JPH0563906B2 - - Google Patents
Info
- Publication number
- JPH0563906B2 JPH0563906B2 JP61190858A JP19085886A JPH0563906B2 JP H0563906 B2 JPH0563906 B2 JP H0563906B2 JP 61190858 A JP61190858 A JP 61190858A JP 19085886 A JP19085886 A JP 19085886A JP H0563906 B2 JPH0563906 B2 JP H0563906B2
- Authority
- JP
- Japan
- Prior art keywords
- fine particles
- catalyst
- dispersion
- electrode
- catalyst layer
- 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.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 claims description 58
- 239000010419 fine particle Substances 0.000 claims description 50
- 239000006185 dispersion Substances 0.000 claims description 19
- 239000000446 fuel Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate 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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8896—Pressing, rolling, calendering
-
- 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
- H01M4/8864—Extrusion
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inert Electrodes (AREA)
Description
【発明の詳細な説明】
〔発明の属する技術分野〕
この発明なリン酸型燃料電池用電極触媒層の製
造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical field to which the invention pertains] The present invention relates to a method for manufacturing an electrode catalyst layer for a phosphoric acid fuel cell.
燃料電池は燃料のもつ化学エネルギを直接電気
エネルギに変換する装置であり、その構成は、リ
ン酸よりなる電解液層（図示せず）をはさんで第
２図に示すような電極６（カーボン電極基板４の
上に電極触媒層５を融着させたもの）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 electrical energy, and its configuration consists of electrodes 6 (carbon (electrode catalyst layer 5 fused onto electrode substrate 4) are arranged facing each other, and fuel gas and oxidant gas are supplied to each electrode from an external gas supply system, and catalyst fine particles 7 of each electrode are disposed facing each other. The oxidizing gas and the fuel gas are individually electrochemically reacted on top of the system, and as a result, electrical energy can be taken out of the system.
触媒微粒子７としてはカーボンブラツクなどの
触媒担体２の上に白金などの貴金属微粒子１を担
持したものが用いられ、この触媒微粒子７がポリ
テトラフロロエチレン（PTFE）からなる弗素樹
脂の微粒子３により結着され電極触媒層５が形成
される。 The fine catalyst particles 7 used are those in which fine metal particles 1 such as platinum are supported on a catalyst carrier 2 such as carbon black, and the fine catalyst particles 7 are bonded by fine particles 3 of fluororesin made of polytetrafluoroethylene (PTFE). The electrode catalyst layer 5 is formed.
このような電極触媒層５にあつては弗素樹脂の
微粒子３は触媒微粒子７を結着する作用のほかそ
の撥水効果により電極触媒層５に対しリン酸より
なる電解液に対する適度のぬれ性を生じさせ電極
触媒層５の内部に電気化学反応に必要なガス（燃
料あるいは酸化剤ガス）と固体（触媒微粒子７）
と液体（リン酸型電解液）よりなる３相界面を形
成させる。 In such an electrode catalyst layer 5, the fluororesin fine particles 3 not only bind the catalyst fine particles 7, but also provide the electrode catalyst layer 5 with appropriate wettability to the electrolytic solution made of phosphoric acid due to its water-repellent effect. Gas (fuel or oxidant gas) and solid (catalyst fine particles 7) necessary for electrochemical reaction are generated inside the electrode catalyst layer 5.
and a liquid (phosphoric acid type electrolyte) to form a three-phase interface.
従来電極触媒層５は触媒微粒子７を界面活性剤
の水溶液に分散させたのち揮発性の少ない有機溶
媒を加えてよく混合し、これにPTFEからなる弗
素樹脂のデイスパージヨンを加え、得られたペー
ストを成膜して電極触媒層５を得ていた。 Conventionally, the electrode catalyst layer 5 was obtained by dispersing catalyst fine particles 7 in an aqueous solution of a surfactant, adding a less volatile organic solvent, mixing well, and adding a fluororesin dispersion made of PTFE to this. The electrode catalyst layer 5 was obtained by forming a paste.
しかしながらこのような方法で電極触媒層５を
調製すると、第２図に示すように触媒微粒子７も
弗素樹脂の微粒子３も凝集により大きな集落を形
成し、そのために触媒微粒子７と弗素樹脂の微粒
子３の均一混合体を得ることができず、その結果
この電極触媒層を燃料電池用電極として用いた場
合、その電池の特性劣化がはやく寿命が短いとい
う問題があつた。 However, when the electrode catalyst layer 5 is prepared by such a method, as shown in FIG. As a result, when this electrode catalyst layer was used as an electrode for a fuel cell, there was a problem that the characteristics of the cell deteriorated quickly and the life of the cell was short.
