JPH01132055A - Manufacture of electrode catalyst layer for fuel cell - Google Patents
Manufacture of electrode catalyst layer for fuel cellInfo
- Publication number
- JPH01132055A JPH01132055A JP62290972A JP29097287A JPH01132055A JP H01132055 A JPH01132055 A JP H01132055A JP 62290972 A JP62290972 A JP 62290972A JP 29097287 A JP29097287 A JP 29097287A JP H01132055 A JPH01132055 A JP H01132055A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- fine particles
- catalyst layer
- catalyst carrier
- carbon black
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 239000000446 fuel Substances 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000010419 fine particle Substances 0.000 claims abstract description 39
- 239000006229 carbon black Substances 0.000 claims abstract description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001260 Pt alloy Inorganic materials 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 9
- 230000007704 transition Effects 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- 239000010948 rhodium Substances 0.000 claims abstract description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 18
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000282330 Procyon lotor Species 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
-
- 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〕
この発明は燃料電池電極触媒層の製造方法に保り、特に
電極触媒層の触媒微粒子の製法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for manufacturing a fuel cell electrode catalyst layer, and particularly to a method for manufacturing catalyst fine particles for the electrode catalyst layer.
燃料電池は燃料の持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、その構成は電解液層をはさんで
第５図に示すようなｉ！電極を対向して配し、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、各々の電極の触媒上で燃料ガスおよび酸化剤ガ
スを電気化学的に反応させるもので、その結果として系
外に電気エネルギを取出す、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 is as shown in Figure 5, with an electrolyte layer sandwiched between the i! Electrodes are arranged facing each other, and fuel gas and oxidizing gas are supplied to each electrode from an external gas supply system, and the fuel gas and oxidizing gas are electrochemically reacted on the catalyst of each electrode. As a result, it is possible to extract electrical energy outside the system.
電極６は多孔質の電極基材４の上に電極触媒層５が付着
する構造であり、ざらにこの電極触媒層５は触媒担体２
の表面に合金の微粒子１が担持された触媒微粒子７がフ
ッ素樹脂の微粒子３を介して結着された構造となってい
る。The electrode 6 has a structure in which an electrode catalyst layer 5 is attached on a porous electrode base material 4, and this electrode catalyst layer 5 is roughly attached to the catalyst carrier 2.
It has a structure in which catalyst fine particles 7 on which alloy fine particles 1 are supported are bound together via fluororesin fine particles 3.
電極触媒層５の内部においては触媒微粒子７の表面にお
いて電解液と反応ガスが接触して３相界面を形成し電気
化学反応がおこる。電気化学反応が進行するにはこの３
相界面が電極触媒層５の内７とを均一によく混合分散さ
せることがＴＬ要となる。また、電池の特性、、寿命を
向上させるためには電極触媒層５の触媒微粒子７中の触
媒担体２の選定が１要となる。Inside the electrode catalyst layer 5, the electrolytic solution and the reaction gas come into contact with each other on the surface of the catalyst fine particles 7 to form a three-phase interface and an electrochemical reaction occurs. These three things are necessary for the electrochemical reaction to proceed.
It is essential for the phase interface to uniformly and well mix and disperse the electrode catalyst layer 5 and the electrode catalyst layer 5. In addition, in order to improve the characteristics and life of the battery, it is necessary to select the catalyst carrier 2 in the catalyst fine particles 7 of the electrode catalyst layer 5.
従来は、触媒担体２として、比表面積が４００〜７００
ｒｒ？／ｇと比較的大きなカーボンブラックが用いられ
ていた。Conventionally, the catalyst carrier 2 has a specific surface area of 400 to 700.
rr? /g, a relatively large carbon black was used.
しかしながら上述のようなカーボンブラックを触媒担体
として用いる場合においては、これに通常の方法に従っ
て白金等の貴金属を担持させて電極触媒層を形成し、電
池を組立てると、電池作動条件下、特に高電位のもとて
触媒担体２がリン酸に腐蝕され１合金の微粒子が脱落し
、その結果電池の寿命が短か（なるという問題が生ずる
。However, when using carbon black as a catalyst carrier as described above, when a noble metal such as platinum is supported on carbon black according to a normal method to form an electrode catalyst layer and a battery is assembled, it is difficult to maintain high potential under battery operating conditions, especially when a battery is assembled. At this point, the catalyst carrier 2 is corroded by the phosphoric acid and fine particles of Alloy 1 fall off, resulting in a problem that the life of the battery is shortened.
この問題に対処するためカーボンブラックを３０００℃
の温度で熱処理してグラファイト化することが試みられ
た。このようにすると、熱処理されない場合°に比較し
て腐蝕の程度は１１５に減り耐蝕性は向上する。しかし
このグラファイト化された触媒担体はその比表面積がｘ
ｏｒｒｔ／ｇと非常に小さく合金の微粒子１を触媒担体
２の上に高分散状態で担持することができず、高電位下
において長時間電池を運転した場合１合金の微粒子１の
シンタリングがおこり、比較的短かい時間で電池の特性
が劣化するという欠点がある。To deal with this problem, carbon black was heated to 3000℃.
Attempts were made to graphitize by heat treatment at a temperature of . In this way, the degree of corrosion is reduced to 115% compared to the case without heat treatment, and the corrosion resistance is improved. However, the specific surface area of this graphitized catalyst support is x
The alloy particles 1, which are extremely small (orrt/g), cannot be supported in a highly dispersed state on the catalyst carrier 2, and when the battery is operated for a long time under a high potential, sintering of the alloy particles 1 occurs. However, the disadvantage is that the battery characteristics deteriorate in a relatively short period of time.
この発明は上述の点に鑑みてなされ、その目的はカーボ
ン触媒担体を部分的にグラファイト化することにより合
金の微粒子が高分散化するとともに触媒担体の耐蝕性が
良好な電極触媒層の製造方法を提供することにある。This invention has been made in view of the above points, and its purpose is to provide a method for producing an electrode catalyst layer in which the fine particles of the alloy are highly dispersed by partially graphitizing the carbon catalyst carrier, and the catalyst carrier has good corrosion resistance. It is about providing.
上記の目的はこの発明によれば触媒金属の微粒子をカー
ボンの触媒担体上に担持させて触媒微粒子となしこれを
フッ素樹脂微粒子で結Ｈさせる電極触媒層の製造方法に
おいて、カーボンブラックを不活性ガス中で熱処理し、
ついでこれに第１成分としての白金の微粒子と第２成分
としての遷移元素またはロジウムの微粒子とを被着させ
かつ熱処理して白金合金の微粒子を触媒担体上に担持さ
せた触媒微粒子を形成することにより達成される。According to the present invention, the above object is achieved by a method for producing an electrode catalyst layer in which catalyst metal fine particles are supported on a carbon catalyst carrier to form catalyst fine particles, which are then sulfurized with fluororesin fine particles. heat treated in
Next, fine particles of platinum as a first component and fine particles of a transition element or rhodium as a second component are deposited on this and heat treated to form fine catalyst particles in which fine particles of platinum alloy are supported on a catalyst carrier. This is achieved by
カーボンの触媒担体としてはアセチレンブラック、ファ
ーネスブラックなどのカーボンブラックが用いられる。Carbon black such as acetylene black and furnace black is used as the carbon catalyst carrier.
不活性ガスはアルゴン、ヘリウム等が用いられる。熱処
理温度は１４００℃乃至２２００℃の範囲が好適である
。この温度でカーボンブラックは部分的にグラファイト
化される。第２成分としての遷移元素は、鉄、クロム、
コバルト、バナジウム等が用いられる。第１成分と第２
成分とがカーボン担体に被着されたあと熱処理によりこ
れらは合金化され触媒金属である白金合金となる。Argon, helium, etc. are used as the inert gas. The heat treatment temperature is preferably in the range of 1400°C to 2200°C. At this temperature the carbon black becomes partially graphitized. The transition elements as the second component are iron, chromium,
Cobalt, vanadium, etc. are used. 1st component and 2nd component
After the components are deposited on the carbon carrier, they are alloyed by heat treatment to form a platinum alloy, which is the catalyst metal.
カーボンブラックは熱処理により部分的にグラファイト
化され、耐蝕性が増す。カーボンブラックのアモルファ
スの部分は第１成分の貴金属と第２成分の遷移元素とが
合金化する際に結晶子径の成長を阻害する。Carbon black is partially graphitized by heat treatment, increasing its corrosion resistance. The amorphous portion of carbon black inhibits the growth of crystallite size when the first component of the noble metal and the second component of the transition element are alloyed.
次にこの発明の実施例を図面に基いて説明する。 Next, embodiments of the present invention will be described based on the drawings.
触媒担体として用いるカーボンブラックを不活性ガス中
で熱処理し、カーボンブラックを部分的にグラファイト
化する。熱処理温度（時間は２時間）と得られた触媒担
体の比表面積との関係を第１図に示す。また熱処理温度
と得られた触媒担体の腐蝕電流との関係を第２図に示す
。腐蝕電流は触媒担体をリン酸中でアノード分極したと
きの電極の溶解にもとづく電流である。第２図は、カー
ボンブラックの熱処理温・度が１４００℃以上で腐蝕電
流が殆んどフラットな低い値を示している。一方第１図
は熱処理温度が高くなる程触媒担体の比表面積が減るこ
とを示すが経験上１００ ｄ１９以上の比表面積が有効
なことがわかっているので熱処理温度としては２２００
℃以下が適当であることがわかる。結局第１図と第２図
とからカーボンブラックの熱処理温度としては１４００
℃〜２２００℃の範囲が好適であると考えられる。この
範囲ではカーボンブラックは部分的にグラファイト化さ
れる。Carbon black used as a catalyst carrier is heat treated in an inert gas to partially graphitize the carbon black. FIG. 1 shows the relationship between the heat treatment temperature (duration: 2 hours) and the specific surface area of the obtained catalyst carrier. Further, FIG. 2 shows the relationship between the heat treatment temperature and the corrosion current of the obtained catalyst carrier. The corrosion current is the current based on the dissolution of the electrode when the catalyst carrier is anodic polarized in phosphoric acid. FIG. 2 shows that when the carbon black heat treatment temperature is 1400° C. or higher, the corrosion current is almost flat and low. On the other hand, Figure 1 shows that the higher the heat treatment temperature, the lower the specific surface area of the catalyst carrier, but experience has shown that a specific surface area of 100 d19 or more is effective, so the heat treatment temperature should be 2200.
It can be seen that a temperature below ℃ is appropriate. In the end, from Figures 1 and 2, the heat treatment temperature for carbon black was 1400.
It is considered that a range of 0.degree. C. to 2200.degree. C. is suitable. In this range the carbon black is partially graphitized.
次にカーボンブラックの熱処理温度と得られた触媒担体
に担持される白金合金の微粒子の結晶子径との関係を調
べた。触媒担体を塩化白金酸の水溶液中に分散させ公知
の方法で塩化白金酸を還元して触媒担体上にｄ金の微粒
子を被着させる。続いて白金の被着した触媒担体を硝酸
第２鉄の水溶液中に分散させ、硝酸第２鉄をアンモニア
を用いてアルカリ還元し、鉄の微粒子を担体衣面上ｆこ
被着させる。次に白金と鉄の微粒子の被着した触媒担体
を窒素雰囲気中、９００℃の温度で２時間反応させ白金
と鉄を合金化させ、合金の微粒子を触媒担体上に担持さ
せる。このようにして得られた白金合金の微粒子の結晶
子径を触媒担体の熱処理温度との関係において求めたも
のが第３図である。Next, the relationship between the heat treatment temperature of carbon black and the crystallite diameter of the platinum alloy fine particles supported on the obtained catalyst carrier was investigated. The catalyst carrier is dispersed in an aqueous solution of chloroplatinic acid, and the chloroplatinic acid is reduced by a known method to deposit fine gold particles on the catalyst carrier. Subsequently, the catalyst carrier coated with platinum is dispersed in an aqueous solution of ferric nitrate, and the ferric nitrate is reduced with alkali using ammonia to deposit fine iron particles on the surface of the carrier. Next, the catalyst carrier on which the fine particles of platinum and iron are adhered is reacted in a nitrogen atmosphere at a temperature of 900° C. for 2 hours to alloy platinum and iron, and the fine particles of the alloy are supported on the catalyst carrier. FIG. 3 shows the crystallite diameter of the platinum alloy fine particles thus obtained in relation to the heat treatment temperature of the catalyst carrier.
