JPS6247346B2 - - Google Patents
Info
- Publication number
- JPS6247346B2 JPS6247346B2 JP55054961A JP5496180A JPS6247346B2 JP S6247346 B2 JPS6247346 B2 JP S6247346B2 JP 55054961 A JP55054961 A JP 55054961A JP 5496180 A JP5496180 A JP 5496180A JP S6247346 B2 JPS6247346 B2 JP S6247346B2
- Authority
- JP
- Japan
- Prior art keywords
- sheet
- carbon
- catalyst
- gas diffusion
- agent
- 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
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000009792 diffusion process Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000004067 bulking agent Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 238000010828 elution Methods 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005406 washing 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
-
- 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】
本発明は燃料電池用ガス拡散電池の製法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a gas diffusion cell for a fuel cell.
一般にガス拡散電極の触媒層は、触媒金属を担
持した炭素粉末に結着剤を混合して成型後、熱処
理する方法、又は多孔質基板に触媒金属の塩溶液
を含浸して後還元して触媒金属を基板多孔部に析
出させる方法などにより作られる。 Generally, the catalyst layer of a gas diffusion electrode is formed by mixing carbon powder supporting a catalyst metal with a binder, molding it, and then heat-treating it, or by impregnating a porous substrate with a salt solution of the catalyst metal and post-reducing the catalyst. It is made by depositing metal into the porous parts of the substrate.
しかしこれらの方法は均一な厚みの薄い触媒層
を得ることがむづかしく、電極面積が大きくなる
にしたがいその傾向が強くなるという問題があつ
た。 However, these methods have the problem that it is difficult to obtain a thin catalyst layer with a uniform thickness, and this tendency becomes stronger as the electrode area becomes larger.
本発明はかゝる問題点を解決し、燐酸マトリツ
クスタイプの燃料電池に好適する極薄質のガス拡
散電極を提供するもので、その特徴とする所は、
触媒を付着した炭素粉末に酸化亜鉛などの可溶性
バルク剤を混合し、この混合粉末材に弗素樹脂デ
イスパージヨンを加えて混練し、前記弗素樹脂が
繊維状となつた塊状体をシート状にして乾燥後、
このシートをカーボンペーパー上に添着した状態
で前記バルク剤の溶出液中に浸漬してバルク剤を
シートから溶解除去する点にある。 The present invention solves these problems and provides an ultra-thin gas diffusion electrode suitable for phosphoric acid matrix type fuel cells, which is characterized by:
A soluble bulking agent such as zinc oxide is mixed with the carbon powder to which the catalyst is attached, and a fluororesin dispersion is added and kneaded to this mixed powder material, and the fluororesin is made into a sheet in the form of a fibrous mass. After drying,
The sheet is immersed in the eluate of the bulking agent while attached to the carbon paper to dissolve and remove the bulking agent from the sheet.
以下本発明の実施例を説明する。 Examples of the present invention will be described below.
周知の方法で白金触媒を夫々付着した活性炭と
グラフアイトとの等量混合物５ｇに、可溶性バル
ク剤として酸化亜鉛20ｇ及び10％PTFEデイスパ
ージヨン８mlを加え、加圧式混合機で混練すると
PTFEが繊維状となつた塊状体が得られる。これ
をローラーで0.1〜0.2mm厚のシートにした後空気
中で乾燥して水分を除く。 When 20 g of zinc oxide and 8 ml of 10% PTFE dispersion are added as a soluble bulking agent to 5 g of a mixture of equal amounts of activated carbon and graphite each coated with a platinum catalyst by a well-known method, and the mixture is kneaded with a pressure mixer.
A fibrous mass of PTFE is obtained. This is rolled into a sheet with a thickness of 0.1 to 0.2 mm and then dried in the air to remove moisture.
ついでこのシート（触媒層）を厚み0.4mmのカ
ーボンペーパー上に固定する。この固定は後述す
るバルク剤の溶出処理時シートが収縮するのを防
止するためのもので、シートの周囲のみを接着剤
などで貼付ければよい。上記カーボンペーパーは
拡散層（防水層）となるものであるから、周知の
方法で弗素樹脂を用いて予め防水処理が施された
ものを用いる。 This sheet (catalyst layer) was then fixed onto a 0.4 mm thick carbon paper. This fixation is to prevent the sheet from shrinking during the elution process of the bulk agent, which will be described later, and it is sufficient to attach only the periphery of the sheet with an adhesive or the like. Since the above-mentioned carbon paper serves as a diffusion layer (waterproof layer), it should be waterproofed in advance using a fluororesin by a well-known method.
