JPS626305B2 - - Google Patents
Info
- Publication number
- JPS626305B2 JPS626305B2 JP56061418A JP6141881A JPS626305B2 JP S626305 B2 JPS626305 B2 JP S626305B2 JP 56061418 A JP56061418 A JP 56061418A JP 6141881 A JP6141881 A JP 6141881A JP S626305 B2 JPS626305 B2 JP S626305B2
- Authority
- JP
- Japan
- Prior art keywords
- platinum
- solution
- plate
- electrode
- compound
- 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
- 239000002344 surface layer Substances 0.000 claims description 8
- 239000000446 fuel Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 27
- 229910052799 carbon Inorganic materials 0.000 description 14
- 229910052697 platinum Inorganic materials 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 150000003058 platinum compounds Chemical class 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 229920003319 Araldite® Polymers 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- -1 platinum Chemical class 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 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)
- Inert Electrodes (AREA)
Description
この発明は、液体燃料電池、特に酸性メタノー
ル燃料電池用電極板の製造方法に関する。
従来の多孔質板に白金等の触媒を付着した燃料
電池用電極板としては、代表的なものとして、多
孔質カーボンに白金を付けたものがある。この電
極の製法としては、特開昭54−154048号公封に記
載されているように、多孔質カーボン板を塩化白
金酸水溶液に含浸した後、600℃程度に加熱され
た不活性ガス気流中で塩化白金酸を熱分解して、
カーボン板に白金を固定するか、又は塩化白金酸
水溶液に含浸した後10重量％程度のKOH水溶液
を用いて酸化白金として固定した後、ヒドラジン
を用いて還元する等の方法が実施されている。
しかしながら、このような従来の製造方法にあ
つては、付着された白金はカーボン細孔内深部ま
で入つてしまい、この部分は電極反応に関与せず
不用でありかつ無駄であるという問題点があつ
た。従つて、不用の触媒金属例えば白金をいかに
低減し、かつ電極反応に有効な表面層に触媒をい
かに多く付着させるかということが大きな課題で
あつた。
この発明は、このような従来の問題点に着目し
てなされたもので、多孔質板をその電極とする一
面を除いて気密に被覆し、次いで触媒金属化合物
の溶液に浸漬した後、細孔内にたまつた溶液を、
加熱による細孔内残留空気の圧力上昇によつて表
面層に圧送移動させるとともに蒸発によつて濃縮
し、多孔質板表面層の触媒金属を増大させること
により、上記問題点を解決することを目的として
いる。
以下、この発明を実施例により説明する。
カーボン・ブラツクを主成分とする多孔質カー
ボン板（例えば日本カーボン(株)製のカーボン・ブ
ラツクを主成分とした焼結板；気孔率40％）（10
mm×10mm×２mm）に対し、その電極として使用す
る一面を除いて接着剤アラルダイト（商品名；チ
バガイギー社製）で被覆した。次いで、このカー
ボン板５枚を白金濃度40ｇ／の塩化白金酸水溶
液150c.c.（80℃）に一時間浸漬した後、10重量％
KOH水溶液（25℃）に３分間浸漬してカーボン
板表面層に存在する塩化白金酸水溶液を水に不溶
性の白金化合物としてカーボン板に固定する。次
いで、これを80℃、大気中（１時間）で加熱し、
細孔深部にまで入つた塩化白金酸水溶液を加熱に
よるカーボン板細孔内に残留した空気の圧力上昇
によつて表面層まで圧送・移動させ、かつ蒸発に
よつてカーボン板の表面層にこの液を濃縮させ
る。
ついで、このカーボン板を100％抱水ヒドラジ
ンに25℃、30分間浸漬し、付着している不溶性の
白金化合物を白金に還元しかつ固定する。
このように作成したカーボン板を電極として電
位走査法を用いて白金上に吸着した水素量を測定
することにより、白金表面積の比較を行なつた。
なお、比較のため、被覆をしない点とKOH溶液
で白金の不溶性白金化合物をつくつた後ただちに
ヒドラジンで還元する点以外は上記実施例と同じ
ものをつくり、同じ方法で白金表面積を測定し
た。この表面積を測定する方法は、白金原子１個
に水素原子が１個吸着するという原理を利用し
て、まず水素を十分に白金に吸着させた後、これ
を電気的にイオン化し、このイオン化に要する電
気量によつて表面積を求めた。その結果を次表に
示す。
The present invention relates to a method for manufacturing an electrode plate for a liquid fuel cell, particularly an acidic methanol fuel cell. A typical example of a conventional fuel cell electrode plate in which a catalyst such as platinum is attached to a porous plate is one in which platinum is attached to porous carbon. As described in JP-A-54-154048, this electrode is manufactured by impregnating a porous carbon plate with an aqueous solution of chloroplatinic acid and then placing it in a stream of inert gas heated to about 600°C. pyrolyze chloroplatinic acid with
Methods such as fixing platinum on a carbon plate, or impregnating it in an aqueous solution of chloroplatinic acid, fixing it as platinum oxide using an aqueous solution of KOH of about 10% by weight, and then reducing it with hydrazine have been implemented. However, in such conventional manufacturing methods, there is a problem that the deposited platinum enters deep into the carbon pores, and this part does not participate in the electrode reaction and is unnecessary and wasteful. Ta. Therefore, a major problem has been how to reduce unnecessary catalyst metals, such as platinum, and how to attach a large amount of catalyst to the surface layer that is effective for electrode reactions. This invention was made by focusing on these conventional problems. A porous plate is airtightly coated except for one side that will be used as an electrode, and then immersed in a solution of a catalytic metal compound. The solution accumulated inside
The purpose is to solve the above problems by increasing the pressure of residual air in the pores due to heating, forcing it to move to the surface layer, and concentrating it by evaporation, thereby increasing the amount of catalyst metal in the surface layer of the porous plate. It is said that This invention will be explained below with reference to Examples. Porous carbon plate mainly composed of carbon black (for example, a sintered plate mainly composed of carbon black manufactured by Nippon Carbon Co., Ltd.; porosity 40%) (10
mm x 10 mm x 2 mm) was coated with adhesive Araldite (trade name; manufactured by Ciba Geigy) except for one side to be used as an electrode. Next, five of these carbon plates were immersed for one hour in a 150 c.c. (80°C) chloroplatinic acid aqueous solution with a platinum concentration of 40 g/10% by weight.
The carbon plate is immersed in a KOH aqueous solution (25°C) for 3 minutes to fix the chloroplatinic acid aqueous solution present in the surface layer of the carbon plate as a water-insoluble platinum compound on the carbon plate. Next, this was heated at 80°C in the air (1 hour),
The chloroplatinic acid aqueous solution that has penetrated deep into the pores is pumped and moved to the surface layer by the pressure increase of the air remaining in the pores of the carbon plate due to heating, and this liquid is transferred to the surface layer of the carbon plate by evaporation. Concentrate. Next, this carbon plate is immersed in 100% hydrazine hydrate at 25°C for 30 minutes to reduce and fix the attached insoluble platinum compound to platinum. The platinum surface area was compared by measuring the amount of hydrogen adsorbed on platinum using the potential scanning method using the carbon plate thus prepared as an electrode.
For comparison, the same product as in the above example was made, except that it was not coated and that an insoluble platinum compound of platinum was prepared with a KOH solution and then immediately reduced with hydrazine, and the platinum surface area was measured using the same method. The method of measuring this surface area utilizes the principle that one hydrogen atom is adsorbed to one platinum atom. First, hydrogen is sufficiently adsorbed on platinum, and then it is electrically ionized. The surface area was determined by the amount of electricity required. The results are shown in the table below.
【表】
この結果から、本発明の製造方法によつて作成
した電極は、表面に白金が多く付着していること
がわかる。したがつて、燃料電池の電極として良
い性能を示す。すなわち、1M―H2SO4の電解質
を用いたメタノール燃料電池では、上記のように
３倍の表面積を得られるときには、電極の見かけ
の表面積が同じであつても９倍の電流を取りだす
ことができるというすぐれた結果を得ることがで
きる。
以上説明してきたように、この発明によれば、
多孔質板の細孔深部に入つた塩化白金酸水溶液等
の触媒金属の化合物の溶液を、加熱によつて生ず
る多孔質板細孔内の残留空気の圧力上昇によつて
当該溶液を表面積に圧送・移動しかつ濃縮させた
ため、多孔質板表面層の触媒付着量をかなり増大
でき、液体燃料電池用電極板としての性能を著し
く増大することができるというすぐれた効果が得
られる。[Table] From the results, it can be seen that the electrode produced by the manufacturing method of the present invention has a large amount of platinum attached to the surface. Therefore, it exhibits good performance as an electrode for fuel cells. In other words, in a methanol fuel cell using a 1M-H 2 SO 4 electrolyte, if three times the surface area can be obtained as described above, nine times the current can be extracted even if the apparent surface area of the electrode is the same. You can get excellent results. As explained above, according to this invention,
A solution of a catalytic metal compound such as an aqueous solution of chloroplatinic acid that has entered the deep pores of a porous plate is pumped to the surface area by increasing the pressure of residual air in the pores of the porous plate caused by heating. - Since the catalyst is moved and concentrated, the amount of catalyst attached to the surface layer of the porous plate can be considerably increased, and the excellent effect of significantly increasing the performance as an electrode plate for liquid fuel cells can be obtained.
Claims (1)
次いで触媒金属の化合物の溶液に浸漬した後、該
溶液から引上げて加熱し、細孔深部内残留空気の
圧力上昇によつて前記化合物の溶液を多孔質板の
表面層に移動させ、次いで該化合物を還元して固
定するようにしたことを特徴とする液体燃料電池
用電極板の製造方法。1 Cover the porous plate airtight except for one side,
Next, after being immersed in a solution of the compound of the catalytic metal, it is pulled out from the solution and heated, and the solution of the compound is moved to the surface layer of the porous plate by the pressure increase of the air remaining deep inside the pores, and then the compound is immersed in the solution. 1. A method for manufacturing an electrode plate for a liquid fuel cell, characterized in that the electrode plate is fixed by reducing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56061418A JPS57176670A (en) | 1981-04-24 | 1981-04-24 | Manufacture of electrode for liquid-fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56061418A JPS57176670A (en) | 1981-04-24 | 1981-04-24 | Manufacture of electrode for liquid-fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57176670A JPS57176670A (en) | 1982-10-30 |
| JPS626305B2 true JPS626305B2 (en) | 1987-02-10 |
Family
ID=13170528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56061418A Granted JPS57176670A (en) | 1981-04-24 | 1981-04-24 | Manufacture of electrode for liquid-fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57176670A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6433509U (en) * | 1987-08-25 | 1989-03-01 |
-
1981
- 1981-04-24 JP JP56061418A patent/JPS57176670A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6433509U (en) * | 1987-08-25 | 1989-03-01 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57176670A (en) | 1982-10-30 |
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