第３図は熱処理温度が１４００℃と２２００℃の間にお
いて白金合金の微粒子の結晶子径がほとんど平たんで３
０Ａ〜３８Ａの範囲にあることがわかる。Figure 3 shows that when the heat treatment temperature is between 1400°C and 2200°C, the crystallite diameter of the platinum alloy fine particles becomes almost flat and 3.
It can be seen that it is in the range of 0A to 38A.
このようにして得られた触媒微粒子７を用いて電極触媒
層を形成し、電池を組立ててその寿命特性を調べた。結
果を第４図に示す。電池は温度２００℃、電流密度２０
０ ｍＡ／ｃｍ” 、動作ガス圧力は４に９／α２で運
転された。第４図において曲線１２が本発明の実施例に
係る電極触媒層を用いた電池の特性で、曲線１１はカー
ボンブラックを熱処理して完全にグラファイト化した触
媒担体を用いて電極触媒層を形成した電池の寿命特性で
ある。この発明に係る電極触媒層を用いた電池の４期信
頼性が優れていることがわかる。この理由はこの発明に
係る電極触媒層の触媒担体が部分的にグラファイト化し
、アモルファスの部分を残しているためこの部分が白金
合金の微粒子の成長を阻止し結果として白金合金の微粒
子の結晶子径を最適化したためで、これにより電池特性
、耐久性共に優れた燃料電池を可能にしたものである。An electrode catalyst layer was formed using the catalyst fine particles 7 thus obtained, a battery was assembled, and its life characteristics were investigated. The results are shown in Figure 4. The battery has a temperature of 200℃ and a current density of 20
0 mA/cm", and the operating gas pressure was 4:9/α2. In FIG. These are the life characteristics of a battery in which an electrode catalyst layer is formed using a catalyst carrier that has been completely graphitized by heat treatment.It can be seen that the battery using the electrode catalyst layer according to the present invention has excellent 4-term reliability. The reason for this is that the catalyst carrier of the electrode catalyst layer according to the present invention is partially graphitized and leaves an amorphous portion, which prevents the growth of the platinum alloy fine particles and, as a result, crystallites of the platinum alloy fine particles. This is because the diameter has been optimized, making it possible to create a fuel cell with excellent cell characteristics and durability.
この発明によれば触媒金属の微粒子をカーボンの触媒担
体上に担持させて触媒微粒子となしこれをフッ素樹脂微
粒子で結着させる電極触媒層の製造方法において、カー
ボンブラックを不活性ガス中で熱処理し、ついでこれに
第１成分としての白金の微粒子と第２成分としての遷移
元素またはロジウムの微粒子とを被着させかつ熱処理し
て白金合金の微粒子を触媒担体すに担持させた触媒微粒
子を形成するのでカーボンの触媒担体は部分的にグラフ
ァイト化して耐蝕性が向上するとともにカーボン触ａｍ
体のアモルファス部分が白金合金の微粒子の結晶成長を
妨げて、その結晶半径を最適化し、その結果特性と長期
信頼性に優れる燃料電池の電極触媒層が得られる。According to this invention, in the method for producing an electrode catalyst layer in which catalyst metal fine particles are supported on a carbon catalyst carrier to form catalyst fine particles and these are bound with fluororesin fine particles, carbon black is heat-treated in an inert gas. Then, fine particles of platinum as a first component and fine particles of a transition element or rhodium as a second component are deposited on this and heat treated to form fine catalyst particles in which fine particles of platinum alloy are supported on a catalyst carrier. Therefore, the carbon catalyst carrier is partially graphitized to improve corrosion resistance and to improve the carbon catalyst carrier.
The amorphous part of the body impedes the crystal growth of the platinum alloy fine particles and optimizes the crystal radius, resulting in a fuel cell electrode catalyst layer with excellent characteristics and long-term reliability.
第１図はカーボンブラックの熱処理温度と得られた触媒
担体の比責面積の関係を示す特性図％第２図はカーボン
ブラックの熱処理温度と得られた触媒担体の腐蝕電流の
関係を示す特性図、第３図はカーボンブラックの熱処理
温度とそれに担持される合金の微粒子の結晶子径の関係
を示す特性図、第４図はこの発明の実施例に係る電極触
媒層を用いた電池と従来の電極触媒層を用いる電池の寿
命特性図、第５図は燃料電池の＠極を示す模式断面図で
ある。
１・・・白金合金の微粒子、２・・・触媒担体、５・・
・電極触媒層、６・・・電極、７・・・触媒微粒子。
」１５ｑヒノｅｕ−シ味（’Ｃ）
Ｃ第１図
稗処珪五友（”Ｃ）
第２図
熱息狸龜度（０Ｃ）
第３図
運ｉＰ＠時間（Ｈｒ）
第４図
第５図Figure 1 is a characteristic diagram showing the relationship between the heat treatment temperature of carbon black and the specific area of the catalyst carrier obtained. Figure 2 is a characteristic diagram showing the relationship between the heat treatment temperature of carbon black and the corrosion current of the catalyst carrier obtained. , Fig. 3 is a characteristic diagram showing the relationship between the heat treatment temperature of carbon black and the crystallite diameter of the fine particles of the alloy supported thereon, and Fig. 4 shows the relationship between the battery using the electrode catalyst layer according to the embodiment of the present invention and the conventional FIG. 5 is a life characteristic diagram of a battery using an electrode catalyst layer, and is a schematic cross-sectional view showing the @ electrode of a fuel cell. 1... Platinum alloy fine particles, 2... Catalyst carrier, 5...
- Electrode catalyst layer, 6... electrode, 7... catalyst fine particles. 15q Hino eu-shi taste ('C) C Fig. 1 Hidokoro Keigoyu (''C) Fig. 2 Heat breath raccoon temperature (0C) Fig. 3 Luck iP @ time (Hr) Fig. 4 Fig. 5 figure
Claims (1)
せて触媒微粒子となしこれをフッ素樹脂微粒子で結着さ
せる電極触媒層の製造方法において、カーボンブラック
を不活性ガス中で熱処理し、ついでこれに第１成分とし
ての白金の微粒子と第２成分としての遷移元素またはロ
ジウムの微粒子とを被着させかつ熱処理して白金合金の
微粒子を触媒担体上に担持させた触媒微粒子を形成する
ことを特徴とする燃料電池用電極触媒層の製造方法。1) In the method for manufacturing an electrode catalyst layer in which catalyst metal fine particles are supported on a carbon catalyst carrier to form catalyst fine particles and these are bound with fluororesin fine particles, carbon black is heat treated in an inert gas, and then this is It is characterized by depositing fine particles of platinum as a first component and fine particles of a transition element or rhodium as a second component and heat-treating the catalyst to form fine catalyst particles in which fine particles of platinum alloy are supported on a catalyst carrier. A method for producing an electrode catalyst layer for a fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62290972A JPH01132055A (en) | 1987-11-18 | 1987-11-18 | Manufacture of electrode catalyst layer for fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62290972A JPH01132055A (en) | 1987-11-18 | 1987-11-18 | Manufacture of electrode catalyst layer for fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01132055A true JPH01132055A (en) | 1989-05-24 |
Family
ID=17762815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62290972A Pending JPH01132055A (en) | 1987-11-18 | 1987-11-18 | Manufacture of electrode catalyst layer for fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01132055A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005158350A (en) * | 2003-11-21 | 2005-06-16 | Mitsubishi Pencil Co Ltd | Electrode catalyst for fuel cell and its manufacturing method |
| JP2006313756A (en) * | 2006-07-07 | 2006-11-16 | Mitsubishi Pencil Co Ltd | Direct methanol type fuel cell |
| US7556877B2 (en) | 2002-07-26 | 2009-07-07 | Mitsubishi Pencil Kabushiki Kaisha | Direct methanol fuel cell |
-
1987
- 1987-11-18 JP JP62290972A patent/JPH01132055A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7556877B2 (en) | 2002-07-26 | 2009-07-07 | Mitsubishi Pencil Kabushiki Kaisha | Direct methanol fuel cell |
| US7625656B2 (en) | 2002-07-26 | 2009-12-01 | Mitsubishi Pencil Kabushiki Kaisha | Direct methanol fuel cell |
| JP2005158350A (en) * | 2003-11-21 | 2005-06-16 | Mitsubishi Pencil Co Ltd | Electrode catalyst for fuel cell and its manufacturing method |
| JP2006313756A (en) * | 2006-07-07 | 2006-11-16 | Mitsubishi Pencil Co Ltd | Direct methanol type fuel cell |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS59141169A (en) | 3-element metal alloy catalyst for fuel battery and method of producing same | |
| KR101202104B1 (en) | Catalyst, method for producing the same, and use of the same | |
| JPS62155940A (en) | Ternary alloy catalyst and its production | |
| JP5374387B2 (en) | Catalyst, method for producing the same and use thereof | |
| JPS5919731B2 (en) | Precious metal-base metal alloy catalyst | |
| CA2666634A1 (en) | Catalyst support for fuel cell | |
| JPH09167620A (en) | Electrode catalyst for fuel cell and its manufacture, and electrode and fuel cell using the catalyst | |
| JP2003200051A (en) | Catalyst for oxygen oxidation-reduction device and electrode using the same | |
| JP4448792B2 (en) | Metal oxynitride oxygen reduction electrode catalyst and method for producing the same | |
| US4711829A (en) | Ordered ternary fuel cell catalysts containing platinum and cobalt | |
| US5126216A (en) | Ternary alloy electrocatalysts | |
| JPH05217586A (en) | Fuel cell and manufacture thereof | |
| KR100797173B1 (en) | Metal oxide electrode catalyst | |
| JP3236686B2 (en) | Gas electrode and its manufacturing method | |
| JPH01132055A (en) | Manufacture of electrode catalyst layer for fuel cell | |
| JP2013164929A (en) | Method of producing electrode catalyst for fuel cell | |
| JP2006236778A (en) | Catalyst for fuel cell, membrane electrode complex, and solid polymer electrolyte fuel cell | |
| JPH0629027A (en) | Fuel cell and its manufacture | |
| JP2504397B2 (en) | Hydrogen storage alloy electrode | |
| JPH03236160A (en) | Electrode catalyst layer for fuel cell and manufacture thereof | |
| JPS60150558A (en) | Production method of fuel electrode for melted carbonate type fuel cell | |
| JP2009001846A (en) | Electroplating method with noble metal, noble metal-carried conductive material, electrode for solid polymer type fuel cell, and solid polymer type fuel cell | |
| JPH01132057A (en) | Electrode catalyst layer of fuel cell | |
| JP2009001845A (en) | Electroplating method with noble metal, noble metal-carried conductive material, electrode for solid polymer type fuel cell, and solid polymer type fuel cell | |
| JPH08138683A (en) | Manufacture of electrode for fuel cell |