JP2010221126A - Catalyst carrier, catalyst body, and manufacturing method therefor - Google Patents
Catalyst carrier, catalyst body, and manufacturing method therefor Download PDFInfo
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- JP2010221126A JP2010221126A JP2009071140A JP2009071140A JP2010221126A JP 2010221126 A JP2010221126 A JP 2010221126A JP 2009071140 A JP2009071140 A JP 2009071140A JP 2009071140 A JP2009071140 A JP 2009071140A JP 2010221126 A JP2010221126 A JP 2010221126A
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- catalyst
- catalyst carrier
- heteroatom
- mixed solution
- fibrous carbon
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- 229940082509 xanthan gum Drugs 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Classifications
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Catalysts (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
Description
本発明は触媒担体及びこれを利用した触媒体ならびにこれらの製造方法に関し、より詳細には、白金を使用することなく高い酸素還元触媒活性が得られるとともに、触媒物質が粒状物を生じることなく多くの触媒活性点を形成できるため、燃料電池用途に好適に利用可能な触媒担体に関する。 The present invention relates to a catalyst carrier, a catalyst body using the same, and a method for producing the same, and more specifically, high oxygen reduction catalytic activity can be obtained without using platinum, and the catalyst material can be produced without generating particulate matter. It is related with the catalyst support | carrier which can be utilized suitably for a fuel cell use.
燃料電池は、水素またはアルコール等の炭化水素などを燃料とし、空気中の酸素などを酸化剤として利用することで、その酸化還元反応によって得られる化学エネルギーを電気エネルギーに変換する発電システムである。このような燃料電池は、クリーンな発電システムとして注目されており、水素を燃料源とした固体高分子型燃料電池（ＰＥＦＣ）や直接メタノール型燃料電池（ＤＭＦＣ）の研究開発が盛んに行われている。 A fuel cell is a power generation system that converts chemical energy obtained by the oxidation-reduction reaction into electrical energy by using hydrocarbons such as hydrogen or alcohol as fuel and using oxygen in the air as an oxidant. Such fuel cells are attracting attention as clean power generation systems, and research and development of solid polymer fuel cells (PEFC) and direct methanol fuel cells (DMFC) using hydrogen as a fuel source are actively conducted. Yes.
なかでもＰＥＦＣは最も盛んに研究開発が行われ、ここに用いられる触媒体としてはカーボン等の触媒担体上に触媒活性成分である貴金属を分散担持させたものが広く用いられている。この貴金属としては白金（Ｐｔ）が主に検討されているが、白金は高価な上、資源供給面でも不安があるとされ、安価で供給不安のない触媒体及びそれを利用する燃料電池用電極の開発が求められている。 Among them, PEFC has been most actively researched and developed, and as a catalyst body used here, a catalyst carrier such as carbon on which a noble metal as a catalytic active component is supported in a dispersed manner is widely used. Platinum (Pt) is mainly studied as the noble metal, but platinum is expensive and is considered uneasy in terms of resource supply, and is a low-cost catalyst body with no fear of supply, and a fuel cell electrode using the catalyst body Development is required.
従来用いられている白金触媒における担体カーボンの役割は、その表面に白金粒子を均一に分散保持することであり、該カーボン担体基材としては比表面積が大きく、かつ導電性に優れるものが用いられ、一般的には一次粒子径が１０ｎｍ〜５０μｍの導電性カーボン粒子が使用される。 The role of the carrier carbon in the conventionally used platinum catalyst is to uniformly disperse and hold platinum particles on the surface thereof. As the carbon carrier base material, a material having a large specific surface area and excellent conductivity is used. Generally, conductive carbon particles having a primary particle diameter of 10 nm to 50 μm are used.
一方、燃料電池用触媒は、用いられる白金触媒自体の活性のみに依存せず、電極の中で最適な構造をとらなければ触媒性能を十分に発揮することはできない。すなわち、燃料電池は、カーボン粒子表面に白金を担持した白金触媒、高分子固体電解質及び導電補助剤として導電性カーボンなどを複合することにより電極を形成し、触媒、電解質、反応ガスの三相界面にて反応を進行させるのが一般的である。この三相界面では下記のような反応が進行し、生成した水の排出がスムースに行われ、反応ガスの供給が効果的に行われることにより、安定的に発電を行うことができる。
カソード側：Ｏ２＋４Ｈ＋＋４ｅ−→２Ｈ２Ｏ
アノード側：Ｈ２→２Ｈ＋＋２ｅ−
On the other hand, the catalyst for a fuel cell does not depend only on the activity of the platinum catalyst used, and the catalyst performance cannot be sufficiently exhibited unless an optimum structure is taken in the electrode. That is, a fuel cell is formed by combining a platinum catalyst carrying platinum on the surface of carbon particles, a polymer solid electrolyte, and conductive carbon as a conductive auxiliary agent to form an electrode, and a three-phase interface of the catalyst, electrolyte, and reactive gas. In general, the reaction is allowed to proceed. The following reaction proceeds at this three-phase interface, and the generated water is discharged smoothly, and the reaction gas is effectively supplied, so that stable power generation can be performed.
Cathode side: O 2 + 4H + + 4e − → 2H 2 O
Anode side: H 2 → 2H + + 2e −
したがって、触媒体は燃料ガスとの反応部位から集電体に至るまでの経路において電気抵抗が低いことが重要であり、また、燃料ガスや酸化剤ガスなどの反応ガスは効率的に触媒体表面の反応部位に供給される必要があり、さらに反応過程で生成した水が反応系外へ効率的に排出されなければ反応を効率的に持続させるための障害となる。 Therefore, it is important that the catalyst body has a low electric resistance in the path from the reaction site with the fuel gas to the current collector, and the reaction gas such as the fuel gas and the oxidant gas efficiently If the water generated in the reaction process is not efficiently discharged out of the reaction system, it will be an obstacle to efficiently maintaining the reaction.
このような課題を解決することを目的として種々の提案がなされており、特許文献１には、ガス拡散経路および生成した水を効率よく排出する構造の重要性などが説明されている。 Various proposals have been made for the purpose of solving such problems, and Patent Document 1 describes the importance of a gas diffusion path and a structure for efficiently discharging generated water.
また、特許文献２には、触媒体と導電経路形成材料間の電気抵抗を減らし触媒活性を効果的に引出そうとする目的で、繊維状のカーボン担体基材上に、中間層を形成し、その上に白金触媒金属を担持したものが開示されている。さらに特許文献３には、ガス拡散層と触媒体を一体化することでガス透過性および電気導電性を向上できるものが開示されている。 Further, in Patent Document 2, an intermediate layer is formed on a fibrous carbon support substrate for the purpose of reducing the electrical resistance between the catalyst body and the conductive path forming material and effectively extracting the catalytic activity. A material in which a platinum catalyst metal is supported thereon is disclosed. Further, Patent Document 3 discloses a gas diffusion layer and a catalyst body that can be integrated to improve gas permeability and electrical conductivity.
ここで、高い出力を得るためには触媒活性点を増やし、かつガス拡散孔を確保する必要があるが、触媒活性点を多くするのに白金担持カーボン粒子配合量を増やすとガス拡散孔が狭められ、反応ガスの導入経路の障害となり、結果的に出力低下を招く。特許文献２の技術では、触媒活性を示す白金の析出面積を増やすために中間層として第２金属で凹凸を有する層を形成しており、その構造からして、より活性点を増やした場合ではガス拡散空孔を狭め、出力特性に悪影響をもたらすことが想定される。同様に特許文献３の技術も、白金担持粒子をガス拡散層空間内に分散させたものであるため、使用触媒量を増やした場合にはガス拡散空間が閉塞され、ガス拡散の障害となることが予想される。 Here, in order to obtain a high output, it is necessary to increase the catalyst active points and secure gas diffusion holes. However, increasing the amount of platinum-supported carbon particles to increase the catalyst active points narrows the gas diffusion holes. As a result, the reaction gas introduction path is obstructed, resulting in a decrease in output. In the technique of Patent Document 2, an uneven layer is formed of a second metal as an intermediate layer in order to increase the deposition area of platinum showing catalytic activity. It is assumed that the gas diffusion holes are narrowed and the output characteristics are adversely affected. Similarly, in the technique of Patent Document 3, since platinum-supported particles are dispersed in the gas diffusion layer space, when the amount of catalyst used is increased, the gas diffusion space is blocked, which may hinder gas diffusion. Is expected.
一方で、カーボン担体単位量あたりの白金担持量を増やせば反応ガス導入経路への障害は軽減するが、カーボン担体上に白金粒子が密に担持されることにより白金粒子同士の結合が起こりやすくなり、触媒性能が劣化するという問題が生じる。現状では従来の白金担持触媒は白金担持量が４０〜６０質量％であるが、シンタリングによる触媒劣化は防げない状況にある。 On the other hand, if the amount of platinum supported per unit amount of carbon carrier is increased, the obstacle to the reaction gas introduction path is reduced, but the platinum particles are supported closely on the carbon carrier, so that the bonding between the platinum particles tends to occur. As a result, the catalyst performance deteriorates. At present, the conventional platinum-supported catalyst has a platinum-supported amount of 40 to 60% by mass, but catalyst deterioration due to sintering cannot be prevented.
このように、従来の技術では三相界面を形成する構造上の問題に起因する出力の制限、および白金担持量が密であることに起因する耐久性の問題があり、また、出力特性を向上するためには白金担持体を多く使用する必要があり、適した三相界面を形成しつつ反応ガス拡散の障害となる水を効率的に排出する構造を形成するのが難しいなどの問題があった。 As described above, the conventional technology has a limitation in output due to a structural problem forming a three-phase interface, and a durability problem due to a dense platinum loading, and also improves output characteristics. In order to achieve this, it is necessary to use a large amount of a platinum support, and there is a problem that it is difficult to form a structure that efficiently discharges water that hinders reaction gas diffusion while forming a suitable three-phase interface. It was.
上記問題に加えて、触媒活性点を確保するのに担持した白金触媒のみに頼ると、自動車などにこの燃料電池を応用した場合では白金使用量が膨大なものとなり、部品製造コストおよび資源確保の点から大きな問題であることが従来から指摘されていた。 In addition to the above problems, if only the supported platinum catalyst is used to secure the catalyst active point, when this fuel cell is applied to an automobile or the like, the amount of platinum used becomes enormous, which reduces the cost of manufacturing parts and securing resources. It has been pointed out that this is a big problem.
また、白金触媒に代わる触媒技術として特許文献４〜６などが提案されている。特許文献４は生体のたんぱく質を応用し６００〜１０００℃で焼成することにより触媒体を得ているが触媒構造自体は最適化されておらず、実用性を考えるとさらに改善する必要がある。特許文献５および６はフタロシアニン誘導体を応用した例である。特許文献５はフタロシアニンの構造を保持しかつ活性点を維持するために６００℃以下の焼成温度としているが、この場合だと焼成温度が低すぎるために十分な導電性を得ることができず結果的に触媒性能は低い。特許文献６ではフタロシアニンを用い、焼成温度を６００〜１０００℃としているが、焼成温度を高くしたことで導電性は改善できるが、単に導電性担体上にフタロシアニンを担持して焼成しただけでは触媒活性は十分に引出せないと考えられる。
このように、白金触媒を使用しない活性賦与技術はこれまでいくつも検討されているが、いずれも未だ活性が低く実用に供するものは見出されていなかった。
In addition, Patent Documents 4 to 6 and the like have been proposed as catalyst technologies that replace platinum catalysts. In Patent Document 4, a catalytic body is obtained by applying a protein from a living body and calcined at 600 to 1000 ° C. However, the catalyst structure itself is not optimized, and further improvement is necessary in view of practicality. Patent Documents 5 and 6 are examples in which phthalocyanine derivatives are applied. Patent Document 5 uses a calcination temperature of 600 ° C. or lower in order to maintain the structure of phthalocyanine and maintain the active site, but in this case, the calcination temperature is too low, so that sufficient conductivity cannot be obtained. In particular, the catalyst performance is low. In Patent Document 6, phthalocyanine is used and the firing temperature is set to 600 to 1000 ° C., but the conductivity can be improved by increasing the firing temperature. However, catalytic activity is merely achieved by firing phthalocyanine on a conductive support. Is not considered to be fully extracted.
