JP5055815B2 - Method for forming catalyst layer for electrode of fuel cell and catalyst layer for electrode - Google Patents

Method for forming catalyst layer for electrode of fuel cell and catalyst layer for electrode Download PDF

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JP5055815B2
JP5055815B2 JP2006112277A JP2006112277A JP5055815B2 JP 5055815 B2 JP5055815 B2 JP 5055815B2 JP 2006112277 A JP2006112277 A JP 2006112277A JP 2006112277 A JP2006112277 A JP 2006112277A JP 5055815 B2 JP5055815 B2 JP 5055815B2
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catalyst
electrolyte membrane
fuel cell
electrode
ink
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智之 夏目
愛 板垣
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Nissan Motor Co Ltd
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    • 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
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    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Description

本発明は、触媒担持カーボン粒子と、電解質と、溶媒とを混合、分散させて触媒インクとし、この触媒インクを電解質膜に塗布する燃料電池の電極用触媒層の形成方法に関する。   The present invention relates to a method for forming a catalyst layer for an electrode of a fuel cell, in which catalyst-supported carbon particles, an electrolyte, and a solvent are mixed and dispersed to form a catalyst ink, and this catalyst ink is applied to an electrolyte membrane.

例えば、固体高分子型の燃料電池は、高分子電解質膜の両面に電極をそれぞれ設けてなる膜電極接合体（MEA:membrane electrode assembly）を、燃料ガス流路または酸化剤ガス流路が形成されたセパレータで挟み込むことで燃料電池単セルを構成し、その燃料電池単セルの複数個を積層することで規定の起電力を発生する燃料電池スタックとしている。   For example, a polymer electrolyte fuel cell has a membrane electrode assembly (MEA) formed by providing electrodes on both sides of a polymer electrolyte membrane, and a fuel gas channel or an oxidant gas channel. A fuel cell stack is formed by sandwiching a plurality of fuel cell single cells by sandwiching them with a separator and generating a prescribed electromotive force.

電極は、例えば高分子電解質膜に接触して設けられる触媒層と、触媒層上のガス拡散層とから構成される。触媒層は、例えば、Ｐｔ（白金）などの触媒粒子が表面に担持された触媒担持カーボン粒子と、電解質と、溶媒とを混合し分散させることで製造される触媒インク（スラリー）を、高分子電解質膜の表面に塗布し乾燥させることで形成される（例えば下記特許文献１参照）。   The electrode is composed of, for example, a catalyst layer provided in contact with the polymer electrolyte membrane and a gas diffusion layer on the catalyst layer. The catalyst layer is made of, for example, a catalyst ink (slurry) produced by mixing and dispersing catalyst-carrying carbon particles having catalyst particles such as Pt (platinum) carried on the surface, an electrolyte, and a solvent. It is formed by applying to the surface of the electrolyte membrane and drying (see, for example, Patent Document 1 below).

特開２００５−１６６３３５号公報JP 2005-166335 A

ところで、上記のような、高分子電解質膜の表面に塗布する触媒インクには、燃料電池の発電性特に初期発電性に効果のあるものと、燃料電池の耐久性に効果のあるものとがあり、このような性能の相違は、電極触媒材料中の電解質成分材料のインク内での分散量や分散状態に影響されると考えられている。   By the way, as described above, the catalyst ink applied to the surface of the polymer electrolyte membrane includes those that are effective for the power generation performance of the fuel cell, particularly the initial power generation performance, and those that are effective for the durability of the fuel cell. Such a difference in performance is considered to be affected by the amount and state of dispersion of the electrolyte component material in the electrode catalyst material in the ink.

そして、通常では、上記した発電性と耐久性の双方の性能を適度に確保した触媒インクを用いて高分子電解質膜に塗布しているが、この場合には、発電性および耐久性のいずれにおいても中間程度の性能を維持していることとなり、結果的に良好な燃料電池性能を確保できていないことになる。   And usually, it is applied to the polymer electrolyte membrane by using the catalyst ink that has ensured both the power generation performance and durability performance as described above, but in this case, in either power generation performance or durability In other words, the intermediate performance is maintained, and as a result, good fuel cell performance cannot be secured.

そこで、本発明は、燃料電池の発電性および耐久性を共に高めて良好な燃料電池性能を確保することを目的としている。   Accordingly, an object of the present invention is to improve fuel generation performance and durability of a fuel cell and to ensure good fuel cell performance.