〔発明の目的〕
この発明は上記の点に鑑みてなされたものであ
りその目的とするところは、触媒微粒子と弗素樹
脂の微粒子とが均一によく混合されて電池寿命の
長い燃料電池用電極触媒層の製造方法を提供する
にある。[Object of the Invention] The present invention has been made in view of the above points, and its object is to provide an electrode catalyst for fuel cells in which catalyst fine particles and fluororesin fine particles are uniformly and well mixed and have a long battery life. The present invention provides a method for manufacturing a layer.
この発明は
(イ) 触媒微粒子を界面活性剤の水溶液に分散させ
て触媒微粒子の分散液を調製する工程、
(ロ) 上記分散液に弗素樹脂のデイスパージヨンを
加えて触媒微粒子と弗素樹脂の微粒子の混合分
散液を調製する工程、
(ハ) 上記混合分散液に揮発性の少ない有機溶媒を
加えて触媒微粒子と弗素樹脂の微粒子を凝集さ
せる工程、
とにより燃料電池用電極触媒層を調製するのでそ
の目的を達する。
This invention comprises (a) a step of dispersing catalyst fine particles in an aqueous solution of a surfactant to prepare a dispersion of catalyst fine particles, and (b) adding a fluororesin dispersion to the above dispersion to separate the catalyst fine particles and fluororesin. preparing a mixed dispersion of fine particles; (c) adding a less volatile organic solvent to the mixed dispersion to agglomerate catalyst fine particles and fluororesin fine particles; preparing an electrode catalyst layer for a fuel cell; So reach that goal.
すなわち工程(イ)、(ロ)により得られた触媒微粒子
と弗素樹脂の微粒子の混合分散に揮発性の少ない
有機溶媒を加えよく混合された触媒微粒子と弗素
樹脂の相互の相互のブロツキング作用によりそれ
ぞれの微粒子を小さくかつ均一な混合状態におい
て凝集させるようにしたものである。 That is, by adding a low-volatility organic solvent to the mixed dispersion of the catalyst fine particles and fluororesin fine particles obtained in steps (a) and (b), the mutual blocking action of the well-mixed catalyst fine particles and the fluororesin causes a mutual blocking effect, respectively. The microparticles are aggregated in a small and uniformly mixed state.
次にこの発明の実施例を図面にもとづいて説明
する。第１図はこの発明の実施例を示すもので、
電極触媒層５においては、触媒微粒子７、および
PTFEの微粒子３は第２図に示す従来の電極触媒
層に比し凝集サイズが小さくかつそれぞれの凝集
された微粒子が均一に混合している状態を示す。
このような電極触媒層は次のようにして調製する
ことができる。約25Åの白金微粒子１を約1000Å
のカーボンブラツク製触媒担体２に担持した触媒
微粒子７を100ｇとり、これを界面活性剤の水溶
液200mlないし500mlに分散させる。触媒微粒子７
の分散液にPTFEのデイスパージヨン（濃度60重
量％、比重1.5）を触媒微粒子７の重量100に対し
30ないし60重量のPTFE微粒子が混合されるよう
調整して加える。よく混合させてから、エチレン
グリコール等の揮発性の少ない有機溶媒を数100
ml加えて触媒微粒子７とPTFEの微粒子３のそれ
ぞれを凝集させる。このとき、各微粒子はよく混
合されているので相互に相手方の凝集を阻害す
る。そのため各微粒子の凝集は大きく進み得ず凝
集のサイズは小さい。しかも各微粒子の凝集は、
相互によく混合された状態において進行する。こ
のようにして得られた粘稠なペーストをニーダに
用いてよく混練し押出成形し、カレンダロールに
て100ないし200μｍの厚さに展延して電極触媒層
の薄膜を形成する。この薄膜状電極触媒層５を乾
燥し、カーボン電極基材４の上に載置してPTFE
の溶融する温度（350℃）で加圧し、電極触媒層
５をカーボン電極基材４に融着するとともに触媒
微粒子７をPTFEの微粒子３で結着させた。
Next, embodiments of the present invention will be described based on the drawings. FIG. 1 shows an embodiment of this invention.
In the electrode catalyst layer 5, catalyst fine particles 7, and
The PTFE fine particles 3 have a smaller aggregate size than the conventional electrode catalyst layer shown in FIG. 2, and each aggregated fine particle is uniformly mixed.