ついでカーボンペーパーとシートとの積層体を
稀塩酸溶液中に浸漬し、シートより酸化亜鉛を溶
解除去して、PTFE繊維のネツトワークとこのネ
ツトワーク内に保持された触媒粒子とが残つたシ
ートを構成する。これを水洗乾燥後350℃で熱処
理してシート中の繊維状PTFEを結着する。 Next, the laminate of carbon paper and sheet is immersed in a dilute hydrochloric acid solution to dissolve and remove the zinc oxide from the sheet, leaving the sheet with the PTFE fiber network and catalyst particles held within this network. Configure. This is washed with water, dried, and then heat treated at 350°C to bind the fibrous PTFE in the sheet.
尚前記熱処理による結着は本発明法においては
必ずしも必要でなく、熱処理をしない場合でも電
極特性上差は見られなかつた。又、この二重層ガ
ス拡散電極は、組立時その全面にわたりガス分離
板と電解液保持マトリツクスとの間で挾持される
ので、カーボンペーパーとシートの機械的強度及
び両者間の結合力も余り問題とならない点も熱処
理による結着を必要としない理由である。 It should be noted that binding by the heat treatment is not necessarily necessary in the method of the present invention, and no difference in electrode properties was observed even when no heat treatment was performed. In addition, since this double-layer gas diffusion electrode is sandwiched between the gas separation plate and the electrolyte retention matrix over its entire surface during assembly, the mechanical strength of the carbon paper and the sheet and the bonding force between the two do not matter much. This is also the reason why bonding by heat treatment is not required.
このようにして作成した触媒層（シート）の厚
みは、バルク剤の溶出によつて溶出前に比し0.05
〜0.1mm程度に半減し、その白金触媒量は0.2mg／
cm2程度である。 The thickness of the catalyst layer (sheet) created in this way is 0.05% compared to before elution due to the elution of the bulk agent.
The amount of platinum catalyst was reduced by half to about 0.1 mm, and the amount of platinum catalyst was 0.2 mg/
It is about cm2 .
一方白金付活性炭とグラフアイトの代りに白金
黒を使用し、その他は本発明と同様の方法で作成
した触媒層は、本発明電極と同性能を得るために
白金量は４mg／cm2を要し、本発明により白金量が
10〜20分の１に減少出来る。又白金黒使用の場
合、バルク剤溶出後の水洗いに続く乾燥工程でシ
ートのひび割れが生じて使用不能となるが、本発
明の場合白金触媒の担体となる活性炭及びグラフ
アイトの粒径を数10μ〜150μ程度に選定するこ
とによりひび割れの問題を解消できる。 On the other hand, a catalyst layer prepared using platinum black instead of platinized activated carbon and graphite, but otherwise using the same method as the present invention, requires a platinum amount of 4 mg/cm 2 in order to obtain the same performance as the present electrode. However, according to the present invention, the amount of platinum can be reduced.
It can be reduced to 1/10 to 20 times. Furthermore, when platinum black is used, the sheet cracks during the drying process following water washing after elution of the bulk agent, making it unusable; however, in the present invention, the particle size of activated carbon and graphite, which serve as the carrier for the platinum catalyst, is reduced to several tens of microns. By selecting a thickness of ~150μ, the problem of cracks can be solved.
本発明法ではシートを防水層上に固定して後バ
ルク剤の溶出処理を行うので溶出によりシートが
収縮して防水層上に密着する状態となり、シート
のまゝでバルク剤の溶出処理を行つた場合のよう
に処理後のプレス及び防水層に添着後のプレスは
不用である。 In the method of the present invention, the bulk agent is eluted after the sheet is fixed on the waterproof layer, so the sheet shrinks due to elution and comes into close contact with the waterproof layer, and the bulk agent is eluted while the sheet is still in place. It is not necessary to press after treatment and after adhesion to the waterproof layer, as in the case of polyester.
本発明による触媒層は、そのシート作成時予め
混入したバルク剤を溶出して繊維状弗素樹脂のネ
ツトワーク内に触媒粒子を保持した状態とするの
で、極めて薄くすることが可能であり、且この溶
出処理はシートをカーボンペーパー上に添着した
状態で行われ、溶出時の収縮によりシートがペー
パーに密着するので、シートのまゝで溶出処理す
る場合のようなプレス工程を必要とせず工程の簡
略化が達成される。 The catalyst layer according to the present invention can be made extremely thin because the bulk agent mixed in advance is eluted when the sheet is prepared, and the catalyst particles are retained within the network of the fibrous fluororesin. The elution process is performed with the sheet attached to the carbon paper, and the sheet adheres to the paper due to shrinkage during elution, which simplifies the process by eliminating the need for the pressing process that would be required when performing the elution process as a sheet. is achieved.
又触媒金属の担体として活性炭・グラフアイト
などの炭素粒子を用いるので、触媒量を低減し得
ると共に粒径の比較的大きい（白金黒に比し）炭
素粒子の存在により、溶出処理後の乾燥工程で触
媒層にひび割れを生ずるおそれがない、などの特
長を有し、燐酸マトリツクスタイプの燃料電池に
好適する薄質で厚みの均一なガス拡散電極を提供
することができる。 In addition, since carbon particles such as activated carbon and graphite are used as carriers for the catalytic metal, the amount of catalyst can be reduced, and the presence of carbon particles with a relatively large particle size (compared to platinum black) reduces the drying process after elution treatment. The present invention has the advantage that there is no risk of cracks in the catalyst layer during the process, and can provide a thin and uniformly thick gas diffusion electrode suitable for phosphoric acid matrix type fuel cells.
Claims (1)
剤を混合し、この混合粉末材に弗素樹脂デイスパ
ージヨンを加えて混練し、前記弗素樹脂が繊維状
となつた塊状体をシートに引延し、乾燥後このシ
ートをカーボンペーパー上に添着した状態で前記
バルク剤の溶出液中に浸漬してシートからバルク
剤を溶解除去せしめることを特徴とするガス拡散
電極の製法。 ２ 触媒金属を付着した炭素粉末は、活性炭及び
グラフアイトに夫々触媒金属を担持させた混合粉
末よりなることを特徴とする前記特許請求の範囲
第１項記載のガス拡散電極の製法。[Scope of Claims] 1. A soluble bulking agent is mixed with carbon powder to which a catalyst metal is attached, and a fluororesin dispersion is added and kneaded to this mixed powder material to form a fibrous aggregate of the fluororesin. 1. A method for producing a gas diffusion electrode, which comprises stretching the sheet into a sheet, drying the sheet, adhering it to carbon paper, and immersing the sheet in an eluent of the bulk agent to dissolve and remove the bulk agent from the sheet. 2. The method for producing a gas diffusion electrode according to claim 1, wherein the carbon powder to which the catalytic metal is attached is a mixed powder in which the catalytic metal is supported on activated carbon and graphite, respectively.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5496180A JPS56152166A (en) | 1980-04-24 | 1980-04-24 | Preparation of gas diffusion electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5496180A JPS56152166A (en) | 1980-04-24 | 1980-04-24 | Preparation of gas diffusion electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56152166A JPS56152166A (en) | 1981-11-25 |
| JPS6247346B2 true JPS6247346B2 (en) | 1987-10-07 |
Family
ID=12985260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5496180A Granted JPS56152166A (en) | 1980-04-24 | 1980-04-24 | Preparation of gas diffusion electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56152166A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9724053B2 (en) | 2011-01-07 | 2017-08-08 | Toshiba Medical Systems Corporation | X-ray CT apparatus |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0722020B2 (en) * | 1983-03-31 | 1995-03-08 | 株式会社東芝 | Method for manufacturing gas diffusion electrode |
| CN107408705A (en) * | 2014-09-24 | 2017-11-28 | 美国范德堡大学 | Polymer solution, fiber mat and nanofiber membrane electrode assembly and its manufacture method with the fiber mat |
-
1980
- 1980-04-24 JP JP5496180A patent/JPS56152166A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9724053B2 (en) | 2011-01-07 | 2017-08-08 | Toshiba Medical Systems Corporation | X-ray CT apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56152166A (en) | 1981-11-25 |
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