本発明は、触媒担持カーボン粒子と、電解質と、溶媒とを混合、分散させて触媒インクとし、この触媒インクを電解質膜に塗布する際に、前記触媒担持カーボン粒子の触媒担持率と、前記電解質の量と、前記触媒担持カーボン粒子の粉砕度合いとの少なくとも一つの条件が異なる複数種類の触媒インクを製造し、この複数種類の触媒インクを、前記電解質膜に互いに別々の層となるよう塗り分けして塗布する燃料電池の電極用触媒層の形成方法であって、前記複数種類の触媒インクの前記三つの条件すべてを異なるものとし、この三つの条件すべてが大となる触媒インクが、前記電解質膜側となるよう前記触媒インクを前記電解質膜に塗布することを最も主要な特徴とする。 The present invention includes a catalyst-carrying carbon particles, an electrolyte, and a solvent mixture, is dispersed as a catalyst ink, when applying the catalyst ink to the electrolyte membrane, a catalyst supporting ratio of the catalyst-carrying carbon particles, the electrolyte A plurality of types of catalyst inks having different conditions of at least one of the amount of the catalyst-carrying carbon particles and the degree of pulverization of the catalyst-carrying carbon particles. A method for forming a catalyst layer for an electrode of a fuel cell to be applied , wherein all of the three conditions of the plurality of types of catalyst inks are different from each other, and the catalyst ink in which all of the three conditions become large is the electrolyte. The most important feature is that the catalyst ink is applied to the electrolyte membrane so as to be on the membrane side .

本発明によれば、触媒担持カーボン粒子の触媒担持率と、電解質の量と、触媒担持カーボン粒子の粉砕度合いとの三つの条件すべてを異なるものとした複数種類の触媒インクのうち、三つの条件すべてが大となる触媒インクが電解質膜側となるよう触媒インクを、電解質膜に互いに別々の層となるよう塗り分けして塗布するようにしている。 According to the present invention , the three conditions among the plurality of types of catalyst ink in which all three conditions of the catalyst supporting rate of the catalyst supporting carbon particles, the amount of the electrolyte, and the degree of pulverization of the catalyst supporting carbon particles are different. The catalyst ink is applied separately on the electrolyte membrane so as to be in separate layers so that the catalyst ink that is all large is on the electrolyte membrane side .

ここで、例えば触媒担持カーボン粒子の触媒担持率と、電解質の量と、触媒担持カーボン粒子の粉砕度合いを、いずれも大とした触媒インクは、触媒濃度が高く、多量の電解質によって液水を保持しやすく、粉砕度合いが大きいことからカーボン表面積が大きくなる。この結果、このような触媒インクは、電解質膜と馴染みやすく、カーボン粒子に担持する触媒の表面積が大きくなって反応性が良好となり、発電性が重視されたものとなる。   Here, for example, the catalyst ink in which the catalyst supporting rate of the catalyst supporting carbon particles, the amount of the electrolyte, and the degree of pulverization of the catalyst supporting carbon particles are all large, the catalyst concentration is high, and liquid water is retained by a large amount of electrolyte. The carbon surface area is increased because the degree of pulverization is easy. As a result, such a catalyst ink is easily compatible with the electrolyte membrane, the surface area of the catalyst supported on the carbon particles is increased, the reactivity is improved, and power generation is emphasized.

一方、触媒担持カーボンの触媒担持率と、電解質の量と、触媒担持カーボン粒子の粉砕度合いを、いずれも小とした触媒インクは、上記した触媒インクとは逆に、触媒濃度が低く、液水を保持しにくく、カーボン表面積が小さくなる。この結果、このような触媒インクは、カーボン粒子周囲の液水が少なくなり、起動停止による触媒・カーボンの腐食が抑制され、またカーボン表面積が小さいことから、反応ガスと接触しにくく、起動停止によるカーボンの腐食が抑制され、耐久性が重視されたものとなる。さらに、触媒担持カーボン粒子の粉砕度合いが小さいために、粉砕後の触媒担持カーボン粒子相互間の隙間が大きくなり、反応ガスや液水の拡散性が向上する。   On the other hand, a catalyst ink in which the catalyst supporting rate of the catalyst supporting carbon, the amount of the electrolyte, and the degree of pulverization of the catalyst supporting carbon particles are all small, contrary to the catalyst ink described above, has a low catalyst concentration and liquid water. Is difficult to hold, and the carbon surface area is reduced. As a result, such catalyst ink reduces liquid water around the carbon particles, suppresses corrosion of the catalyst and carbon due to start / stop, and has a small carbon surface area. Carbon corrosion is suppressed and durability is emphasized. Further, since the degree of pulverization of the catalyst-carrying carbon particles is small, the gap between the crushed catalyst-carrying carbon particles is increased, and the diffusibility of the reaction gas and liquid water is improved.

上記したような発電性が重視された触媒インクと、耐久性が重視された触媒インクとを、電解質膜に互いに別々の層となるよう塗り分けして塗布し、その際、複数種類の触媒インクのうち、三つの条件すべてが大となる触媒インクが、電解質膜側となるよう触媒インクを電解質膜に塗布することで、燃料電池の発電性および耐久性を共に高めて良好な燃料電池性能を確保することができる A catalyst ink generation property is emphasized as described above, and a catalyst ink durability is emphasized, and by applying separate application so as to be mutually separate layers to the electrolyte membrane, in which a plurality of types of catalyst ink By applying the catalyst ink to the electrolyte membrane so that the catalyst ink that increases all three conditions is on the electrolyte membrane side , both the power generation performance and durability of the fuel cell are improved, and good fuel cell performance is achieved. Can be secured

以下、本発明の実施の形態を図面に基づき説明する。   Hereinafter, embodiments of the present invention will be described with reference to the drawings.

