JP2003045439A - Manufacturing method of catalyst for polymer electrolyte fuel cell, electrolyte membrane/electrode assembly using it, and polymer electrolyte fuel cell - Google Patents

Manufacturing method of catalyst for polymer electrolyte fuel cell, electrolyte membrane/electrode assembly using it, and polymer electrolyte fuel cell

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Publication number
JP2003045439A
JP2003045439A JP2001235969A JP2001235969A JP2003045439A JP 2003045439 A JP2003045439 A JP 2003045439A JP 2001235969 A JP2001235969 A JP 2001235969A JP 2001235969 A JP2001235969 A JP 2001235969A JP 2003045439 A JP2003045439 A JP 2003045439A
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JP
Japan
Prior art keywords
polymer electrolyte
hydrogen ion
ion conductive
conductive polymer
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2001235969A
Other languages
Japanese (ja)
Inventor
Takeshi Yonamine
毅 与那嶺
Yoshihiro Hori
堀　　喜博
Shinichi Arisaka
伸一 有坂
Makoto Uchida
誠 内田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Holdings Corp
Original Assignee
Matsushita Electric Industrial Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Priority to JP2001235969A priority Critical patent/JP2003045439A/en
Publication of JP2003045439A publication Critical patent/JP2003045439A/en
Pending legal-status Critical Current

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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

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  • Fuel Cell (AREA)
  • Inert Electrodes (AREA)

Abstract

PROBLEM TO BE SOLVED: To solve problems that when hydrogen ion conductive polymer electrolyte is jointed to catalyst powder in a manufacturing process of the catalyst powder covered with the hydrogen ion conductive polymer electrolyte, large aggregates of the hydrogen ion conductive polymer electrolyte are produced to cause uneven joint to the catalyst powder, and thereby, the diffusion of reaction gas is suppressed and the electrode performance drops. SOLUTION: When the hydrogen ion conductive polymer electrolyte is sprayed on the catalyst powder and dried, the spraying velocity of the hydrogen ion conductive polymer electrolyte is specified so that the amount of the hydrogen ion conductive polymer electrode becomes 1000 mg/h per 1 g of the catalyst powder as the upper limit, and the thickness of the sprayed hydrogen ion conductive polymer electrolyte becomes 0.1 μm or less. A polymer electrolyte fuel cell with lving life characteristics is manufactured.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は、高分子電解質型燃
料電池用触媒の製造方法とそれを用いた電解質膜／電極
接合体と高分子電解質型燃料電池に関する。TECHNICAL FIELD The present invention relates to a method for producing a catalyst for a polymer electrolyte fuel cell, an electrolyte membrane / electrode assembly using the catalyst, and a polymer electrolyte fuel cell.

【０００２】[0002]

【従来の技術】水素イオン伝導性高分子電解質を用いた
燃料電池は、水素を含有する燃料ガスと、空気など酸素
を含有する燃料ガスとを、電気化学的に反応させること
で、電力と熱とを同時に発生させるものである。その構
造は、まず、水素イオンを選択的に輸送する水素イオン
伝導性高分子電解質膜の両面に、白金系の貴金属触媒を
担持したカーボン粉末を触媒とし、これに水素イオン伝
導性高分子電解質を混合したもので触媒層を形成する。
次に、この触媒層の外面に、燃料ガスの通気性と、電子
導電性を併せ持つ、例えば撥水処理を施したカーボンペ
ーパーで拡散層を形成する。この触媒層と拡散層とを合
わせて電極と呼ぶ。2. Description of the Related Art A fuel cell using a hydrogen ion conductive polymer electrolyte is designed to electrochemically react a fuel gas containing hydrogen with a fuel gas containing oxygen such as air to generate electricity and heat. And are generated at the same time. The structure is such that, on both sides of a hydrogen ion conductive polymer electrolyte membrane that selectively transports hydrogen ions, a carbon powder carrying a platinum-based noble metal catalyst is used as a catalyst, and a hydrogen ion conductive polymer electrolyte is added to this. The mixture is mixed to form a catalyst layer.
Next, a diffusion layer is formed on the outer surface of the catalyst layer by using, for example, water repellent carbon paper having both fuel gas permeability and electronic conductivity. The catalyst layer and the diffusion layer are collectively called an electrode.

【０００３】次に、燃料を供給する燃料ガスが外にリー
クしたり、燃料ガスと酸化剤ガスとが互いに混合しない
ように、電極の周囲には水素イオン伝導性高分子電解質
膜を挟んでガスシール材やガスケットを配置する。この
シール材やガスケットは、電極及び水素イオン伝導性高
分子電解質膜と一体化し、これを電極電解質膜接合体と
呼ぶ。電極電解質膜接合体の外側には、これを機械的に
固定するとともに、隣接した電極電解質膜接合体を互い
に電気的に直列に接続するための導電性セパレータ板を
配置する。セパレータ板の電極電解質膜接合体と接触す
る部分には、電極面に反応ガスを供給し、生成ガスや余
剰ガスを運び去るためのガス流路を形成する。ガス流路
はセパレータ板とを別に設けることもできるが、セパレ
ータの表面に溝を設けてガス流路とする方式が一般的で
ある。Next, in order to prevent the fuel gas supplying the fuel from leaking to the outside and the fuel gas and the oxidant gas from being mixed with each other, a gas with a hydrogen ion conductive polymer electrolyte membrane is sandwiched around the electrodes. Place sealing materials and gaskets. This sealing material and gasket are integrated with the electrode and the hydrogen ion conductive polymer electrolyte membrane, and this is called an electrode electrolyte membrane assembly. A conductive separator plate for mechanically fixing the electrode-electrolyte membrane assembly and electrically connecting adjacent electrode-electrolyte membrane assemblies to each other in series is arranged outside the electrode-electrolyte membrane assembly. In the portion of the separator plate that comes into contact with the electrode / electrolyte membrane assembly, a reaction gas is supplied to the electrode surface, and a gas flow path for carrying away generated gas and surplus gas is formed. The gas flow path may be provided separately from the separator plate, but it is common to provide a groove on the surface of the separator to form the gas flow path.

【０００４】高分子電解質型燃料電池の電極の拡散層
は、撥水処理を施したカーボン不織布などの多孔質カー
ボン層で構成されることが一般的である。また、触媒層
または水素イオン伝導性高分子電解質膜の保湿を目的と
して、触媒層と拡散層との界面に撥水カーボン層を設け
ることもある。撥水カーボン層は、通常まず、カーボン
粒子と、界面活性剤を含んだポリフルオロテトラエチレ
ン粒子のディスパージョンを混合し、これを乾燥あるい
はろ過などの手法によりカーボン粒子とポリフルオロテ
トラエチレン粒子の混合体を得る。次に、これに水また
は有機溶媒を加えてインク化する。拡散層であるカーボ
ン不織布などの片面に、スクリーン印刷法やスプレー塗
工法、ドクターブレード法やロールコーター法などでこ
のインクを塗工し、３００℃から４００℃程度の温度で
焼成し界面活性剤を焼散することで、撥水カーボン層を
形成することが一般的である。The diffusion layer of the electrode of the polymer electrolyte fuel cell is generally composed of a porous carbon layer such as a carbon non-woven fabric that has been subjected to a water repellent treatment. In addition, a water repellent carbon layer may be provided at the interface between the catalyst layer and the diffusion layer for the purpose of retaining the moisture of the catalyst layer or the hydrogen ion conductive polymer electrolyte membrane. The water-repellent carbon layer is usually prepared by first mixing carbon particles and a dispersion of polyfluorotetraethylene particles containing a surfactant, and then drying or filtering the mixture to mix the carbon particles and polyfluorotetraethylene particles. Get the body. Next, water or an organic solvent is added thereto to form an ink. This ink is applied to one side of the diffusion layer such as carbon non-woven fabric by screen printing method, spray coating method, doctor blade method or roll coater method, and is baked at a temperature of about 300 to 400 ° C to remove the surfactant. It is common to form a water repellent carbon layer by burning.

【０００５】また、触媒層は、一般に貴金属触媒を担持
した炭素粉末と水素イオン伝導性高分子電解質との混合
物で形成する。現在、水素イオン伝導性高分子電解質と
しては、パーフルオロカーボンスルホン酸が一般的に使
用されている。触媒層の形成は、貴金属触媒を担持した
炭素粉末と、エタノールなどのアルコール系溶媒に水素
イオン伝導性高分子電解質を溶解させた水素イオン伝導
性高分子電解質溶液とを混合し、これにイソプロピルア
ルコールやブチルアルコールなどの比較的高沸点の有機
溶媒を添加することでインク化し、このインクをスクリ
ーン印刷法やスプレー塗工法、ドクターブレード法やロ
ールコーター法などを用いて塗布し乾燥させる方法で行
われている。The catalyst layer is generally formed of a mixture of carbon powder carrying a noble metal catalyst and a hydrogen ion conductive polymer electrolyte. At present, perfluorocarbon sulfonic acid is generally used as the hydrogen ion conductive polymer electrolyte. The catalyst layer is formed by mixing a carbon powder carrying a noble metal catalyst and a hydrogen ion conductive polymer electrolyte solution in which a hydrogen ion conductive polymer electrolyte is dissolved in an alcohol solvent such as ethanol, and isopropyl alcohol is added thereto. It is made into an ink by adding a relatively high boiling point organic solvent such as butyl alcohol or butyl alcohol, and this ink is applied by a screen printing method, a spray coating method, a doctor blade method or a roll coater method, and then dried. ing.

【０００６】一方、あらかじめ水素イオン伝導性高分子
電解質溶液と貴金属触媒を担持した炭素粉末との混合物
をいったん蒸発乾固させ、これにイソプロピルアルコー
ルやブチルアルコールなどの比較的高沸点の有機溶媒に
再溶解させて高粘度のインクを調製し、このインクを用
いて同様に塗布乾燥させる方法で触媒層を形成する方法
もある。On the other hand, a mixture of a hydrogen ion conductive polymer electrolyte solution and a carbon powder carrying a noble metal catalyst is once evaporated to dryness, and then reconstituted in an organic solvent having a relatively high boiling point such as isopropyl alcohol or butyl alcohol. There is also a method in which a high-viscosity ink is dissolved to prepare a high-viscosity ink, and the catalyst layer is formed by a similar method of applying and drying the ink.

【０００７】[0007]

【発明が解決しようとする課題】燃料電池を実用化する
ためには、さらなる効率の向上が必要である。そのため
には、触媒層中の貴金属触媒を担持したカーボン粒子の
表面に薄く均一な水素イオン伝導性高分子電解質の層を
つけることや、多くの貴金属触媒を担持したカーボン粒
子に水素イオン伝導性高分子電解質の層をつけることが
重要である。In order to put the fuel cell into practical use, it is necessary to further improve the efficiency. For that purpose, a thin and uniform layer of hydrogen ion conductive polymer electrolyte is attached on the surface of the carbon particles supporting the noble metal catalyst in the catalyst layer, and the carbon particles supporting many noble metal catalysts have high hydrogen ion conductivity. It is important to apply a layer of molecular electrolyte.

【０００８】触媒粉末の表面に水素イオン伝導性高分子
電解質の層をつけるためには、貴金属触媒を担持したカ
ーボン粉末と水素イオン伝導性高分子電解質の溶液を混
合し、乾燥させる工程が必要である。In order to form a layer of the hydrogen ion conductive polymer electrolyte on the surface of the catalyst powder, a step of mixing the carbon powder carrying the noble metal catalyst and the solution of the hydrogen ion conductive polymer electrolyte and drying it is necessary. is there.

【０００９】従来の方法では、水素イオン伝導性高分子
電解質溶液の濃度が１０％程度と低いために、溶媒量が
多くなり、スクリーン印刷法などに適した高粘度のイン
クにするためには、溶媒を蒸発させる必要があった。In the conventional method, since the concentration of the hydrogen ion conductive polymer electrolyte solution is as low as about 10%, the amount of the solvent is large, and in order to obtain a highly viscous ink suitable for the screen printing method, etc., The solvent had to be evaporated.

【００１０】しかしながら、水素イオン伝導性高分子電
解質溶液を蒸発させる場合には、溶液中に溶解している
水素イオン伝導性高分子電解質が、溶媒の減少とともに
水素イオン伝導性高分子電解質同士でしだいに凝集し、
最終的には大きな水素イオン伝導性高分子電解質の凝集
体となりカーボン粒子に接合していた。そして、これを
高粘度のインクにするために少量の高沸点有機溶媒に溶
解させても、水素イオン伝導性高分子電解質の大きな凝
集体が触媒粉末に接合した状態のままであった。その結
果、大きな凝集体である水素イオン伝導性高分子電解質
によって、反応ガスの拡散性が抑制されるために電極の
性能が低下するという問題があった。また、逆に反応ガ
スの拡散性の確保を優先させるために、水素イオン伝導
性高分子電解質の量を減少させると、カーボン粒子上に
水素イオン伝導性高分子電解質の接合しないものが発生
し、有効反応面積の減少とともに水素イオン伝導性が低
下し、電極の性能が低下するという問題があった。However, in the case of evaporating the hydrogen ion conductive polymer electrolyte solution, the hydrogen ion conductive polymer electrolyte dissolved in the solution depends on the hydrogen ion conductive polymer electrolytes as the solvent decreases. Agglomerates into
Eventually, it became a large aggregate of hydrogen ion conductive polymer electrolyte and was bonded to the carbon particles. Then, even if it was dissolved in a small amount of a high-boiling point organic solvent to obtain a highly viscous ink, large aggregates of the hydrogen ion conductive polymer electrolyte remained in a state of being bonded to the catalyst powder. As a result, there is a problem in that the hydrogen ion conductive polymer electrolyte, which is a large aggregate, suppresses the diffusivity of the reaction gas, and thus the performance of the electrode deteriorates. On the contrary, in order to prioritize ensuring the diffusivity of the reaction gas, when the amount of the hydrogen ion conductive polymer electrolyte is reduced, some of the hydrogen ion conductive polymer electrolytes do not bond to the carbon particles, There has been a problem that the hydrogen ion conductivity is lowered as the effective reaction area is reduced, and the performance of the electrode is lowered.

【００１１】本発明は上記課題を解決するもので、水素
イオン伝導性高分子電解質が触媒粉末上に接合する際
に、水素イオン伝導性高分子電解質が大きな凝集体にな
らずに接合し、しかも多くの貴金属触媒を担持したカー
ボン粒子上に薄く均一に接合することで、反応ガスの拡
散性に有利に作用し、電極の特性を向上させるという有
利な効果を得る手段を提供することを目的とするもので
ある。The present invention is intended to solve the above problems, and when the hydrogen ion conductive polymer electrolyte is bonded onto the catalyst powder, the hydrogen ion conductive polymer electrolyte is bonded to the catalyst powder without forming large aggregates, and The purpose of the present invention is to provide a means for obtaining the advantageous effect of improving the characteristics of the electrode by acting thinly and uniformly on carbon particles carrying many noble metal catalysts, which has an advantageous effect on the diffusivity of the reaction gas. To do.

【００１２】[0012]

【課題を解決するための手段】以上の課題を解決するた
めに本発明の高分子電解質型燃料電池用触媒の製造方法
は、貴金属触媒を担持した導電性炭素粒子が気体中を流
動し、その中に前記水素イオン伝導性高分子電解質の溶
液あるいは分散液を噴霧することで、前記貴金属触媒を
担持した導電性炭素粒子の少なくとも一部に前記水素イ
オン伝導性高分子電解質を配する工程において、前記気
体中の導電性炭素の濃度が０．１ｋｇ／ｍ3〜９．０ｋ
ｇ／ｍ3であり、かつ前記噴霧の速度が、前記貴金属触
媒を担持した導電性炭素粒子に含まれる導電性炭素１ｇ
重量あたりの前記水素イオン伝導性高分子電解質重量で
１０００ｍｇ／ｈ以下の速度であることを特徴とする。In order to solve the above problems, a method for producing a catalyst for a polymer electrolyte fuel cell according to the present invention comprises a conductive carbon particle carrying a noble metal catalyst flowing in a gas, By spraying a solution or dispersion of the hydrogen ion conductive polymer electrolyte in, in the step of disposing the hydrogen ion conductive polymer electrolyte to at least a portion of the conductive carbon particles carrying the noble metal catalyst, The concentration of conductive carbon in the gas is 0.1 kg / m 3 to 9.0 k.
g / m 3 and the spraying speed is 1 g of conductive carbon contained in the conductive carbon particles carrying the noble metal catalyst.
The hydrogen ion conductive polymer electrolyte weight per weight is 1000 mg / h or less.

【００１３】また、前記水素イオン伝導性高分子電解質
の溶液中あるいは分散液中の前記水素イオン伝導性高分
子電解質の濃度が０．３重量％以上でかつ３０重量％以
下であると有効である。Further, it is effective that the concentration of the hydrogen ion conductive polymer electrolyte in the solution or dispersion of the hydrogen ion conductive polymer electrolyte is 0.3% by weight or more and 30% by weight or less. .

【００１４】また、前記貴金属触媒を担持した導電性炭
素粒子の少なくとも一部を被覆する水素イオン伝導性高
分子電解質の厚みの平均値が、０．１μｍ以下であると
有効である。Further, it is effective that the average value of the thickness of the hydrogen ion conductive polymer electrolyte coating at least a part of the conductive carbon particles carrying the noble metal catalyst is 0.1 μm or less.

【００１５】また、本発明の電解質膜／電極接合体は、
高分子電解質膜と、前記高分子電解質膜を挟む一対の触
媒層と、前記触媒層を挟む一対のガス拡散層とを有し、
前記触媒層が前述の高分子電解質型燃料電池用触媒を含
有することを特徴とする。Further, the electrolyte membrane / electrode assembly of the present invention comprises
A polymer electrolyte membrane, a pair of catalyst layers sandwiching the polymer electrolyte membrane, and a pair of gas diffusion layers sandwiching the catalyst layer,
The catalyst layer contains the above-mentioned catalyst for polymer electrolyte fuel cell.

【００１６】また、本発明の高分子電解質型燃料電池
は、前記電解質膜／電極接合体と、前記電解質膜／電極
接合体の両面に配置されたガス流露を有する導電性セパ
レータとを有する単セルを複数個積層してなることを特
徴とする。Further, the polymer electrolyte fuel cell of the present invention is a single cell having the electrolyte membrane / electrode assembly and conductive separators having gas flow on both sides of the electrolyte membrane / electrode assembly. It is characterized in that a plurality of are laminated.

【００１７】[0017]

【発明の実施の形態】以下、本発明の実施の形態につい
て図１を用いて説明する。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to FIG.

【００１８】図１は、水素イオン伝導性高分子電解質溶
液および分散液を、触媒粉末上に噴霧するとともに、乾
燥、粉砕、造粒工程を行う装置の一つの概念図である。FIG. 1 is a conceptual diagram of an apparatus for spraying a hydrogen ion conductive polymer electrolyte solution and a dispersion liquid onto a catalyst powder and performing a drying, pulverizing and granulating step.

【００１９】この装置においては、下部円柱状容器１に
貴金属触媒を担持したカーボン粉末を入れ、高圧スプレ
ー１１から、水素イオン伝導性高分子電解質溶液または
分散液を噴霧することができる。この時、高圧スプレー
入り口１１ａから高圧スプレー１１へ供給される水素イ
オン伝導性高分子電解質溶液および分散液の速度は変化
させることが可能であり、これにより貴金属触媒を担持
したカーボン粉末に含まれるカーボン１ｇ重量当りの水
素イオン伝導性高分子電解質の供給速度を変化させるこ
とが可能である。また、前記カーボン粉末は、ガス導入
口５から供給される一定温度の不活性ガスにより容器内
で乾燥させることができる。導入した不活性ガスは、ガ
ス流れ方向を示した矢印５ａ、５ｂにしたがって、流通
する。そして、下部円柱状容器部１の外周縁部にはスリ
ットと、造粒プレート６が設けてあり、導入した不活性
ガスは流動風量が外周に向かって大きくなるように開孔
した通気スリットを通過し、下部円柱状容器１の内部に
吹き上がる。この不活性ガスによる流動風により、下部
円柱状容器１に投入した触媒粉末を逆円錐上に広がった
流動部２で流動させることができる。In this apparatus, carbon powder carrying a noble metal catalyst can be placed in the lower cylindrical container 1 and the hydrogen ion conductive polymer electrolyte solution or dispersion can be sprayed from the high pressure spray 11. At this time, the speed of the hydrogen ion conductive polymer electrolyte solution and the dispersion liquid supplied from the high pressure spray inlet 11a to the high pressure spray 11 can be changed, whereby the carbon contained in the carbon powder carrying the noble metal catalyst can be changed. It is possible to change the supply rate of the hydrogen ion conductive polymer electrolyte per 1 g weight. Further, the carbon powder can be dried in the container with an inert gas at a constant temperature supplied from the gas inlet 5. The introduced inert gas flows according to the arrows 5a and 5b indicating the gas flow direction. A slit and a granulating plate 6 are provided on the outer peripheral edge of the lower cylindrical container portion 1, and the introduced inert gas passes through a ventilation slit that is opened so that the flow rate of air increases toward the outer periphery. Then, it blows up inside the lower cylindrical container 1. By the flowing air of this inert gas, the catalyst powder put into the lower cylindrical container 1 can be made to flow in the flowing portion 2 spread on the inverted cone.

【００２０】さらに、造粒プレート６の上部に撹拌羽根
７を設けてあり、これにより、沈降してきた触媒粉末
は、造粒プレート６と撹拌羽根７の間のギャップ８で造
粒することができる。また、撹拌羽根７は触媒粉末を撹
拌、流動させる役目と、粉砕する役目を果たすことがで
きる。パルスジェット９は、下部円柱状容器１の側面に
設けた圧縮ガス噴射ノズルである。高圧ガス流れ方向を
示す９ａに従って、撹拌羽根７の中心部に位置する円錐
状の衝突ターゲット１０に向かって、高圧ジェットを間
欠的に吹き込めるようにした。これにより、流動状態の
触媒粉末の凝集体をジェット粉砕により、粉砕すること
ができる。また、系内に導入された不活性ガスは、上部
円柱状容器部３に配置されたバグフィルター４によっ
て、触媒粉末をフィルトレーションし、不活性ガスのみ
をガス流れ方向を示す５ｃにしたがい系外に排出でき
る。系外に排出した不活性ガスは、外部に別途設けた熱
交換器により冷却して、水素イオン伝導性高分子電解質
の溶液に含まれる蒸発したアルコールのみを回収して、
再び不活性ガス導入口５から導入することで、不活性ガ
スはリサイクルすることができる。Further, a stirring blade 7 is provided on the upper part of the granulating plate 6, whereby the precipitated catalyst powder can be granulated in the gap 8 between the granulating plate 6 and the stirring blade 7. . Further, the stirring blade 7 can serve to stir and fluidize the catalyst powder and to crush it. The pulse jet 9 is a compressed gas injection nozzle provided on the side surface of the lower cylindrical container 1. The high-pressure jet was intermittently blown toward the conical collision target 10 located at the center of the stirring blade 7 according to 9a indicating the high-pressure gas flow direction. Thereby, the aggregate of the catalyst powder in a fluid state can be crushed by jet crushing. Further, the inert gas introduced into the system is filtered by the bag filter 4 arranged in the upper cylindrical container portion 3 to filter the catalyst powder, and only the inert gas is flowed according to the gas flow direction 5c. Can be discharged outside. The inert gas discharged to the outside of the system is cooled by a heat exchanger separately provided outside to collect only the evaporated alcohol contained in the solution of the hydrogen ion conductive polymer electrolyte,
By introducing the inert gas through the inert gas inlet 5 again, the inert gas can be recycled.

【００２１】上記図１の装置により、触媒粉末を流動さ
せ、撹拌、粉砕しながら、水素イオン伝導性高分子電解
質溶液または分散液を、噴霧速度を変化させ供給するこ
とができ、造粒も乾燥もさせることができる。With the apparatus shown in FIG. 1, the catalyst powder can be made to flow, stirred, and crushed, while the hydrogen ion conductive polymer electrolyte solution or dispersion can be supplied while changing the spraying rate, and the granulation is also dried. Can also be done.

【００２２】このような装置を用い、不活性ガス中を流
動する導電性炭素粒子の濃度が０．１ｋｇ／ｍ3〜９．
０ｋｇ／ｍ3であり、かつ貴金属触媒を担持したカーボ
ン粉末に含まれるカーボン１ｇ重量あたりの水素イオン
伝導性高分子電解質重量で、１０００ｍｇ／ｈ以下の速
度を上限として水素イオン伝導性高分子電解質溶液およ
び水素イオン伝導性高分子電解質の分散液を噴霧する
と、電極の性能を高くすることができる。１０００ｍｇ
／ｈよりも噴霧速度を速くすると多量の水素イオン伝導
性高分子電解質が一度に供給されることになる。その結
果、水素イオン伝導性高分子電解質は、スプレー近くに
流動している一部のカーボン粉末の一部分に集中的に噴
霧されることとなり、貴金属触媒を担持したカーボン粒
子の表面に厚くかつ不均一接合される。したがって、ガ
ス拡散性に不利に作用することとなる。Using such an apparatus, the concentration of conductive carbon particles flowing in an inert gas is 0.1 kg / m 3 to 9.
The hydrogen ion conductive polymer electrolyte solution is 0 kg / m 3 and the weight of the hydrogen ion conductive polymer electrolyte per 1 g weight of carbon contained in the carbon powder carrying the noble metal catalyst is 1000 mg / h or less as the upper limit. Spraying a dispersion liquid of hydrogen ion conductive polymer electrolyte and the performance of the electrode can be improved. 1000 mg
When the spraying speed is higher than / h, a large amount of hydrogen ion conductive polymer electrolyte is supplied at once. As a result, the hydrogen ion conductive polymer electrolyte is intensively sprayed on a part of a part of the carbon powder flowing near the spray, which is thick and non-uniform on the surface of the carbon particles carrying the noble metal catalyst. To be joined. Therefore, the gas diffusivity is adversely affected.

【００２３】また、水素イオン伝導性高分子電解質溶
液、および水素イオン伝導性高分子電解質の分散液の濃
度が、０．３重量％以上３０重量％以下にすることで電
極の性能を高くすることができる。３０重量％以上の濃
度で、触媒上に水素イオン伝導性高分子電解質を均等に
つけるため噴霧すると、溶液または分散液の噴霧速度を
遅くする必要がある。しかし、噴霧速度を遅くすれば乾
燥のために流れている一定温度の不活性ガスによりスプ
レー内が乾燥し、前記分散液中の溶媒が蒸発する結果、
スプレーが前記カーボン粒子により詰まる恐れがある。
水素イオン伝導性高分子電解質の濃度が３０％以下であ
れば、乾燥によりスプレー内がつまらず、水素イオン伝
導性高分子電解質を均等に触媒粉末上につけることがで
きる。一方、濃度が薄くなれば、実用上、反応時間の長
時間化を抑制するため、溶液および分散液の噴霧速度を
速くする必要がある。しかし、噴霧速度が速くなれば単
位時間あたりに供給される溶液量が増える結果、乾燥温
度が低下し触媒を担持したカーボン粒子が凝集しやすく
なる。このカーボン粒子が図２のイのように凝集すれ
ば、表面積が減少し、カーボン粉末上に剥き出しになっ
ている貴金属が減少する。このため、水素イオン伝導性
高分子電解質に接合されない貴金属が生じることとな
り、有効反応面積が減少する。その一方で、カーボン粉
末上に剥き出しになっている貴金属には、水素イオン伝
導性高分子電解質が厚く接合するため、反応ガス拡散性
が抑制されることになる。高分子水素イオン濃度が０．
３％以上であれば、カーボン粒子のの凝集が起こりにく
いため、水素イオン伝導性高分子電解質を触媒粉末上に
均等に接合させることができる。Further, the concentration of the hydrogen ion conductive polymer electrolyte solution and the dispersion liquid of the hydrogen ion conductive polymer electrolyte is set to 0.3% by weight or more and 30% by weight or less to improve the performance of the electrode. You can When the concentration of 30% by weight or more is used to evenly spray the hydrogen ion conductive polymer electrolyte onto the catalyst, it is necessary to slow down the spray rate of the solution or dispersion. However, if the spraying speed is slowed, the inside of the spray is dried by an inert gas flowing at a constant temperature for drying, and as a result, the solvent in the dispersion liquid is evaporated,
The carbon particles can clogging the spray.
If the concentration of the hydrogen ion conductive polymer electrolyte is 30% or less, the inside of the spray will not be blocked due to drying, and the hydrogen ion conductive polymer electrolyte can be evenly applied onto the catalyst powder. On the other hand, if the concentration becomes low, it is necessary to increase the spraying speed of the solution and the dispersion liquid in order to suppress the extension of the reaction time in practical use. However, if the spraying speed is increased, the amount of solution supplied per unit time is increased, and as a result, the drying temperature is lowered and the carbon particles supporting the catalyst are likely to aggregate. If the carbon particles agglomerate as shown in FIG. 2A, the surface area is reduced and the amount of noble metal exposed on the carbon powder is reduced. Therefore, a noble metal that is not bonded to the hydrogen ion conductive polymer electrolyte is generated, and the effective reaction area is reduced. On the other hand, since the hydrogen ion conductive polymer electrolyte is thickly bonded to the noble metal exposed on the carbon powder, the reaction gas diffusivity is suppressed. Polymer hydrogen ion concentration is 0.
If it is 3% or more, aggregation of carbon particles is unlikely to occur, so that the hydrogen ion conductive polymer electrolyte can be evenly bonded onto the catalyst powder.

【００２４】また、図１の装置で粉砕工程と造粒工程を
行うことで、図２のイ、ロのように触媒粉末を一定の粒
子径の範囲内で水素イオン伝導性高分子電解質と接合さ
せることができる。このため、触媒粉末上に水素イオン
伝導性高分子を薄く均等に被覆させることができる結
果、電極の性能を向上させることができる。Further, by carrying out the crushing step and the granulating step with the apparatus shown in FIG. 1, the catalyst powder is bonded to the hydrogen ion conductive polymer electrolyte within a certain particle diameter range as shown in a and b of FIG. Can be made. Therefore, the hydrogen ion conductive polymer can be thinly and evenly coated on the catalyst powder, so that the performance of the electrode can be improved.

【００２５】また、触媒粉末は触媒活性が高いために、
アルコールなどの有機溶媒に接すると発火する可能性が
ある。そこで、触媒粉末にアルコール溶液系の水素イオ
ン伝導性高分子電解質溶液および水素イオン伝導性伝導
性高分子電解質の分散液を混合する系においては、不活
性ガス雰囲気中で行うことで、発火の可能性を回避する
ことができる。なお、水素イオン伝導性高分子電解質の
溶液または分散媒の溶媒がアルコール系以外の発火の起
こりにくい溶媒（例えば水系溶媒）である場合には、酸
素を含む雰囲気中でも構わない。Further, since the catalyst powder has a high catalytic activity,
Contact with organic solvents such as alcohol may cause ignition. Therefore, in a system in which an alcohol solution-based hydrogen ion conductive polymer electrolyte solution and a dispersion of hydrogen ion conductive conductive polymer electrolyte are mixed with catalyst powder, it is possible to ignite by performing in an inert gas atmosphere. Sexuality can be avoided. When the solution of the hydrogen ion conductive polymer electrolyte or the solvent of the dispersion medium is a solvent other than alcohols that does not easily ignite (for example, an aqueous solvent), it may be in an atmosphere containing oxygen.

【００２６】また、カーボン粉末上に接合した水素イオ
ン伝導性高分子電解質の厚みが０．１μｍ以下であると
反応ガスの拡散性が損なわれないために電極の性能を高
くすることができる。また、金属担持カーボン粉末の一
次粒子径よりも薄く均等に接合させることは困難であ
り、接合されていない部分が生じるため、水素イオン伝
導性が低下する。このため、薄く均等に接合できる一次
粒子径（ケッチェンブラックＥＣの場合は０．０３μ
ｍ）よりも厚みをもたせることで、電極の性能を高くす
ることができる。If the thickness of the hydrogen ion conductive polymer electrolyte bonded onto the carbon powder is 0.1 μm or less, the diffusibility of the reaction gas is not impaired, and the performance of the electrode can be improved. Further, it is difficult to make the metal-supporting carbon powder thinner than the primary particle diameter and to bond them uniformly, and since there are unbonded portions, the hydrogen ion conductivity is lowered. For this reason, the primary particle diameter that allows thin and uniform bonding (0.03μ for Ketjenblack EC)
The performance of the electrode can be improved by having a thickness larger than that of m).

【００２７】[0027]

【実施例】次に本発明の具体例を説明する。EXAMPLES Next, specific examples of the present invention will be described.

【００２８】（実施例１）本実施例では、まず、図１に
示す装置を用い造粒プレートと撹拌羽根との間のギャッ
プを調節した後、触媒粉末上の少なくとも一部に水素イ
オン伝導性高分子電解質を不活性ガス中で噴霧、乾燥す
ることで接合させるとともに、造粒工程と粉砕工程も同
時に行い、触媒粉末上に水素イオン伝導性高分子電解質
を被覆させた。そして、その後この触媒を用いて電解質
膜／電極接合体を作製した。Example 1 In this example, first, the gap between the granulation plate and the stirring blade was adjusted using the apparatus shown in FIG. The polymer electrolyte was sprayed and dried in an inert gas to bond the polymer electrolyte, and the granulation step and the pulverization step were simultaneously performed to coat the catalyst powder with the hydrogen ion conductive polymer electrolyte. Then, after that, an electrolyte membrane / electrode assembly was produced using this catalyst.

【００２９】３０ｎｍの平均一次粒子径を持つ導電性カ
ーボン粒子であるケッチェンブラックEC（オランダ国、
ＡＫＺＯ Ｃｈｅｍｉｅ社）に、平均粒子径約３０Åの
白金粒子を５０重量％担持したものを、空気極側の貴金
属担持触媒粒子とした。またケッチェンブラックECに平
均粒子径約３０Åの白金粒子とルテニウム粒子をそれぞ
れ２５重量％担持したものを燃料極側の触媒粉末とし
た。Ketjen Black EC (Netherlands, which is a conductive carbon particle having an average primary particle diameter of 30 nm)
AKZO Chemie) carrying 50% by weight of platinum particles having an average particle size of about 30Å was used as noble metal-supported catalyst particles on the air electrode side. Also, a catalyst powder on the fuel electrode side was prepared by supporting 25% by weight of platinum particles and ruthenium particles each having an average particle diameter of about 30Å on Ketjen Black EC.

【００３０】まず、０．３重量％の水素イオン伝導性高
分子電解質を溶解したアルコール溶液を用いて、高圧ス
プレー１１から貴金属触媒を担持したカーボン粉末に含
まれるカーボン１ｇ重量あたりの水素イオン伝導性高分
子電解質重量が１０００ｍｇ／ｈの速さになるように触
媒粉末上へ水素イオン伝導性高分子電解質の噴霧を行っ
た。First, using an alcohol solution in which 0.3% by weight of a hydrogen ion conductive polymer electrolyte is dissolved, hydrogen ion conductivity per 1 g weight of carbon contained in the carbon powder carrying the noble metal catalyst from the high pressure spray 11 is obtained. The hydrogen ion conductive polymer electrolyte was sprayed onto the catalyst powder so that the weight of the polymer electrolyte was 1000 mg / h.

【００３１】このようにして得られた触媒は、表面に水
素イオン伝導性高分子電解質を均一に配置していた。そ
して、触媒を担持したカーボン粒子上の水素イオン伝導
性高分子電解質の厚みは０．１μｍであった。In the catalyst thus obtained, the hydrogen ion conductive polymer electrolyte was uniformly arranged on the surface. The thickness of the hydrogen ion conductive polymer electrolyte on the carbon particles supporting the catalyst was 0.1 μm.

【００３２】この触媒を、蒸留水と混合し、電極触媒層
用のペースト状のインクを調製した。つぎに、外寸が２
０ｃｍ×３２ｃｍの水素イオン伝導性高分子電解質膜
（デュポン社製ナフィオン１１２）の裏表両面に、電極
触媒層用ペーストをスクリーン印刷法により塗布し、１
５０℃のホットローラーを通過させることで、電極触媒
層を高分子電解質膜に定着させた。形成後の反応電極中
に含まれる白金量は、０．２ｍｇ／ｃｍ2となるよう調
製した。This catalyst was mixed with distilled water to prepare a paste ink for the electrode catalyst layer. Next, the outer size is 2
A 0 cm × 32 cm hydrogen ion conductive polymer electrolyte membrane (Nafion 112 manufactured by DuPont) was coated with a paste for an electrode catalyst layer by a screen printing method, and 1
The electrode catalyst layer was fixed to the polymer electrolyte membrane by passing through a hot roller at 50 ° C. The amount of platinum contained in the reaction electrode after formation was adjusted to 0.2 mg / cm 2 .

【００３３】一方、電極の拡散層となるカーボンペーパ
ーを撥水処理した。外寸１６ｃｍ×２０ｃｍ、厚み３６
０μｍの導電性カーボン粒子のカーボン不織布（東レ
製、ＴＧＰ―Ｈ―１２０）を、フッ素樹脂含有の水性デ
ィスパージョン（ダイキン工業製、ネオフロンＮＤ１）
に含浸した後、これを乾燥し、４００℃で３０分加熱す
ることで、撥水性を与えた。さらに、このカーボン不織
布の一方の面に、導電性カーボン粉末とポリフルオロテ
トラエチレン粉末を分散させた水溶液とを混合したイン
クを、スクリーン印刷法を用いて塗布することで撥水層
を形成した。このとき、撥水層の一部を、カーボン不織
布の中に埋め込んだ。On the other hand, the carbon paper to be the diffusion layer of the electrode was subjected to water repellent treatment. External size 16 cm x 20 cm, thickness 36
A carbon nonwoven fabric of 0 μm conductive carbon particles (TGP-H-120 manufactured by Toray) is used as an aqueous dispersion containing a fluororesin (Daikin Industries, Neoflon ND1).
After being impregnated in the solution, it was dried and heated at 400 ° C. for 30 minutes to give water repellency. Further, an ink prepared by mixing conductive carbon powder and an aqueous solution in which polyfluorotetraethylene powder was dispersed was applied to one surface of this carbon nonwoven fabric by a screen printing method to form a water repellent layer. At this time, a part of the water repellent layer was embedded in the carbon nonwoven fabric.

【００３４】つぎに、空気極側の触媒層と燃料極側の触
媒層とを水素イオン伝導性高分子電解質膜の裏表に形成
したのち、前述のカーボンペーパーを撥水層の塗布した
面が触媒層の側に接するようにホットプレスで接合し、
これを電解質膜／電極接合体とした。さらに、同時に、
作製した電解質膜／電極接合体の水素イオン伝導性高分
子電解質膜の外周部にゴム製のガスケット板を接合し、
冷却水と燃料ガス及び酸化剤ガス流通用のマニホールド
穴を形成した。Next, after forming the catalyst layer on the air electrode side and the catalyst layer on the fuel electrode side on both sides of the hydrogen ion conductive polymer electrolyte membrane, the surface coated with the above-mentioned carbon paper as the water repellent layer is the catalyst. Join with a hot press so that it touches the side of the layer,
This was used as an electrolyte membrane / electrode assembly. Furthermore, at the same time,
A rubber gasket plate is joined to the outer periphery of the hydrogen ion conductive polymer electrolyte membrane of the produced electrolyte membrane / electrode assembly,
Manifold holes for forming cooling water, fuel gas and oxidant gas were formed.

【００３５】つぎに、外寸が２０ｃｍ×３２ｃｍ、厚み
が１．３ｍｍ、ガス流路および冷却水流路の深さが０．
５ｍｍの樹脂含浸黒鉛板から構成したセパレータを準備
し、セパレータ２枚を用い、電解質膜／電極接合体シー
トの一方の面に酸化剤ガス流路が形成されたセパレータ
を、裏面に燃料ガス流路が形成されたセパレータを重ね
合わせ、これを単電池とした。この単電池を２セル積層
した後、冷却水路溝を形成したセパレータでこの２セル
積層電池を挟み込み、このパターンを繰り返して１００
セル積層の電池スタックを作製した。このとき、電池ス
タックの両端部には、ステンレス製の集電板と電気絶縁
材料の絶縁板、さらに端板と締結ロッドで固定した。こ
のときの締結圧はセパレータの面積あたり１５ｋｇｆ／
ｃｍ2とした。Next, the outer dimensions are 20 cm × 32 cm, the thickness is 1.3 mm, and the depths of the gas passage and the cooling water passage are 0.
A separator composed of a 5 mm resin-impregnated graphite plate was prepared, and two separators were used. A separator having an oxidant gas flow channel formed on one surface of an electrolyte membrane / electrode assembly sheet and a fuel gas flow channel on the back surface. The separators formed with were stacked to form a single cell. After stacking two cells of this unit cell, the two-cell stack battery is sandwiched between separators having cooling water channel grooves, and this pattern is repeated 100 times.
A cell stack battery stack was prepared. At this time, at both ends of the battery stack, a stainless steel collector plate and an insulating plate made of an electrically insulating material, and further an end plate and a fastening rod were fixed. The fastening pressure at this time is 15 kgf / per separator area.
It was set to cm 2 .

【００３６】このように作製した本実施例の高分子電解
質型燃料電池を、８０℃に保持し、燃料極側に７５℃の
露点となるよう加湿・加温した水素ガスを空気極側に６
０℃の露点となるように加湿・加温した空気を供給し
た。その結果、電流を外部に出力しない無負荷時には、
９８Ｖの電池開放電圧を得た。The polymer electrolyte fuel cell of this example produced in this way was kept at 80 ° C., and hydrogen gas humidified and heated so that the dew point of 75 ° C. was applied to the fuel electrode side.
Air that was humidified and heated so that the dew point was 0 ° C was supplied. As a result, when there is no load that does not output the current to the outside,
A battery open circuit voltage of 98V was obtained.

【００３７】また、この電池を燃料利用率８５％、酸素
利用率６０％、電流密度０．７Ａ／ｃｍ2の条件で連続
発電試験を行い、出力特性の時間変化を測定した。その
結果、本実施例の電池は、８０００時間以上にわたって
約１４．６ｋＷ（６５Ｖ−２２４Ａ）の電池出力を維持
することを確認した。Further, this battery was subjected to a continuous power generation test under the conditions of a fuel utilization rate of 85%, an oxygen utilization rate of 60% and a current density of 0.7 A / cm 2 , and the time change of the output characteristics was measured. As a result, it was confirmed that the battery of this example maintained a battery output of about 14.6 kW (65V-224A) over 8000 hours or more.

【００３８】なお、本実施例では触媒を、蒸留水と混合
し、電極触媒層用のペースト状のインクを調製したが、
この触媒を、発火防止のために、まず少量の蒸留水と混
合し、その後、インク溶媒であるブタノールと混合し、
塗工用インクを調製しても、燃料電池として優れた特性
を得た。さらに、塗工用インクにするために、イソプロ
パノールやヘキサン、ヘプタンを用いても、同様の高性
能が得られることを確認した。In this example, the catalyst was mixed with distilled water to prepare a paste ink for the electrode catalyst layer.
To prevent ignition, this catalyst was first mixed with a small amount of distilled water, and then with the ink solvent butanol,
Even when the coating ink was prepared, excellent properties as a fuel cell were obtained. Furthermore, it was confirmed that the same high performance was obtained even when isopropanol, hexane, or heptane was used to form the coating ink.

【００３９】（実施例２）本実施例では、０．３重量％
の水素イオン伝導性高分子電解質を溶解したアルコール
溶液を用いて、実施例１に基づき触媒粉末に水素イオン
伝導性高分子電解質を触媒１ｇ重量あたり水素イオン伝
導性高分子電解質が１００ｍｇ／ｈの速さになるように
噴霧して触媒を調製した。Example 2 In this example, 0.3% by weight
Using an alcohol solution in which the hydrogen ion conductive polymer electrolyte of Example 1 was dissolved, the hydrogen ion conductive polymer electrolyte was added to the catalyst powder based on Example 1 at a rate of 100 mg / h of hydrogen ion conductive polymer electrolyte per 1 g of the catalyst. To prepare a catalyst.

【００４０】このようにして得られた触媒は、表面に水
素イオン伝導性高分子電解質を均一に配置していた。そ
して、触媒を担持したカーボン粒子上の水素イオン伝導
性高分子電解質の厚みは０．０４μｍであった。In the catalyst thus obtained, the hydrogen ion conductive polymer electrolyte was uniformly arranged on the surface. The thickness of the hydrogen ion conductive polymer electrolyte on the carbon particles supporting the catalyst was 0.04 μm.

【００４１】実施例１に基づきこの触媒から高分子電解
質型燃料電池を作製した。Based on Example 1, a polymer electrolyte fuel cell was produced from this catalyst.

【００４２】この後、実施例１と同様の評価を行ったと
ころ、電流を外部に出力しない無負荷時には、９８Ｖの
電池開放電圧を得た。After that, the same evaluation as in Example 1 was carried out. As a result, a battery open circuit voltage of 98 V was obtained when there was no load and no current was output to the outside.

【００４３】また、この電池を燃料利用率８５％、酸素
利用率６０％、電流密度０．７Ａ／ｃｍ2の条件で連続
発電試験を行い、出力特性の時間変化を測定した。その
結果、本実施例の電池は、８０００時間以上にわたって
約１４．６ｋＷ（６５Ｖ−２２４Ａ）の電池出力を維持
することを確認した。Further, this battery was subjected to a continuous power generation test under the conditions of a fuel utilization rate of 85%, an oxygen utilization rate of 60% and a current density of 0.7 A / cm 2 , and the time change of the output characteristics was measured. As a result, it was confirmed that the battery of this example maintained a battery output of about 14.6 kW (65V-224A) over 8000 hours or more.

【００４４】（実施例３）本実施例では、実施例１に基
づき高分子電解質型燃料電池を作製した。実施例１との
相違点は、３０重量％の水素イオン伝導性高分子電解質
を溶解したアルコール溶液を用いたことである。このよ
うにして、実施例１と同様に高分子電解質型燃料電池を
作製した。また、実施例１と同様の評価を行ったとこ
ろ、電流を外部に出力しない無負荷時には、９８Ｖの電
池開放電圧を得た。(Example 3) In this example, a polymer electrolyte fuel cell was prepared based on Example 1. The difference from Example 1 is that an alcohol solution in which 30% by weight of a hydrogen ion conductive polymer electrolyte was dissolved was used. In this way, a polymer electrolyte fuel cell was produced in the same manner as in Example 1. When the same evaluation as in Example 1 was performed, a battery open circuit voltage of 98 V was obtained when there was no load and no current was output to the outside.

【００４５】また、この電池を燃料利用率８５％、酸素
利用率６０％、電流密度０．７Ａ／ｃｍ2の条件で連続
発電試験を行い、出力特性の時間変化を測定した。その
結果、本実施例の電池は、８０００時間以上にわたって
約１４．８ｋＷ（６６Ｖ−２２４Ａ）の電池出力を維持
することを確認した。Further, this battery was subjected to a continuous power generation test under the conditions of a fuel utilization rate of 85%, an oxygen utilization rate of 60% and a current density of 0.7 A / cm 2 , and the time change of the output characteristics was measured. As a result, it was confirmed that the battery of this example maintained a battery output of about 14.8 kW (66V-224A) over 8000 hours or more.

【００４６】（実施例４）本実施例では、実施例２に基
づき高分子電解質型燃料電池を作製した。実施例２との
相違点は、３０重量％の水素イオン伝導性高分子電解質
を溶解したアルコール溶液を用いたことである。このよ
うにして、実施例２と同様に高分子電解質型燃料電池を
作製した。また、実施例１と同様の評価を行ったとこ
ろ、電流を外部に出力しない無負荷時には、９８Ｖの電
池開放電圧を得た。Example 4 In this example, a polymer electrolyte fuel cell was prepared based on Example 2. The difference from Example 2 is that an alcohol solution containing 30% by weight of a hydrogen ion conductive polymer electrolyte was used. In this way, a polymer electrolyte fuel cell was produced in the same manner as in Example 2. When the same evaluation as in Example 1 was performed, a battery open circuit voltage of 98 V was obtained when there was no load and no current was output to the outside.

【００４７】また、この電池を燃料利用率８５％、酸素
利用率６０％、電流密度０．７Ａ／ｃｍ2の条件で連続
発電試験を行い、出力特性の時間変化を測定した。その
結果、本実施例の電池は、８０００時間以上にわたって
約１４．８ｋＷ（６６Ｖ−２２４Ａ）の電池出力を維持
することを確認した。Further, this cell was subjected to a continuous power generation test under the conditions of a fuel utilization rate of 85%, an oxygen utilization rate of 60%, and a current density of 0.7 A / cm 2 , and the time change of the output characteristics was measured. As a result, it was confirmed that the battery of this example maintained a battery output of about 14.8 kW (66V-224A) over 8000 hours or more.

【００４８】（実施例５）本実施例では、まず、図１に
示す装置で触媒を担持したカーボン粒子上に水素イオン
伝導性高分子電解質を不活性ガス中で噴霧、乾燥するこ
とで接合し、その後この触媒を用いて電解質膜／電極接
合体を作製した。この時、造粒プレートと撹拌羽根との
間のギャップをなくし造粒工程をなくすとともに、ジェ
ット粉砕による粉砕工程も行わずに装置を運転した。Example 5 In this example, first, hydrogen ion conductive polymer electrolyte was sprayed in an inert gas on carbon particles supporting a catalyst in the apparatus shown in FIG. Then, an electrolyte membrane / electrode assembly was produced using this catalyst. At this time, the gap between the granulating plate and the stirring blade was eliminated to eliminate the granulating step, and the apparatus was operated without performing the crushing step by jet crushing.

【００４９】水素イオン伝導性高分子電解質を溶解した
アルコール溶液には、０．３重量％のものを用いて、実
施例１に基づき触媒粉末に水素イオン伝導性高分子電解
質を触媒１ｇ重量あたり水素イオン伝導性高分子電解質
が１０００ｍｇ／ｈの速さになるように噴霧して触媒を
調製した。The alcohol solution in which the hydrogen ion conductive polymer electrolyte was dissolved was 0.3% by weight, and the hydrogen ion conductive polymer electrolyte was added to the catalyst powder in accordance with Example 1 with hydrogen per 1 g weight of the catalyst. A catalyst was prepared by spraying the ion conductive polymer electrolyte at a rate of 1000 mg / h.

【００５０】このようにして得られた触媒は、表面に水
素イオン伝導性高分子電解質を均一に配置していた。そ
して、触媒を担持したカーボン粒子上の水素イオン伝導
性高分子電解質の厚みは０．１μｍであった。In the catalyst thus obtained, the hydrogen ion conductive polymer electrolyte was uniformly arranged on the surface. The thickness of the hydrogen ion conductive polymer electrolyte on the carbon particles supporting the catalyst was 0.1 μm.

【００５１】この触媒を実施例１に基づき単電池から高
分子電解質型燃料電池を作製した。この後、実施例１と
同様の評価を行ったところ、電流を外部に出力しない無
負荷時には、９８Ｖの電池開放電圧を得た。Based on Example 1 of this catalyst, a polymer electrolyte fuel cell was produced from a single cell. After that, when the same evaluation as in Example 1 was performed, a battery open circuit voltage of 98 V was obtained when there was no load and no current was output to the outside.

【００５２】この電池を燃料利用率８５％、酸素利用率
６０％、電流密度０．７Ａ／ｃｍ2の条件で連続発電試
験を行い、出力特性の時間変化を測定した。その結果、
本実施例の電池は、８０００時間以上にわたって約１
４．３ｋＷ（６４Ｖ−２２４Ａ）の電池出力を維持する
ことを確認した。This battery was subjected to a continuous power generation test under the conditions of a fuel utilization rate of 85%, an oxygen utilization rate of 60%, and a current density of 0.7 A / cm 2 , and the time change of the output characteristics was measured. as a result,
The battery of this example has about 1 hour over 8000 hours.
It was confirmed that the battery output of 4.3 kW (64V-224A) was maintained.

【００５３】（実施例６）本実施例では、０．３重量％
の水素イオン伝導性高分子電解質を溶解したアルコール
溶液を用いて、実施例５に基づき触媒粉末に水素イオン
伝導性高分子電解質を貴金属触媒を担持したカーボン粒
子１ｇ重量あたり水素イオン伝導性高分子電解質が１０
０ｍｇ／ｈの速さになるように噴霧して触媒を調製し
た。Example 6 In this example, 0.3% by weight
Using an alcohol solution in which the hydrogen ion conductive polymer electrolyte of Example 1 was dissolved, the hydrogen ion conductive polymer electrolyte was added to the catalyst powder based on Example 5 based on 1 g of carbon particles carrying the noble metal catalyst. Is 10
The catalyst was prepared by spraying at a rate of 0 mg / h.

【００５４】このようにして得られたカーボン粒子は、
表面に水素イオン伝導性高分子電解質を均一に配置して
いた。そして、触媒近傍の水素イオン伝導性高分子電解
質の厚みは０．０４μｍであった。The carbon particles thus obtained are
The hydrogen ion conductive polymer electrolyte was uniformly arranged on the surface. The thickness of the hydrogen ion conductive polymer electrolyte near the catalyst was 0.04 μm.

【００５５】実施例１に基づきこの触媒から高分子電解
質型燃料電池を作製した。Based on Example 1, a polymer electrolyte fuel cell was produced from this catalyst.

【００５６】この後、実施例１と同様の評価を行ったと
ころ、電流を外部に出力しない無負荷時には、９８Ｖの
電池開放電圧を得た。After that, when the same evaluation as in Example 1 was performed, a battery open circuit voltage of 98 V was obtained when no load was applied and no current was output to the outside.

【００５７】また、この電池を燃料利用率８５％、酸素
利用率６０％、電流密度０．７Ａ／ｃｍ2の条件で連続
発電試験を行い、出力特性の時間変化を測定した。その
結果、本実施例の電池は、８０００時間以上にわたって
約１４．３ｋＷ（６４Ｖ−２２４Ａ）の電池出力を維持
することを確認した。Further, this battery was subjected to a continuous power generation test under the conditions of a fuel utilization rate of 85%, an oxygen utilization rate of 60%, and a current density of 0.7 A / cm 2 , and the time change of output characteristics was measured. As a result, it was confirmed that the battery of this example maintained a battery output of about 14.3 kW (64V-224A) over 8000 hours or more.

【００５８】（実施例７）本実施例では、実施例５に基
づき高分子電解質型燃料電池を作製した。実施例５との
相違点は、３０重量％の水素イオン伝導性高分子電解質
を溶解したアルコール溶液を用いたことである。このよ
うにして、実施例５と同様に高分子電解質型燃料電池を
作製した。また、実施例１と同様の評価を行ったとこ
ろ、電流を外部に出力しない無負荷時には、９８Ｖの電
池開放電圧を得た。(Example 7) In this example, a polymer electrolyte fuel cell was prepared based on Example 5. The difference from Example 5 is that an alcohol solution in which 30% by weight of a hydrogen ion conductive polymer electrolyte was dissolved was used. In this way, a polymer electrolyte fuel cell was produced in the same manner as in Example 5. When the same evaluation as in Example 1 was performed, a battery open circuit voltage of 98 V was obtained when there was no load and no current was output to the outside.

【００５９】また、この電池を燃料利用率８５％、酸素
利用率６０％、電流密度０．７Ａ／ｃｍ2の条件で連続
発電試験を行い、出力特性の時間変化を測定した。その
結果、本実施例の電池は、８０００時間以上にわたって
約１４．６ｋＷ（６５Ｖ−２２４Ａ）の電池出力を維持
することを確認した。Further, this battery was subjected to a continuous power generation test under the conditions of a fuel utilization rate of 85%, an oxygen utilization rate of 60%, and a current density of 0.7 A / cm 2 , and the time change of output characteristics was measured. As a result, it was confirmed that the battery of this example maintained a battery output of about 14.6 kW (65V-224A) over 8000 hours or more.

【００６０】（実施例８）本実施例では、実施例６に基
づき高分子電解質型燃料電池を作製した。実施例６との
相違点は、３０重量％の水素イオン伝導性高分子電解質
を溶解したアルコール溶液を用いたことである。このよ
うにして、実施例６と同様に高分子電解質型燃料電池を
作製した。また、実施例１と同様の評価を行ったとこ
ろ、電流を外部に出力しない無負荷時には、９８Ｖの電
池開放電圧を得た。Example 8 In this example, a polymer electrolyte fuel cell was prepared based on Example 6. The difference from Example 6 is that an alcohol solution in which 30% by weight of a hydrogen ion conductive polymer electrolyte was dissolved was used. In this way, a polymer electrolyte fuel cell was produced in the same manner as in Example 6. When the same evaluation as in Example 1 was performed, a battery open circuit voltage of 98 V was obtained when there was no load and no current was output to the outside.

【００６１】また、この電池を燃料利用率８５％、酸素
利用率６０％、電流密度０．７Ａ／ｃｍ2の条件で連続
発電試験を行い、出力特性の時間変化を測定した。その
結果、本実施例の電池は、８０００時間以上にわたって
約１４．６ｋＷ（６５Ｖ−２２４Ａ）の電池出力を維持
することを確認した。Further, this battery was subjected to a continuous power generation test under the conditions of a fuel utilization rate of 85%, an oxygen utilization rate of 60%, and a current density of 0.7 A / cm 2 , and the time change of output characteristics was measured. As a result, it was confirmed that the battery of this example maintained a battery output of about 14.6 kW (65V-224A) over 8000 hours or more.

【００６２】（比較例１）本比較例では、まず、図１に
示す装置を用い造粒プレートと撹拌羽根との間のギャッ
プを調節した後、触媒粉末上に水素イオン伝導性高分子
電解質を不活性ガス中で噴霧、乾燥することで接合する
とともに、造粒工程と粉砕工程も同時に行い、触媒上に
水素イオン伝導性高分子電解質を接合させた。そして、
この触媒を用いて電極電解質膜接合体を作製した。Comparative Example 1 In this comparative example, first, the gap between the granulating plate and the stirring blade was adjusted using the apparatus shown in FIG. 1, and then the hydrogen ion conductive polymer electrolyte was placed on the catalyst powder. In addition to joining by spraying and drying in an inert gas, the granulation step and the crushing step were also performed at the same time to join the hydrogen ion conductive polymer electrolyte onto the catalyst. And
An electrode / electrolyte membrane assembly was prepared using this catalyst.

【００６３】水素イオン伝導性高分子電解質を溶解した
アルコール溶液には、０．３重量％のものを用いて、実
施例１に基づき触媒粉末に水素イオン伝導性高分子電解
質を触媒１ｇ重量あたり水素イオン伝導性高分子電解質
が１２００ｍｇ／ｈの速さになるように噴霧して触媒を
調製した。An alcohol solution in which the hydrogen ion conductive polymer electrolyte was dissolved was 0.3% by weight, and the hydrogen ion conductive polymer electrolyte was added to the catalyst powder based on Example 1 with hydrogen per 1 g weight of the catalyst. The catalyst was prepared by spraying the ion conductive polymer electrolyte at a rate of 1200 mg / h.

【００６４】このようにして得られた触媒近傍の水素イ
オン伝導性高分子電解質の大きさは０．１２μｍであっ
た。実施例１に基づきこの触媒から高分子電解質型燃料
電池を作製した。The size of the hydrogen ion conductive polymer electrolyte near the catalyst thus obtained was 0.12 μm. Based on Example 1, a polymer electrolyte fuel cell was produced from this catalyst.

【００６５】この後、実施例１と同様の評価を行ったと
ころ、電流を外部に出力しない無負荷時には、９８Ｖの
電池開放電圧を得た。After that, the same evaluation as in Example 1 was carried out. As a result, a battery open circuit voltage of 98 V was obtained when there was no load and no current was output to the outside.

【００６６】この電池を燃料利用率８５％、酸素利用率
６０％、電流密度０．７Ａ／ｃｍ2の条件で連続発電試
験を行い、出力特性の時間変化を測定した。その結果、
本実施例の電池は、８０００時間以上にわたって約１
３．４ｋＷ（６０Ｖ−２２４Ａ）の電池出力を維持する
ことを確認した。This battery was subjected to a continuous power generation test under the conditions of a fuel utilization rate of 85%, an oxygen utilization rate of 60%, and a current density of 0.7 A / cm 2 , and the time change of output characteristics was measured. as a result,
The battery of this example has about 1 hour over 8000 hours.
It was confirmed that the battery output of 3.4 kW (60V-224A) was maintained.

【００６７】（比較例２）本比較例では、まず、図１に
示す装置を用い造粒プレートと撹拌羽根との間のギャッ
プを調節した後、触媒粉末上に水素イオン伝導性高分子
電解質を不活性ガス中で噴霧、乾燥することで接合する
とともに、造粒工程と粉砕工程も同時に行い、触媒上に
水素イオン伝導性高分子電解質を接合させた。そして、
この触媒を用いて電極電解質膜接合体を作製した。Comparative Example 2 In this comparative example, first, the gap between the granulation plate and the stirring blade was adjusted using the apparatus shown in FIG. 1, and then the hydrogen ion conductive polymer electrolyte was placed on the catalyst powder. In addition to joining by spraying and drying in an inert gas, the granulation step and the crushing step were also performed at the same time to join the hydrogen ion conductive polymer electrolyte onto the catalyst. And
An electrode / electrolyte membrane assembly was prepared using this catalyst.

【００６８】水素イオン伝導性高分子電解質を溶解した
アルコール溶液には、０．１重量％のものを用いて、実
施例１に基づき触媒粉末に水素イオン伝導性高分子電解
質を貴金属触媒を担持したカーボン粒子中のカーボン１
ｇ重量あたり水素イオン伝導性高分子電解質が１０００
ｍｇ／ｈの速さになるように噴霧して触媒を調製した。An alcohol solution in which the hydrogen ion conductive polymer electrolyte was dissolved was 0.1% by weight, and the catalyst powder was loaded with the hydrogen ion conductive polymer electrolyte and the noble metal catalyst according to Example 1. Carbon 1 in carbon particles
1000 g hydrogen ion conductive polymer electrolyte per g weight
The catalyst was prepared by spraying at a rate of mg / h.

【００６９】このようにして得られた触媒近傍の水素イ
オン伝導性高分子電解質の大きさは０．１μｍであっ
た。この触媒を実施例１に基づき単電池から高分子電解
質型燃料電池を作製した。The size of the hydrogen ion conductive polymer electrolyte in the vicinity of the catalyst thus obtained was 0.1 μm. Based on this catalyst, a polymer electrolyte fuel cell was produced from a single cell based on Example 1.

【００７０】この後、実施例１と同様の評価を行ったと
ころ、電流を外部に出力しない無負荷時には、９８Ｖの
電池開放電圧を得た。After that, when the same evaluation as in Example 1 was performed, a battery open circuit voltage of 98 V was obtained when no load was applied and no current was output to the outside.

【００７１】この電池を燃料利用率８５％、酸素利用率
６０％、電流密度０．７Ａ／ｃｍ2の条件で連続発電試
験を行い、出力特性の時間変化を測定した。その結果、
本実施例の電池は、８０００時間以上にわたって約１
３．２ｋＷ（５９Ｖ−２２４Ａ）の電池出力を維持する
ことを確認した。This battery was subjected to a continuous power generation test under the conditions of a fuel utilization rate of 85%, an oxygen utilization rate of 60%, and a current density of 0.7 A / cm 2 , and the time change of the output characteristics was measured. as a result,
The battery of this example has about 1 hour over 8000 hours.
It was confirmed that the battery output of 3.2 kW (59V-224A) was maintained.

【００７２】（比較例３）本比較例では、０．３重量％
の水素イオン伝導性高分子電解質を溶解したアルコール
溶液を用いて、実施例１に基づき触媒粉末に水素イオン
伝導性高分子電解質を貴金属触媒を担持したカーボン粒
子中のカーボン１ｇ重量あたり水素イオン伝導性高分子
電解質が１２００ｍｇ／ｈの速さになるように噴霧して
触媒を調製した。この時、造粒プレートと撹拌羽根との
間のギャップはなくすとともに、ジェット粉砕による粉
砕工程も行わずに装置を運転した。(Comparative Example 3) In this comparative example, 0.3% by weight
Using an alcohol solution in which the hydrogen ion conductive polymer electrolyte of Example 1 was dissolved, hydrogen ion conductivity per 1 g weight of carbon in the carbon particles in which the catalyst powder was loaded with the hydrogen ion conductive polymer electrolyte on the basis of Example 1 was used. The catalyst was prepared by spraying the polymer electrolyte at a rate of 1200 mg / h. At this time, the gap between the granulation plate and the stirring blade was eliminated, and the apparatus was operated without the crushing step by jet crushing.

【００７３】このようにして得られた触媒は、表面に水
素イオン伝導性高分子電解質を均一に配置していた。そ
して、水素イオン伝導性高分子電解質の大きさは０．１
２μｍであった。In the catalyst thus obtained, the hydrogen ion conductive polymer electrolyte was uniformly arranged on the surface. The size of the hydrogen ion conductive polymer electrolyte is 0.1.
It was 2 μm.

【００７４】実施例１に基づきこの触媒から高分子電解
質型燃料電池を作製した。Based on Example 1, a polymer electrolyte fuel cell was produced from this catalyst.

【００７５】この後、実施例１と同様の評価を行ったと
ころ、電流を外部に出力しない無負荷時には、９８Ｖの
電池開放電圧を得た。After that, when the same evaluation as in Example 1 was performed, a battery open-circuit voltage of 98 V was obtained when no load was applied and no current was output to the outside.

【００７６】この電池を燃料利用率８５％、酸素利用率
６０％、電流密度０．７Ａ／ｃｍ2の条件で連続発電試
験を行い、出力特性の時間変化を測定した。その結果、
本実施例の電池は、８０００時間以上にわたって約１
３．２ｋＷ（５９Ｖ−２２４Ａ）の電池出力を維持する
ことを確認した。This battery was subjected to a continuous power generation test under the conditions of a fuel utilization rate of 85%, an oxygen utilization rate of 60%, and a current density of 0.7 A / cm 2 , and the time change of output characteristics was measured. as a result,
The battery of this example has about 1 hour over 8000 hours.
It was confirmed that the battery output of 3.2 kW (59V-224A) was maintained.

【００７７】（比較例４）本比較例では、０．１重量％
の水素イオン伝導性高分子電解質を溶解したアルコール
溶液を用いて、実施例１に基づき触媒粉末に水素イオン
伝導性高分子電解質を触媒１ｇ重量あたり水素イオン伝
導性高分子電解質が１０００ｍｇ／ｈの速さになるよう
に噴霧して触媒を調製した。この時、造粒プレートと撹
拌羽根との間のギャップはなくすとともに、ジェット粉
砕による粉砕工程も行わずに装置を運転した。このよう
にして得られた触媒は、表面に水素イオン伝導性高分子
電解質を均一に配置していた。そして、水素イオン伝導
性高分子電解質の大きさは０．１μｍであった。(Comparative Example 4) In this comparative example, 0.1% by weight was used.
Using the alcohol solution in which the hydrogen ion conductive polymer electrolyte of Example 1 was dissolved, the hydrogen ion conductive polymer electrolyte was added to the catalyst powder based on Example 1 at a rate of 1000 mg / h of hydrogen ion conductive polymer electrolyte per 1 g of the catalyst. To prepare a catalyst. At this time, the gap between the granulation plate and the stirring blade was eliminated, and the apparatus was operated without the crushing step by jet crushing. The catalyst thus obtained had the hydrogen ion conductive polymer electrolyte uniformly arranged on the surface. The size of the hydrogen ion conductive polymer electrolyte was 0.1 μm.

【００７８】実施例１に基づきこの触媒から高分子電解
質型燃料電池を作製した。Based on Example 1, a polymer electrolyte fuel cell was produced from this catalyst.

【００７９】この後、実施例１と同様の評価を行ったと
ころ、電流を外部に出力しない無負荷時には、９８Ｖの
電池開放電圧を得た。After that, the same evaluation as in Example 1 was carried out. As a result, a battery open circuit voltage of 98 V was obtained when there was no load and no current was output to the outside.

【００８０】この電池を燃料利用率８５％、酸素利用率
６０％、電流密度０．７Ａ／ｃｍ2の条件で連続発電試
験を行い、出力特性の時間変化を測定した。その結果、
本実施例の電池は、８０００時間以上にわたって約１
３．０ｋＷ（５８Ｖ−２２４Ａ）の電池出力を維持する
ことを確認した。This battery was subjected to a continuous power generation test under the conditions of a fuel utilization rate of 85%, an oxygen utilization rate of 60%, and a current density of 0.7 A / cm 2 , and the time change of output characteristics was measured. as a result,
The battery of this example has about 1 hour over 8000 hours.
It was confirmed that the battery output of 3.0 kW (58V-224A) was maintained.

【００８１】（表１）に、実施例１〜８、比較例１〜４
のそれぞれにおける水素イオン伝導性高分子溶液および
分散液の濃度（％）、触媒１ｇ重量あたりの水素イオン
伝導性高分子電解質噴霧速度（ｍｇ／時）、水素イオン
伝導性高分子電解質の触媒上の厚み（μｍ）、触媒１ｇ
重量あたりの水素イオン伝導性高分子電解質溶液および
分散液の噴霧速度（ｍｇ／分）、８０００時間後の電力
（ｋｗ）と電圧（Ｖ）を記載する。Table 1 shows Examples 1 to 8 and Comparative Examples 1 to 4.
Concentration (%) of hydrogen ion conductive polymer solution and dispersion in each of the above, hydrogen ion conductive polymer electrolyte spray rate (mg / hr) per 1 g weight of catalyst, on the catalyst of hydrogen ion conductive polymer electrolyte Thickness (μm), catalyst 1g
The spray rate (mg / min) of the hydrogen ion conductive polymer electrolyte solution and the dispersion per weight, the power (kw) after 8000 hours and the voltage (V) are described.

【００８２】[0082]

【表１】 [Table 1]

【００８３】実施例１、２、５および６においては、触
媒１ｇ重量あたりの触媒粉末に噴霧される水素イオン伝
導性高分子電解質の速度が比較例１および３に比べて遅
い。この結果、触媒粉末上に噴霧された液滴が乾燥する
時にできた水素イオン伝導性高分子電解質凝集体は、比
較例１および３と比べて実施例１、２、５および６の方
が小さくなり、触媒粉末表面により緻密に薄く均一に被
覆されている。さらに、比較例１の触媒粉末上に接合す
る高分子電解質の厚みが、噴霧速度が速くなることで
０．１２μｍになると貴金属表面への反応ガスの拡散が
抑制されるために、電流密度０．７Ａ／ｃｍ2の条件で
の電極の性能は低下する。また、実施例２、６において
は、０．０４μｍと水素イオン伝導性高分子が薄くつい
ているが、電極性能としてはそれぞれ実施例１、５と同
等である。これは、水素イオン伝導性経路として考えた
場合に、あまりにも薄く均一に水素イオン伝導性高分子
電解質を触媒粉末上全体につけることは困難であるた
め、水素イオン伝導性が低下し、厚みが０．０４μｍの
ものと０．１μｍのものの電池性能が同じであると考え
られる。In Examples 1, 2, 5 and 6, the rate of the hydrogen ion conductive polymer electrolyte sprayed on the catalyst powder per 1 g of the catalyst was slower than that of Comparative Examples 1 and 3. As a result, the hydrogen ion conductive polymer electrolyte aggregates formed when the droplets sprayed on the catalyst powder were dried were smaller in Examples 1, 2, 5 and 6 than in Comparative Examples 1 and 3. Therefore, the surface of the catalyst powder is densely and thinly and uniformly coated. Furthermore, when the thickness of the polymer electrolyte to be bonded onto the catalyst powder of Comparative Example 1 becomes 0.12 μm due to the increased spraying speed, the diffusion of the reaction gas to the surface of the noble metal is suppressed, so that the current density of 0. The performance of the electrode is deteriorated under the condition of 7 A / cm 2 . Further, in Examples 2 and 6, the hydrogen ion conductive polymer was as thin as 0.04 μm, but the electrode performance was the same as in Examples 1 and 5, respectively. This is because it is difficult to apply the hydrogen ion conductive polymer electrolyte over the catalyst powder too thinly and uniformly when considering it as the hydrogen ion conductive route, so the hydrogen ion conductivity is reduced and the thickness is reduced. It is considered that the battery performance of 0.04 μm and that of 0.1 μm are the same.

【００８４】触媒粉末上に接合される水素イオン伝導性
高分子電解質の厚みは、薄くなるほど触媒粉末上に均等
につけることが難しくなる。そのため、水素イオン伝導
性高分子電解質の触媒粉末上に接合される厚みとして
は、触媒粉末の一次粒子径よりも大きく、かつ反応ガス
拡散性の低下が起こりにくい０．１μｍ以下にすると反
応ガスの拡散性に有利に作用し電極性能を向上させるこ
とができる。The thinner the thickness of the hydrogen ion conductive polymer electrolyte bonded onto the catalyst powder, the more difficult it is to evenly apply it onto the catalyst powder. Therefore, the thickness of the hydrogen ion conductive polymer electrolyte to be bonded onto the catalyst powder is larger than the primary particle diameter of the catalyst powder and is 0.1 μm or less at which the reaction gas diffusibility is less likely to decrease. It can advantageously act on the diffusivity and improve the electrode performance.

【００８５】また、実施例５、６および比較例３のもの
の電極性能は、それぞれ実施例１、２および比較例１よ
りも低くでている。これは、実施例１、２および比較例
１のものが噴霧工程中に、造粒工程、粉砕工程も行って
いるために、触媒粉末がある粒子径サイズの範囲内で水
素イオン伝導性高分子電解質の噴霧をうけ、実施例５、
６および比較例３よりもより一層均一に水素イオン伝導
性高分子電解質が触媒粉末上に被覆されているために、
反応ガス拡散性や水素イオン伝導性に有利に作用してい
るためであると考えられる。The electrode performances of Examples 5 and 6 and Comparative Example 3 are lower than those of Examples 1 and 2 and Comparative Example 1, respectively. This is because the particles of Examples 1 and 2 and Comparative Example 1 also perform the granulating step and the pulverizing step during the spraying step, so that the hydrogen ion conductive polymer within the range of a certain particle size of the catalyst powder. Example 5 after being sprayed with electrolyte
Since the hydrogen ion conductive polymer electrolyte is more uniformly coated on the catalyst powder than in Comparative Example 6 and Comparative Example 3,
It is considered that this is because it has an advantageous effect on the reaction gas diffusivity and hydrogen ion conductivity.

【００８６】つぎに実施例１、３および比較例２におい
ては、水素イオン伝導性高分子電解質溶液および分散液
の濃度が異なっている。比較例２においては、水素イオ
ン伝導性高分子電解質溶液の濃度が０．１％と低いた
め、触媒１ｇ重量あたりの水素イオン伝導性高分子電解
質の噴霧速度を１０００ｍｇ／ｈに保つためには、たく
さんの溶液を供給する必要がある。その結果、乾燥温度
が低下し、触媒粉末が凝集しやすくなり、カーボン粉末
の表面積およびカーボン粉末上に剥き出しになっている
貴金属量が減少し、有効反応面積の減少とともに、反応
ガス拡散性も低下して電極性能が低下しているものと考
えられる。実施例３のほうが実施例１よりも性能がよい
のも同様の理由であると考えられる。Next, in Examples 1 and 3 and Comparative Example 2, the concentrations of the hydrogen ion conductive polymer electrolyte solution and the dispersion are different. In Comparative Example 2, since the concentration of the hydrogen ion conductive polymer electrolyte solution was as low as 0.1%, in order to keep the spray rate of the hydrogen ion conductive polymer electrolyte per 1 g weight of the catalyst at 1000 mg / h, It is necessary to supply a lot of solution. As a result, the drying temperature decreases, the catalyst powder easily aggregates, the surface area of the carbon powder and the amount of noble metal exposed on the carbon powder decrease, the effective reaction area decreases, and the reaction gas diffusivity also decreases. Therefore, it is considered that the electrode performance is deteriorated. The reason why the performance of the third embodiment is better than that of the first embodiment is considered to be the same reason.

【００８７】また、実施例５、７および比較例４につい
ても同様の理由によるものである。The same reason is applied to Examples 5 and 7 and Comparative Example 4.

【００８８】[0088]

【発明の効果】以上のように本発明によれば、水素イオ
ン伝導性高分子電解質を触媒粉末上に噴霧しながら乾燥
し、さらに噴霧速度を触媒１ｇ重量あたりの水素イオン
伝導性高分子電解質重量で１０００ｍｇ／ｈ以下にする
こと、触媒粉末を被覆している水素イオン伝導性高分子
電解質の厚みを０．１μｍ以下にすること、噴霧する水
素イオン伝導性高分子電解質溶液および分散液の濃度を
０．３重量％以上３０重量％以下にすること、触媒粉末
を造粒したり粉砕したりすることにより、水素イオン伝
導性高分子電解質を触媒粉末表面へ被覆する際に生じて
いた水素イオン伝導性高分子電解質の凝集サイズを小さ
くすることが可能となる。その結果、触媒粉末表面へ緻
密に薄く均一に被覆することが可能となり、反応ガス拡
散性に有利に作用し、電極の特性を向上させるという有
利な効果が得られる。As described above, according to the present invention, the hydrogen ion conductive polymer electrolyte is dried while being sprayed onto the catalyst powder, and the spraying rate is changed to the weight of the hydrogen ion conductive polymer electrolyte per 1 g of the catalyst. Is 1000 mg / h or less, the thickness of the hydrogen ion conductive polymer electrolyte coating the catalyst powder is 0.1 μm or less, and the concentration of the sprayed hydrogen ion conductive polymer electrolyte solution and dispersion is The hydrogen ion conduction that occurred when the surface of the catalyst powder was coated with the hydrogen ion conductive polymer electrolyte by adjusting the content of the catalyst powder to 0.3% by weight or more and 30% by weight or less and by granulating or crushing the catalyst powder. It is possible to reduce the aggregate size of the hydrophilic polymer electrolyte. As a result, it becomes possible to coat the surface of the catalyst powder densely and thinly, which has an advantageous effect on the reaction gas diffusivity and improves the characteristics of the electrode.

【図面の簡単な説明】[Brief description of drawings]

【図１】第１の実施例で用いた製造装置の概念を示す図FIG. 1 is a diagram showing a concept of a manufacturing apparatus used in a first embodiment.

【図２】（イ）触媒粉末の集合体の概念図 （ロ）集合体になる前および粉砕工程で粉砕された触媒
粉末の概念図FIG. 2 (a) A conceptual diagram of an aggregate of catalyst powders. (B) A conceptual diagram of a catalyst powder pulverized before the aggregates and in the pulverization process

【符号の説明】[Explanation of symbols]

１ 下部円柱状容器部 ２ 流動部 ３ 上部円柱状容器部 ４ バグフィルター ５ ガス導入口 ６ 造粒プレート ７ 撹拌羽根 ８ 造粒プレートと撹拌羽根との間のギャップ ９ パルスジェット １０ 衝突ターゲット １１ 高圧スプレー １２ カーボン粒子上に担持された貴金属 １３ カーボン粒子の凝集体 １４ 凝集体になる前または粉砕された触媒粉末 1 Lower cylindrical container 2 Flow section 3 Upper cylindrical container 4 Bug filter 5 gas inlet 6 granulation plate 7 stirring blades 8 Gap between granulation plate and stirring blade 9 pulse jet 10 collision target 11 high pressure spray 12 Noble metal supported on carbon particles 13 Aggregates of carbon particles 14 Catalyst powder before being agglomerated or crushed

───────────────────────────────────────────────────── フロントページの続き (72)発明者 有坂 伸一 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 内田 誠 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 Ｆターム(参考） 5H018 AA06 AS01 BB01 BB05 BB06 BB08 BB11 BB12 CC06 DD06 EE02 EE03 EE08 EE18 EE19 HH00 HH03 HH05 5H026 AA06 BB04 CC03 CX05 EE02 EE05 EE18 HH00 HH03 HH05   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shinichi Arisaka             1006 Kadoma, Kadoma-shi, Osaka Matsushita Electric             Sangyo Co., Ltd. (72) Inventor Makoto Uchida             1006 Kadoma, Kadoma-shi, Osaka Matsushita Electric             Sangyo Co., Ltd. F-term (reference) 5H018 AA06 AS01 BB01 BB05 BB06                       BB08 BB11 BB12 CC06 DD06                       EE02 EE03 EE08 EE18 EE19                       HH00 HH03 HH05                 5H026 AA06 BB04 CC03 CX05 EE02                       EE05 EE18 HH00 HH03 HH05

Claims (5)

【特許請求の範囲】[Claims] 【請求項１】 貴金属触媒を担持した導電性炭素粒子が
気体中を流動し、その中に前記水素イオン伝導性高分子
電解質の溶液あるいは分散液を噴霧することで、前記貴
金属触媒を担持した導電性炭素粒子の少なくとも一部に
前記水素イオン伝導性高分子電解質を配する工程におい
て、前記気体中の導電性炭素の濃度が０．１ｋｇ／ｍ3
〜９．０ｋｇ／ｍ3であり、かつ前記噴霧の速度が、前
記貴金属触媒を担持した導電性炭素粒子に含まれる導電
性炭素１ｇ重量あたりの前記水素イオン伝導性高分子電
解質重量で１０００ｍｇ／ｈ以下の速度であることを特
徴とする高分子電解質型燃料電池用触媒の製造方法。1. A conductive carbon particle carrying a noble metal catalyst, wherein conductive carbon particles carrying a noble metal catalyst flow in a gas and a solution or dispersion of the hydrogen ion conductive polymer electrolyte is sprayed into the gas. In the step of disposing the hydrogen ion conductive polymer electrolyte on at least a part of the conductive carbon particles, the concentration of conductive carbon in the gas is 0.1 kg / m 3
˜9.0 kg / m 3 , and the spraying rate is 1000 mg / h by weight of the hydrogen ion conductive polymer electrolyte per 1 g weight of conductive carbon contained in the conductive carbon particles supporting the noble metal catalyst. The method for producing a polymer electrolyte fuel cell catalyst is characterized by the following rates. 【請求項２】 前記水素イオン伝導性高分子電解質の溶
液中あるいは分散液中の前記水素イオン伝導性高分子電
解質の濃度が０．３重量％以上でかつ３０重量％以下で
あることを特徴とする請求項１記載の高分子電解質型燃
料電池用触媒の製造方法。2. The concentration of the hydrogen ion conductive polymer electrolyte in the solution or dispersion of the hydrogen ion conductive polymer electrolyte is 0.3% by weight or more and 30% by weight or less. The method for producing a polymer electrolyte fuel cell catalyst according to claim 1. 【請求項３】 前記貴金属触媒を担持した導電性炭素粒
子の少なくとも一部を被覆する水素イオン伝導性高分子
電解質の厚みの平均値が、０．１μｍ以下であることを
特徴とする請求項１記載の高分子電解質型燃料電池。3. The average value of the thickness of the hydrogen ion conductive polymer electrolyte coating at least a part of the conductive carbon particles supporting the noble metal catalyst is 0.1 μm or less. The polymer electrolyte fuel cell described. 【請求項４】 高分子電解質膜と、前記高分子電解質膜
を挟む一対の触媒層と、前記触媒層を挟む一対のガス拡
散層とを有し、前記触媒層が請求項１〜３に記載の高分
子電解質型燃料電池用触媒を含有する電解質膜／電極接
合体。4. A polymer electrolyte membrane, a pair of catalyst layers sandwiching the polymer electrolyte membrane, and a pair of gas diffusion layers sandwiching the catalyst layer, wherein the catalyst layer is one of claims 1 to 3. An electrolyte membrane / electrode assembly containing the catalyst for polymer electrolyte fuel cell as described above. 【請求項５】 請求項４に記載の電解質膜／電極接合体
と、前記電解質膜／電極接合体の両面に配置されたガス
流露を有する導電性セパレータとを有する単セルを複数
個積層してなる高分子電解質型燃料電池。5. A plurality of unit cells each having the electrolyte membrane / electrode assembly according to claim 4 and a conductive separator having gas outflow disposed on both surfaces of the electrolyte membrane / electrode assembly are stacked. Polymer electrolyte fuel cell
JP2001235969A 2001-08-03 2001-08-03 Manufacturing method of catalyst for polymer electrolyte fuel cell, electrolyte membrane/electrode assembly using it, and polymer electrolyte fuel cell Pending JP2003045439A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004311057A (en) * 2003-04-02 2004-11-04 Dainippon Printing Co Ltd Paste composition for forming catalyst layer, and transfer sheet for manufacturing catalyst layer-electrolyte film laminate
JP2007508677A (en) * 2003-10-17 2007-04-05 ゼネラル・モーターズ・コーポレーション Control of polymer surface distribution on diffusion media for improved fuel cell performance
WO2008032597A1 (en) * 2006-09-13 2008-03-20 Toagosei Co., Ltd. Membrane electrode assembly and method for producing the same
JP2009277404A (en) * 2008-05-13 2009-11-26 Asahi Kasei E-Materials Corp Solid polymer fuel cell

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004311057A (en) * 2003-04-02 2004-11-04 Dainippon Printing Co Ltd Paste composition for forming catalyst layer, and transfer sheet for manufacturing catalyst layer-electrolyte film laminate
JP2007508677A (en) * 2003-10-17 2007-04-05 ゼネラル・モーターズ・コーポレーション Control of polymer surface distribution on diffusion media for improved fuel cell performance
JP4838721B2 (en) * 2003-10-17 2011-12-14 ゼネラル・モーターズ・コーポレーション Control of polymer surface distribution on diffusion media for improved fuel cell performance
WO2008032597A1 (en) * 2006-09-13 2008-03-20 Toagosei Co., Ltd. Membrane electrode assembly and method for producing the same
JP2009277404A (en) * 2008-05-13 2009-11-26 Asahi Kasei E-Materials Corp Solid polymer fuel cell

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