JP2001118582A - Electrode of fuel cell and method for manufacturing the same - Google Patents
Electrode of fuel cell and method for manufacturing the sameInfo
- Publication number
- JP2001118582A JP2001118582A JP29730299A JP29730299A JP2001118582A JP 2001118582 A JP2001118582 A JP 2001118582A JP 29730299 A JP29730299 A JP 29730299A JP 29730299 A JP29730299 A JP 29730299A JP 2001118582 A JP2001118582 A JP 2001118582A
- Authority
- JP
- Japan
- Prior art keywords
- exchange resin
- metal
- cation exchange
- electrode
- cation
- 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.)
- Granted
Links
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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、燃料電池用電極と
その製造方法とに関するものである。The present invention relates to a fuel cell electrode and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】固体高分子電解質型燃料電池（ＰＥＦ
Ｃ）は、比較的低温で作動し、エネルギー効率が高いた
めに電気自動車用電源としての期待が高い。固体高分子
電解質型燃料電池は、パーフルオロカーボンスルフォン
酸膜等のイオン交換膜を電解質とし、このイオン交換膜
の両面にアノードとカソードの各電極を接合して構成さ
れ、アノードに燃料、カソードに酸化剤を供給して電気
化学反応により発電する装置である。2. Description of the Related Art Solid polymer electrolyte fuel cells (PEF)
C) is expected to be used as a power source for electric vehicles because it operates at a relatively low temperature and has high energy efficiency. A solid polymer electrolyte fuel cell is composed of an ion exchange membrane such as a perfluorocarbon sulfonic acid membrane as an electrolyte, and an anode and a cathode joined to both sides of the ion exchange membrane. This is a device that supplies an agent and generates power by an electrochemical reaction.
【０００３】燃料としては水素を用いるものとメタノー
ルを用いるものがある。水素を燃料に用いる場合には、
その実用性を考慮して車上にメタノールを貯蔵し、メタ
ノールと水との化学反応を利用した改質器を用いて必要
な量だけメタノールを水素に変えてＰＥＦＣに供給す
る。ここで用いられるＰＥＦＣがメタノール改質燃料電
池である。[0003] There are fuels using hydrogen and fuels using methanol. When using hydrogen as fuel,
Considering its practicality, methanol is stored on the car, and the necessary amount of methanol is converted to hydrogen using a reformer utilizing the chemical reaction between methanol and water, and then supplied to the PEFC. The PEFC used here is a methanol reformed fuel cell.
【０００４】一方、後者のメタノールを燃料として用い
る場合、メタノールを直接ＰＥＦＣに供給して，ＰＥＦ
Ｃ内でメタノールを直接電気化学的に酸化をする。ここ
で用いられるＰＥＦＣが直接メタノール燃料電池(ＤＭ
ＦＣ，Ｄｉｒｅｃｔ Ｍｅｔｈａｎｏｌ Ｆｕｅｌ Ｃｅ
ｌｌ)である。On the other hand, when the latter methanol is used as a fuel, methanol is directly supplied to PEFC,
In methanol, methanol is directly oxidized electrochemically. The PEFC used here is a direct methanol fuel cell (DM
FC, Direct Methanol Fuel Ce
11).
【０００５】まず、燃料に水素、酸化剤に酸素を用いた
際に各電極で生じる電気化学反応を下記に示す。[0005] First, the electrochemical reaction that occurs at each electrode when hydrogen is used as the fuel and oxygen is used as the oxidizing agent will be described below.
【０００６】アノード：Ｈ2→２Ｈ+＋２ｅ- カソード：1／２Ｏ2＋２Ｈ+＋２ｅ-→Ｈ2Ｏ 全反応： Ｈ2＋1/２Ｏ2→Ｈ2Ｏ つぎに、燃料にメタノール、酸化剤に酸素を用いた際に
各電極で生じる電気化学反応を下記に示す。Anode: H 2 → 2H + + 2e − Cathode: 1 / 2O 2 + 2H + + 2e − → H 2 O Total reaction: H 2 + 1 / 2O 2 → H 2 O Next, methanol is used as fuel and oxygen is used as oxidant. The electrochemical reaction that occurs at each electrode when is used is shown below.
【０００７】 アノード：ＣＨ3ＯＨ＋ Ｈ2Ｏ →ＣＯ2＋６Ｈ+＋６ｅ- カソード：３／２Ｏ2＋６Ｈ+＋６ｅ-→３Ｈ2Ｏ 全反応： ＣＨ3ＯＨ＋３／２Ｏ2＋ Ｈ2Ｏ →ＣＯ2＋３
Ｈ2Ｏ これらの反応式から明らかなように、いずれの燃料電池
においても、各電極の反応は活物質である燃料または酸
化剤（水素、メタノールまたは酸素）、プロトン
（Ｈ+）および電子（ｅ-）の授受が同時におこなうこと
ができる電極内の三相界面でのみ進行する。Anode: CH 3 OH + H 2 O → CO 2 + 6H + + 6e − Cathode: 3 / 2O 2 + 6H + + 6e − → 3H 2 O Total reaction: CH 3 OH + 3 / 2O 2 + H 2 O → CO 2 +3
H 2 O As is apparent from these reaction formulas, in each of the fuel cells, the reaction of each electrode is carried out by the active material of the fuel or oxidant (hydrogen, methanol or oxygen), proton (H + ) and electron (e + ). - ) Transfer only at the three-phase interface within the electrode where transfer can take place simultaneously.
【０００８】このような機能を有する燃料電池用電極と
しては、固体高分子電解質である陽イオン交換樹脂とカ
ーボン粒子と触媒金属とを含む固体高分子電解質−触媒
複合電極がある。例えば、固体高分子電解質であるであ
る陽イオン交換樹脂とカーボン粒子と白金等の触媒金属
を含む陽イオン交換樹脂−触媒複合電極の構造の例を図
２に示す。図２において、６はカーボン粒子、７は陽イ
オン交換樹脂、８はイオン交換膜、９は細孔である。As a fuel cell electrode having such a function, there is a solid polymer electrolyte-catalyst composite electrode containing a cation exchange resin, which is a solid polymer electrolyte, carbon particles and a catalyst metal. For example, FIG. 2 shows an example of the structure of a cation exchange resin-catalyst composite electrode containing a cation exchange resin, which is a solid polymer electrolyte, carbon particles, and a catalyst metal such as platinum. In FIG. 2, reference numeral 6 denotes carbon particles, 7 denotes a cation exchange resin, 8 denotes an ion exchange membrane, and 9 denotes pores.
【０００９】図２に示されるように、触媒金属が高分散
担持されたカーボン粒子６と陽イオン交換樹脂７とが混
ざり合ってこれらが三次元に分布するとともに、内部に
複数の細孔９が形成された多孔性の電極であって、触媒
金属の担体であるカーボンが電子伝導チャンネルを形成
し、陽イオン交換樹脂がプロトン伝導チャンネルを形成
し、細孔が、酸素または水素および生成物である水の供
給排出チャンネルを形成している。そして電極内にこれ
ら３つのチャンネルが三次元的に広がり、ガス、プロト
ン（Ｈ+）および電子（ｅ-）の授受を同時におこなうこ
とのできる三相界面が無数に形成されて、電極反応の場
が提供されている。As shown in FIG. 2, carbon particles 6 on which a catalyst metal is highly dispersed and supported and cation exchange resin 7 are mixed and distributed three-dimensionally, and a plurality of pores 9 are formed inside. The formed porous electrode, wherein carbon as a catalyst metal carrier forms an electron conduction channel, a cation exchange resin forms a proton conduction channel, and pores are oxygen or hydrogen and a product. It forms a water supply and discharge channel. Then, these three channels are three-dimensionally spread in the electrode, and a myriad of three-phase interfaces capable of simultaneously transmitting and receiving gas, protons (H + ) and electrons (e − ) are formed. Is provided.
【００１０】従来、このような構造を有する電極は、上
記触媒金属担持カーボン粒子と陽イオン交換樹脂溶液
と、さらに必要に応じてＰＴＦＥ粒子とを含むペースト
を高分子フィルムや導電性多孔質体のカーボン電極基材
上に製膜（一般に膜厚３〜３０μｍ）した後、加熱乾燥
する方法等により作製されていた。なお、陽イオン交換
樹脂溶液としては、先に述べたイオン交換膜と同じ組成
からなるものをアルコールで溶解し、液状にしたもの
が、 ＰＴＦＥ粒子分散溶液としては、粒子径約０．２
３μｍのＰＴＦＥ粒子の分散溶液が用いられている。Conventionally, an electrode having such a structure has been prepared by adding a paste containing the above-mentioned catalyst metal-carrying carbon particles, a cation exchange resin solution and, if necessary, PTFE particles to a polymer film or a conductive porous material. It was produced by a method of forming a film (generally a film thickness of 3 to 30 μm) on a carbon electrode substrate and then heating and drying. As the cation exchange resin solution, a solution having the same composition as that of the above-described ion exchange membrane dissolved in alcohol and made into a liquid state is used.
A dispersion solution of 3 μm PTFE particles is used.
【００１１】ここで、カソードの触媒粒子としてはメタ
ノール改質燃料電池、直接メタノール燃料電池ともに、
酸素の還元反応に高い触媒活性を示す白金粒子または比
表面積のおおきなカーボン粒子に白金を高分散担持した
ものが用いられている。Here, as the catalyst particles of the cathode, both the methanol reformed fuel cell and the direct methanol fuel cell are used.
Platinum particles exhibiting a high catalytic activity in the reduction reaction of oxygen or carbon particles having a large specific surface area, in which platinum is highly dispersed and supported, are used.
【００１２】メタノール改質燃料電池に送られる水素
は、メタノールと水との化学反応を利用して車上で製造
されたものであり、１００ｐｐｍ程度のＣＯを含んでい
る。そのために純白金ではＣＯ被毒の影響により大きな
出力が得られないために、先のアノードの触媒金属とし
て一般には耐ＣＯ被毒性能の高い白金族金属元素を含む
合金、たとえばＰｔ−Ｒｕ合金が用いられている。[0012] Hydrogen sent to the methanol reformed fuel cell is produced on a vehicle by utilizing a chemical reaction between methanol and water, and contains about 100 ppm of CO. For this reason, since a large output cannot be obtained due to the influence of CO poisoning with pure platinum, an alloy containing a platinum group metal element having high resistance to CO poisoning, such as a Pt-Ru alloy, is generally used as the catalytic metal of the anode. Used.
【００１３】また、白金のメタノールの電気化学酸化に
対する活性が低いために直接メタノール燃料電池では、
メタノールの電気化学的酸化反応に対する活性が高い触
媒金属として白金族金属元素を含む合金、たとえばＰｔ
−Ｒｕ合金やＰｔ−Ｓｎ合金などが用いられている。[0013] Further, since the activity of platinum for the electrochemical oxidation of methanol is low, in a direct methanol fuel cell,
An alloy containing a platinum group metal element as a catalytic metal having high activity for the electrochemical oxidation reaction of methanol, for example, Pt
-Ru alloy, Pt-Sn alloy, or the like is used.
【００１４】ここで、従来の触媒金属担持カーボンは、
担体となるカーボン粒子をたとえば塩化ルテニウムと塩
化白金酸との混合水溶液中に浸漬してカーボン粒子表面
に塩化ルテニウムと塩化白金酸とを同時に物理吸着させ
た後、それを水素還元してルテニウムと白金を同時に担
持して作製している。または、担体となるカーボン粒子
を塩化ルテニウム水溶液中に浸漬してカーボン粒子表面
に塩化ルテニウムを物理吸着さて、それを水素により還
元してルテニウムを担持させた後、続いてそのカーボン
粒子を塩化白金酸の水溶液中に浸漬して、ルテニウムが
担持されたカーボン粒子表面に塩化白金酸を物理吸着さ
せた後、水素により還元して白金を担持して製作してい
る。Here, the conventional catalyst metal-carrying carbon is:
Carrier carbon particles are immersed, for example, in a mixed aqueous solution of ruthenium chloride and chloroplatinic acid to simultaneously physically adsorb ruthenium chloride and chloroplatinic acid on the surface of the carbon particles, and then reduce the hydrogen to form ruthenium and platinum. At the same time. Alternatively, the carbon particles serving as a carrier are immersed in a ruthenium chloride aqueous solution to physically adsorb ruthenium chloride on the surface of the carbon particles, and then reduced with hydrogen to carry ruthenium, and then the carbon particles are subjected to chloroplatinic acid. Chloroplatinic acid is physically adsorbed on the surface of the carbon particles carrying ruthenium, and then reduced with hydrogen to carry platinum.
【００１５】[0015]
【発明が解決しようとする課題】ＰＥＦＣはコストが高
く、そのことがＰＥＦＣ実用化の障壁となっている。と
くに、触媒金属として用いられる白金族金属のコストが
高く、ＰＥＦＣコストを引き上げる主な要因となってい
るために、電極に担持する白金族金属量をいかに減らす
かが技術開発の焦点となっている。SUMMARY OF THE INVENTION The cost of PEFC is high, which is a barrier to the practical use of PEFC. In particular, since the cost of platinum group metals used as catalyst metals is high and is a major factor in raising PEFC costs, how to reduce the amount of platinum group metals supported on electrodes is the focus of technological development. .
【００１６】上記のように、ひとつの白金族金属元素で
は得られない活性を、白金族金属元素を含む２種類以上
の金属元素を合金化することにより得る試みは、カーボ
ン粒子への白金族金属元素を含む２種類以上の金属の担
持量が多いときは成果を上げているが、 ＰＥＦＣコス
トを引きさげるために白金族金属元素を含む２種類以上
の金属の担持量を低減しようとすると、必ずしもその効
果があらわれないといった問題がある。 これは、単位重量あたりの表面積が著しく大きなカーボ
ン粒子に白金族金属元素を含む２種類以上の触媒金属を
同時に、または順次含浸担持して合金を形成しようとし
ても、それぞれの白金族金属を含む２種類以上の金属が
分離して、各金属が単独で高分散し、合金化率が大きく
低下するためであり、そのために、耐ＣＯ被毒性能およ
びメタノールの電気化学的酸化反応に対する活性が低下
するのである。As described above, an attempt to obtain an activity that cannot be obtained with one platinum group metal element by alloying two or more kinds of metal elements including the platinum group metal element has been attempted by adding platinum group metal elements to carbon particles. The results are good when the loadings of two or more metals including elements are large, but when trying to reduce the loadings of two or more metals containing platinum group metal elements to reduce the PEFC cost, it is not always necessary. There is a problem that the effect does not appear. This is because even if an alloy is formed by simultaneously or sequentially impregnating and supporting two or more kinds of catalyst metals containing a platinum group metal element on carbon particles having a remarkably large surface area per unit weight, each platinum group metal containing a platinum group metal element is contained. This is because more than one kind of metal is separated, each metal is highly dispersed alone, and the alloying rate is greatly reduced, thereby reducing the CO poisoning resistance and the activity of methanol for electrochemical oxidation reaction. It is.
【００１７】しかも、上記で説明したような製造方法に
より作製された電極では、カーボンに担持された白金族
金属を含む触媒金属の利用率が低く、例えばわずかに１
０％程度であることが報告されており（Ｅｄｓｏｎ
Ａ．Ｔｉｃｉａｎｅｌｌｉ，Ｊ．Ｅｌｅｃｔｒｏａｎａ
ｌ． Ｃｈｅｍ．，２５１，２７５（１９８８）参
照）、電極全体の電極反応に対する活性をさらに低下さ
せている。Moreover, in the electrode manufactured by the above-described manufacturing method, the utilization rate of the catalyst metal containing the platinum group metal supported on carbon is low, for example, only 1%.
It is reported to be about 0% (Edson
A. Ticianelli, J .; Electroana
l. Chem. , 251 , 275 (1988)), further reducing the activity of the entire electrode with respect to the electrode reaction.
【００１８】この原因は、これまでの製造方法が、あら
かじめカーボン粒子に白金族金属を含む触媒金属粒子を
担持させた後、そのカーボン粒子と陽イオン交換樹脂と
を混合する方法を用いていることに起因するものであ
る。The reason for this is that the conventional production method employs a method in which catalytic metal particles containing a platinum group metal are previously supported on carbon particles, and then the carbon particles are mixed with a cation exchange resin. It is caused by
【００１９】すなわち、担体であるカーボンの粒子径は
例えば３０ｎｍと小さく、陽イオン交換樹脂と混合する
前のカーボン粒子の状態は、カーボン粒子がいくつか集
合し、表面にかなり緻密な凹凸が形成されたカーボン粒
子集合体を形成した状態となっている。That is, the particle diameter of carbon as a carrier is as small as 30 nm, for example, and the state of the carbon particles before being mixed with the cation exchange resin is such that some carbon particles are aggregated and the surface thereof has very fine irregularities. In this state, an aggregated carbon particle is formed.
【００２０】一方、陽イオン交換樹脂溶液は、ある一定
の粘度を有しており、そのため、カーボン粒子とＰＴＦ
Ｅ粒子とよりなる分散層に陽イオン交換樹脂溶液を含浸
する方法によっても、また、カーボン粒子とＰＴＦＥ粒
子と陽イオン交換樹脂溶液とを混合したペーストを用い
る方法によっても、陽イオン交換樹脂溶液がカーボン粒
子集合体の凹部の深部までは浸透せず、カーボン粒子集
合体の深部で三相界面が形成されない。そのため、カー
ボン集合体の深部に位置する触媒金属である白金族金属
粒子は電極反応に関与することなく触媒金属の利用率の
低下を招いているのである。On the other hand, the cation exchange resin solution has a certain viscosity, so that carbon particles and PTF
The method of impregnating the dispersion layer composed of E particles with the cation exchange resin solution or the method of using a paste obtained by mixing carbon particles, PTFE particles, and the cation exchange resin solution, It does not penetrate to the deep part of the concave part of the carbon particle aggregate, and the three-phase interface is not formed in the deep part of the carbon particle aggregate. Therefore, the platinum group metal particles, which are the catalyst metal located deep in the carbon aggregate, do not participate in the electrode reaction and cause a reduction in the utilization rate of the catalyst metal.
【００２１】触媒金属の利用率を高めるために、カーボ
ン粒子と陽イオン交換樹脂との接触面に触媒金属を担持
する研究がなされているが、まだ不十分である。In order to increase the utilization rate of the catalyst metal, studies have been made on supporting the catalyst metal on the contact surface between the carbon particles and the cation exchange resin, but this is still insufficient.
【００２２】これに対し、本願発明者は、たとえば還元
されて触媒金属を生成する触媒金属原料化合物と陽イオ
ン交換樹脂とカーボン粒子との混合物を用意し、その混
合物中の触媒金属原料化合物を化学的に還元する方法を
見出し、触媒金属がカーボン粒子と陽イオン交換樹脂と
の接触面に主として担持されている構造の電極を作製す
ることによって、上記問題を解決することを当初検討し
た。On the other hand, the inventor of the present application prepared a mixture of, for example, a catalyst metal raw material compound which is reduced to produce a catalyst metal, a cation exchange resin and carbon particles, and chemically prepared the catalyst metal raw material compound in the mixture. At first, they found a method for reducing the catalyst, and studied at first to solve the above problem by producing an electrode having a structure in which the catalytic metal was mainly supported on the contact surface between the carbon particles and the cation exchange resin.
【００２３】しかしながら、触媒金属の利用率を飛躍的
に向上させるためには、電極の三相界面の構造を従来の
ようにマクロ的にとらえて、触媒金属担持カーボンと陽
イオン交換樹脂とを電極内にいかに三次元的に配置する
かを検討するだけでは限界があり、電極の三相界面の構
造をもっとミクロ的にとらえた電極のミクロ的三相界面
の構造について検討することが必要であることが明らか
になった。However, in order to dramatically improve the utilization rate of the catalyst metal, the structure of the three-phase interface of the electrode is macroscopically taken as in the prior art, and the carbon supporting the catalyst metal and the cation exchange resin are separated from the electrode. There is a limit in just examining how to arrange three-dimensionally in the electrode, and it is necessary to study the structure of the microscopic three-phase interface of the electrode by capturing the structure of the three-phase interface of the electrode more microscopically It became clear.
【００２４】すなわち、例えばＨ．Ｌ． Ｙｅａｇｅｒ
等の報告（Ｊ．Ｅｌｅｃｔｒｏｃｈｅｍ．Ｓｏｃ．，１
２８，１８８０，（１９８１）） および、小久見等の
報告（ Ｊ．Ｅｌｅｃｔｒｏｃｈｅｍ．Ｓｏｃ．，１３
２，２６０１（１９８５））にも記載されているよう
に、陽イオン交換樹脂の構造をミクロ的にとらえると，
プロトンはもちろん、反応活物質であるガス（水素また
は酸素）およびカソードの生成物である水は、陽イオン
交換樹脂の親水性の交換基とその対イオンとが水ととも
に集合したクラスターと呼ばれるプロトン伝導経路を移
動し、テフロンなどからなる骨格部である疎水性の部分
は移動経路となり得ない。That is, for example, L. Yeager
(J. Electrochem. Soc., 1
28 , 1880, (1981)) and a report by Kokumi et al. (J. Electrochem. Soc., 13 ).
2 , 2601 (1985)), when the structure of the cation exchange resin is microscopically grasped,
Not only protons but also gas (hydrogen or oxygen) as a reaction active material and water as a product of a cathode are formed by a proton conduction called a cluster in which a hydrophilic exchange group of a cation exchange resin and its counter ion gather together with water. The hydrophobic part which moves along the route and is a skeleton part made of Teflon or the like cannot be a movement route.
【００２５】このため、本発明者は、燃料電池電極とし
ての反応の進行する三相界面は、陽イオン交換樹脂のプ
ロトン伝導経路とカーボン粒子表面との接面のみに存在
すると考え、このような陽イオン交換樹脂内のプロトン
伝導経路に対する触媒金属の位置関係と分布状態を検討
する必要がある事が分かったのである。Therefore, the present inventor believes that the three-phase interface where the reaction proceeds as a fuel cell electrode exists only at the interface between the proton conduction path of the cation exchange resin and the surface of the carbon particles. It was found that it was necessary to study the positional relationship and distribution of the catalyst metal with respect to the proton conduction path in the cation exchange resin.
【００２６】しかし、従来の電極の製造方法は先に説明
したようにあらかじめカーボン粒子に触媒金属粒子を担
持させた後、そのカーボン粒子と陽イオン交換樹脂とを
混合する方法を用いており、あらかじめカーボンに担持
した白金族金属粒子が偶然に陽イオン交換樹脂内のプロ
トン伝導経路に接することを期待しているために、触媒
金属の利用率が低くなっていた。However, the conventional method of manufacturing an electrode uses a method in which catalytic metal particles are supported on carbon particles in advance and then mixed with the cation exchange resin, as described above. Since it is expected that the platinum group metal particles supported on carbon will accidentally come into contact with the proton conduction path in the cation exchange resin, the utilization rate of the catalyst metal has been low.
【００２７】図３は従来の電極の陽イオン交換樹脂と接
触したカーボン粒子の表層の状態を示す概念図である。
図３において、１はカーボン粒子、２は陽イオン交換樹
脂のプロトン伝導経路、３は陽イオン交換樹脂のテフロ
ン骨格部、４および５は触媒金属粒子である。FIG. 3 is a conceptual diagram showing a state of a surface layer of carbon particles in contact with a cation exchange resin of a conventional electrode.
In FIG. 3, 1 is a carbon particle, 2 is a proton conduction path of a cation exchange resin, 3 is a Teflon skeleton of the cation exchange resin, and 4 and 5 are catalytic metal particles.
【００２８】従来の電極では、例えば図３に示すよう
に、カーボン粒子１の表層をプロトン伝導経路２とテフ
ロン骨格部３とを含む陽イオン交換樹脂が被覆してお
り、カーボン粒子１表面に触媒金属粒子４，５が担持さ
れている。In the conventional electrode, for example, as shown in FIG. 3, the surface layer of the carbon particles 1 is coated with a cation exchange resin containing a proton conduction path 2 and a Teflon skeleton 3, and the surface of the carbon particles 1 is a catalyst. Metal particles 4 and 5 are supported.
【００２９】ところが、触媒金属粒子５は、プロトン伝
導経路２に位置しているために触媒として有効に作用す
るが、触媒金属粒子４は、テフロン骨格部３に位置して
いるために有効に作用しないと考えられるのである。However, the catalytic metal particles 5 function effectively as a catalyst because they are located in the proton conduction path 2, whereas the catalytic metal particles 4 function effectively because they are located in the Teflon skeleton 3. It is not considered.
【００３０】また、Ｚの領域は、三相界面が形成されて
いる領域ではあるが、触媒金属粒子が担持されていない
ために反応に関与しない領域となっていると考えられ
る。すなわち、このような電極においては、触媒金属粒
子４の存在は触媒金属の利用率の低下を、三相界面Ａの
存在は電極の活性度の低下を招いているのである。The region Z is considered to be a region where a three-phase interface is formed but is not involved in the reaction because no catalytic metal particles are supported. That is, in such an electrode, the presence of the catalyst metal particles 4 causes a reduction in the utilization rate of the catalyst metal, and the presence of the three-phase interface A causes a reduction in the activity of the electrode.
【００３１】以上に鑑み、本発明は、触媒金属粒子自体
の構造の改善と電極のミクロ的三相界面の構造とを改善
することにより、燃料電池用電極の性能を向上させるこ
と目的とする。In view of the above, an object of the present invention is to improve the performance of a fuel cell electrode by improving the structure of the catalyst metal particles themselves and the structure of the microscopic three-phase interface of the electrode.
【００３２】[0032]
【課題を解決するための手段】本発明の燃料電池用電極
は、陽イオン交換樹脂とカーボン粒子と触媒金属とを含
む燃料電池用電極であって、その触媒金属が核と外層と
を有し、前記核は白金、ルテニウム、ロジウム、パラジ
ウム、イリジウムからなる群より選ばれた１種以上４種
以下の金属（Ｘ）（以下、「金属（Ｘ）」と略す）から
なり、前記外層は白金、ルテニウム、ロジウム、パラジ
ウム、イリジウムからなる群より選ばれた少なくとも１
種であって前記核とは異なる金属（Ｙ）（以下、「金属
（Ｙ）」と略す）からなり、陽イオン交換樹脂のプロト
ン伝導経路に接するカーボン粒子の表面に担持された触
媒金属量が全触媒金属担持量の５０ｗｔ％を越えている
ことを特徴とする。The fuel cell electrode of the present invention is a fuel cell electrode comprising a cation exchange resin, carbon particles and a catalyst metal, the catalyst metal having a core and an outer layer. The core comprises one or more and four or less metals (X) (hereinafter abbreviated as “metal (X)”) selected from the group consisting of platinum, ruthenium, rhodium, palladium and iridium; , Ruthenium, rhodium, palladium, at least one selected from the group consisting of iridium
The amount of catalytic metal supported on the surface of carbon particles that is a seed and is different from the nucleus and is different from the core (hereinafter, abbreviated as “metal (Y)”) and is in contact with the proton conduction path of the cation exchange resin It is characterized by exceeding 50% by weight of the total amount of the supported catalyst metal.
【００３３】また、本発明の燃料電池用電極の製造方法
は、陽イオン交換樹脂とカーボン粒子とを含む混合体
に、その陽イオン交換樹脂の対イオンと白金、ルテニウ
ム、ロジウム、パラジウム、イリジウムからなる群より
選ばれた１種以上４種以下の金属元素（Ｘ’）（以下、
「金属元素（Ｘ’）」と略す）を含む陽イオンとのイオ
ン交換反応により、金属元素（Ｘ’）を含む陽イオンを
陽イオン交換樹脂に吸着させる第１の工程と、第１の工
程で得られた混合体中の金属元素（Ｘ’）を含む陽イオ
ンを化学的に還元する第２の工程とを経たのちに、さら
にその陽イオン交換樹脂の対イオンと金属元素（Ｘ’）
以外の金属元素（Ｙ’）（以下、「金属元素（Ｙ’）」
と略す）を含む陽イオンとのイオン交換反応により、金
属元素（Ｙ’）を含む陽イオンを陽イオン交換樹脂に吸
着させる第３の工程と、第３の工程で得られた混合体中
の金属元素（Ｙ’）を含む陽イオンを化学的に還元する
第４の工程とを経ることを特徴とする。The method for producing an electrode for a fuel cell according to the present invention is characterized in that a mixture containing a cation exchange resin and carbon particles is added to a mixture of the cation exchange resin and platinum, ruthenium, rhodium, palladium or iridium. One or more and four or less metal elements (X ′) selected from the group consisting of
A first step of adsorbing a cation containing a metal element (X ′) to a cation exchange resin by an ion exchange reaction with a cation containing the “metal element (X ′)”; and a first step And a second step of chemically reducing a cation containing the metal element (X ′) in the mixture obtained in the above step, and further, a counter ion of the cation exchange resin and the metal element (X ′)
Other metal elements (Y ') (hereinafter, "metal element (Y')")
A third step of adsorbing a cation containing a metal element (Y ′) onto a cation exchange resin by an ion exchange reaction with a cation containing the same, and the mixture in the mixture obtained in the third step. And a fourth step of chemically reducing cations containing the metal element (Y ′).
【００３４】さらに、本発明の燃料電池用電極の製造方
法は、第２または第４の工程において、金属元素
（Ｘ’）または金属元素（Ｙ’）を含む陽イオンを、水
素ガスまたは水素混合ガスやヒドラジンを含む不活性ガ
スによって還元することを特徴とし、陽イオン交換樹脂
単体に含まれる陽イオン交換樹脂の対イオンが還元され
る温度よりも低い温度で還元することを特徴とする。Further, in the method for producing a fuel cell electrode according to the present invention, in the second or fourth step, the cation containing the metal element (X ′) or the metal element (Y ′) is converted into hydrogen gas or hydrogen mixed gas. The reduction is carried out by an inert gas containing gas or hydrazine, and the reduction is performed at a temperature lower than the temperature at which the counter ion of the cation exchange resin contained in the cation exchange resin alone is reduced.
【００３５】また、本発明になるメタノール改質燃料電
池または直接メタノール燃料電池は上記燃料電池用電極
または上記製造方法により得られた燃料電池用電極をア
ノードとして用いることを特徴とする。Further, the methanol reformed fuel cell or the direct methanol fuel cell according to the present invention is characterized in that the fuel cell electrode or the fuel cell electrode obtained by the above manufacturing method is used as an anode.
【００３６】[0036]
【発明の実施の形態】本発明は、金属（Ｘ）からなる核
を金属（Ｙ）からなる外層で覆った触媒金属は、ＣＯ被
毒特性またはメタノールの電気化学的酸化反応に対する
活性がが向上することと、陽イオン交換樹脂とカーボン
粒子と触媒金属とを含む燃料電池用電極であって、陽イ
オン交換樹脂のプロトン伝導経路に接するカーボン粒子
の表面に担持された触媒金属量が全触媒金属担持量の５
０ｗｔ％を越えるようにすることにより、触媒金属の利
用率が飛躍的に向上することとに着目してなされたもの
である。BEST MODE FOR CARRYING OUT THE INVENTION According to the present invention, a catalytic metal in which a nucleus composed of a metal (X) is covered with an outer layer composed of a metal (Y) has an improved CO poisoning property or an activity for an electrochemical oxidation reaction of methanol. And a fuel cell electrode comprising a cation exchange resin, carbon particles, and a catalyst metal, wherein the amount of the catalyst metal supported on the surface of the carbon particles in contact with the proton conduction path of the cation exchange resin is equal to the total amount of the catalyst metal. 5 of carrying amount
It has been made by paying attention to the fact that the utilization ratio of the catalyst metal is significantly improved by exceeding 0 wt%.
【００３７】本発明の電極の構造について、図を参照し
て説明する。図１は本発明による電極の陽イオン交換樹
脂と接触したカーボン粒子の表層の状態を示す概念図で
ある。図１において、１はカーボン粒子、２は陽イオン
交換樹脂のプロトン伝導経路、３は陽イオン交換樹脂の
テフロン骨格部、５は触媒金属粒子である。The structure of the electrode of the present invention will be described with reference to the drawings. FIG. 1 is a conceptual diagram showing a state of a surface layer of carbon particles in contact with a cation exchange resin of an electrode according to the present invention. In FIG. 1, reference numeral 1 denotes carbon particles, 2 denotes a proton conduction path of a cation exchange resin, 3 denotes a Teflon skeleton of the cation exchange resin, and 5 denotes catalytic metal particles.
【００３８】本発明の電極は、陽イオン交換樹脂とカー
ボン粒子と触媒金属とを含む多孔性の電極であり、カー
ボン粒子により形成された電子伝導チャンネル、陽イオ
ン交換樹脂により形成されたプロトン伝導チャンネル、
多数の細孔により形成された活物質および生成物の供
給、排出チャンネルを有するものであり、例えば図１に
示すように、カーボン粒子１の表層をプロトン伝導経路
２とテフロン骨格部３よりなる陽イオン交換樹脂が被覆
し、プロトン伝導経路２接するカーボン粒子１表面に触
媒金属粒子５が担持された構造を有するものである。The electrode of the present invention is a porous electrode containing a cation exchange resin, carbon particles and a catalyst metal, and includes an electron conduction channel formed by carbon particles and a proton conduction channel formed by a cation exchange resin. ,
It has an active material and product supply and discharge channel formed by a large number of pores. For example, as shown in FIG. 1, a surface layer of carbon particles 1 is formed by a proton conduction path 2 and a Teflon skeleton 3. It has a structure in which the catalyst metal particles 5 are supported on the surface of the carbon particles 1 covered with the ion exchange resin and in contact with the proton conduction path 2.
【００３９】本発明によれば、陽イオン交換樹脂のプロ
トン伝導経路に接するカーボン粒子表面に担持された触
媒金属量が全触媒金属担持量の５０ｗｔ％を超えている
ため、カーボン粒子表層に形成された三相界面に触媒金
属が担持されていることとなって、触媒金属の利用率が
向上する。According to the present invention, since the amount of the catalyst metal supported on the surface of the carbon particles in contact with the proton conduction path of the cation exchange resin exceeds 50 wt% of the total amount of the supported catalyst metal, the catalyst metal formed on the surface layer of the carbon particles. Since the catalyst metal is supported on the three-phase interface, the utilization rate of the catalyst metal is improved.
【００４０】また、本発明においては、陽イオン交換樹
脂のプロトン伝導経路に接するカーボン粒子表面に担持
された触媒金属量の全触媒金属担持量に対する割合は高
いほど好ましく、特に８０ｗｔ％を超えていることが好
ましい。このようにして、プロトン伝導経路とカーボン
粒子との接触面に触媒金属を高率で担持させることによ
って、図３に示したＺの領域が減り、電極の高活性化が
はかられる。In the present invention, the ratio of the amount of the catalyst metal supported on the surface of the carbon particles in contact with the proton conduction path of the cation exchange resin to the total amount of the supported catalyst metal is preferably as high as possible, and particularly more than 80 wt%. Is preferred. Thus, by supporting the catalyst metal at a high rate on the contact surface between the proton conduction path and the carbon particles, the region of Z shown in FIG. 3 is reduced, and the electrode is highly activated.
【００４１】また、本発明によれば、例えば上記のよう
に、主としてプロトン伝導経路に接するカーボン粒子の
表面、つまり三相界面に優先的に触媒金属が担持されて
いるため、著しく大きなカーボン表面の限られた場所に
必要最低限の極めて少ない触媒金属を担持した構造とな
り、触媒金属の利用率が向上し、わずかな量の２種類以
上の触媒金属を順次担持してもそれらが独立に分散して
合金化率を下げるということが生じない。Further, according to the present invention, as described above, for example, the catalytic metal is preferentially supported mainly on the surface of the carbon particles in contact with the proton conduction path, that is, on the three-phase interface, so that the extremely large carbon surface It has a structure in which the minimum required amount of catalyst metal is supported in a limited area, the utilization rate of catalyst metal is improved, and even if a small amount of two or more types of catalyst metals are sequentially supported, they are dispersed independently. Therefore, the alloying rate is not lowered.
【００４２】本発明による触媒金属は、金属（Ｘ）から
なる核を金属（Ｙ）からなる外層で被った二層構造であ
り、核は白金、ルテニウム、ロジウム、パラジウム、イ
リジウムからなる群より選ばれた１種以上４種以下の金
属（Ｘ）からなり、前記外層は白金、ルテニウム、ロジ
ウム、パラジウム、イリジウムからなる群より選ばれた
少なくとも１種であって前記核とは異なる金属（Ｙ）か
らなっており、そのために、その触媒金属はＣＯ被毒特
性またはメタノールの電気化学的酸化反応に対する活性
が高い。The catalyst metal according to the present invention has a two-layer structure in which a nucleus made of metal (X) is covered with an outer layer made of metal (Y), and the nucleus is selected from the group consisting of platinum, ruthenium, rhodium, palladium and iridium. The outer layer is at least one selected from the group consisting of platinum, ruthenium, rhodium, palladium, and iridium, and the outer layer is a metal (Y) different from the nucleus. For which the catalytic metal has high CO poisoning properties or high activity for the electrochemical oxidation of methanol.
【００４３】この場合、核は白金、ルテニウム、ロジウ
ム、パラジウム、イリジウムそれぞれ単独でもよいし、
これらの金属の４種 以下の混合物や合金としても、そ
の効果は同じである。また、外層は核に使用した金属と
異なっていれば、白金、ルテニウム、ロジウム、パラジ
ウム、イリジウムを単独で、あるいは混合物や合金とし
て用いてもその効果は同じである。In this case, the nucleus may be platinum, ruthenium, rhodium, palladium, iridium alone,
The effect is the same even when a mixture or alloy of four or less of these metals is used. If the outer layer is different from the metal used for the nucleus, the effect is the same even when platinum, ruthenium, rhodium, palladium, and iridium are used alone or as a mixture or alloy.
【００４４】また、本発明の金属（Ｙ）は酸素の還元反
応に対する活性が高いことより白金が好ましいが、これ
に限るものではない。また、本発明の陽イオン交換樹脂
としては、パーフルオロカーボンスルフォン酸またはス
チレン−ジビニルベンゼン系のスルフォン酸型陽イオン
交換樹脂が好ましい。The metal (Y) of the present invention is preferably platinum because of its high activity in reducing oxygen, but is not limited thereto. The cation exchange resin of the present invention is preferably a perfluorocarbon sulfonic acid or a sulfonic acid type cation exchange resin of styrene-divinylbenzene system.
【００４５】また、Ｔ．Ｄ．Ｇｉｅｒｋｅ等の研究
（Ｊ．Ｍｅｍｂｒａｎｅ Ｓｃｉ．，１３，３０７（１
９８９））にもあるようにプロトン伝導経路のクラスタ
ーの直径は４０オングストローム程度であり、このこと
から上記接触面に担持される触媒金属の平均粒子径は４
０オングストローム以下であることが水やガスの拡散の
妨げにならず効率的で好ましい。Further, T.I. D. Gierke et al. (J. Membrane Sci., 13 , 307 (1
989)), the diameter of the cluster of the proton conduction path is about 40 angstroms, which indicates that the average particle diameter of the catalyst metal supported on the contact surface is 4.
It is efficient and preferably not less than 0 angstroms because it does not hinder the diffusion of water or gas.
【００４６】このようなＣＯ被毒特性とメタノールの電
気化学的酸化反応に対する活性と触媒金属の利用率とが
著しく高い本発明の燃料電池用電極は、たとえば、陽イ
オン交換樹脂とカーボン粒子とを含む混合体に、その陽
イオン交換樹脂の対イオンと金属元素（Ｘ’）を含む陽
イオンとのイオン交換反応により、金属元素（Ｘ’）を
含む陽イオンを陽イオン交換樹脂に吸着させる第１の工
程と、第１の工程で得られた混合体中の金属元素
（Ｘ’）を含む陽イオンを化学的に還元する第２の工程
とを経たのちに、さらにその陽イオン交換樹脂の対イオ
ンと金属元素（Ｙ’）を含む陽イオンとのイオン交換反
応により、金属元素（Ｙ’）を含む陽イオンを陽イオン
交換樹脂に吸着させる第３の工程と、第３の工程で得ら
れた混合体中の金属元素（Ｙ’）を含む陽イオンを化学
的に還元する第４の工程とを経る、本発明の燃料電池用
電極の製造方法を用いることによって製造できる。The fuel cell electrode of the present invention having such a high CO poisoning property, an activity for methanol electrochemical oxidation reaction and a remarkably high utilization rate of the catalyst metal can be obtained, for example, by using a cation exchange resin and carbon particles. A cation containing the metal element (X ′) is adsorbed on the cation exchange resin by an ion exchange reaction between the counter ion of the cation exchange resin and a cation containing the metal element (X ′). After the first step and the second step of chemically reducing the cation containing the metal element (X ′) in the mixture obtained in the first step, the cation exchange resin A third step in which a cation containing the metal element (Y ′) is adsorbed on the cation exchange resin by an ion exchange reaction between the counter ion and a cation containing the metal element (Y ′), and a third step. Element (Y ') in the mixture obtained Cations including through the fourth step of chemical reduction, can be prepared by using the method for manufacturing a fuel cell electrode of the present invention.
【００４７】本発明の製造方法では、第１工程と第２工
程をおこなった後、さらに第１工程、第２工程とを１回
以上繰り返すことで、最初に担持された金属（Ｘ）を核
としてさらに金属（Ｘ）を成長させることが可能であ
り、核となる金属（Ｘ）の粒径を任意に制御することが
できる。また、第３工程と第４工程をおこなった後、さ
らに第３工程、第４工程とを１回以上繰り返すことで、
金属（Ｙ）からなる外層の厚みを制御することができ
る。In the manufacturing method of the present invention, after the first step and the second step are performed, the first step and the second step are further repeated one or more times, so that the metal (X) initially supported is nucleated. It is possible to further grow the metal (X), and it is possible to arbitrarily control the particle size of the core metal (X). In addition, after performing the third step and the fourth step, the third step and the fourth step are further repeated one or more times.
The thickness of the outer layer made of metal (Y) can be controlled.
【００４８】このような本発明の製造方法は、陽イオン
交換樹脂の交換基の対イオンと金属元素（Ｘ’）を含む
陽イオンとのイオン交換反応により、陽イオン交換樹脂
のプロトン伝導経路に優先的に金属元素（Ｘ’）を含む
陽イオンを吸着させることが可能であること、その吸着
した金属元素（Ｘ’）を含む陽イオンを還元して金属
（Ｘ）を生成することが可能であること、陽イオン交換
樹脂の交換基の対イオンと金属元素（Ｙ’）を含む陽イ
オンとのイオン交換反応により、陽イオン交換樹脂のプ
ロトン伝導経路に優先的に金属元素（Ｙ’）を含む陽イ
オンを吸着させることが可能であること、その吸着した
金属元素（Ｙ’）を含む陽イオンを還元して金属（Ｙ）
を生成することが可能であること、さらに、カーボン粒
子が上記金属元素（Ｘ’）または金属元素（Ｙ’）を含
む陽イオンの還元反応に触媒活性を示すこと、２回目以
降の第２工程または第４工程の金属元素（Ｘ’）または
金属元素（Ｙ’）を含む陽イオンの化学的還元反応は先
に担持された金属（Ｘ）または金属（Ｙ）を核として進
むことに着目することでなされたものであり、上記本発
明の電極に限らず他の構造の燃料電池用電極の製造方法
としても用いることのできるものである。According to the production method of the present invention, the ion exchange reaction between the counter ion of the exchange group of the cation exchange resin and the cation containing the metal element (X ') causes the proton conduction path of the cation exchange resin to pass through. It is possible to preferentially adsorb a cation containing a metal element (X '), and it is possible to generate a metal (X) by reducing the cation containing the adsorbed metal element (X') By the ion exchange reaction between the counter ion of the exchange group of the cation exchange resin and the cation containing the metal element (Y ′), the metal element (Y ′) is preferentially given to the proton conduction path of the cation exchange resin. Can be adsorbed, and the cation containing the adsorbed metal element (Y ′) can be reduced to reduce the metal (Y)
And that the carbon particles exhibit catalytic activity in the reduction reaction of the cation containing the metal element (X ′) or the metal element (Y ′) in the second and subsequent second steps. Alternatively, it is noted that the chemical reduction reaction of the cation containing the metal element (X ′) or the metal element (Y ′) in the fourth step proceeds with the previously supported metal (X) or metal (Y) as a nucleus. The present invention is not limited to the electrode of the present invention, and can be used as a method for manufacturing a fuel cell electrode having another structure.
【００４９】本発明の製造方法において用いられる金属
元素（Ｘ’）を含む陽イオンは、その陽イオンが還元さ
れることで金属（Ｘ）となることが可能な陽イオンであ
る。また、本発明に用いる金属元素（Ｘ’）を含む陽イ
オンは、陽イオン交換樹脂が被覆せずに露出しているカ
ーボン表面には吸着し難く、陽イオン交換樹脂の対イオ
ンとのイオン交換反応により陽イオン交換樹脂のプロト
ン伝導経路に優先的に吸着することが好ましい。The cation containing the metal element (X ′) used in the production method of the present invention is a cation that can be converted to a metal (X) by reducing the cation. Further, the cation containing the metal element (X ′) used in the present invention is hardly adsorbed on the carbon surface which is exposed without being coated with the cation exchange resin, and the ion exchange with the counter ion of the cation exchange resin is performed. It is preferred that the cation exchange resin is preferentially adsorbed to the proton conduction pathway by the reaction.
【００５０】つぎに本発明の製造方法において用いられ
る金属元素（Ｙ’）を含む陽イオンは、その陽イオンが
還元されることで金属（Ｙ）となることが可能な陽イオ
ンであって、その金属（Ｙ）は触媒として機能すればよ
い。Next, the cation containing the metal element (Y ′) used in the production method of the present invention is a cation that can be converted to a metal (Y) by reducing the cation, The metal (Y) may function as a catalyst.
【００５１】また、陽イオンの形態はその吸着特性に大
きくかかわり、本発明に用いる金属元素（Ｘ’または
Ｙ’）を含む陽イオンは、陽イオン交換樹脂が被覆せず
に露出しているカーボン表面には吸着し難く、陽イオン
交換樹脂の対イオンとのイオン交換反応により陽イオン
交換樹脂のプロトン伝導経路に優先的に吸着することが
好ましく、たとえばそのような吸着特性を持つ金属の錯
イオン、とくに[Ｍ（ＮＨ3）4]2 +または[Ｍ（ＮＨ3）6]
4 +（Ｍは金属）などとあらわすことができる白金族金属
のアンミン錯イオンが好ましく、なかでも白金の2価の
アンミン錯イオンが好ましい。The form of the cation has a great influence on its adsorption characteristics, and the cation containing the metal element (X ′ or Y ′) used in the present invention is exposed to carbon without being covered with the cation exchange resin. It is difficult to be adsorbed on the surface, and it is preferable to preferentially adsorb to the proton conduction path of the cation exchange resin by ion exchange reaction with the counter ion of the cation exchange resin. For example, a metal complex ion having such adsorption characteristics Especially [M (NH 3 ) 4 ] 2 + or [M (NH 3 ) 6 ]
An ammine complex ion of a platinum group metal, which can be represented as 4 + (M is a metal) or the like, is preferable, and a divalent ammine complex ion of platinum is particularly preferable.
【００５２】陽イオン交換樹脂とカーボン粒子とを含む
混合体に、その陽イオン交換樹脂の交換基の対イオンと
金属元素（Ｘ’）を含む陽イオンとのイオン交換反応に
より、金属元素（Ｘ’）を含む陽イオンを陽イオン交換
樹脂に吸着させる第１の工程は、たとえば、水溶液中ま
たはアルコールを含む溶液中で金属元素（Ｘ’）を含む
陽イオンを生成する金属元素（Ｘ’）の化合物を水また
はアルコール水溶液などに溶解し、陽イオン交換樹脂と
カーボン粒子とを含む混合体をその水溶液に浸漬させる
ことでなされる。The mixture containing the cation exchange resin and the carbon particles is subjected to an ion exchange reaction between a counter ion of the exchange group of the cation exchange resin and a cation containing the metal element (X ′) to form a mixture of the metal element (X). The first step of adsorbing the cation containing the metal element (X ′) to the cation exchange resin is, for example, a metal element (X ′) that generates a cation containing the metal element (X ′) in an aqueous solution or a solution containing an alcohol. Is dissolved in water or an aqueous alcohol solution or the like, and a mixture containing a cation exchange resin and carbon particles is immersed in the aqueous solution.
【００５３】陽イオン交換樹脂とカーボン粒子とを含む
混合体に、その陽イオン交換樹脂と金属元素（Ｙ’）を
含む陽イオンとのイオン交換反応により、金属元素
（Ｙ’）を含む陽イオンを吸着させる第３の工程は、た
とえば、水溶液中またはアルコールを含む溶液中で金属
元素（Ｙ’）を含む陽イオンを生成する金属化合物を水
またはアルコール水溶液などに溶解し、陽イオン交換樹
脂とカーボン粒子とを含む混合体をその水溶液に浸漬さ
せることでなされる。また、ここで、水溶液中またはア
ルコールを含む溶液中で金属元素（Ｙ’）を含む陽イオ
ンを生成する金属化合物を用いる場合、いくつかの金属
化合物の混合溶液を用いても良い。The mixture containing the cation exchange resin and the carbon particles is subjected to an ion exchange reaction between the cation exchange resin and the cation containing the metal element (Y ′) to form a cation containing the metal element (Y ′). In the third step of adsorbing a cation-exchange resin, for example, a metal compound that generates a cation containing a metal element (Y ′) is dissolved in water or an alcohol aqueous solution in an aqueous solution or an alcohol-containing solution, and This is performed by immersing a mixture containing carbon particles in the aqueous solution. When a metal compound that generates a cation containing the metal element (Y ′) is used in an aqueous solution or a solution containing an alcohol, a mixed solution of several metal compounds may be used.
【００５４】例えば、白金の化合物とルテニウムの化合
物とを混ぜた水溶液を用いることで、吸着工程で白金を
含む陽イオンとルテニウムを含む陽イオンとが陽イオン
交換樹脂の対イオンとのイオン交換反応により同時に陽
イオン交換樹脂のプロトン伝導経路に吸着するために、
つぎの還元工程により、白金−ルテニウム合金の外層の
形成が期待できる。また、吸着工程で用いる水溶液中ま
たはアルコールを含む溶液中で白金族金属元素を含む陽
イオンを生成する白金族金属化合物は、生成される白金
族金属元素を含む陽イオンが、陽イオン交換樹脂が被覆
せずに露出しているカーボン表面には吸着し難く、陽イ
オン交換樹脂の対イオンとのイオン交換反応により陽イ
オン交換樹脂のプロトン伝導経路に優先的に吸着するこ
とが好ましく、たとえば金属の錯体、とくに[Ｍ（Ｎ
Ｈ3）4]Ｑ2または[Ｍ（ＮＨ3）6]Ｑ4（Ｍは金属、Ｑは
１価の陰イオン）などとあらわすことができるアンミン
錯体が好ましく、Ｑが塩素であることが好ましい。なか
でも白金の2価のアンミン錯体、とくにテトラアンミン
白金（II）塩化物（［Ｐｔ（ＮＨ3）4］Ｃｌ2 ）やテト
ラアンミン白金（II）水酸化物（［Ｐｔ（ＮＨ3）4］Ｏ
Ｈ2 ）がとくに好ましい。For example, by using an aqueous solution in which a platinum compound and a ruthenium compound are mixed, an ion exchange reaction between a cation containing platinum and a cation containing ruthenium in the adsorption step with a counter ion of a cation exchange resin is performed. To simultaneously adsorb in the proton conduction path of the cation exchange resin,
The formation of the outer layer of the platinum-ruthenium alloy can be expected by the next reduction step. In addition, a platinum group metal compound that generates a cation containing a platinum group metal element in an aqueous solution or a solution containing an alcohol used in the adsorption step, the generated cation containing the platinum group metal element is a cation exchange resin. It is difficult to adsorb to the exposed carbon surface without coating, and it is preferable to preferentially adsorb to the proton conduction path of the cation exchange resin by ion exchange reaction with the counter ion of the cation exchange resin. Complexes, especially [M (N
An ammine complex that can be represented as H 3 ) 4 ] Q 2 or [M (NH 3 ) 6 ] Q 4 (M is a metal and Q is a monovalent anion) is preferable, and Q is preferably chlorine. . Of these divalent ammine complexes of platinum, particularly tetraamine platinum (II) chloride ([Pt (NH 3) 4 ] Cl 2) and tetraammineplatinum (II) hydroxide ([Pt (NH 3) 4 ] O
H 2 ) is particularly preferred.
【００５５】カーボン粒子としては、金属元素（Ｘ’お
よびＹ’）を含む陽イオンの還元反応に対して高い活性
を示すものが好ましく、例えば、、Ｄｅｎｋａ Ｂｌａ
ｃｋ、 Ｖａｌｃａｎ ＸＣ―７２、Ｂｌａｃｋ Ｐｅａ
ｒｌ ２０００等のアセチレンブラックが好ましい。As the carbon particles, those exhibiting high activity for the reduction reaction of cations containing metal elements (X ′ and Y ′) are preferable. For example, Denka Bla
ck, Valcan XC-72, Black Pea
Acetylene black such as rl 2000 is preferred.
【００５６】カーボン粒子と陽イオン交換樹脂との混合
体は、固体状のもので、例えば、陽イオン交換樹脂とカ
ーボン粒子と、必要に応じてＰＴＦＥ粒子とが分散した
多孔体として用意されることは好ましい。とくに、混合
体が陽イオン交換樹脂とカーボン粒子とが均一に分散し
た多孔性の膜状形状を有することが好ましく、その膜の
厚さは３〜３０μｍ以内、さらに好ましくは３〜２０μ
ｍ以内が好ましい。The mixture of the carbon particles and the cation exchange resin is in a solid state. For example, the mixture is prepared as a porous body in which the cation exchange resin, the carbon particles and, if necessary, the PTFE particles are dispersed. Is preferred. In particular, the mixture preferably has a porous film shape in which the cation exchange resin and the carbon particles are uniformly dispersed, and the thickness of the film is within 3 to 30 μm, more preferably 3 to 20 μm.
m is preferable.
【００５７】このような陽イオン交換樹脂とカーボン粒
子との混合体は、カーボン粒子と陽イオン交換樹脂溶
液、さらに必要に応じてＰＴＦＥ粒子分散溶液とよりな
るペーストを高分子フィルム上に製膜（好ましくは膜厚
３〜３０μｍ）して乾燥して、または、カーボン粒子と
ＰＴＦＥ粒子分散溶液とよりなるペーストを高分子フィ
ルム上に製膜（好ましくは膜厚３〜３０μｍ）して乾燥
したのち、陽イオン交換樹脂溶液を塗布、含浸後乾燥さ
せて、または、カーボン粒子と陽イオン交換樹脂溶液
と、さらに必要に応じてＰＴＦＥ粒子分散溶液とよりな
るペーストを導電性多孔質体のカーボン電極基材上に塗
布、乾燥して、または、カーボン粒子とＰＴＦＥ粒子分
散溶液とよりなるペーストを導電性多孔質体のカーボン
電極基材上に塗布して、加熱乾燥した後、陽イオン交換
樹脂溶液を塗布、含浸、乾燥させて作製されるのが好ま
しい。Such a mixture of the cation exchange resin and the carbon particles is used to form a paste comprising the carbon particles and the cation exchange resin solution and, if necessary, a PTFE particle dispersion solution on a polymer film. (Preferably 3 to 30 μm in thickness) and dried, or after forming a paste (preferably 3 to 30 μm in thickness) on a polymer film from a paste comprising carbon particles and a PTFE particle dispersion, A cation exchange resin solution is applied and impregnated and then dried, or a paste comprising a carbon particle and a cation exchange resin solution and, if necessary, a PTFE particle dispersion solution is used as a conductive porous carbon electrode substrate. Coated on top, dried, or coated with a paste consisting of carbon particles and a PTFE particle dispersion on a conductive porous carbon electrode substrate, After heating and drying, it is preferably prepared by applying, impregnating and drying a cation exchange resin solution.
【００５８】さらに、カーボン粒子と陽イオン交換樹脂
溶液とよりなる混合体をイオン交換膜の両面、または片
面に接合した形態としても良い。Further, a mixture of carbon particles and a cation exchange resin solution may be bonded to both sides or one side of the ion exchange membrane.
【００５９】また、用意された陽イオン交換樹脂とカー
ボン粒子とを含む混合体に、その陽イオン交換樹脂の対
イオンと金属元素（Ｘ’）または金属元素（Ｙ’）を含
む陽イオンとのイオン交換反応により、金属元素
（Ｘ’）または金属元素（Ｙ’）を含む陽イオンを陽イ
オン交換樹脂に吸着させた後、その混合体中の金属元素
（Ｘ’）または金属元素（Ｙ’）を含む陽イオンを化学
的に還元する第２または第４の工程には、量産に適した
還元剤を用いる化学的な還元方法が好ましく、とくに、
水素ガスまたは水素含有ガスによって気相還元する方法
またはヒドラジンを含む不活性ガスによって気相還元す
る方法が好ましい。Further, a mixture of the prepared cation exchange resin and carbon particles is mixed with a counter ion of the cation exchange resin and a cation containing a metal element (X ′) or a metal element (Y ′). After the cation containing the metal element (X ′) or the metal element (Y ′) is adsorbed to the cation exchange resin by an ion exchange reaction, the metal element (X ′) or the metal element (Y ′) in the mixture is adsorbed. The chemical reduction method using a reducing agent suitable for mass production is preferable for the second or fourth step of chemically reducing cations containing
A gas phase reduction method using a hydrogen gas or a hydrogen-containing gas or a gas phase reduction method using an inert gas containing hydrazine is preferable.
【００６０】さらに還元に際しては、カーボン粒子が金
属元素（Ｘ’）または金属元素（Ｙ’）を含む陽イオン
の還元反応に対して触媒活性を示すことにより、カーボ
ン粒子表面近傍の金属元素（Ｘ’）または金属元素
（Ｙ’）を含む陽イオンが、陽イオン交換樹脂中の金属
元素（Ｘ’）または金属元素（Ｙ’）を含む陽イオンに
比べて優先的に還元される。In the reduction, the carbon particles exhibit catalytic activity for the reduction reaction of the cation containing the metal element (X ′) or the metal element (Y ′), so that the metal element (X Cations containing ') or metal element (Y') are preferentially reduced compared to cations containing metal element (X ') or metal element (Y') in the cation exchange resin.
【００６１】そこで、還元剤の種類、還元圧力、還元剤
濃度、還元時間、還元温度を適時調整し、カーボン粒子
表面の金属元素（Ｘ’）または金属元素（Ｙ’）を含む
陽イオンが陽イオン交換樹脂中の金属元素（Ｘ’）また
は金属元素（Ｙ’）を含む陽イオンに比べてより優先的
に還元されるようにし、具体的には陽イオン交換樹脂単
体に含まれる触媒金属元素を含む陽イオンが還元される
温度よりも低い温度で還元して、主としてカーボン粒子
と陽イオン交換樹脂との接触面に金属（Ｘ）または金属
（Ｙ）が還元生成されるようにするのが良い。Therefore, the type of the reducing agent, the reducing pressure, the reducing agent concentration, the reducing time, and the reducing temperature are appropriately adjusted so that the cation containing the metal element (X ′) or the metal element (Y ′) on the surface of the carbon particles becomes positive. The reduction is performed more preferentially than the cation containing the metal element (X ′) or the metal element (Y ′) in the ion exchange resin. Specifically, the catalytic metal element contained in the cation exchange resin alone Is carried out at a temperature lower than the temperature at which cations containing cations are reduced, so that metal (X) or metal (Y) is reduced and generated mainly on the contact surface between the carbon particles and the cation exchange resin. good.
【００６２】例えば、還元剤として水素を用い、その還
元温度を調整することでカーボン粒子表面の金属元素
（Ｙ’）を含む陽イオンが陽イオン交換樹脂中の金属元
素（Ｙ’）を含む陽イオンに比べて優先的に還元される
ようにし、主としてカーボン粒子と陽イオン交換樹脂と
の接触面に金属（Ｙ）が還元生成されるようにすること
ができる。For example, by using hydrogen as a reducing agent and adjusting the reduction temperature thereof, the cation containing the metal element (Y ′) on the surface of the carbon particles can be converted into the cation containing the metal element (Y ′) in the cation exchange resin. It is possible to reduce the metal (Y) preferentially compared to the ion and to reduce and generate the metal (Y) mainly on the contact surface between the carbon particles and the cation exchange resin.
【００６３】パーフルオロスルフォン酸型陽イオン交換
樹脂膜中に吸着した白金アンミン錯イオン[Ｐｔ（Ｎ
Ｈ3）4]2 +の水素による還元温度は約３００℃であるが
（境 哲男，大阪工業技術試験所季報、３６，１０（１
９８５））、表面にイオン交換基を修飾したカーボン粒
子（ Ｄｅｎｋａ Ｂｌａｃｋ， Ｖａｌｃａｎ ＸＣ−７
２， Ｂｌａｃｋ Ｐｅａｌ ２０００等）の表面に吸着
した[Ｐｔ（ＮＨ3）4]2 + のそれは，１８０℃であるこ
とが報告されている（Ｋ． Ａｍｉｎｅ， Ｍ． Ｍｉｚ
ｕｈａｔａ， Ｋ． Ｏｇｕｒｏ， Ｈ．Ｔａｋｅｎａｋ
ａ，Ｊ． Ｃｈｅｍ．Ｓｏｃ． Ｆａｒａｄａｙ Ｔｒａ
ｎｓ．， ９１， ４４５１（１９９５））。The platinum ammine complex ion [Pt (N) adsorbed on the perfluorosulfonic acid type cation exchange resin membrane
The reduction temperature of H 3 ) 4 ] 2 + with hydrogen is about 300 ° C. (Tetsuo Sakai, Osaka Industrial Technology Research Institute, 36, 10 (1
985)), carbon particles having a surface modified with an ion exchange group (Denka Black, Valcan XC-7)
2, [Pt (NH 3 ) 4 ] 2 + adsorbed on the surface of Black Peal 2000 etc. is reported to be 180 ° C. (K. Amine, M. Miz)
uhata, K .; Oguro, H .; Takenak
a, J. et al. Chem. Soc. Faraday Tra
ns. , 91 , 4451 (1995)).
【００６４】つまり、カーボン粒子としてたとえばＶａ
ｌｃａｎ ＸＣ−７２を用い、白金原料化合物として
［Ｐｔ（ＮＨ3）4］Ｃｌ2を用い、陽イオン交換樹脂と
カーボン粒子とを含む混合体をその水溶液に浸漬させ
て、陽イオン交換樹脂の対イオン（Ｈ+）ととのイオン
交換反応により、 [Ｐｔ（ＮＨ3）4]2 +を陽イオン交換
樹脂のプロトン伝導経路に吸着させた後、水素ガスによ
りその混合体を１８０℃で還元することで、陽イオン交
換樹脂とカーボン粒子と白金とを含む固体高分子電解質
−触媒複合電極であって、白金が陽イオン交換樹脂のプ
ロトン伝導経路に接するカーボン粒子の表面に主として
担持されていることを特徴とする燃料電池用電極の作製
が可能となる。 ここで、還元されずに電極内に残った白金を含む陽イオ
ン（[Ｐｔ（ＮＨ3）4] 2 +）は、還元工程後に電極を酸性
水溶液に浸漬することにより電極内より溶出させて、回
収することができる。That is, as the carbon particles, for example, Va
Using lcan XC-72 as a platinum raw material compound
[Pt (NHThree)Four] ClTwoUsing a cation exchange resin
And immersing the mixture containing carbon particles in the aqueous solution.
And the counter ion (H+) And Ion
By the exchange reaction, [Pt (NHThree)Four]Two +The cation exchange
After being adsorbed in the proton conduction path of the resin,
By reducing the mixture at 180 ° C, cation exchange
Polymer electrolyte containing exchange resin, carbon particles and platinum
-A catalytic composite electrode in which platinum is a cation exchange resin
Mainly on the surface of the carbon particles in contact with the roton conduction path
Fabrication of fuel cell electrode characterized by being carried
Becomes possible. Here, the cation containing platinum remaining in the electrode without being reduced
([Pt (NHThree)Four] Two +) Acidifies the electrode after the reduction step
It is eluted from the electrode by immersing it in an aqueous solution,
Can be collected.
【００６５】このように、適当な金属元素（Ｘ’または
Ｙ’）を含む陽イオンとカーボン粒子との組み合わせを
選択して、たとえば水素ガスによる還元温度を制御する
ことで、陽イオン交換樹脂とカーボン粒子と触媒金属と
を含む固体高分子電解質−触媒複合電極であって、陽イ
オン交換樹脂のプロトン伝導経路に接するカーボン粒子
の表面に担持された白金量が、全触媒金属担持量の５０
ｗｔ％を越えていることを特徴とする燃料電池用電極の
作製が可能となる。 ここで、水素による還元温度は、陽イオン交換樹脂を劣
化させないために、その分解温度より低いことが好まし
く、さらに好ましくは、そのガラス転移温度より低いこ
とが望ましい。よって、カーボン粒子と金属元素
（Ｘ’）または金属元素（Ｙ’）を含む陽イオンとの選
択は、水素ガスによる金属元素（Ｘ’）または金属元素
（Ｙ’）を含む陽イオンの還元温度が、陽イオン交換樹
脂の分解温度または、ガラス転移温度より低くなるよう
に組み合わせることが好ましい。As described above, by selecting an appropriate combination of a cation containing a metal element (X ′ or Y ′) and a carbon particle and controlling the reduction temperature by, for example, hydrogen gas, the cation exchange resin can be used. A solid polymer electrolyte-catalyst composite electrode containing carbon particles and a catalyst metal, wherein the amount of platinum supported on the surface of the carbon particles in contact with the proton conduction path of the cation exchange resin is 50% of the total amount of the supported catalyst metal.
It is possible to produce a fuel cell electrode characterized by exceeding 0.1 wt%. Here, the reduction temperature by hydrogen is preferably lower than its decomposition temperature, more preferably lower than its glass transition temperature, so as not to deteriorate the cation exchange resin. Therefore, the selection between the carbon particles and the cation containing the metal element (X ′) or the metal element (Y ′) depends on the reduction temperature of the cation containing the metal element (X ′) or the metal element (Y ′) by the hydrogen gas. Are preferably combined so as to be lower than the decomposition temperature of the cation exchange resin or the glass transition temperature.
【００６６】燃料電池用電極で、一般に用いられている
陽イオン交換樹脂はパーフルオロカーボンスルフォン酸
型であり、その分解温度は２８０℃であり、それより低
い温度で還元することで、電極内の陽イオン交換樹脂の
劣化を押さえることができる。The cation exchange resin generally used in the fuel cell electrode is a perfluorocarbon sulfonic acid type resin, and its decomposition temperature is 280 ° C. Deterioration of the ion exchange resin can be suppressed.
【００６７】また、還元されずに、陽イオン交換樹脂内
にとどまった、金属原料化合物は、水素ガスによる還元
後、塩酸などの酸性水溶液に電極を浸漬することで、電
極より抽出することができる。The metal raw material compound which is not reduced and stays in the cation exchange resin can be extracted from the electrode by immersing the electrode in an acidic aqueous solution such as hydrochloric acid after reduction with hydrogen gas. .
【００６８】このようにして得られた本発明になる燃料
電池用電極は、燃料の酸化反応に合金触媒を必要とする
改質メタノール燃料電池またはＤＭＦＣのアノードとし
て好ましい。The fuel cell electrode according to the present invention thus obtained is preferably used as a modified methanol fuel cell or DMFC anode which requires an alloy catalyst for the fuel oxidation reaction.
【００６９】[0069]
【実施例】以下、本発明を好適な実施例を用いて説明す
る。 ［実施例１］陽イオン交換樹脂（アルドリッチ社製、ナ
フィオン５ｗｔ％溶液）とカーボン粒子（Ｖａｌｃａｎ
ＸＣ−７２（田中貴金属製））を混錬してペースト状
にして、撥水性を付与した導電性多孔質体のカーボン電
極基材（０．５ｍｍ）上に塗布し、窒素雰囲気中で８０
℃、１時間乾燥した。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to preferred embodiments. [Example 1] A cation exchange resin (manufactured by Aldrich, Nafion 5 wt% solution) and carbon particles (Valcan)
XC-72 (manufactured by Tanaka Kikinzoku)) is kneaded to form a paste, which is applied on a conductive porous carbon electrode substrate (0.5 mm) provided with water repellency, and is applied in a nitrogen atmosphere.
C. and dried for 1 hour.
【００７０】ひきつづき、上記陽イオン交換樹脂とカー
ボン粒子の混合体を５０ｍｍｏｌ／ｌの［Ｒｕ（Ｎ
Ｈ3）6］Ｃｌ2水溶液中に２４時間浸漬し、イオン交換
反応により陽イオン交換樹脂のプロトン伝導経路に［Ｒ
ｕ（ＮＨ3）4］2+を吸着（第１工程）させた後、精製水
で充分洗浄・乾燥後３０気圧、２００℃の水素雰囲気中
で約６時間還元(第２工程)してＲｕを担持した。そし
て、第１工程〜第２工程をさらに１回おこなった。Subsequently, the mixture of the cation exchange resin and the carbon particles was mixed with 50 mmol / l of [Ru (N
H 3 ) 6 ] Cl 2 aqueous solution for 24 hours, and [R]
After adsorbing u (NH 3 ) 4 ] 2+ (first step), it is sufficiently washed and dried with purified water, and then reduced in a hydrogen atmosphere at 30 atm and 200 ° C. for about 6 hours (second step) to obtain Ru. Was carried. Then, the first and second steps were further performed once.
【００７１】つぎに、それを、［Ｐｔ（ＮＨ3）4］Ｃｌ
2水溶液中に２日間浸漬し、イオン交換反応により陽イ
オン交換樹脂のプロトン伝導経路に［Ｐｔ（ＮＨ3）4］
2+を吸着（第３工程）させた後、精製水で充分洗浄・乾
燥後１気圧、１８０℃の水素雰囲気中で約６時間還元
(第４工程)した。そして、第３工程〜第４工程さらに２
回おこなって、Ｒｕを核としＰｔの外層を有する触媒金
属を、陽イオン交換樹脂のプロトン伝導経路に接するカ
ーボン粒子の表面に優先的に担持させた。Next, it is converted to [Pt (NH 3 ) 4 ] Cl
During 2 aqueous solution was immersed for 2 days, by an ion exchange reaction in the proton conduction paths of the cation exchange resin [Pt (NH 3) 4]
After adsorbing 2+ (third step), thoroughly wash and dry with purified water and reduce in a hydrogen atmosphere at 1 atm and 180 ° C for about 6 hours
(Fourth step). Then, the third step to the fourth step and further 2
The catalyst metal having Ru as a nucleus and an outer layer of Pt was preferentially supported on the surface of the carbon particles in contact with the proton conduction path of the cation exchange resin.
【００７２】つぎに、０．５ｍｏｌ／ｌの硫酸に１時間
浸漬して不要なＲｕ（ＮＨ3）4］Ｃｌ2および［Ｐｔ
（ＮＨ3）4］Ｃｌ2を抽出して実施例の電極Ａを得た。
別途行った分析により電極Ａに担持された白金量は約
０．０４ｍｇ／ｃｍ2であることを確認した。 ［比較例１］Ｈ2ＰｔＣｌ6および、ＲｕＣｌ3の混合水
溶液中(モル比１：１)を作製し、これをカーボン粒子
（Ｖａｌｃａｎ ＸＣ−７２（田中貴金属））に含浸さ
せたのち、洗浄、乾燥して水素ガス(３００℃)にて還元
をおこない、ＰｔとＲｕ合金が担持されたＰｔ−Ｒｕ担
持カーボンを得た。このカーボン粒子の白金担持量は１
５ｗｔ％であった。Then, unnecessary Ru (NH 3 ) 4 ] Cl 2 and [Pt] were immersed in 0.5 mol / l sulfuric acid for 1 hour.
(NH 3 ) 4 ] Cl 2 was extracted to obtain Electrode A of Example.
The analysis performed separately confirmed that the amount of platinum carried on the electrode A was about 0.04 mg / cm 2 . Comparative Example 1 A mixed aqueous solution of H 2 PtCl 6 and RuCl 3 (molar ratio 1: 1) was prepared, and impregnated with carbon particles (Valcan XC-72 (Tanaka Kikinzoku)), washed, After drying, reduction was performed with hydrogen gas (300 ° C.) to obtain Pt—Ru-supported carbon on which Pt and a Ru alloy were supported. The amount of platinum supported on the carbon particles is 1
It was 5 wt%.
【００７３】このＰｔ−Ｒｕ担持カーボンと、実施例１
で使用したのと同じ固体高分子電解質およびＰＴＦＥ粒
子を混錬したペーストを、撥水性を付与した導電性多孔
質体のカーボン電極基材（０．５ｍｍ）上に塗布して、
窒素雰囲気中で１２０℃、１Ｈｒ乾燥して比較例の電極
Ｃを得た。 電極Ｃの白金量は、約０．１２ｍｇ／ｃｍ2
となるように、ペースト作製時のＰｔ−Ｒｕ担持カーボ
ンの量を調整した。The Pt-Ru-supported carbon and
A paste obtained by kneading the same solid polymer electrolyte and PTFE particles as used in the above was applied to a conductive porous carbon electrode substrate (0.5 mm) provided with water repellency,
The electrode C of the comparative example was obtained by drying at 120 ° C. for 1 hour in a nitrogen atmosphere. The platinum amount of the electrode C is about 0.12 mg / cm 2
The amount of Pt-Ru-supported carbon at the time of preparing the paste was adjusted so as to be as follows.
【００７４】実施例の電極ＡおよびＢそれぞれをホット
プレス（１４０℃）にてイオン交換膜（デュポン社製，
ナフィオン，膜厚約５０μm）の両面にそれぞれ接合し
て２種類の電極接合体を得た。つぎに、各接合体を、電
極接合後燃料電池の単セルホルダーに組んでセルＡおよ
びＢを得た。Each of the electrodes A and B of the example was hot-pressed (140 ° C.) using an ion exchange membrane (manufactured by DuPont).
(Nafion, about 50 μm thick) to obtain two types of electrode assemblies. Next, each of the assemblies was assembled into a single cell holder of a fuel cell after the electrodes were joined to obtain cells A and B.
【００７５】つぎに、セルＡおよびＢのカソード供給ガ
スにＯ2（２気圧、８０℃）、アノ−ド供給ガスにＨ2と
ＣＯの混合ガス（ＣＯ：１０ｐｐｍ、２気圧、９０℃）
を用い、出力電圧を０．６Ｖに固定した際の時間に対す
る出力電流を図４に示した。Next, O 2 (2 atm, 80 ° C.) was used as the cathode supply gas for the cells A and B, and a mixed gas of H 2 and CO (CO: 10 ppm, 2 atm, 90 ° C.) was used as the anode supply gas.
FIG. 4 shows the output current with respect to time when the output voltage was fixed at 0.6 V.
【００７６】図４より、本発明によるセルＡは、白金担
持量が従来のものＢに比べてわずか約１／３であるにも
かかわらず高い出力特性を示した。これは、セルＡの触
媒金属の利用率および合金化率が高いことと、ルテニウ
ムの核を白金の外層で覆うことにより、耐ＣＯ被毒性能
が向上したことのよる。As shown in FIG. 4, the cell A according to the present invention exhibited high output characteristics even though the amount of supported platinum was only about 1/3 of that of the conventional cell B. This is because the utilization rate and the alloying rate of the catalyst metal of the cell A are high, and the resistance to CO poisoning is improved by covering the ruthenium nucleus with the outer layer of platinum.
【００７７】[0077]
【発明の効果】本発明の燃料電池用電極によれば、耐Ｃ
Ｏ被毒性能、およびメタノールの電気化学的酸化反応に
対する活性が高く、触媒金属の利用率および合金化率の
高い電極となる。According to the fuel cell electrode of the present invention, the C resistance
The electrode has high O poisoning performance and high activity for the electrochemical oxidation reaction of methanol, and has a high catalyst metal utilization and alloying rate.
【００７８】また、本発明の燃料電池用電極の製造方法
によれば、金属（Ｘ）を核とし、その核が金属（Ｙ）か
らなる外層で覆われている触媒金属を電極の三相界面に
優先的に担持することができ、そのために少ない白金族
金属担持量でも従来と同等の性能を持つ電極を製造する
ことが可能となり、安価で高性能な燃料電池の製造が可
能となる。Further, according to the method for producing an electrode for a fuel cell of the present invention, a catalyst metal whose core is a metal (X) and whose nucleus is covered with an outer layer made of a metal (Y) is a three-phase interface of the electrode. Therefore, it is possible to manufacture an electrode having the same performance as the conventional one even with a small amount of the platinum group metal supported, and to manufacture an inexpensive and high-performance fuel cell.
【図１】本発明の電極のカーボン粒子の表層の状態を示
す概念図。FIG. 1 is a conceptual diagram showing a state of a surface layer of carbon particles of an electrode of the present invention.
【図２】陽イオン交換樹脂−触媒複合電極の構造を説明
する図。FIG. 2 is a diagram illustrating the structure of a cation exchange resin-catalyst composite electrode.
【図３】従来の電極のカーボン粒子の表層の状態を示す
概念図。FIG. 3 is a conceptual diagram showing a state of a surface layer of carbon particles of a conventional electrode.
【図４】各セルの電流の径時特性を示す図。FIG. 4 is a diagram showing a time characteristic of a current of each cell.
１、６ カーボン粒子 ２ 陽イオン交換樹脂のプロトン伝導経路 ３ 陽イオン交換樹脂のテフロン骨格部 ４、５ 触媒金属粒子 ７ 陽イオン交換樹脂 ８ イオン交換膜 ９ 細孔 1, 6 Carbon particles 2 Proton conduction path of cation exchange resin 3 Teflon skeleton of cation exchange resin 4, 5 Catalytic metal particles 7 Cation exchange resin 8 Ion exchange membrane 9 Pore
Claims (6)
金属とを含む燃料電池用電極であって、前記触媒金属が
核と外層とを有し、前記核は白金、ルテニウム、ロジウ
ム、パラジウム、イリジウムからなる群より選ばれた１
種以上４種以下の金属（Ｘ）からなり、前記外層は白
金、ルテニウム、ロジウム、パラジウム、イリジウムか
らなる群より選ばれた少なくとも１種であって前記核と
は異なる金属（Ｙ）からなり、陽イオン交換樹脂のプロ
トン伝導経路に接するカーボン粒子の表面に担持された
触媒金属量が全触媒金属担持量の５０ｗｔ％を越えるこ
とを特徴とする燃料電池用電極。1. An electrode for a fuel cell comprising a cation exchange resin, carbon particles and a catalyst metal, wherein the catalyst metal has a core and an outer layer, and the core is platinum, ruthenium, rhodium, palladium, iridium. 1 selected from the group consisting of
The outer layer is at least one selected from the group consisting of platinum, ruthenium, rhodium, palladium, and iridium, and is made of a metal (Y) different from the nucleus; An electrode for a fuel cell, wherein the amount of the catalyst metal supported on the surface of the carbon particles in contact with the proton conduction path of the cation exchange resin exceeds 50 wt% of the total amount of the supported catalyst metal.
む混合体に、その陽イオン交換樹脂の対イオンと、白
金、ルテニウム、ロジウム、パラジウム、イリジウムか
らなる群より選ばれた１種以上４種以下の金属元素
（Ｘ’）を含む陽イオンとのイオン交換反応により、金
属元素（Ｘ’）を含む陽イオンを陽イオン交換樹脂に吸
着させる第１の工程と、第１の工程で得られた混合体中
の金属元素（Ｘ’）を含む陽イオンを化学的に還元する
第２の工程とを経たのちに、さらにその陽イオン交換樹
脂の対イオンと金属元素（Ｘ’）以外の金属元素
（Ｙ’）を含む陽イオンとのイオン交換反応により、金
属元素（Ｙ’）を含む陽イオンを陽イオン交換樹脂に吸
着させる第３の工程と、第３の工程で得られた混合体中
の金属元素（Ｙ’）を含む陽イオンを化学的に還元する
第４の工程とを経ることを特徴とする燃料電池用電極の
製造方法。2. A mixture containing a cation exchange resin and carbon particles, a counter ion of the cation exchange resin and one or more selected from the group consisting of platinum, ruthenium, rhodium, palladium, and iridium. A first step of adsorbing a cation containing a metal element (X ′) to a cation exchange resin by an ion exchange reaction with a cation containing a metal element (X ′) below, and a first step obtained by the first step And a second step of chemically reducing the cation containing the metal element (X ′) in the mixed mixture, and further removing the counter ion of the cation exchange resin and a metal other than the metal element (X ′). A third step of adsorbing a cation containing the metal element (Y ′) on the cation exchange resin by an ion exchange reaction with a cation containing the element (Y ′), and a mixture obtained in the third step Cation containing metal element (Y ') The fourth step in the method of manufacturing the fuel cell electrode, characterized in that through the reduced to.
素（Ｘ’）または金属元素（Ｙ’）を含む陽イオンを水
素ガスまたは水素混合ガスによって還元することを特徴
とする請求項２記載の燃料電池用電極の製造方法。3. The method according to claim 2, wherein the cation containing the metal element (X ′) or the metal element (Y ′) is reduced by a hydrogen gas or a hydrogen mixed gas in the second or fourth step. Method for producing an electrode for a fuel cell.
素（Ｘ’）または金属元素（Ｙ’）を含む陽イオンをヒ
ドラジンを含む不活性ガスによって還元することを特徴
とする請求項２記載の燃料電池用電極の製造方法。4. The method according to claim 2, wherein the cation containing the metal element (X ′) or the metal element (Y ′) is reduced by an inert gas containing hydrazine in the second or fourth step. Method for producing an electrode for a fuel cell.
ン交換樹脂単体に含まれる陽イオン交換樹脂の対イオン
が還元される温度よりも低い温度で還元することを特徴
とする請求項2〜４記載の燃料電池用電極の製造方法。5. The method according to claim 2, wherein in the second or fourth step, the cation exchange resin is reduced at a temperature lower than a temperature at which a counter ion of the cation exchange resin contained in the cation exchange resin alone is reduced. 5. The method for producing an electrode for a fuel cell according to item 4.
求項２〜５記載の製造方法により得られた燃料電池用電
極をアノードとして用いることを特徴とするメタノール
改質燃料電池または直接メタノール燃料電池。6. A methanol reforming fuel cell or a direct methanol fuel, wherein the fuel cell electrode according to claim 1 or the fuel cell electrode obtained by the production method according to claim 2 is used as an anode. battery.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29730299A JP3649061B2 (en) | 1999-10-19 | 1999-10-19 | Fuel cell electrode and manufacturing method thereof |
| US09/670,344 US6528201B1 (en) | 1999-09-27 | 2000-09-27 | Electrode for fuel cell and process for producing the same |
| DE10047935A DE10047935A1 (en) | 1999-09-27 | 2000-09-27 | Electrode manufacturing method for solid polymer electrolyte fuel cell, involves reducing cation such as complex ion of platinum group metal at specific temperature by gas having hydrogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29730299A JP3649061B2 (en) | 1999-10-19 | 1999-10-19 | Fuel cell electrode and manufacturing method thereof |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2001118582A true JP2001118582A (en) | 2001-04-27 |
| JP2001118582A5 JP2001118582A5 (en) | 2004-09-16 |
| JP3649061B2 JP3649061B2 (en) | 2005-05-18 |
Family
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| JP29730299A Expired - Fee Related JP3649061B2 (en) | 1999-09-27 | 1999-10-19 | Fuel cell electrode and manufacturing method thereof |
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| JP2005522015A (en) * | 2002-04-04 | 2005-07-21 | ザ ボード オブ トラスティーズ オブ ザ ユニバーシティ オブ イリノイ | Fuel cell and fuel cell catalyst |
| WO2005081340A1 (en) * | 2004-02-23 | 2005-09-01 | Cataler Corporation | Supported catalyst for fuel cell, method for producing same and fuel cell |
| EP1653535A1 (en) * | 2004-10-28 | 2006-05-03 | Samsung SDI Co., Ltd. | Catalyst for fuel cell, method for preparing the same, and membrane-electrode assembly and fuel cell system comprising the same |
| KR100691117B1 (en) | 2004-05-25 | 2007-03-09 | 주식회사 엘지화학 | Ruthenium-rhodium alloy electrode catalyst and fuel cell comprising the same |
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| JP2002358971A (en) * | 2001-05-31 | 2002-12-13 | Japan Storage Battery Co Ltd | Fuel cell electrode and its manufacturing method and fuel cell using the same |
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