As described above, a number of activity imparting techniques that do not use a platinum catalyst have been studied so far, but none of them has yet been found to be practically useful because of low activity.
そこで、本発明は白金を使用せずとも高い酸素還元触媒活性を有し、触媒、高分子電解質、反応ガスの三相構造を高い自由度をもって形成できる触媒体を提供することを課題とした。また白金を併用した場合でもその使用量を大幅に低減できることをもう一つの課題とした。 Accordingly, an object of the present invention is to provide a catalyst body having high oxygen reduction catalytic activity without using platinum and capable of forming a three-phase structure of a catalyst, a polymer electrolyte, and a reaction gas with a high degree of freedom. Another problem is that even when platinum is used in combination, the amount used can be greatly reduced.
本発明者等は、鋭意検討を行った結果、繊維状カーボン表面に高い触媒活性を賦与する技術を見出し、本発明に至った。より具体的には繊維状カーボン表面に窒素原子とそれ以外のヘテロ原子を、炭素原子と窒素原子、および窒素原子とそれ以外のヘテロ原子が特定の比率となるように導入し、ここに遷移金属を配位結合させて触媒活性を賦与することにより、触媒金属を極めて安定的に担持できるとともに、繊維状カーボンの表面部位に対しガス拡散経路に障害となる構造を形成することなく効果的に活性点を付与することができることから、触媒活性点を増加させても反応ガスの拡散経路を確保し得ることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have found a technique for imparting high catalytic activity to the surface of the fibrous carbon, and have reached the present invention. More specifically, nitrogen atoms and other heteroatoms are introduced on the surface of the fibrous carbon so that carbon atoms and nitrogen atoms, and nitrogen atoms and other heteroatoms are in a specific ratio, and transition metals are introduced here. By coordinating and providing catalytic activity, the catalyst metal can be supported extremely stably and effectively without forming a structure that obstructs the gas diffusion path with respect to the surface portion of the fibrous carbon. Since a point can be imparted, it has been found that a diffusion path of the reaction gas can be secured even if the catalyst active point is increased, and the present invention has been completed.
すなわち、本発明は、
繊維状カーボンの表面に窒素原子を含む２種以上のヘテロ原子が導入されてなる触媒担体であって、触媒担体表面の炭素原子とヘテロ原子の含有比率が９４：６〜８６：１４であり、かつ窒素原子に対する窒素原子以外のヘテロ原子の含有比率が０．５〜１．４であることを特徴とする触媒担体である。
That is, the present invention
A catalyst carrier in which two or more kinds of heteroatoms containing nitrogen atoms are introduced on the surface of fibrous carbon, wherein the content ratio of carbon atoms and heteroatoms on the surface of the catalyst carrier is 94: 6 to 86:14, The catalyst carrier is characterized in that the content ratio of heteroatoms other than nitrogen atoms to nitrogen atoms is 0.5 to 1.4.
また本発明は、
繊維状カーボンの表面に窒素原子を含む２種以上のヘテロ原子が導入されてなり、前記繊維状カーボンの表面の炭素原子とヘテロ原子の含有比率が９４：６〜８６：１４であり、かつ窒素原子に対する窒素原子以外のヘテロ原子の含有比率が０．５〜１．４である触媒担体を含む触媒体であって、導入されたヘテロ原子に金属を配位してなることを特徴とする触媒体である。
The present invention also provides
Two or more kinds of heteroatoms containing nitrogen atoms are introduced on the surface of the fibrous carbon, the content ratio of carbon atoms and heteroatoms on the surface of the fibrous carbon is 94: 6 to 86:14, and nitrogen A catalyst body comprising a catalyst carrier having a heteroatom content ratio other than nitrogen atoms to atoms of 0.5 to 1.4, wherein a metal is coordinated to the introduced heteroatom. It is a medium.
さらに本発明は、
次の工程（１）ないし（３）
（１）繊維状カーボン粉末およびヘテロ原子含有有機化合物を溶媒中で分散ないし溶解して混合液を作成する工程
（２）工程（１）で得られた混合液を乾燥して触媒担体前駆体を得る工程
（３）工程（２）で得られた触媒担体前駆体を不活性雰囲気下、６５０〜１２００℃の温度にて焼成する工程
を含む触媒担体の製造方法である。
Furthermore, the present invention provides
Next steps (1) to (3)
(1) Step of preparing a mixed solution by dispersing or dissolving fibrous carbon powder and heteroatom-containing organic compound in a solvent (2) Drying the mixed solution obtained in step (1) to obtain a catalyst carrier precursor A step (3) of obtaining a catalyst carrier comprising a step of calcining the catalyst carrier precursor obtained in step (2) at a temperature of 650 to 1200 ° C. in an inert atmosphere.
さらにまた本発明は、次の工程（１）ないし（４）
（１）繊維状カーボン粉末およびヘテロ原子含有有機化合物を溶媒中で分散ないし溶解して混合液を作成する工程
（２）工程（１）で得られた混合液に金属化合物を溶解する工程
（３）工程（２）で得られた溶液を乾燥して触媒前駆体を得る工程
（４）工程（３）で得られた触媒前駆体を不活性雰囲気下、６５０〜１２００℃の温度にて焼成する工程
を含む触媒体の製造方法である。
また本発明は、
次の工程（１）ないし（３）
（１）繊維状カーボン粉末、ヘテロ原子含有有機化合物および金属化合物を溶媒中で分散ないし溶解して混合液を作成する工程
（２）工程（１）で得られた混合液を乾燥して触媒前駆体を得る工程
（３）工程（２）で得られた触媒前駆体を不活性雰囲気下、６５０〜１２００℃の温度にて焼成する工程
を含む触媒体の製造方法である。
Furthermore, the present invention provides the following steps (1) to (4).
(1) Step of creating a mixed solution by dispersing or dissolving fibrous carbon powder and heteroatom-containing organic compound in a solvent (2) Step of dissolving a metal compound in the mixed solution obtained in step (1) (3 ) The solution obtained in step (2) is dried to obtain a catalyst precursor (4) The catalyst precursor obtained in step (3) is calcined at a temperature of 650 to 1200 ° C. in an inert atmosphere. It is a manufacturing method of the catalyst body including a process.
The present invention also provides
Next steps (1) to (3)
(1) Step of creating a mixed solution by dispersing or dissolving fibrous carbon powder, heteroatom-containing organic compound and metal compound in a solvent (2) Drying the mixed solution obtained in step (1) to prepare a catalyst precursor A process for producing a catalyst body (3) is a method for producing a catalyst body comprising a step of calcining the catalyst precursor obtained in step (2) at a temperature of 650 to 1200 ° C. in an inert atmosphere.
さらにまた本発明は、
次の工程（１）ないし（４）
（１）繊維状カーボン粉末およびヘテロ原子含有有機化合物を溶媒中で分散ないし溶解して混合液を作成する工程
（２）工程（１）で得られた混合液を乾燥して触媒担体前駆体を得る工程
（３）工程（２）で得られた触媒担体前駆体を不活性雰囲気下、６５０〜１２００℃の温度にて焼成して触媒担体を得る工程
（４）工程（３）で得られた触媒担体と金属化合物を溶媒中に分散ないし溶解し、金属を触媒担体に配位する工程
を含む触媒体の製造方法である。
Furthermore, the present invention provides
Next steps (1) to (4)
(1) Step of preparing a mixed solution by dispersing or dissolving fibrous carbon powder and heteroatom-containing organic compound in a solvent (2) Drying the mixed solution obtained in step (1) to obtain a catalyst carrier precursor Obtaining step (3) Obtaining the catalyst carrier by calcining the catalyst carrier precursor obtained in step (2) at a temperature of 650 to 1200 ° C. in an inert atmosphere (4) Obtaining in step (3) A method for producing a catalyst body comprising a step of dispersing or dissolving a catalyst carrier and a metal compound in a solvent and coordinating metal to the catalyst carrier.
本発明の触媒体は、遷移金属を安定して担持することができ、白金を使用せずに高い酸素還元触媒活性を示すものである。また、多孔構造を形成する繊維状カーボン材に触媒活性を賦与することにより、触媒、電解質、および反応ガスに適切な三相界面を確保しつつ触媒活性点を飛躍的に増加させることができ、燃料電池の出力特性を向上することが可能である。このため、白金触媒（白金担持カーボン粒子）と併用した場合には、担持させる白金触媒量を低減することができ、また白金触媒中の白金担持密度を下げることによりシンタリングによる劣化を防ぐことが可能となり、白金利用効率が向上できると同時に触媒体の安定性を高めることができる。
さらに、本発明の触媒体は、ガス拡散経路の障害となる粒状物を生じないため、これを用いてガス拡散層を形成すればガス拡散層自体にも触媒活性を付与することができ、燃料電池の出力特性を向上させることが可能である。
The catalyst body of the present invention can stably support a transition metal and exhibits high oxygen reduction catalytic activity without using platinum. In addition, by imparting catalytic activity to the fibrous carbon material that forms the porous structure, it is possible to dramatically increase the catalytic activity point while ensuring an appropriate three-phase interface for the catalyst, electrolyte, and reaction gas, It is possible to improve the output characteristics of the fuel cell. Therefore, when used in combination with a platinum catalyst (platinum-supported carbon particles), the amount of platinum catalyst to be supported can be reduced, and deterioration due to sintering can be prevented by lowering the platinum support density in the platinum catalyst. Thus, the platinum utilization efficiency can be improved, and at the same time, the stability of the catalyst body can be enhanced.
Furthermore, since the catalyst body of the present invention does not generate particulate matter that obstructs the gas diffusion path, if the gas diffusion layer is formed using this, the catalytic activity can be imparted to the gas diffusion layer itself, and the fuel It is possible to improve the output characteristics of the battery.
以下、本発明を実施するための形態を説明する。 Hereinafter, modes for carrying out the present invention will be described.
本発明に用いる繊維状カーボンは、繊維状であり導電性を兼ね備えるものであれば特に制限されるものではなく、例えば、従来燃料電池の電極形成においてガス拡散孔形成および導電経路形成を目的に用いられていたものを用いることができる。具体的には、一般的に電池用電極形成用途に使われる気相法炭素繊維（昭和電工製ＶＧＣＦ、登録商標）や、燃料電池のガス拡散層を形成するカーボンペーパー（東レ製）などが例示できる。この繊維状カーボンは、直径が１０ｎｍ〜５０μｍであることが好ましく、また、比表面積が０．１〜１０００ｍ２／ｇであることが好ましい。 The fibrous carbon used in the present invention is not particularly limited as long as it is fibrous and has electrical conductivity. For example, it is used for the purpose of gas diffusion hole formation and conductive path formation in conventional fuel cell electrode formation. What has been used can be used. Specific examples include vapor grown carbon fiber (VGCF, registered trademark) manufactured by Showa Denko, which is generally used for battery electrode formation, and carbon paper (manufactured by Toray) that forms a gas diffusion layer for fuel cells. it can. The fibrous carbon preferably has a diameter of 10 nm to 50 μm and a specific surface area of 0.1 to 1000 m 2 / g.