Such an electrode catalyst layer can be prepared as follows. Approximately 1000 Å of platinum fine particles 1 of approximately 25 Å
100 g of catalyst fine particles 7 supported on a carbon black catalyst carrier 2 are taken and dispersed in 200 ml to 500 ml of an aqueous surfactant solution. Catalyst fine particles 7
A dispersion of PTFE (concentration 60% by weight, specific gravity 1.5) was added to the dispersion of 100% by weight of catalyst fine particles 7.
Add 30 to 60 weight of PTFE fine particles so that they are mixed. After mixing well, add a few hundred ounces of a less volatile organic solvent such as ethylene glycol.
ml and each of catalyst fine particles 7 and PTFE fine particles 3 is aggregated. At this time, each fine particle is well mixed and therefore mutually inhibits the aggregation of the other. Therefore, the aggregation of each fine particle cannot proceed significantly and the size of the aggregation is small. Moreover, the aggregation of each fine particle is
proceed in a well-mixed state. The viscous paste thus obtained is thoroughly kneaded using a kneader, extruded, and spread to a thickness of 100 to 200 μm using a calender roll to form a thin film of an electrode catalyst layer. This thin film electrode catalyst layer 5 is dried, placed on the carbon electrode base material 4, and made of PTFE.
Pressure was applied at a melting temperature (350° C.) to fuse the electrode catalyst layer 5 to the carbon electrode base material 4 and bind the catalyst fine particles 7 with the PTFE fine particles 3.
先に述べたように本発明の製法による電極触媒
層５においては、触媒微粒子７とPTFEの微粒子
３はそれぞれ小さな凝集体の状態で相互によく均
一に混合されているため、多数のガス拡散通路網
が形成されて３相界面が安定化するものと推定さ
れる。そのためこの電極層をリン酸型燃料電池に
組込み温度190℃、電流密度200ｍＡ／cm3、ガス圧
力4.0Kg／cm2の条件で運転したところ、その特性
劣化率を従来のものに比して約1/4以下に減らす
ことができる。 As mentioned above, in the electrode catalyst layer 5 manufactured by the manufacturing method of the present invention, the catalyst fine particles 7 and the PTFE fine particles 3 are well and uniformly mixed with each other in the state of small aggregates, so that a large number of gas diffusion passages are formed. It is presumed that a network is formed and the three-phase interface is stabilized. Therefore, when this electrode layer was incorporated into a phosphoric acid fuel cell and operated at a temperature of 190°C, a current density of 200 mA/cm 3 , and a gas pressure of 4.0 Kg/cm 2 , the rate of deterioration of its characteristics was approximately It can be reduced to less than 1/4.
この発明によれば
(イ) 触媒微粒子を界面活性剤の水溶液に分散させ
て触媒微粒子の分散液を調製する工程、
(ロ) 上記分散液に弗素樹脂のデイスパージヨンを
加えて触媒微粒子と、弗素樹脂の微粒子の混合
分散液を調製する工程、
(ハ) 上記混合分散液に揮発性の少ない有機溶媒を
加える工程、
により燃料電池用の電極触媒層を製造することと
したので、工程(イ)、(ロ)で得られた触媒微粒子と弗
素樹脂の微粒子の混合分散液に揮発性の少ない有
機溶媒を加えると触媒微粒子と弗素樹脂の微粒子
は、それぞれ相互に相手方を阻害しながら、小さ
く、かつ均一に混合状態で凝集することになる。
その結果このようにして得られたペーストを成膜
して得た電極触媒層は寿命が長く高い信頼性をも
つことが実証された。
According to this invention, (a) dispersing catalyst fine particles in an aqueous solution of a surfactant to prepare a dispersion of catalyst fine particles; (b) adding a fluororesin dispersion to the dispersion to form catalyst fine particles; We decided to manufacture an electrode catalyst layer for a fuel cell by the following steps: (c) preparing a mixed dispersion of fluororesin fine particles; (c) adding a less volatile organic solvent to the mixed dispersion; ), When a low-volatility organic solvent is added to the mixed dispersion of catalyst fine particles and fluororesin fine particles obtained in (b), the catalyst fine particles and the fluororesin fine particles mutually inhibit each other, and become small. In addition, the particles will coagulate in a uniformly mixed state.
As a result, it was demonstrated that the electrode catalyst layer obtained by forming the paste thus obtained had a long life and high reliability.