「燃料電池スタックの全体構成」
まず、燃料電池スタックの全体構成について簡単に説明する。図１は燃料電池スタックの全体構成を示す斜視図、図２は燃料電池単セルの拡大断面図である。 "Overall structure of fuel cell stack"
First, the overall configuration of the fuel cell stack will be briefly described. FIG. 1 is a perspective view showing the overall configuration of a fuel cell stack, and FIG. 2 is an enlarged cross-sectional view of a single fuel cell.

燃料電池スタック１は、図１に示すように、燃料ガス（水素ガス）と酸化剤ガス（酸素）の反応により起電力を生じる単位電池としての燃料電池単セル２を所定数だけ積層した積層体３とされ、その積層体３の両端に集電板４、絶縁板５およびエンドプレート６を配置し、該積層体３をタイロッド７で締め付け、そのタイロッド７の端部にナット１４を螺合させることで構成している。   As shown in FIG. 1, a fuel cell stack 1 is a laminate in which a predetermined number of fuel cell single cells 2 as unit cells that generate an electromotive force by reaction of fuel gas (hydrogen gas) and oxidant gas (oxygen) are stacked. 3, the current collector plate 4, the insulating plate 5 and the end plate 6 are arranged at both ends of the laminate 3, the laminate 3 is fastened with a tie rod 7, and a nut 14 is screwed onto the end of the tie rod 7. It consists of that.

この燃料電池スタック１では、燃料ガス、酸化剤ガスおよび冷媒（冷却水）をそれぞれ各燃料電池単セル２のセパレータ（図示は省略する）に形成された各流路に流通させるための燃料ガス導入口８、燃料ガス排出口９、酸化剤ガス導入口１０、酸化剤ガス排出口１１、冷媒導入口１２および冷媒排出口１３を、一方のエンドプレート６に形成している。   In this fuel cell stack 1, fuel gas introduction for allowing fuel gas, oxidant gas and refrigerant (cooling water) to flow through each flow path formed in a separator (not shown) of each fuel cell single cell 2. A port 8, a fuel gas outlet 9, an oxidant gas inlet 10, an oxidant gas outlet 11, a refrigerant inlet 12 and a refrigerant outlet 13 are formed in one end plate 6.

かかる構成の燃料電池スタック１においては、燃料ガスは、燃料ガス導入口８より導入されてセパレータに形成された燃料ガス流路を流れ、燃料ガス排出口９より排出される。酸化剤ガスは、酸化剤ガス導入口１０より導入されてセパレータに形成された酸化剤ガス流路を流れ、酸化剤ガス排出口１１より排出される。冷媒は、冷媒導入口１２より導入されてセパレータに形成された冷媒流路を流れ、冷媒排出口１３より排出される。   In the fuel cell stack 1 having such a configuration, the fuel gas is introduced from the fuel gas inlet 8, flows through the fuel gas passage formed in the separator, and is discharged from the fuel gas outlet 9. The oxidant gas is introduced from the oxidant gas introduction port 10, flows through the oxidant gas flow path formed in the separator, and is discharged from the oxidant gas discharge port 11. The refrigerant is introduced from the refrigerant introduction port 12, flows through the refrigerant flow path formed in the separator, and is discharged from the refrigerant discharge port 13.

燃料電池単セル２は、図２に示すように、一面側から燃料ガスが供給され、他面側から酸化剤ガスが供給される膜電極接合体（MEA:membrane electrode assembly）１５と、この膜電極接合体１５の一面に配置されるアノードセパレータ１６と、膜電極接合体１５の他面に配置されるカソードセパレータ１７とから構成され、これらアノードセパレータ１６とカソードセパレータ１７で膜電極接合体１５を挟み込むように積層した構造としている。   As shown in FIG. 2, the fuel cell single cell 2 includes a membrane electrode assembly (MEA) 15 to which fuel gas is supplied from one side and oxidant gas is supplied from the other side, and this membrane An anode separator 16 disposed on one surface of the electrode assembly 15 and a cathode separator 17 disposed on the other surface of the membrane electrode assembly 15, and the membrane electrode assembly 15 is formed by the anode separator 16 and the cathode separator 17. The structure is laminated so as to be sandwiched.

膜電極接合体１５は、例えば水素イオン（プロトン）を通す高分子電解質膜である固体高分子電解質膜１８と、この固体高分子電解質膜１８の一面に設けられるアノード電極１９と、固体高分子電解質膜１８の他面に設けられるカソード電極２０とからなる。アノード電極１９は、固体高分子電解質膜１８側に配置される触媒層２１と、アノードセパレータ１６側に配置されるガス拡散層２２とからなり、カソード電極２０も同様に、固体高分子電解質膜１８側に配置される触媒層２３と、カソードセパレータ１７側に配置されるガス拡散層２４とからなる。   The membrane electrode assembly 15 includes, for example, a solid polymer electrolyte membrane 18 that is a polymer electrolyte membrane that allows hydrogen ions (protons) to pass through, an anode electrode 19 provided on one surface of the solid polymer electrolyte membrane 18, and a solid polymer electrolyte. The cathode electrode 20 is provided on the other surface of the film 18. The anode electrode 19 includes a catalyst layer 21 disposed on the solid polymer electrolyte membrane 18 side and a gas diffusion layer 22 disposed on the anode separator 16 side, and the cathode electrode 20 similarly includes the solid polymer electrolyte membrane 18. The catalyst layer 23 is disposed on the side, and the gas diffusion layer 24 is disposed on the cathode separator 17 side.

なお、上記した触媒層２１および触媒層２３は電極用触媒層を構成している。   The catalyst layer 21 and the catalyst layer 23 described above constitute an electrode catalyst layer.

アノードセパレータ１６には、発電に寄与するアクティブ領域（固体高分子電解質膜１８と接する中央部分の領域）に、燃料ガスを流通させるための燃料ガス流路２５を形成している。一方、カソードセパレータ１７には、アクティブ領域に酸化剤ガスを流通させるための酸化剤ガス流路２６を形成している。   The anode separator 16 is formed with a fuel gas flow path 25 for allowing the fuel gas to flow in an active region contributing to power generation (a central region in contact with the solid polymer electrolyte membrane 18). On the other hand, the cathode separator 17 is formed with an oxidant gas flow path 26 for circulating an oxidant gas in the active region.

そして、本発明の第１の実施形態として、固体高分子電解質膜１８上に形成する触媒層２１，２３を、図３に示すように、固体高分子電解質膜１８側の第１の層２１ａ，２３ａと、拡散層２２，２４（図２）側の第２の層２１ｂ，２３ｂとの２層構造としている。   As a first embodiment of the present invention, the catalyst layers 21 and 23 formed on the solid polymer electrolyte membrane 18 are, as shown in FIG. 3, the first layers 21a and 21a on the solid polymer electrolyte membrane 18 side. 23a and the second layers 21b and 23b on the diffusion layers 22 and 24 (FIG. 2) side.

ここで、固体高分子電解質膜１８側の第１の層２１ａ，２３ａは、燃料電池の発電性、特に初期発電性を重視した触媒インク５３ａ（図４参照）からなり、一方、拡散層２２，２４（図２）側の第２の層２１ｂ，２３ｂは、燃料電池の耐久性を重視した触媒インク５３ｂからなる。   Here, the first layers 21a and 23a on the side of the solid polymer electrolyte membrane 18 are made of a catalyst ink 53a (see FIG. 4) that emphasizes the power generation property of the fuel cell, particularly the initial power generation property, while the diffusion layers 22, The second layers 21b and 23b on the 24 (FIG. 2) side are made of a catalyst ink 53b that places importance on the durability of the fuel cell.

すなわち、本実施形態では、複数種類の触媒インク５３ａ，５３ｂを、固体高分子電解質膜１８に互いに別々の層となるよう塗り分けして塗布していることになる。   That is, in the present embodiment, a plurality of types of catalyst inks 53a and 53b are separately applied to the solid polymer electrolyte membrane 18 so as to be separate layers.

次に、上記した第１の層２１ａ，２３ａからなる触媒インク５３ａと、第２の層２１ｂ，２３ｂからなる触媒インク５３ｂの相違について説明する。   Next, the difference between the catalyst ink 53a composed of the first layers 21a and 23a and the catalyst ink 53b composed of the second layers 21b and 23b will be described.

ここでの触媒インク５３ａ，５３ｂは、触媒担持カーボン粒子と、電解質と、溶媒とを混合し分散させることで製造する。触媒担持カーボン粒子は、カーボン粒子に白金触媒ＴＥＣ１０Ｅ５０Ｅ（田中貴金属社製）を担持させたもので、電解質は、プロトン伝導物質であるナフィオン（デュポン社製）を使用する。また、溶媒は、純水にイソプロパノールを含有させている。   The catalyst inks 53a and 53b here are manufactured by mixing and dispersing catalyst-carrying carbon particles, an electrolyte, and a solvent. The catalyst-supporting carbon particles are obtained by supporting platinum catalyst TEC10E50E (manufactured by Tanaka Kikinzoku Co., Ltd.) on carbon particles, and the electrolyte is Nafion (manufactured by DuPont) which is a proton conductive material. The solvent contains pure water with isopropanol.

ここで前記した第１の層２１ａ，２３ａからなる触媒インク５３ａは、第２の層２１ｂ，２３ｂからなる触媒インク５３ｂに比較して、触媒担持カーボン粒子の触媒担持率を高く、電解質の量を多く、触媒担持カーボン粒子の粉砕度合いを大きくして（粒径を小さく）している。   Here, the catalyst ink 53a composed of the first layers 21a and 23a described above has a higher catalyst loading rate of the catalyst-supporting carbon particles and the amount of the electrolyte than the catalyst ink 53b composed of the second layers 21b and 23b. In many cases, the degree of pulverization of the catalyst-supporting carbon particles is increased (the particle size is decreased).

図４（ａ）は、第１の層２１ａ，２３ａからなる触媒インク５３ａの調整工程を、図４（ｂ）は、第２の層２１ｂ，２３ｂからなる触媒インク５３ｂの調整工程を、それぞれ示す。   4A shows an adjustment process of the catalyst ink 53a composed of the first layers 21a and 23a, and FIG. 4B shows an adjustment process of the catalyst ink 53b composed of the second layers 21b and 23b. .

図４（ａ），（ｂ）の工程Ｉでは、容器２７内の溶媒２８中にカーボン粒子２９Ａ，２９Ｂをそれぞれ投入した状態で粉砕し、この際、図４（ａ）でのカーボン粒子２９Ａは、図４（ｂ）でのカーボン粒子２９Ｂよりも触媒担持率を高くしている。   In Step I of FIGS. 4A and 4B, the carbon particles 29A and 29B are pulverized in a state where the carbon particles 29A and 29B are put into the solvent 28 in the container 27, and at this time, the carbon particles 29A in FIG. The catalyst loading rate is higher than that of the carbon particles 29B in FIG.

なお、カーボン粒子２９Ａ，２９Ｂを粉砕する際には、ホモジナイザを用いるが、ホモジナイザのほかに、ジェットミル、ボールミル、振動ボールミル、マイクロカッターなどを用いることができる。また、有機溶媒、界面活性剤を加えることにより、粉砕した触媒担持カーボン粒子を高分散の状態に保つことができる。   When the carbon particles 29A and 29B are pulverized, a homogenizer is used. In addition to the homogenizer, a jet mill, a ball mill, a vibrating ball mill, a microcutter, or the like can be used. Further, by adding an organic solvent and a surfactant, the pulverized catalyst-carrying carbon particles can be kept in a highly dispersed state.

次に、工程IIで示すように、図４（ａ）のカーボン粒子２９Ａを、粉砕粒子２９０Ａとなるように、図４（ｂ）のカーボン粒子２９Ｂの粉砕粒子２９０Ｂに比較して大きく粉砕してその粒径を小さくする。   Next, as shown in Step II, the carbon particles 29A in FIG. 4A are pulverized to be larger than the pulverized particles 290B of the carbon particles 29B in FIG. Reduce the particle size.

粉砕後に、電解質を容器２７内に投入するが、この際、電解質の量を、図４（ａ）では図４（ｂ）に比較して多くして工程IIIの状態で示すような２種類の触媒インク５３ａ，５３ｂが製造される。この際電解質１００が、粉砕粒子２９０Ａおよび粉砕粒子２９０Ｂの表面に付着した状態となる。   After pulverization, the electrolyte is put into the container 27. At this time, the amount of the electrolyte is increased in FIG. 4 (a) as compared with FIG. Catalyst inks 53a and 53b are manufactured. At this time, the electrolyte 100 is attached to the surfaces of the pulverized particles 290A and the pulverized particles 290B.

「触媒塗布装置の構成」
次に、上記のようにして製造した２種類の触媒インク５３ａ，５３ｂを、固体高分子電解質膜１８に塗布するための触媒塗布装置について説明する。 "Configuration of catalyst coating device"
Next, a catalyst coating apparatus for coating the solid polymer electrolyte membrane 18 with the two types of catalyst inks 53a and 53b manufactured as described above will be described.

図５は本実施形態の触媒塗布装置の斜視図、図６は同分解斜視図、図７は同平面図である。   5 is a perspective view of the catalyst coating apparatus of the present embodiment, FIG. 6 is an exploded perspective view thereof, and FIG. 7 is a plan view thereof.

本実施形態の触媒塗布装置は、図５から図７に示すように、固体高分子電解質膜１８を内壁面に装着させるドラム３０と、ドラム３０を、軸芯を中心として円周方向に回転させるとともに軸芯に沿って上下動（移動）させる駆動手段である駆動機構部３１と、固体高分子電解質膜１８がドラム３０の回転による遠心力で該ドラム３０の内壁面に貼り付くまで吸引する吸引手段である吸引機構部３２と、ドラム３０の内側（中心）に挿入され、回転するドラム３０の内壁面に装着された固体高分子電解質膜１８に触媒インクを塗布する触媒塗布手段であるスプレー３３とを備える。   As shown in FIGS. 5 to 7, the catalyst coating apparatus of the present embodiment rotates the drum 30 on which the solid polymer electrolyte membrane 18 is attached to the inner wall surface and the drum 30 in the circumferential direction around the axis. At the same time, the suction is performed until the solid polymer electrolyte membrane 18 is attached to the inner wall surface of the drum 30 by the centrifugal force generated by the rotation of the drum 30 and the driving mechanism 31 that is a driving means that moves up and down (moves) along the axis. A suction mechanism 32 as a means, and a spray 33 as a catalyst application means for applying a catalyst ink to the solid polymer electrolyte membrane 18 inserted on the inner wall (center) of the drum 30 and mounted on the inner wall surface of the rotating drum 30. With.

ドラム３０は、図８に平面図で示すように、固体高分子電解質膜１８をその内壁面に装着させたときに外にはみ出さない程度の高さを備えた円筒体をほぼ半分に分割した分割構造とし、半円形状をなす一方のドラム分割体３４を他方の半円形状をなすドラム分割体３５に対して回動軸３６を介して開閉自在としている。また、一方のドラム分割体３４の先端部３４ａは、他方のドラム分割体３５の先端の結合部３７に形成した溝部３８に挿入係合され、図示を省略するロック手段にて開かないようにロックされる。   As shown in the plan view of FIG. 8, the drum 30 has a cylindrical body having a height that does not protrude outside when the solid polymer electrolyte membrane 18 is attached to the inner wall surface of the drum 30. With a divided structure, one drum divided body 34 having a semicircular shape can be freely opened and closed with respect to the other drum divided body 35 having a semicircular shape via a rotation shaft 36. Further, the leading end 34a of one drum divided body 34 is inserted and engaged with a groove 38 formed in the coupling portion 37 at the leading end of the other drum divided body 35, and is locked so as not to be opened by a locking means (not shown). Is done.

なお、図８（ａ）は高分子電解質膜１８をドラムに装着する前の状態、同図（ｂ）は高分子電解質膜１８に触媒インクを塗布後の状態をそれぞれ示す。   8A shows a state before the polymer electrolyte membrane 18 is mounted on the drum, and FIG. 8B shows a state after the catalyst ink is applied to the polymer electrolyte membrane 18.

他方のドラム分割体３５の内壁面３９には、図５のＡ−Ａ線断面図である図９に示すように、固体高分子電解質膜１８を吸引して密着装着させるための複数の吸引孔４０が形成されている。かかる吸引孔４０は、固体高分子電解質膜１８のアクティブ領域（発電に寄与する領域）を除くその外周囲を取り囲むようにして形成されている。また、このドラム分割体３５は、図５のＢ−Ｂ線断面図である図９（ｂ）に示すように、前記各吸引孔４０と連通する空隙部４１を、その板厚の中心部に形成した内部空間構造としている。さらに、このドラム分割体３５の下端底面には、後述する吸引機構部３２の吸引ポンプ５０によりエアを吸引するための吸引口となる孔部４２が形成されている。かかる孔部４２は、前記空隙部４１を通して前記吸引孔４０と連通している。   As shown in FIG. 9, which is a cross-sectional view taken along line AA of FIG. 5, a plurality of suction holes for sucking and attaching the solid polymer electrolyte membrane 18 to the inner wall surface 39 of the other drum divided body 35 as shown in FIG. 40 is formed. The suction hole 40 is formed so as to surround the outer periphery of the solid polymer electrolyte membrane 18 except for the active region (region contributing to power generation). Further, as shown in FIG. 9B, which is a cross-sectional view taken along the line BB of FIG. 5, the drum divided body 35 has a gap 41 communicating with each suction hole 40 at the center of the plate thickness. The internal space structure is formed. Further, a hole 42 serving as a suction port for sucking air by a suction pump 50 of the suction mechanism portion 32 described later is formed on the bottom surface of the lower end of the drum divided body 35. The hole portion 42 communicates with the suction hole 40 through the gap portion 41.

なお、一方のドラム分割体３４の内壁面４３には、固体高分子電解質膜１８を装着しないため、前記した吸引孔４０、空隙部４１及び孔部４２は形成されていない。   In addition, since the solid polymer electrolyte membrane 18 is not attached to the inner wall surface 43 of the one drum divided body 34, the above-described suction hole 40, gap 41, and hole 42 are not formed.

また、ドラム分割体３４、３５の内壁面３９、４３には、固体高分子電解質膜１８の片面への触媒インク塗布後にもう片面に触媒インクを塗布する際に、内壁面３９、４３に塗布済みの触媒粉末が付着しないように静電防止処理と撥水処理を施している。   Further, the inner wall surfaces 39 and 43 of the drum divided bodies 34 and 35 are already applied to the inner wall surfaces 39 and 43 when the catalyst ink is applied to the other surface after the catalyst ink is applied to one surface of the solid polymer electrolyte membrane 18. An antistatic treatment and a water repellent treatment are applied to prevent the catalyst powder from adhering.

駆動機構部３１は、前記ドラム３０を装着固定させる装着部４４を有した回転体４５と、この回転体４５を、該ドラム３０の軸芯を中心として円周方向（図６中矢印Ｘ方向）に回転させると共に軸芯に沿って移動（図６中矢印Ｙ方向に上下動）させる駆動部４６とからなる。回転体４５は、ドラム３０のほぼ中心に配置され、その周面に複数設けられた装着部４４に前記ドラム３０を装着固定させて、当該ドラム３０を円周方向に回転させるようになっている。   The drive mechanism 31 includes a rotating body 45 having a mounting portion 44 for mounting and fixing the drum 30, and the rotating body 45 in the circumferential direction (in the direction of arrow X in FIG. 6) around the axis of the drum 30. And a drive unit 46 that moves along the axis (moves up and down in the direction of arrow Y in FIG. 6). The rotating body 45 is disposed substantially at the center of the drum 30, and the drum 30 is mounted and fixed to a plurality of mounting portions 44 provided on the peripheral surface thereof to rotate the drum 30 in the circumferential direction. .

装着部４４は、回転体４５の外周面から外方へ延びるように放射状に複数設けられている。この装着部４４の先端側には、前記ドラム３０の下端底面３０ａを嵌合させて該ドラム３０を装着固定する装着凹部４７と、ドラム３０の外壁面に接する上方へ折れ曲がった位置規制部４８とを形成している。そして、装着凹部４７には、ドラム分割体３５の下端底面に形成された孔部４２と連通する開口孔４９を形成している。この開口孔４９は、装着部４４の長手方向に沿ってその内部に形成されたエア通路（図示は省略する）に連通しており、後述する吸引ポンプ５０と接続されている。   A plurality of mounting portions 44 are provided radially so as to extend outward from the outer peripheral surface of the rotating body 45. On the front end side of the mounting portion 44, a mounting recess 47 for fitting and fixing the lower end bottom surface 30 a of the drum 30, and a position restricting portion 48 bent upward in contact with the outer wall surface of the drum 30, Is forming. The mounting recess 47 is formed with an opening hole 49 that communicates with a hole 42 formed on the bottom surface of the lower end of the drum divided body 35. The opening hole 49 communicates with an air passage (not shown) formed in the interior of the mounting portion 44 along the longitudinal direction, and is connected to a suction pump 50 described later.

駆動部４６は、回転体４５を軸芯を中心として回転させる回転機構と、回転体４５を軸芯に沿って移動（上下動）させる上下動機構とを備えている。回転機構としては、駆動モータの駆動軸に回転体４５を直接取り付けた構成、ベルトやチェーンなどで駆動モータの駆動力を回転体４５に伝達する構成、あるいは歯車で駆動モータの駆動力を回転体４５に伝達する構成などが使用できる。上下動機構としては、ボールねじとこのボールねじに螺合するナット部材を回転体４５に取り付けた構成、スライダレールとこのスライダレールにスライドするスライダを回転体４５に取り付けた構成などが使用できる。また、回転機構と上下動機構を一つの機構としたものを駆動部４６とすることもできる。なお、本実施形態では、駆動部４６の具体的な構成に関しては従来公知の機構がいずれも採用できる。   The drive unit 46 includes a rotating mechanism that rotates the rotating body 45 about the axis, and a vertical movement mechanism that moves (moves up and down) the rotating body 45 along the axis. As the rotation mechanism, a structure in which the rotating body 45 is directly attached to the drive shaft of the drive motor, a structure in which the driving force of the driving motor is transmitted to the rotating body 45 by a belt or a chain, or the driving force of the driving motor by a gear is used as the rotating body. The structure etc. which transmit to 45 can be used. As the vertical movement mechanism, a configuration in which a ball screw and a nut member screwed into the ball screw are attached to the rotating body 45, a configuration in which a slider rail and a slider that slides on the slider rail are attached to the rotating body 45, and the like can be used. Further, the drive unit 46 may be a mechanism in which the rotation mechanism and the vertical movement mechanism are combined into one mechanism. In the present embodiment, any conventionally known mechanism can be employed for the specific configuration of the drive unit 46.

吸引機構部３２は、吸引ポンプ５０と、この吸引ポンプ５０に接続されるホース５１に接続する前記した装着部４４に形成したエア通路、開口孔４９およびドラム分割体３５に形成した吸引孔４０、空隙部４１および孔部４２とからなる。吸引ポンプ５０でエアを吸引（真空引き）すると、ドラム分割体３５の空隙部４１内が負圧となり、当該ドラム３０の内壁面３９に開口する吸引孔４０からエアが引かれ、その内壁面３９に装着される固体高分子電解質膜１８が密着して保持される。 The suction mechanism section 32 includes a suction pump 50 and an air passage formed in the mounting section 44 connected to the hose 51 connected to the suction pump 50, an opening hole 49, and a suction hole 40 formed in the drum divided body 35. It consists of a gap 41 and a hole 42. When air is sucked (evacuated) by the suction pump 50, the inside of the gap 41 of the drum divided body 35 becomes negative pressure, and air is drawn from the suction hole 40 opened in the inner wall surface 39 of the drum 30. The solid polymer electrolyte membrane 18 to be attached to is closely attached and held.