本発明の触媒担体は、その表面に窒素原子を含む２種以上のヘテロ原子が導入されたものである。窒素原子以外のヘテロ原子としては、周期表において第１３族から第１７族の炭素以外の原子であり、金属が配位可能な非共有電子対を有しているものであればよい。中でも、金属をより安定的に配位できるため、酸素原子、硫黄原子およびリン原子よりなる群から選ばれる１種以上が好ましく、特に酸素原子が好ましい。 The catalyst carrier of the present invention has two or more heteroatoms containing nitrogen atoms introduced on its surface. The hetero atom other than the nitrogen atom may be any atom other than the carbons in Group 13 to Group 17 in the periodic table and having an unshared electron pair to which the metal can coordinate. Especially, since a metal can be coordinated more stably, 1 or more types chosen from the group which consists of an oxygen atom, a sulfur atom, and a phosphorus atom are preferable, and an oxygen atom is especially preferable.
触媒担体表面の炭素原子と導入されたヘテロ原子との含有比率は９４：６〜８６：１４である。このような範囲であれば、触媒金属を安定的に配位でき、高い触媒活性を発現、維持することが可能となる。ヘテロ原子の含有比率が、この範囲よりも低い場合には、触媒金属の担持能に劣るため、触媒活性の向上効果が得難く、一方、この範囲よりも高い場合には、触媒担体自体の導電性が損なわれ、目的とする触媒能が得られ難くなる。触媒担体表面の炭素原子には、繊維状カーボン由来のものと後述するヘテロ原子含有有機化合物由来のものが含まれる。 The content ratio of carbon atoms on the surface of the catalyst support and introduced heteroatoms is 94: 6 to 86:14. If it is such a range, a catalyst metal can be coordinated stably and it will become possible to express and maintain a high catalyst activity. When the heteroatom content is lower than this range, the catalyst metal loading ability is inferior, so that it is difficult to improve the catalytic activity. On the other hand, when the heteroatom content is higher than this range, the conductivity of the catalyst support itself is poor. And the target catalytic ability becomes difficult to obtain. The carbon atoms on the surface of the catalyst support include those derived from fibrous carbon and those derived from a hetero atom-containing organic compound described later.
またヘテロ原子の構成は、触媒担体表面の窒素原子に対する窒素原子以外のヘテロ原子の含有比率（窒素原子以外のヘテロ原子／窒素原子）が０．５〜１．４であることが好ましい。このような範囲であると、触媒金属を配位させたときに活性が大きく向上する。この比率が０．５未満または１．４を超える場合には、触媒活性に低下が見られる。これら窒素原子及び他のへテロ原子を双方導入することで活性が高まる理由について詳細は明確ではないが、金属を用いて賦活した場合に、より安定した金属配位構造が形成されるものと考えられる。 In addition, it is preferable that the hetero atom composition is such that the content ratio of hetero atoms other than nitrogen atoms to the nitrogen atoms on the surface of the catalyst support (hetero atoms other than nitrogen atoms / nitrogen atoms) is 0.5 to 1.4. Within such a range, the activity is greatly improved when the catalytic metal is coordinated. When this ratio is less than 0.5 or exceeds 1.4, the catalytic activity is reduced. The details of why the activity increases by introducing both of these nitrogen atoms and other heteroatoms are not clear, but it is considered that a more stable metal coordination structure is formed when activated using a metal. It is done.
なお、上記した原子の含有比率は、ＸＰＳによって測定した結果から算出した原子数の含有比率を示す。 The above-described content ratio of atoms indicates the content ratio of the number of atoms calculated from the result of measurement by XPS.
繊維状カーボンへのヘテロ原子の導入は、窒素原子含有有機化合物、それ以外のヘテロ原子含有有機化合物および繊維状カーボンの粉末を分散媒中で分散ないし溶解させ、固形分を分離した後、これを加熱処理して炭素化することによって行うことができる。 Hetero atoms are introduced into the fibrous carbon by dispersing or dissolving the nitrogen atom-containing organic compound, the other hetero atom-containing organic compound and the fibrous carbon powder in a dispersion medium, and separating the solid content. It can carry out by heat-processing and carbonizing.
ヘテロ原子含有有機化合物のうち、含窒素有機化合物としては、例えばピリジン類、ビピリジン類、テルピリジン類、フェナントロリン類、メラミン類、ピラジン類、ピリミジン類、ピラゾール類、イミダゾール類またはトリアゾール類等の含窒素芳香族化合物のほか、ポルフィリン類やフタロシアニン類などの大環状物質や、ピロール類またはアニリン類などがあげられる。さらに、他の含窒素有機化合物の好適な例として、テトラシアノキノジメタンまたはその塩があげられるが、その他窒素を含有する有機化合物を用いることができ、これら例に限定されない。 Among the heteroatom-containing organic compounds, examples of nitrogen-containing organic compounds include nitrogen-containing aromatic compounds such as pyridines, bipyridines, terpyridines, phenanthrolines, melamines, pyrazines, pyrimidines, pyrazoles, imidazoles, and triazoles. In addition to group compounds, examples include macrocyclic substances such as porphyrins and phthalocyanines, pyrroles, and anilines. Furthermore, although a suitable example of other nitrogen-containing organic compounds includes tetracyanoquinodimethane or a salt thereof, other organic compounds containing nitrogen can be used and are not limited to these examples.
また窒素原子以外のヘテロ原子含有有機化合物のうち、含酸素有機化合物としては例えば、ペクチン、トラガント、グアガム、アラビアガム、カラギーナン、ローカストビーンガム、アミロース、アミロペクチン、デキストリン、キサンタンガムなどの多糖類系天然高分子類、ゼラチン、カゼイン、コンドロイチンなどのタンパク質系天然高分子類、エチルセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、メチルセルロースなどの天然高分子誘導体類、アルギン酸類、ヒアルロン酸類、フェノール類、ポリエチレングリコール類、ポリアクリル酸類、カルボキシビニルポリマー類、ポリアクリルアミド類、ポリビニルアルコール類、ポリビニルピロリドン類、アクリルアミド／アクリレート共重合体、ビニルピロリドン／ビニルアセテート共重合体、ニトロセルロース類、ポリアミジン類などがあげられるがその他酸素を含有する有機化合物を用いることができ、これらの例に限定されない。 Among organic compounds containing hetero atoms other than nitrogen atoms, examples of oxygen-containing organic compounds include polysaccharides such as pectin, tragacanth, guar gum, gum arabic, carrageenan, locust bean gum, amylose, amylopectin, dextrin, and xanthan gum. Molecules, protein-based natural polymers such as gelatin, casein, chondroitin, natural polymer derivatives such as ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, alginic acids, hyaluronic acids, phenols, polyethylene glycols , Polyacrylic acids, carboxyvinyl polymers, polyacrylamides, polyvinyl alcohols, polyvinylpyrrolidones, acrylamide / acrylic Rate copolymer, vinylpyrrolidone / vinyl acetate copolymer, nitrocellulose include, but like polyamidine compounds may be mentioned can be used an organic compound containing more oxygen, but are not limited to these examples.
含硫黄有機化合物としては、チオフェン類、チアゾール類、チアナフタレン類など環状構造の中にＳ原子を有するもののほか、ｐ−トルエンスルホン酸、ベンゼンスルホン酸などスルホン酸基を有するもの、３−メルカプトプロピルメトキシシランなどのメルカプト基を有するもの、ビス（３−トリエトキシシリル）プロピルジスルフィドなどのポリスルフィド基を有するものなどを例示できる。また含リン化合物としては、有機化合物に限らずホスフィン酸、ホスホン酸、次亜リン酸などのリンのオキソ酸類、三酸化二リンや五酸化二リンなどのリン酸化物類、燐酸亜鉛、リン酸アシルなどのリン化合物などが例示できる。 Sulfur-containing organic compounds include those having an S atom in a cyclic structure such as thiophenes, thiazoles, and thiaphthalenes, those having a sulfonic acid group such as p-toluenesulfonic acid and benzenesulfonic acid, and 3-mercaptopropyl Examples thereof include those having a mercapto group such as methoxysilane and those having a polysulfide group such as bis (3-triethoxysilyl) propyl disulfide. The phosphorus-containing compounds are not limited to organic compounds, but include phosphorus oxo acids such as phosphinic acid, phosphonic acid and hypophosphorous acid, phosphorus oxides such as diphosphorus trioxide and diphosphorus pentoxide, zinc phosphate and phosphoric acid. Examples thereof include phosphorus compounds such as acyl.
上記窒素含有有機化合物または窒素原子以外のヘテロ原子含有有機化合物は、構造を均質化できる点で高分子化合物または重合性のものであることが好ましい。重合性ヘテロ原子含有有機化合物としては、メチロールメラミン、ピロール、アニリン等が例示できる。 The nitrogen-containing organic compound or the heteroatom-containing organic compound other than the nitrogen atom is preferably a polymer compound or a polymerizable compound in that the structure can be homogenized. Examples of the polymerizable heteroatom-containing organic compound include methylol melamine, pyrrole, and aniline.
分散媒としては、水、アルコール類、フェノール類、エステル類、ケトン類、エーテル類、芳香族化合物等の公知の溶媒が挙げられ、分散媒中に繊維状カーボンを分散させるとともに、窒素含有有機化合物およびそれ以外のヘテロ原子含有有機化合物を分散ないし溶解させる。繊維状カーボン粉末等を分散させるにあたっては、超音波、ビーズミル、ホモジナイザー等の公知の分散手段を用いてもよい。また、カーボン繊維同士の接点の電導性を補助することを目的として別途カーボン粒子を繊維状カーボンとの合計量に対して１〜５０質量％程度添加してもよい。このカーボン粒子としては、ケッチェンブラックやアセチレンブラックなどに代表される直径１０ｎｍ〜５０μｍの導電性カーボン粒子やカーボンナノチューブを使用することができる。 Examples of the dispersion medium include known solvents such as water, alcohols, phenols, esters, ketones, ethers, aromatic compounds, and the like. In addition to dispersing fibrous carbon in the dispersion medium, nitrogen-containing organic compounds And other heteroatom-containing organic compounds are dispersed or dissolved. In dispersing the fibrous carbon powder or the like, a known dispersing means such as an ultrasonic wave, a bead mill, or a homogenizer may be used. Moreover, you may add about 1-50 mass% separately about carbon particle with respect to the total amount with fibrous carbon for the purpose of assisting the electrical conductivity of the contact of carbon fibers. As the carbon particles, conductive carbon particles and carbon nanotubes having a diameter of 10 nm to 50 μm, represented by ketjen black and acetylene black, can be used.
また、上記へテロ原子含有有機化合物のうち、重合性のものを用いる場合には、これを分散媒中で重合させることができる。このようにヘテロ原子含有有機化合物を重合させると、均質化できるという点で好ましい。重合条件は、使用するヘテロ原子含有有機化合物の種類等に応じて適宜設定できるが、通常２０〜８０℃で１〜３時間程度加熱撹拌すればよく、これにより繊維状カーボン粉末の表面はヘテロ原子含有有機化合物のポリマーで被覆される。 Moreover, when using a polymeric thing among the said hetero atom containing organic compound, this can be polymerized in a dispersion medium. When the heteroatom-containing organic compound is polymerized in this way, it is preferable in that it can be homogenized. The polymerization conditions can be appropriately set depending on the type of the heteroatom-containing organic compound to be used, etc., but it is usually sufficient to heat and stir at 20 to 80 ° C. for about 1 to 3 hours. It is coated with a polymer of organic compounds.
上記分散液または重合反応後の反応液（分散液と反応液を総称して「混合液」とする）について、必要に応じ、濃縮、乾燥等行い固形分を分離して触媒担体前駆体が得られる。次いでこの触媒担体前駆体を加熱処理する。加熱処理は、用いる導電性基体の比表面積や細孔構造、および混合するヘテロ原子含有有機化合物の種類や量、およびその組み合わせにより最適加熱条件が異なるが、好ましくは６５０〜１２００℃の温度で３０分〜６０分加熱するのが適当である。この理由として加熱温度が６５０℃未満では炭化が効率的に進行せず、１２００℃を超える加熱温度では導入した窒素が脱離しやすいためである。 Concentration and drying of the above dispersion or the reaction liquid after the polymerization reaction (the dispersion liquid and the reaction liquid are collectively referred to as “mixed liquid”) are separated as necessary to obtain a catalyst carrier precursor. It is done. Next, the catalyst carrier precursor is heat-treated. The heat treatment varies depending on the specific surface area and pore structure of the conductive substrate to be used, the type and amount of the heteroatom-containing organic compound to be mixed, and the combination thereof, but it is preferably 30 at a temperature of 650 to 1200 ° C. It is appropriate to heat for 60 minutes. This is because the carbonization does not proceed efficiently when the heating temperature is less than 650 ° C., and the introduced nitrogen is easily desorbed at the heating temperature exceeding 1200 ° C.
加熱処理後の触媒担体前駆体を酸洗、水洗後減圧乾燥し本発明の触媒担体を得ることができる。 The catalyst carrier precursor after the heat treatment can be pickled, washed with water and then dried under reduced pressure to obtain the catalyst carrier of the present invention.
触媒担体表面のへテロ原子含有量の制御方法について具体的に示せば、窒素含有量は加熱温度および加熱時間に影響を受け、加熱温度が高いほど、または加熱時間が長いほど、この場合は減少する傾向にある。また窒素含有量は含窒素有機化合物に含まれる窒素量や流通ガス速度などにも影響を受け、含窒素有機化合物の窒素含有量が高いほど、またはガス流通速度が速いほど、この場合には窒素含有量低下率は高くなる傾向にある。さらには、炭素材料の比表面積などの影響も受け、比表面積が大きい炭素材料を用いた場合は窒素含有量が低下しにくい傾向にある。一方、酸素含有量は含酸素有機化合物に含まれる酸素量に大きく影響を受けると同時に、加熱環境下における酸素不純物の影響を大きく受ける。従って、これら加熱環境、前駆体構成材料などを考慮しつつ、雰囲気ガス流通速度、加熱温度などを調整しながら目的とするヘテロ原子含有量を調整できる。 Explaining in detail how to control the heteroatom content on the surface of the catalyst support, the nitrogen content is affected by the heating temperature and the heating time. In this case, the higher the heating temperature or the longer the heating time, the lower the content. Tend to. The nitrogen content is also affected by the amount of nitrogen contained in the nitrogen-containing organic compound and the flow rate of the gas. The higher the nitrogen content of the nitrogen-containing organic compound or the faster the gas flow rate, The content reduction rate tends to increase. Furthermore, it is also affected by the specific surface area of the carbon material, and when a carbon material having a large specific surface area is used, the nitrogen content tends not to decrease. On the other hand, the oxygen content is greatly affected by the amount of oxygen contained in the oxygen-containing organic compound, and at the same time, it is greatly affected by oxygen impurities in the heating environment. Accordingly, the target heteroatom content can be adjusted while adjusting the atmospheric gas flow rate, the heating temperature, and the like while taking into consideration the heating environment, the precursor constituent materials, and the like.
本発明の触媒体は、上記のようにして繊維状カーボンの表面に導入されたヘテロ原子に金属が配位されてなるものである。 In the catalyst body of the present invention, a metal is coordinated to a hetero atom introduced on the surface of fibrous carbon as described above.
金属としては、第４〜第６周期遷移金属元素に含まれる少なくとも１種を使用することができ、好適にはコバルト、ニッケル、鉄及び銅よりなる群から選ばれる１種または２種以上である。 As the metal, at least one selected from the fourth to sixth transition metal elements can be used, and preferably one or more selected from the group consisting of cobalt, nickel, iron and copper. .
上記金属を繊維状カーボン表面に導入したヘテロ原子に配位結合させるには、分散媒中に繊維状カーボン粉末およびヘテロ原子含有有機化合物を分散ないし溶解させた後、分散媒中に溶解可能な金属化合物を溶解、混合すればよい。この場合必要に応じて溶液をＰＨ調整する操作などを行っても良い。分散媒や分散方法等は上記と同様である。金属化合物としては、硝酸コバルト、コバルトフタロシアニン、コバルトフェナントロリン、コバルト−βジケトン錯体等が例示できる。またヘテロ原子の導入において、重合性へテロ原子含有有機化合物を使用してこれを重合させる場合には、重合反応前の分散媒中に金属化合物を添加、溶解させてもよく、重合反応後に添加、溶解させてもよい。 In order to coordinate and bond the metal to the heteroatom introduced on the surface of the fibrous carbon, the metal that can be dissolved in the dispersion medium after the fibrous carbon powder and the heteroatom-containing organic compound are dispersed or dissolved in the dispersion medium. What is necessary is just to melt | dissolve and mix a compound. In this case, an operation of adjusting the pH of the solution may be performed as necessary. The dispersion medium and the dispersion method are the same as described above. Examples of the metal compound include cobalt nitrate, cobalt phthalocyanine, cobalt phenanthroline, and cobalt-β diketone complex. In addition, in the introduction of heteroatoms, when a polymerizable heteroatom-containing organic compound is used for polymerization, a metal compound may be added and dissolved in the dispersion medium before the polymerization reaction, or added after the polymerization reaction. , May be dissolved.
このようにして得られた溶液について、上記触媒担体の場合と同様にして、必要に応じ、濃縮、乾燥等行い固形分を分離して触媒前駆体を得て、次いでこの触媒前駆体を加熱処理した後、酸洗、水洗後減圧乾燥することにより本発明の触媒体を得ることができる。加熱処理等は、上記と同様にして行えばよい。 For the solution thus obtained, in the same manner as in the case of the catalyst carrier, if necessary, the solid content is separated by concentration, drying, etc. to obtain a catalyst precursor, and then the catalyst precursor is heat-treated. Then, the catalyst body of the present invention can be obtained by pickling, washing with water and then drying under reduced pressure. Heat treatment and the like may be performed in the same manner as described above.
上記のようにして得られた本発明の触媒体を用いて、燃料電池用電極は一般的には以下のように作製することができる。 Using the catalyst body of the present invention obtained as described above, a fuel cell electrode can be generally prepared as follows.
白金担持カーボン触媒、高分子材料、本発明の触媒体、また必要に応じてバインダ等を混合および分散して触媒含有ペーストを作製する。このペーストを固体高分子電解質膜の両面に塗布および乾燥し、次いでその両側から、カーボンペーパーなどのガス拡散層で挟み込み、ホットプレスして一体化させ膜電極接合体を得ることができる。 A catalyst-containing paste is prepared by mixing and dispersing a platinum-supported carbon catalyst, a polymer material, the catalyst body of the present invention, and a binder as required. This paste can be applied to both sides of the solid polymer electrolyte membrane and dried, and then sandwiched from both sides with a gas diffusion layer such as carbon paper and integrated by hot pressing to obtain a membrane electrode assembly.
このようにして得られた膜電極接合体は、空気極側および燃料極側のそれぞれに集電板を設けて電気的な接合を行い、燃料極に水素を、空気極に空気（酸素）をそれぞれ供給することにより、燃料電池として作用させることができる。 In the membrane electrode assembly thus obtained, current collector plates are provided on each of the air electrode side and the fuel electrode side to perform electrical bonding, hydrogen is supplied to the fuel electrode, and air (oxygen) is supplied to the air electrode. By supplying each, it can be made to act as a fuel cell.
固体高分子電解質膜としてはパーフルオロスルホン酸系樹脂膜を用いることができ、デュポン社製ナフィオン（登録商標）、旭硝子社製フレミオン（登録商標）、旭化成工業社製アシプレックス（登録商標）など市販のものを使用できる。 A perfluorosulfonic acid resin membrane can be used as the solid polymer electrolyte membrane, and commercially available products such as Nafion (registered trademark) manufactured by DuPont, Flemion (registered trademark) manufactured by Asahi Glass Co., Ltd., and Aciplex (registered trademark) manufactured by Asahi Kasei Kogyo Co., Ltd. Can be used.
ガス拡散層としてはカーボンペーパー（東レ社製）やカーボンクロスなどが用いられ、これらは撥水処理して用いることもできる。この場合、撥水材として三井デュポンケミカル社製ＰＴＦＥディスパージョンなどを用いることができる。また、本発明の触媒体を使用してガス拡散層を形成することにより、電極のみならず、従来触媒活性に寄与できなかったガス拡散層部分にも触媒活性を付与することができ、燃料電池全体としての出力特性を向上することが可能となる。 As the gas diffusion layer, carbon paper (manufactured by Toray Industries, Inc.), carbon cloth or the like is used, and these can be used after being subjected to water repellent treatment. In this case, PTFE dispersion manufactured by Mitsui DuPont Chemical Co., Ltd. can be used as the water repellent material. Further, by forming a gas diffusion layer using the catalyst body of the present invention, catalytic activity can be imparted not only to the electrode but also to the gas diffusion layer portion that has not been able to contribute to the catalytic activity in the past. It is possible to improve the output characteristics as a whole.
（分析方法）
前記触媒体中に含まれる炭素および酸素および窒素およびその他の原子の含有量は、分析方法としてＸ線光電子分光分析（以下、ＸＰＳと記載）による測定、および熱伝導度法を応用した有機元素測定装置による測定などがあげられるが、ＸＰＳによる分析は基体表面（おおよそ１０ｎｍ以内の表面層）に含まれる元素が検出でき、熱伝導度法を応用した有機元素測定装置による分析では全体に含まれる窒素量を検出することができる。触媒作用は表面での反応であることから、表面組成分析であるＸＰＳによる分析評価が好適である。
(Analysis method)
The contents of carbon, oxygen, nitrogen and other atoms contained in the catalyst body are measured by X-ray photoelectron spectroscopy (hereinafter referred to as XPS) as an analytical method, and organic element measurement is applied by a thermal conductivity method. The measurement by an apparatus can be mentioned, but the analysis by XPS can detect the elements contained in the substrate surface (surface layer within about 10 nm), and the analysis by the organic element measurement apparatus applying the thermal conductivity method contains nitrogen contained in the whole The amount can be detected. Since the catalytic action is a reaction on the surface, analysis evaluation by XPS which is a surface composition analysis is suitable.