第１図はこの発明の電極触媒層を示す断面図、
第２図は従来の電極触媒層の断面図である。
１……白金微粒子、２……触媒担体、３……
PTFEの微粒子、４……カーボン電極基材、５…
…電極触媒層、６……電極、７……触媒微粒子。
FIG. 1 is a sectional view showing the electrode catalyst layer of the present invention;
FIG. 2 is a cross-sectional view of a conventional electrode catalyst layer. 1... Platinum fine particles, 2... Catalyst carrier, 3...
PTFE fine particles, 4... carbon electrode base material, 5...
...electrode catalyst layer, 6...electrode, 7...catalyst fine particles.
Claims (1)
させて触媒微粒子の分散液を調製する工程、 (ロ) 上記分散液に弗素樹脂のデイスパージヨンを
加えて触媒微粒子と弗素樹脂の微粒子の混合分
散液を調製する工程、 (ハ) 上記混合分散液に揮発性の少ない有機溶媒を
加えて触媒微粒子と弗素樹脂の微粒子を凝集さ
せる工程、 を備えることを特徴とする燃料電池用電極触媒層
の製造方法。[Claims] 1. (a) Dispersing catalyst fine particles in an aqueous solution of a surfactant to prepare a dispersion of catalyst fine particles; (b) Adding a fluororesin dispersion to the above dispersion to form catalyst fine particles. and (c) a step of adding a less volatile organic solvent to the mixed dispersion to agglomerate the catalyst fine particles and the fluororesin fine particles. A method for producing an electrode catalyst layer for a fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61190858A JPS6348753A (en) | 1986-08-14 | 1986-08-14 | Manufacture of electrode catalyst layer for fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61190858A JPS6348753A (en) | 1986-08-14 | 1986-08-14 | Manufacture of electrode catalyst layer for fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6348753A JPS6348753A (en) | 1988-03-01 |
| JPH0563906B2 true JPH0563906B2 (en) | 1993-09-13 |
Family
ID=16264943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61190858A Granted JPS6348753A (en) | 1986-08-14 | 1986-08-14 | Manufacture of electrode catalyst layer for fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6348753A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2620889B2 (en) * | 1990-03-05 | 1997-06-18 | 本田技研工業 株式会社 | Method and apparatus for supplying vehicle lid member |
| US6368365B1 (en) * | 2000-03-23 | 2002-04-09 | The Gillette Company | Method of making a battery |
-
1986
- 1986-08-14 JP JP61190858A patent/JPS6348753A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6348753A (en) | 1988-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5846670A (en) | Gas diffusion electrode for electrochemical cell and process of preparing same | |
| US6015635A (en) | Electrode for fuel cell and method of manufacturing electrode for fuel cell | |
| JPH0536418A (en) | Solid polymer electrolytic fuel cell and manufacture of the same | |
| JPH0652862A (en) | Porous electrode and its manufacture | |
| JP2004185863A (en) | Electrode for fuel cell, and fuel cell using it | |
| JPH1131515A (en) | High molecular electrolyte film-gas diffusion electrode body and its manufacture | |
| JP5217131B2 (en) | Catalyst ink for fuel cell, membrane electrode assembly, and production method thereof | |
| US7056615B2 (en) | Electrode for polymer electrolyte fuel cells and manufacturing method therefor | |
| CN101978536B (en) | Membrane electrode assembly and fuel cell | |
| JP2003115299A (en) | Solid polymer fuel cell | |
| JPH0563906B2 (en) | ||
| JPH0544145B2 (en) | ||
| JP2002280002A (en) | Solid polymer fuel cell and its damage preventing method | |
| JP4996823B2 (en) | Fuel cell electrode and fuel cell using the same | |
| JP2001076734A (en) | Solid polymer fuel cell | |
| JP2741574B2 (en) | Solid polymer electrolyte fuel cell | |
| JP5057798B2 (en) | Fuel cell electrode and fuel cell | |
| JP2002015746A (en) | Fuel cell and fuel cell electrode member | |
| JP2001126737A (en) | Electrode for a fuel cell, method for preparing the fuel cell, and the fuel cell | |
| JP2006066309A (en) | Method of manufacturing catalyst for solid polymer type fuel cell | |
| JPH061700B2 (en) | Composite electrode for fuel cell | |
| JPH0563912B2 (en) | ||
| JP2005166310A (en) | Gas diffusion electrode and its manufacturing method and fuel cell | |
| JP2005071851A (en) | Manufacturing method of gas diffusion electrode | |
| JPS6348752A (en) | Manufacture of electrode for fuel cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |