、次いで、約３６０
℃で焼成して電橋触媒Ｎ５が電極基材上に結着された電
極６を得た。Example 1 2 g of catalyst particles having 10% by weight of precious metal particles supported on carbon black and 300 g of pure water were mixed, and a dispersion solution of polytetrafluoroethylene was added to the carbon black so that the amount was 100 parts by weight. and mixed to form a suspension. To this, aluminum nitrate was added and then ammonia was added to form a floc of catalyst particles and polytetrafluoroethylene particles on the aluminum hydroxide precipitate. This floc was applied onto carbon paper to give a catalyst metal density of 0.5 mg/-.
It was dried by freeze-vacuum drying method. This is followed by heating at about 300°C to remove the surfactant, and then heating at about 360°C.
C. to obtain an electrode 6 in which the electric bridge catalyst N5 was bonded onto the electrode base material.
実施例２
実施例１の硝酸アルミニウムの代わりに硫酸アルミニウ
ムを用いてフロックを形成し、水でよく洗浄し、その後
は実施例１と同様にして電極を作製した。Example 2 A floc was formed using aluminum sulfate in place of the aluminum nitrate in Example 1, and thoroughly washed with water. Thereafter, an electrode was produced in the same manner as in Example 1.
比較例
実施例１の硝酸アルミニウムの代わりに塩化アルミニウ
ムを用いた以外は実施例１と同様にして電極を作製した
。この電極を単電池に組み、１５０時間運転後、初期と
運転後の触媒金属密度を測定したところ、第１表の結果
を得た。Comparative Example An electrode was produced in the same manner as in Example 1 except that aluminum chloride was used instead of aluminum nitrate. This electrode was assembled into a cell, and after 150 hours of operation, the catalyst metal density at the initial stage and after the operation was measured, and the results shown in Table 1 were obtained.
第１表
これより、塩化アルミニウムを用いたものは触媒貴金属
の溶解が起こっており、塩化アルミニウムを硝酸アルミ
ニウムあるいは硫酸アルミニウムに代えてフロックを形
成した場合は触媒貴金属の溶解は皆無あるいは殆んどな
いことがわかる。Table 1 From this table, it can be seen that in the case of using aluminum chloride, dissolution of the catalyst noble metal occurs, and when flocs are formed by replacing aluminum chloride with aluminum nitrate or aluminum sulfate, there is no or almost no dissolution of the catalyst noble metal. I understand that.
この発明によれば
触媒粒子とフッ素樹脂の粒子からなる電極触媒層を１ｉ
極基材上に結着してなる燃料電池電極の製造方法におい
て、
触媒粒子とフン素樹脂の粒子の懸濁液を形成し、この懸
濁液に硝酸アルミニウムまたは硫酸アルミニウムを添加
し、次いでｐＨを調整して触媒粒子とフッ素樹脂の粒子
のフロックを形成し、このフロックを電極基材上に付着
させる工程を備えるので塩化物イオンがフロックに吸着
されることがなく、電極触媒層に塩素が存在しないので
、運転中における貴金属粒子の溶解がなくなって、信鎖
性に優れる燃料電池電極が得られる。According to this invention, an electrode catalyst layer consisting of catalyst particles and fluororesin particles can be formed in 1i
In a method for manufacturing a fuel cell electrode bonded on a polar substrate, a suspension of catalyst particles and fluorine resin particles is formed, aluminum nitrate or aluminum sulfate is added to this suspension, and then the pH is adjusted to This method includes the step of adjusting the flow rate to form a floc of catalyst particles and fluororesin particles, and adhering this floc to the electrode base material, so chloride ions are not adsorbed to the floc, and chlorine is not absorbed into the electrode catalyst layer. Since it is not present, there is no dissolution of noble metal particles during operation, and a fuel cell electrode with excellent chain reliability can be obtained.
【図面の簡単な説明】 第１図は燃料電池電極を示す模式断面図である。[Brief explanation of the drawing] FIG. 1 is a schematic cross-sectional view showing a fuel cell electrode.
Claims (1)
電極基材上に結着してなる燃料電池電極の製造方法にお
いて、 触媒粒子とフッ素樹脂の粒子の懸濁液を形成し、この懸
濁液に硝酸アルミニウムまたは硫酸アルミニウムを添加
し、次いでｐＨを調整して触媒粒子とフッ素樹脂の粒子
のフロックを形成し、このフロックを電極基材上に付着
させる工程を備えることを特徴とする燃料電池電極の製
造方法。[Scope of Claims] 1) A method for manufacturing a fuel cell electrode in which an electrode catalyst layer comprising catalyst particles and fluororesin particles is bonded on an electrode base material, comprising: a suspension of catalyst particles and fluororesin particles; and adding aluminum nitrate or aluminum sulfate to this suspension, then adjusting the pH to form a floc of catalyst particles and fluororesin particles, and depositing this floc on an electrode base material. A method for manufacturing a fuel cell electrode, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63325167A JPH02170355A (en) | 1988-12-23 | 1988-12-23 | Manufacturing method of electrode for fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63325167A JPH02170355A (en) | 1988-12-23 | 1988-12-23 | Manufacturing method of electrode for fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02170355A true JPH02170355A (en) | 1990-07-02 |
Family
ID=18173762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63325167A Pending JPH02170355A (en) | 1988-12-23 | 1988-12-23 | Manufacturing method of electrode for fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02170355A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011108544A (en) * | 2009-11-19 | 2011-06-02 | Fuji Electric Holdings Co Ltd | Manufacturing method for gas diffusion electrode |
-
1988
- 1988-12-23 JP JP63325167A patent/JPH02170355A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011108544A (en) * | 2009-11-19 | 2011-06-02 | Fuji Electric Holdings Co Ltd | Manufacturing method for gas diffusion electrode |
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