本実施例においてはＸＰＳにより表面組成を評価した。このとき触媒の性能は炭素成分を主体とする担体と、その表面に担持または結合される金属成分の相互作用により左右されるが、本発明では担体における組成が重要であり、ここで用いる試薬からは担体としての成分は意図的に添加した金属成分以外はほぼ炭素、窒素、酸素のみであることから、担体または触媒の組成分析としては意図的に添加した金属成分を含めない炭素、窒素および酸素の量のみを評価した。従って、ここでのＮ/Ｃ比またはＯ／Ｎ比はこの炭素、窒素および酸素の検出値をもとに計算した。 In this example, the surface composition was evaluated by XPS. At this time, the performance of the catalyst depends on the interaction between the support mainly composed of the carbon component and the metal component supported or bound on the surface thereof. However, in the present invention, the composition of the support is important. Since the component as a support is almost only carbon, nitrogen, and oxygen except for the intentionally added metal component, carbon, nitrogen and oxygen not including the intentionally added metal component are included in the composition analysis of the support or catalyst. Only the amount of was evaluated. Therefore, the N / C ratio or O / N ratio here was calculated based on the detected values of carbon, nitrogen and oxygen.
（触媒活性評価）
次いで本発明の触媒体を用いた評価用酸素還元電極を作製する方法について説明する。まず、得られた触媒体３０ｍｇに、５質量％パーフルオロスルホン酸（登録商標Ｎａｆｉｏｎ）溶液１ｍｌを添加し、分散均一化処理をすることによりペーストを作製することができる。このペーストを、グラッシーカーボン電極上に塗布および風乾することにより評価用電極を得ることができる。こうして作製した電極を作用電極として用い、対極に白金電極を用いて触媒特性の評価を行うことができる。測定は北斗電工製電気化学測定システムＨＺ−３０００により行うことができる。上記作用電極および白金電極を０．５Ｍの硫酸水溶液中に浸漬し、酸素流通下＋１．０Ｖ〜−０．２Ｖ（対Ａｇ／ＡｇＣｌ電極）の走査範囲でＬＳＶ測定を行うことによって評価することができる。
(Catalyst activity evaluation)
Next, a method for producing an oxygen reduction electrode for evaluation using the catalyst body of the present invention will be described. First, 1 ml of a 5 mass% perfluorosulfonic acid (registered trademark Nafion) solution is added to 30 mg of the obtained catalyst body, and a paste can be prepared by carrying out a dispersion homogenization treatment. An electrode for evaluation can be obtained by applying this paste on a glassy carbon electrode and air drying. The thus produced electrode can be used as a working electrode, and a catalyst characteristic can be evaluated using a platinum electrode as a counter electrode. The measurement can be performed by an electrochemical measurement system HZ-3000 manufactured by Hokuto Denko. It is possible to evaluate by immersing the working electrode and platinum electrode in a 0.5 M sulfuric acid aqueous solution and performing LSV measurement in a scanning range of +1.0 V to −0.2 V (vs. Ag / AgCl electrode) under oxygen flow. it can.
作製した触媒性能の比較は上記ＬＳＶ測定において、電流値１．０ｍＡ／ｃｍ２での電圧（対ＳＨＥ）で比較することができる。すなわち、この値が大きいほど酸素還元触媒性能が高いことを示す。 Comparison of the prepared catalyst performance in the LSV measurements can be compared with the voltage at a current value 1.0 mA / cm 2 (vs. SHE). That is, the larger this value, the higher the oxygen reduction catalyst performance.
（セル評価）
また、本発明の触媒体を用いる固体高分子型燃料電池は、電池モジュール内に組み込まれたセルがシート状の固体高分子電解質を挟むようにして対面配置されるアノード（燃料極）およびカソード（空気極）とから構成されている。この固体高分子電解質としては、パーフルオロスルホン酸系樹脂膜に代表されるフッ素系イオン交換樹脂膜などが主に用いられている。触媒粉末はこの固体高分子膜の表面に塗布され層状の電極反応層が形成される。さらに、アノードおよびカソードは、上記燃料電池用電極触媒を含む電極反応層支持とガス拡散層を兼ねた集電体を備えて構成され、ホットプレスにより密着することにより、ＭＥＡ（ｍｅｍｂｒａｎｅ ｅｌｅｃｔｒｏｄｅ ａｓｓｅｍｂｌｙ）として一体化される。
(Cell evaluation)
In addition, a solid polymer fuel cell using the catalyst body of the present invention includes an anode (fuel electrode) and a cathode (air electrode) in which cells built in a battery module are placed facing each other so as to sandwich a sheet-like solid polymer electrolyte. ). As this solid polymer electrolyte, a fluorine ion exchange resin membrane represented by a perfluorosulfonic acid resin membrane is mainly used. The catalyst powder is applied to the surface of the solid polymer film to form a layered electrode reaction layer. Further, the anode and the cathode are configured to include an electrode reaction layer support including the fuel cell electrode catalyst and a current collector that serves as a gas diffusion layer, and are brought into close contact with each other by hot pressing to form MEA (membrane electrode assembly). Integrated.
（反応機構）
上記集電体は、触媒層を保持すると共に反応ガス（燃料ガスと空気）の供給排出を行い、集電体材料としてはカーボンペーパーなど多孔質で導電性の高いシートが用いられる。上記電極のそれぞれに反応ガスが供給されると、両電極に備えられた触媒層と固体高分子電解質膜との境界に気相（反応ガス）、液相（電解質）、固相（触媒）の三相界面が形成され、電気化学反応により直流電流が発生する。
上記電気化学反応において、
カソード側：Ｏ２＋４Ｈ＋＋４ｅ−→２Ｈ２Ｏ
アノード側：Ｈ２→２Ｈ＋＋２ｅ−
の反応が起こり、アノード側で生成したＨ＋イオンは固体高分子電解質膜中をカソード側に向かって移動し、ｅ−（電子）は外部の負荷を通ってカソード側へ移動する。一方、カソード側では空気中に含まれる酸素と、アノード側から移動してきたＨ＋イオンおよびｅ−とが反応して水が生成される。この結果、固体高分子形燃料電池は、水素と酸素とから直流電流を発生し、水を生成することになる。
(Reaction mechanism)
The current collector holds the catalyst layer and supplies and discharges the reaction gas (fuel gas and air). As the current collector material, a porous and highly conductive sheet such as carbon paper is used. When a reactive gas is supplied to each of the electrodes, a gas phase (reactive gas), a liquid phase (electrolyte), a solid phase (catalyst) are formed at the boundary between the catalyst layer and the solid polymer electrolyte membrane provided on both electrodes. A three-phase interface is formed, and a direct current is generated by an electrochemical reaction.
In the above electrochemical reaction,
Cathode: O 2 + 4H + + 4e - → 2H 2 O
Anode side: H 2 → 2H + + 2e −
The H + ions generated on the anode side move toward the cathode side through the solid polymer electrolyte membrane, and e − (electrons) move to the cathode side through an external load. On the other hand, on the cathode side, oxygen contained in the air reacts with H + ions and e − that have moved from the anode side to produce water. As a result, the polymer electrolyte fuel cell generates direct current from hydrogen and oxygen to generate water.
本発明の実施例について具体的に説明する。 Examples of the present invention will be specifically described.
実施例１
市販のカーボン繊維（昭和電工社製ＶＧＣＦ、登録商標）４ｇと導電性カーボン粉末（電気化学工業社製デンカブラック）１ｇに純水５００ｍｌを加え、ポリビニルピロリジノン（関東化学Ｋ−３０）を１ｇ加え超音波にて１０分間分散処理を行い、さらにビーズミルを用いて分散処理を行った。ここにポリビニルアルコール（クラレ社ＰＶＡ−２１７Ｓ）を２．５ｇ加え撹拌した後に、さらにエタノール３５０ｇと純水２５０ｇの混合溶液中にメチロールメラミン（日本カーバイド工業社ニカレジン）を５ｇ溶解させた溶液を加えて６０℃にて３０分間攪拌を行った。さらに、硝酸コバルトを０．５ｇ加え、ホモジナイザーにて１５分間分散処理を行った。得られた溶液はさらにエバポレータにより濃縮し、次いで１０５℃で減圧乾燥することにより前駆体を得た。この前駆体を乳鉢で粉砕したのちに窒素ガス流通下７２０℃で１時間加熱処理し、再度乳鉢にて粉砕し、０．５Ｎ塩酸１Ｌ中にて３０分間撹拌した。次いで、ろ紙にて固形分を回収し、純水にてろ液のＰＨが６〜７になるまで洗浄し、乾燥機内１０５℃で乾燥を行うことで、触媒活性賦与気相法炭素繊維を得た。このＸＰＳにより測定した触媒体の成分およびＬＳＶ測定の結果を表１および表２に示す。
なお、本実施例１において、ポリビニルピロリジノンは酸素、窒素および炭素源であり、ポリビニルアルコールは酸素および炭素源であり、メチロールメラミンは窒素および炭素源である。コバルトフタロシアニンはコバルト金属、窒素および炭素源である。
Example 1
500 g of pure water is added to 4 g of commercially available carbon fiber (VGCF, registered trademark) manufactured by Showa Denko KK and 1 g of conductive carbon powder (Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd.), and 1 g of polyvinylpyrrolidinone (Kanto Chemical K-30) is added. Dispersion treatment was performed for 10 minutes with sonic waves, and further dispersion treatment was performed using a bead mill. After 2.5 g of polyvinyl alcohol (Kuraray PVA-217S) was added and stirred, a solution in which 5 g of methylolmelamine (Nicarresin, Nippon Carbide Industries Co., Ltd.) was dissolved in a mixed solution of 350 g of ethanol and 250 g of pure water was further added. Stirring was performed at 60 ° C. for 30 minutes. Further, 0.5 g of cobalt nitrate was added, and a dispersion treatment was performed for 15 minutes with a homogenizer. The obtained solution was further concentrated by an evaporator and then dried under reduced pressure at 105 ° C. to obtain a precursor. The precursor was pulverized in a mortar, then heat-treated at 720 ° C. for 1 hour under a nitrogen gas flow, pulverized again in a mortar, and stirred in 1 L of 0.5N hydrochloric acid for 30 minutes. Next, the solid content was collected with filter paper, washed with pure water until the pH of the filtrate was 6 to 7, and dried at 105 ° C. in a dryer to obtain catalytic activity-imparting vapor grown carbon fiber. . The components of the catalyst body measured by XPS and the results of LSV measurement are shown in Tables 1 and 2.
In Example 1, polyvinyl pyrrolidinone is an oxygen, nitrogen and carbon source, polyvinyl alcohol is an oxygen and carbon source, and methylol melamine is a nitrogen and carbon source. Cobalt phthalocyanine is a cobalt metal, nitrogen and carbon source.
《電極作製》
市販の白金担持カーボン触媒（石福金属興業社製 ＩＦＰＣ−ＩＩ Ｐｔ＝４０ｗｔ％）と上記触媒活性賦与炭素繊維を７：３となるように量り取り、高分子電解質溶液（旭化成製アシプレックス、登録商標、固形分＝５ｗｔ％）とイソプロピルアルコールと純水を混合し、ホモジナイザーにて１０分間混合、さらに超音波照射を１０分間行うことにより触媒ペーストを作製した。
この触媒ペーストを、乾燥したフッ素系高分子固体電解質膜の両面に塗布し、４０℃にて乾燥後、両面からガス拡散孔を形成するカーボンペーパー（東レ社製 ＴＰＧ−Ｈ−０９０）で挟み込み、ホットプレス処理を行うことにより、膜一体型の電極を作製した。
このときの片面における白金担持量は１．５ｍｇ／ｃｍ２とした。
<Electrode fabrication>
A commercially available platinum-supported carbon catalyst (IFPC-II Pt = 40 wt%, manufactured by Ishifuku Metal Industry Co., Ltd.) and the above-mentioned catalytically active carbon fiber were weighed to 7: 3, and a polymer electrolyte solution (Asaplex, manufactured by Asahi Kasei) was registered. (Trademark, solid content = 5 wt%), isopropyl alcohol and pure water were mixed, mixed with a homogenizer for 10 minutes, and further subjected to ultrasonic irradiation for 10 minutes to prepare a catalyst paste.
This catalyst paste is applied to both sides of a dried fluoropolymer solid electrolyte membrane, dried at 40 ° C., and sandwiched between carbon papers (TPG-H-090 made by Toray Industries, Inc.) that form gas diffusion holes from both sides. A membrane-integrated electrode was produced by performing a hot press process.
The amount of platinum supported on one side at this time was 1.5 mg / cm 2 .
《電気的特性評価》
上記膜一体型電極を、単電池測定用の装置にセットして電池を構成し、電池温度７５℃、燃料利用率８０％、空気利用率３０％とし、ガス加湿については水素ガスは７５℃の露点、空気は６５℃の露点となるように調整した。以上の条件により発電試験を行った。
この電極を用いて電気的特性を評価した結果を表２に示す。
<Electrical characteristics evaluation>
The membrane-integrated electrode is set in an apparatus for measuring a single cell to constitute a battery, and the battery temperature is 75 ° C., the fuel utilization rate is 80%, the air utilization rate is 30%. The dew point and air were adjusted to a dew point of 65 ° C. A power generation test was conducted under the above conditions.
Table 2 shows the results of evaluating the electrical characteristics using this electrode.
参考例１
硝酸コバルトを添加しない以外は実施例１と同様にして触媒担体を得た。この触媒担体の成分およびＬＳＶ測定結果を表１および表２に示す。
また、この触媒担体を用いて実施例１と同様に電極を作製して電気的特性を評価した結果を表２に示す。コバルトが添加されないことで触媒活性は大きく劣るものとなったが、この参考例１の触媒担体を用いて、純水を分散媒としてコバルトイオンを配位させて触媒体としたところ、実施例１と同等のＬＳＶ評価結果が得られ、特定の金属が表面に配位していることが触媒活性発現に必要であることを確認した。
Reference example 1
A catalyst carrier was obtained in the same manner as in Example 1 except that cobalt nitrate was not added. The catalyst carrier components and LSV measurement results are shown in Tables 1 and 2.
In addition, Table 2 shows the results of producing electrodes using this catalyst carrier in the same manner as in Example 1 and evaluating the electrical characteristics. Although the catalytic activity was greatly inferior due to the absence of cobalt, when the catalyst support of this Reference Example 1 was used to form a catalyst body by coordinating cobalt ions with pure water as a dispersion medium, Example 1 was obtained. As a result, it was confirmed that the specific metal is coordinated on the surface for the expression of the catalytic activity.
実施例２
市販の気相法炭素繊維（昭和電工社製ＶＧＣＦ、登録商標）４ｇとカーボン粉末（電気化学工業社製デンカブラック）１ｇに純水５００ｍｌを加え、ポリビニルピロリジノン（関東化学Ｋ−３０）を１ｇ加え超音波にて１０分間分散処理を行い、さらにビーズミルを用いて分散処理を行った。ここにカルボキシメチルセルロース（第一工業製薬社製セロゲン６Ａ）を１．１ｇ加え撹拌した後に、さらにエタノール３５０ｇと純水２５０ｇの混合溶液中にメチロールメラミン（日本カーバイド工業社ニカレジン）を５ｇ溶解させた溶液を加えて、さらにコバルトフタロシアニン２ｇを加え８０℃にて３０分間還流を行った。得られた溶液はさらにエバポレータにより濃縮し、次いで１０５℃で減圧乾燥することにより前駆体を得た。この前駆体を乳鉢で粉砕したのちに窒素ガス流通下８５０℃で１時間加熱処理し、再度乳鉢にて粉砕し、４０℃に保持した０．５Ｎ塩酸１Ｌ中にて６０分間撹拌した。次いで、ろ紙にて固形分を回収し、純水にてろ液のＰＨが６〜７になるまで洗浄し、乾燥機内１０５℃で乾燥を行うことで、触媒活性賦活炭素繊維を得た。この触媒体の成分およびＬＳＶ測定の結果を表１および表２に示す。
なお、本実施例２において、ポリビニルピロリジノンは酸素、窒素および炭素源であり、カルボキシメチルセルロースは酸素および炭素源であり、メチロールメラミンは窒素および炭素源である。コバルトフタロシアニンはコバルト金属、窒素および炭素源である。
Example 2
500 g of pure water is added to 4 g of commercially available vapor grown carbon fiber (VGCF, registered trademark) manufactured by Showa Denko KK and 1 g of carbon powder (Denka Black manufactured by Denki Kagaku Kogyo), and 1 g of polyvinylpyrrolidinone (Kanto Chemical K-30) is added. Dispersion treatment was performed with ultrasonic waves for 10 minutes, and further dispersion treatment was performed using a bead mill. After 1.1 g of carboxymethylcellulose (Serogen 6A manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added and stirred, 5 g of methylol melamine (Nicaridine, Nippon Carbide Industries Co., Ltd.) was dissolved in a mixed solution of 350 g of ethanol and 250 g of pure water. Then, 2 g of cobalt phthalocyanine was further added and refluxed at 80 ° C. for 30 minutes. The obtained solution was further concentrated by an evaporator and then dried under reduced pressure at 105 ° C. to obtain a precursor. This precursor was pulverized in a mortar, then heat-treated at 850 ° C. for 1 hour under a nitrogen gas flow, pulverized again in a mortar, and stirred in 1 L of 0.5N hydrochloric acid maintained at 40 ° C. for 60 minutes. Next, the solid content was collected with filter paper, washed with pure water until the pH of the filtrate reached 6 to 7, and dried at 105 ° C. in a dryer to obtain catalytically activated carbon fibers. Table 1 and Table 2 show the components of this catalyst body and the results of LSV measurement.
In Example 2, polyvinylpyrrolidinone is an oxygen, nitrogen and carbon source, carboxymethylcellulose is an oxygen and carbon source, and methylolmelamine is a nitrogen and carbon source. Cobalt phthalocyanine is a cobalt metal, nitrogen and carbon source.
《電極作製》
市販の白金担持カーボン触媒（石福金属興業社製 ＩＦＰＣ−ＩＩ Ｐｔ＝４０ｗｔ％）と上記触媒活性賦与炭素繊維を７：３となるように量り取り、高分子電解質溶液（旭化成製、アシプレックス、登録商標、固形分＝５ｗｔ％）とイソプロピルアルコールと純水を混合し、ホモジナイザーにて１０分間混合、さらに超音波照射を１０分間行うことにより触媒ペーストを作製した。
この触媒ペーストを、あらかじめ撥水処理したカーボンペーパー（東レ社製 ＴＰＧ−Ｈ−０９０）にスプレー法により塗布し、乾燥後、乾燥したフッ素系高分子固体電解質膜を、両面から触媒塗布面を内側にして挟み込み、ホットプレス処理を行うことにより、膜一体型の電極を作製した。
このときの片面における白金担持量は１．２ｍｇ／ｃｍ２とした。
<Electrode fabrication>
A commercially available platinum-supported carbon catalyst (IFPC-II Pt = 40 wt% manufactured by Ishifuku Metal Industry Co., Ltd.) and the above-mentioned catalytically active carbon fiber were weighed to 7: 3, and a polymer electrolyte solution (Asaplex, manufactured by Asahi Kasei) (Registered trademark, solid content = 5 wt%), isopropyl alcohol and pure water were mixed, mixed for 10 minutes with a homogenizer, and further subjected to ultrasonic irradiation for 10 minutes to prepare a catalyst paste.
This catalyst paste is applied to carbon paper (TPG-H-090 manufactured by Toray Industries, Inc.) that has been subjected to water repellent treatment in advance by a spray method. After drying, the dried fluorine-based polymer solid electrolyte membrane is placed on both sides of the catalyst-coated surface from the inside. The membrane-integrated electrode was manufactured by sandwiching and hot pressing.
Amount of platinum supported in one side at this time was 1.2 mg / cm 2.
《電気的特性評価》
上記膜一体型電極を、単電池測定用の装置にセットして電池を構成し、電池温度７５℃、燃料利用率８０％、空気利用率３０％とし、ガス加湿については水素ガスは７５℃の露点、空気は６５℃の露点となるように調整した。以上の条件により発電試験を行った。
この電極を用いて電気的特性を評価した結果を表１および表２に示す。
<Electrical characteristics evaluation>
The membrane-integrated electrode is set in an apparatus for measuring a single cell to constitute a battery, and the battery temperature is 75 ° C., the fuel utilization rate is 80%, the air utilization rate is 30%. The dew point and air were adjusted to a dew point of 65 ° C. A power generation test was conducted under the above conditions.
The results of evaluating the electrical characteristics using this electrode are shown in Tables 1 and 2.
参考例２
コバルトフタロシアニンを添加しない以外は実施例２と同様にして触媒担体を得た。この触媒担体の成分およびＬＳＶ測定の結果を表１に示す。また、この触媒担体を用いて実施例２と同様にして電極を作製し電気的特性を評価した結果を表１および表２に示す。コバルトが添加されないことで触媒活性は大きく劣るものとなったが、この参考例２の触媒担体を用いて、純水を分散媒としてコバルトイオンを配位させて触媒体としたところ、実施例２と同等のＬＳＶ評価結果が得られ、特定の金属が表面に配位していることが触媒活性発現に必要であることを確認した。
Reference example 2
A catalyst carrier was obtained in the same manner as in Example 2 except that cobalt phthalocyanine was not added. Table 1 shows the components of this catalyst carrier and the LSV measurement results. Tables 1 and 2 show the results of producing electrodes using this catalyst support in the same manner as in Example 2 and evaluating the electrical characteristics. Although the catalytic activity was greatly inferior due to the absence of cobalt, the catalyst carrier of this Reference Example 2 was used to form a catalyst body by coordinating cobalt ions with pure water as a dispersion medium. As a result, it was confirmed that the specific metal is coordinated on the surface for the expression of the catalytic activity.
比較例１
市販のカーボン粉末（ケッチェンブラックインターナショナル社製ケッチェンブラック ＥＣＰ）４ｇと導電性カーボン粉末（電気化学工業社製デンカブラック）１ｇに純水５００ｍｌを加え、ポリビニルピロリジノン（関東化学Ｋ−３０）を１ｇ加え超音波にて１０分間分散処理を行い、さらにビーズミルを用いて分散処理を行った。ここにポリビニルアルコール（クラレ社ＰＶＡ−２１７Ｓ）を２．１ｇ加え撹拌した後に、さらにエタノール３５０ｇと純水２５０ｇの混合溶液中にメチロールメラミン（日本カーバイド工業社ニカレジン）を５ｇ溶解させた溶液を加えて６０℃にて３０分間攪拌を行った。さらに、硝酸コバルトを０．５ｇ加え、ホモジナイザーにて１５分間分散処理を行った。得られた溶液はさらにエバポレータにより濃縮し、次いで１０５℃で減圧乾燥することにより前駆体を得た。この前駆体を乳鉢で粉砕したのちに窒素ガス流通下７３０℃で１時間加熱処理し、再度乳鉢にて粉砕し、０．５Ｎ塩酸１Ｌ中にて３０分間撹拌した。次いで、ろ紙にて固形分を回収し、純水にてろ液のＰＨが６〜７になるまで洗浄し、乾燥機内１０５℃で乾燥を行うことで、触媒活性賦与気相法炭素繊維を得た。この触媒体の成分およびＬＳＶ測定の結果を表１および表２に示す。また、この触媒体を用いて実施例１と同様に電極を作製し、セル電気的特性を評価した結果を表２に示す。繊維状カーボン材に代えて粒子状カーボン材を用いたことで発電試験において出力を得ることができなかった。これはガス拡散孔が適切に形成できなかったためと考えられる。
Comparative Example 1
500 g of pure water is added to 4 g of commercially available carbon powder (Ketjen Black ECP manufactured by Ketchen Black International) and 1 g of conductive carbon powder (Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd.), and 1 g of polyvinylpyrrolidinone (Kanto Chemical K-30). In addition, the dispersion treatment was performed with ultrasonic waves for 10 minutes, and the dispersion treatment was further performed using a bead mill. After 2.1 g of polyvinyl alcohol (Kuraray PVA-217S) was added and stirred, a solution in which 5 g of methylolmelamine (Nicarresin, Nippon Carbide Industries Co., Ltd.) was dissolved in a mixed solution of 350 g of ethanol and 250 g of pure water was further added. Stirring was performed at 60 ° C. for 30 minutes. Further, 0.5 g of cobalt nitrate was added, and a dispersion treatment was performed for 15 minutes with a homogenizer. The obtained solution was further concentrated by an evaporator and then dried under reduced pressure at 105 ° C. to obtain a precursor. The precursor was pulverized in a mortar, then heat-treated at 730 ° C. for 1 hour under a nitrogen gas flow, pulverized again in a mortar, and stirred in 1 L of 0.5N hydrochloric acid for 30 minutes. Next, the solid content was collected with filter paper, washed with pure water until the pH of the filtrate was 6 to 7, and dried at 105 ° C. in a dryer to obtain catalytic activity-imparting vapor grown carbon fiber. . Table 1 and Table 2 show the components of this catalyst body and the results of LSV measurement. Table 2 shows the results of producing electrodes using this catalyst body in the same manner as in Example 1 and evaluating the cell electrical characteristics. An output could not be obtained in the power generation test by using a particulate carbon material instead of the fibrous carbon material. This is probably because the gas diffusion holes could not be formed properly.
比較例２
市販のカーボン繊維（昭和電工社製ＶＧＣＦ、登録商標）４ｇと導電性カーボン粉末（電気化学工業社製デンカブラック）１ｇに純水５００ｍｌを加え、ポリビニルピロリジノン（関東化学Ｋ−３０）を１ｇ加え超音波にて１０分間分散処理を行い、さらにビーズミルを用いて分散処理を行った。ここにカルボキシメチルセルロース（第一工業製薬社セロゲン６Ａ）を３ｇ加え撹拌した後に、さらにエタノール３５０ｇと純水２５０ｇの混合溶液中にメチロールメラミン（日本カーバイド工業社ニカレジン）を５ｇ溶解させた溶液を加えて６０℃にて３０分間攪拌を行った。さらに、硝酸コバルトを０．５ｇ加え、ホモジナイザーにて１５分間分散処理を行った。得られた溶液はさらにエバポレータにより濃縮し、次いで１０５℃で減圧乾燥することにより前駆体を得た。この前駆体を乳鉢で粉砕したのちに窒素ガス流通下７００℃で１時間加熱処理し、再度乳鉢にて粉砕し、０．５Ｎ塩酸１Ｌ中にて３０分間撹拌した。次いで、ろ紙にて固形分を回収し、純水にてろ液のＰＨが６〜７になるまで洗浄し、乾燥機内１０５℃で乾燥を行うことで、触媒活性賦与気相法炭素繊維を得た。この触媒体の成分およびＬＳＶ測定の結果を表１および表２に示す。また、この触媒体を用いて実施例１と同様にして電極を作製し、セル電気的特性を評価した結果を表２に示す。この例では酸素源を多く入れることと、加熱処理温度を低めに抑えることで窒素を多く残留させたが、この場合だとヘテロ元素が多すぎたためか触媒活性は低くなった。
Comparative Example 2
500 g of pure water is added to 4 g of commercially available carbon fiber (VGCF, registered trademark) manufactured by Showa Denko KK and 1 g of conductive carbon powder (Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd.), and 1 g of polyvinylpyrrolidinone (Kanto Chemical K-30) is added. Dispersion treatment was performed for 10 minutes with sonic waves, and further dispersion treatment was performed using a bead mill. After 3 g of carboxymethylcellulose (Daiichi Kogyo Seiyaku Co., Ltd. Cellogen 6A) was added and stirred, a solution of 5 g of methylolmelamine (Nicarresin, Nippon Carbide Industries Co., Ltd.) was added to a mixed solution of 350 g of ethanol and 250 g of pure water. Stirring was performed at 60 ° C. for 30 minutes. Further, 0.5 g of cobalt nitrate was added, and a dispersion treatment was performed for 15 minutes with a homogenizer. The obtained solution was further concentrated by an evaporator and then dried under reduced pressure at 105 ° C. to obtain a precursor. This precursor was pulverized in a mortar, then heat-treated at 700 ° C. for 1 hour under a nitrogen gas flow, pulverized again in a mortar, and stirred in 1 L of 0.5N hydrochloric acid for 30 minutes. Next, the solid content was collected with filter paper, washed with pure water until the pH of the filtrate was 6 to 7, and dried at 105 ° C. in a dryer to obtain catalytic activity-imparting vapor grown carbon fiber. . Table 1 and Table 2 show the components of this catalyst body and the results of LSV measurement. Table 2 shows the results of producing electrodes using this catalyst body in the same manner as in Example 1 and evaluating the cell electrical characteristics. In this example, a large amount of nitrogen was left by adding a large amount of oxygen source and keeping the heat treatment temperature low, but in this case, the catalytic activity was low because of the excessive amount of hetero elements.
比較例３
市販のカーボン繊維（昭和電工社製ＶＧＣＦ、登録商標）４ｇと導電性カーボン粉末（電気化学工業社製デンカブラック）１ｇに純水５００ｍｌを加え、ポリビニルピロリジノン（関東化学Ｋ−３０）を１ｇ加え超音波にて１０分間分散処理を行い、さらにビーズミルを用いて分散処理を行った。ここにカルボキシメチルセルロース（第一工業製薬社セロゲン６Ａ）を３ｇ加え撹拌した後に、さらにエタノール３５０ｇと純水２５０ｇの混合溶液中にメチロールメラミン（日本カーバイド工業社ニカレジン）を５ｇ溶解させた溶液を加えて６０℃にて３０分間攪拌を行った。さらに、硝酸コバルトを０．５ｇ加え、ホモジナイザーにて１５分間分散処理を行った。得られた溶液はさらにエバポレータにより濃縮し、次いで１０５℃で減圧乾燥することにより前駆体を得た。この前駆体を乳鉢で粉砕したのちに窒素ガス流通下７２０℃で１時間加熱処理し、再度乳鉢にて粉砕し、０．５Ｎ塩酸１Ｌ中にて３０分間撹拌した。次いで、ろ紙にて固形分を回収し、純水にてろ液のＰＨが６〜７になるまで洗浄し、乾燥機内１０５℃で乾燥を行うことで、触媒活性賦与気相法炭素繊維を得た。この触媒体の成分およびＬＳＶ測定の結果を表１および表２に示す。また、この触媒体を用いて実施例１と同様にして電極を作製し、セル電気的特性を評価した結果を表２に示す。この例では酸素を多く残留させたが、触媒活性が低かった。
Comparative Example 3
500 g of pure water is added to 4 g of commercially available carbon fiber (VGCF, registered trademark) manufactured by Showa Denko KK and 1 g of conductive carbon powder (Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd.), and 1 g of polyvinylpyrrolidinone (Kanto Chemical K-30) is added. Dispersion treatment was performed for 10 minutes with sonic waves, and further dispersion treatment was performed using a bead mill. After 3 g of carboxymethylcellulose (Daiichi Kogyo Seiyaku Co., Ltd. Cellogen 6A) was added and stirred, a solution of 5 g of methylolmelamine (Nicarresin, Nippon Carbide Industries Co., Ltd.) was added to a mixed solution of 350 g of ethanol and 250 g of pure water. Stirring was performed at 60 ° C. for 30 minutes. Further, 0.5 g of cobalt nitrate was added, and a dispersion treatment was performed for 15 minutes with a homogenizer. The obtained solution was further concentrated by an evaporator and then dried under reduced pressure at 105 ° C. to obtain a precursor. The precursor was pulverized in a mortar, then heat-treated at 720 ° C. for 1 hour under a nitrogen gas flow, pulverized again in a mortar, and stirred in 1 L of 0.5N hydrochloric acid for 30 minutes. Next, the solid content was collected with filter paper, washed with pure water until the pH of the filtrate was 6 to 7, and dried at 105 ° C. in a dryer to obtain catalytic activity-imparting vapor grown carbon fiber. . Table 1 and Table 2 show the components of this catalyst body and the results of LSV measurement. Table 2 shows the results of producing electrodes using this catalyst body in the same manner as in Example 1 and evaluating the cell electrical characteristics. In this example, a large amount of oxygen remained, but the catalytic activity was low.
比較例４
市販のカーボン繊維（昭和電工社製ＶＧＣＦ、登録商標）４ｇと導電性カーボン粉末（電気化学工業社製デンカブラック）１ｇに純水５００ｍｌを加え、ポリビニルピロリジノン（関東化学Ｋ−３０）を０．８ｇ加え超音波にて１０分間分散処理を行い、さらにビーズミルを用いて分散処理を行った。ここにカルボキシメチルセルロース（第一工業製薬社セロゲン６Ａ）を０．８ｇ加え撹拌した後に、さらにエタノール３５０ｇと純水２５０ｇの混合溶液中にメチロールメラミン（日本カーバイド工業社ニカレジン）を５ｇ溶解させた溶液を加えて６０℃にて３０分間攪拌を行った。さらに、硝酸コバルトを０．５ｇ加え、ホモジナイザーにて１５分間分散処理を行った。得られた溶液はさらにエバポレータにより濃縮し、次いで１０５℃で減圧乾燥することにより前駆体を得た。この前駆体を乳鉢で粉砕したのちに窒素ガス流通下８８０℃で１時間加熱処理し、再度乳鉢にて粉砕し、０．５Ｎ塩酸１Ｌ中にて３０分間撹拌した。次いで、ろ紙にて固形分を回収し、純水にてろ液のＰＨが６〜７になるまで洗浄し、乾燥機内１０５℃で乾燥を行うことで、触媒活性賦与気相法炭素繊維を得た。この触媒体の成分およびＬＳＶ測定の結果を表１および表２に示す。また、この触媒体を用いて実施例１と同様にして電極を作製し、セル電気的特性を評価した結果を表２に示す。これは酸素残留比を減らした例であるが、触媒活性は低い結果となった。
Comparative Example 4
500 g of pure water is added to 4 g of commercially available carbon fiber (VGCF, registered trademark) manufactured by Showa Denko KK and 1 g of conductive carbon powder (Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd.), and 0.8 g of polyvinylpyrrolidinone (Kanto Chemical K-30) is added. In addition, the dispersion treatment was performed with ultrasonic waves for 10 minutes, and the dispersion treatment was further performed using a bead mill. After adding 0.8g of carboxymethylcellulose (Daiichi Kogyo Seiyaku Co., Ltd. Cellogen 6A) here and stirring, the solution which further dissolved 5g of methylol melamine (Nippon Carbide Industries Co., Ltd. Nikaresin) in the mixed solution of 350g of ethanol and 250g of pure waters. In addition, the mixture was stirred at 60 ° C. for 30 minutes. Further, 0.5 g of cobalt nitrate was added, and a dispersion treatment was performed for 15 minutes with a homogenizer. The obtained solution was further concentrated by an evaporator and then dried under reduced pressure at 105 ° C. to obtain a precursor. The precursor was pulverized in a mortar, then heat-treated at 880 ° C. for 1 hour under a nitrogen gas flow, pulverized again in a mortar, and stirred in 1 L of 0.5N hydrochloric acid for 30 minutes. Next, the solid content was collected with filter paper, washed with pure water until the pH of the filtrate was 6 to 7, and dried at 105 ° C. in a dryer to obtain catalytic activity-imparting vapor grown carbon fiber. . Table 1 and Table 2 show the components of this catalyst body and the results of LSV measurement. Table 2 shows the results of producing electrodes using this catalyst body in the same manner as in Example 1 and evaluating the cell electrical characteristics. This is an example in which the oxygen residual ratio was reduced, but the catalyst activity was low.
比較例５
実施例１において調整した触媒活性賦与炭素繊維に変えて、賦活処理を施していないカーボン繊維（昭和電工社製ＶＧＣＦ、登録商標）を用いて以下のように電極を作製した。
Comparative Example 5
Instead of the catalytically active carbon fiber prepared in Example 1, an electrode was prepared as follows using carbon fiber (VGCF, registered trademark) manufactured by Showa Denko Co., Ltd., which had not been activated.
《電極作製》
市販の白金担持カーボン触媒（石福金属興業社製 ＩＦＰＣ−ＩＩ Ｐｔ＝４０ｗｔ％）と上記カーボン繊維を７：３となるように量り取り、高分子電解質溶液（旭化成製アシプレックス、登録商標、固形分＝５ｗｔ％）とイソプロピルアルコールと純水を混合し、ホモジナイザーにて１０分間混合、さらに超音波照射を１０分間行うことにより触媒ペーストを作製した。
この触媒ペーストを、乾燥したフッ素系高分子固体電解質膜の両面に塗布し、４０℃にて乾燥後、両面からガス拡散孔を形成するカーボンペーパー（東レ社製 ＴＰＧ−Ｈ−０９０）で挟み込み、ホットプレス処理を行うことにより、膜一体型の電極を作製した。
このときの片面における白金担持量は１．５ｍｇ／ｃｍ２とした。
<Electrode fabrication>
A commercially available platinum-supported carbon catalyst (IFPC-II Pt = 40 wt%, manufactured by Ishifuku Metal Industry Co., Ltd.) and the above carbon fiber are weighed to 7: 3, and a polymer electrolyte solution (Asaplex, Asahi Kasei Corporation, registered trademark, solid) Min = 5 wt%), isopropyl alcohol and pure water were mixed, mixed with a homogenizer for 10 minutes, and further subjected to ultrasonic irradiation for 10 minutes to prepare a catalyst paste.
This catalyst paste is applied to both sides of a dried fluoropolymer solid electrolyte membrane, dried at 40 ° C., and sandwiched between carbon papers (TPG-H-090 made by Toray Industries, Inc.) that form gas diffusion holes from both sides. A membrane-integrated electrode was produced by performing a hot press process.
The amount of platinum supported on one side at this time was 1.5 mg / cm 2 .
《電気的特性評価》
上記膜一体型電極を、単電池測定用の装置にセットして電池を構成し、電池温度７５℃、燃料利用率８０％、空気利用率３０％とし、ガス加湿については水素ガスは７５℃の露点、空気は６５℃の露点となるように調整した。以上の条件により発電試験を行った。
この電極を用いて電気的特性を評価した結果を表２に示す。
<Electrical characteristics evaluation>
The membrane-integrated electrode is set in an apparatus for measuring a single cell to constitute a battery, and the battery temperature is 75 ° C., the fuel utilization rate is 80%, the air utilization rate is 30%. The dew point and air were adjusted to a dew point of 65 ° C. A power generation test was conducted under the above conditions.
Table 2 shows the results of evaluating the electrical characteristics using this electrode.
表１および２から明らかなように、本発明による繊維状カーボンに触媒活性賦与をした触媒体を用いることにより、ガス拡散孔を確保しつつ触媒活性点を増大させることが可能となり、比較例５に示す従来電極よりも高い発電電圧を得ることができた。一方、通常導電材として用いられるカーボン粒子に触媒活性を賦与した触媒体を用いた比較例１では、セル発電試験においてガス拡散孔をうまく形成することができず、その結果発電することができなかった。これらから本発明による繊維状カーボンに触媒活性を賦与した触媒体は、繊維の表面を効果的に触媒活性賦与できたことから、ガス拡散孔形成に支障を与えることなく電極を形成することが可能となり、従来にない高い発電電圧が実現できることを確認できた。 As is apparent from Tables 1 and 2, by using the catalytic body imparted with catalytic activity to the fibrous carbon according to the present invention, it becomes possible to increase the catalytic activity point while ensuring gas diffusion holes. Comparative Example 5 The generated voltage was higher than that of the conventional electrode shown in FIG. On the other hand, in Comparative Example 1 using a catalyst body that imparts catalytic activity to carbon particles that are usually used as a conductive material, gas diffusion holes cannot be successfully formed in the cell power generation test, and as a result, power generation cannot be performed. It was. From these, the catalytic body imparting catalytic activity to the fibrous carbon according to the present invention can effectively impart the catalytic activity to the surface of the fiber, so that an electrode can be formed without hindering the formation of gas diffusion holes. Thus, it was confirmed that an unprecedented high power generation voltage could be realized.
以上説明したような酸素還元複合触媒を作製した後、従来公知の方法で燃料電池の酸素極用の触媒として燃料電池を組み上げることで、従来よりも特性に優れ、高い出力密度の燃料電池を得ることができる。また、白金等の貴金属やその合金を担持した触媒と併用した場合においても、高い出力密度が得られる優れた燃料電池、もしくは、貴金属の使用量を低減し経済性に優れた燃料電池を得ることができる。 After producing the oxygen reduction composite catalyst as described above, the fuel cell is assembled as a catalyst for the oxygen electrode of the fuel cell by a conventionally known method, thereby obtaining a fuel cell with superior characteristics and higher power density than the conventional one. be able to. In addition, even when used in combination with a catalyst supporting a noble metal such as platinum or an alloy thereof, an excellent fuel cell capable of obtaining a high power density, or a fuel cell excellent in economic efficiency by reducing the amount of noble metal used. Can do.
Claims (16)
（１）繊維状カーボン粉末およびヘテロ原子含有有機化合物を溶媒中で分散ないし溶解して混合液を作成する工程
（２）工程（１）で得られた混合液を乾燥して触媒担体前駆体を得る工程
（３）工程（２）で得られた触媒担体前駆体を不活性雰囲気下、６５０〜１２００℃の温度にて焼成する工程
を含む触媒担体の製造方法。 Next steps (1) to (3)
(1) Step of preparing a mixed solution by dispersing or dissolving fibrous carbon powder and heteroatom-containing organic compound in a solvent (2) Drying the mixed solution obtained in step (1) to obtain a catalyst carrier precursor Step of obtaining (3) A method for producing a catalyst carrier comprising a step of calcining the catalyst carrier precursor obtained in Step (2) at a temperature of 650 to 1200 ° C. in an inert atmosphere.
（１）繊維状カーボン粉末およびヘテロ原子含有有機化合物を溶媒中で分散ないし溶解して混合液を作成する工程
（２）工程（１）で得られた混合液に金属化合物を溶解する工程
（３）工程（２）で得られた溶液を乾燥して触媒前駆体を得る工程
（４）工程（３）で得られた触媒前駆体を不活性雰囲気下、６５０〜１２００℃の温度にて焼成する工程
を含む触媒体の製造方法。 Next steps (1) to (4)
(1) Step of creating a mixed solution by dispersing or dissolving fibrous carbon powder and heteroatom-containing organic compound in a solvent (2) Step of dissolving a metal compound in the mixed solution obtained in step (1) (3 ) The solution obtained in step (2) is dried to obtain a catalyst precursor (4) The catalyst precursor obtained in step (3) is calcined at a temperature of 650 to 1200 ° C. in an inert atmosphere. The manufacturing method of the catalyst body containing a process.
（１）繊維状カーボン粉末、ヘテロ原子含有有機化合物および金属化合物を溶媒中で分散ないし溶解して混合液を作成する工程
（２）工程（１）で得られた混合液を乾燥して触媒前駆体を得る工程
（３）工程（２）で得られた触媒前駆体を不活性雰囲気下、６５０〜１２００℃の温度にて焼成する工程
を含む触媒体の製造方法。 Next steps (1) to (3)
(1) Step of creating a mixed solution by dispersing or dissolving fibrous carbon powder, heteroatom-containing organic compound and metal compound in a solvent (2) Drying the mixed solution obtained in step (1) to prepare a catalyst precursor A process for producing a catalyst body comprising a step (3) of calcining the catalyst precursor obtained in step (2) at a temperature of 650 to 1200 ° C. in an inert atmosphere.
（１）繊維状カーボン粉末およびヘテロ原子含有有機化合物を溶媒中で分散ないし溶解して混合液を作成する工程
（２）工程（１）で得られた混合液を乾燥して触媒担体前駆体を得る工程
（３）工程（２）で得られた触媒担体前駆体を不活性雰囲気下、６５０〜１２００℃の温度にて焼成して触媒担体を得る工程
（４）工程（３）で得られた触媒担体と金属化合物を溶媒中に分散ないし溶解し、金属を触媒担体に配位する工程
を含む触媒体の製造方法。 Next steps (1) to (4)
(1) Step of preparing a mixed solution by dispersing or dissolving fibrous carbon powder and heteroatom-containing organic compound in a solvent (2) Drying the mixed solution obtained in step (1) to obtain a catalyst carrier precursor Obtaining step (3) Obtaining the catalyst carrier by calcining the catalyst carrier precursor obtained in step (2) at a temperature of 650 to 1200 ° C. in an inert atmosphere (4) Obtaining in step (3) A method for producing a catalyst body comprising a step of dispersing or dissolving a catalyst carrier and a metal compound in a solvent, and coordinating metal to the catalyst carrier.
16. The catalyst according to claim 13, wherein a polymerizable heteroatom-containing compound is used as the heteroatom-containing organic compound, and the polymerizable heteroatom-containing compound is polymerized in the mixed solution. A method for manufacturing a medium.
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