スプレー３３は、ノズル５２から触媒インクを噴出させるスプレーコータであり、触媒インクを塗布するときにドラム３０の中心に侵入し、塗布後は上昇するようになっている。   The spray 33 is a spray coater that ejects the catalyst ink from the nozzle 52, enters the center of the drum 30 when applying the catalyst ink, and rises after the application.

「触媒塗布方法」
次に、固体高分子電解質膜１８に触媒インクを塗布する触媒塗布方法について説明する。 "Catalyst application method"
Next, a catalyst application method for applying catalyst ink to the solid polymer electrolyte membrane 18 will be described.

まず、図８（ａ）に示すように、一方のドラム分割体３４を他方のドラム分割体３５に対して前記回動軸３６を中心に開く。そして、一方のドラム分割体３５の内壁面３９に、吸引ポンプ５０による吸引前に固体高分子電解質膜１８を仮止めしやすくするために純水を塗る。次いで、一方のドラム分割体３５の内壁面３９にのみ固体高分子電解質膜１８を装着させる。固体高分子電解質膜１８は、純水によって内壁面３９に貼り付く。この固体高分子電解質膜１８を内壁面３９に装着させるに際しては、高分子電解質膜１８をドラム３０の内壁面に装着させた状態を示す、図５のＡ−Ａ線位置での断面図である図１０（ａ）に示すように、アクティブ領域５４が内壁面３９に形成された吸引孔４０に掛からないようにする。   First, as shown in FIG. 8A, one drum divided body 34 is opened with respect to the other drum divided body 35 around the rotation shaft 36. Then, pure water is applied to the inner wall surface 39 of one drum divided body 35 in order to make it easy to temporarily fix the solid polymer electrolyte membrane 18 before suction by the suction pump 50. Next, the solid polymer electrolyte membrane 18 is attached only to the inner wall surface 39 of one drum divided body 35. The solid polymer electrolyte membrane 18 is attached to the inner wall surface 39 with pure water. FIG. 6 is a cross-sectional view taken along the line AA in FIG. 5, showing a state in which the polymer electrolyte membrane 18 is attached to the inner wall surface of the drum 30 when the solid polymer electrolyte membrane 18 is attached to the inner wall surface 39. As shown in FIG. 10A, the active region 54 is prevented from being caught by the suction hole 40 formed in the inner wall surface 39.

次に、ドラム分割体３４、３５を閉じて円筒状とする。そして、ドラム３０を、前記した回転体４５に設けた装着部４４に装着させる。このとき、ドラム分割体３５の下端底面３０ａに形成した孔部４２が前記装着部４４の開口孔４９に対向するようにドラム３０の前記装着部４４に対する装着位置を調整する。この作業を容易なものとするために、前記孔部４２と開口孔４９との位置を、ドラム分割体３５の外周面にマーキングしておくことが望ましい。   Next, the drum divided bodies 34 and 35 are closed to have a cylindrical shape. Then, the drum 30 is mounted on the mounting portion 44 provided on the rotating body 45 described above. At this time, the mounting position of the drum 30 with respect to the mounting portion 44 is adjusted so that the hole 42 formed in the bottom bottom surface 30 a of the drum divided body 35 faces the opening hole 49 of the mounting portion 44. In order to facilitate this work, it is desirable to mark the positions of the hole 42 and the opening hole 49 on the outer peripheral surface of the drum divided body 35.

次に、駆動部４６を駆動して回転体４５を円周方向に回転させるとともに吸引ポンプ５０を作動させる。回転体４５が回転すると、装着部４４に装着固定されたドラム３０が軸芯を中心として円周方向に回転する。この一方、吸引ポンプ５０が作動すると、吸引孔４０からエアが引かれて固体高分子電解質膜１８が内壁面３９に吸着保持される。ドラム３０の遠心力で固体高分子電解質膜１８が内壁面３９に貼り付いたら吸引ポンプ５０の作動を停止して吸引を解除する。吸引を解除してもドラム３０の遠心力が固体高分子電解質膜１８に作用しているので、当該固体高分子電解質膜１８が内壁面３９から剥がれて落ちることはない。   Next, the drive unit 46 is driven to rotate the rotating body 45 in the circumferential direction and the suction pump 50 is operated. When the rotating body 45 rotates, the drum 30 mounted and fixed on the mounting portion 44 rotates in the circumferential direction about the axis. On the other hand, when the suction pump 50 is operated, air is drawn from the suction hole 40 and the solid polymer electrolyte membrane 18 is adsorbed and held on the inner wall surface 39. When the solid polymer electrolyte membrane 18 adheres to the inner wall surface 39 by the centrifugal force of the drum 30, the operation of the suction pump 50 is stopped and the suction is released. Even if the suction is released, the centrifugal force of the drum 30 acts on the solid polymer electrolyte membrane 18, so that the solid polymer electrolyte membrane 18 is not peeled off from the inner wall surface 39.

そして、ドラム３０の回転が一定になったところで、スプレー３３をドラム３０の中心に侵入させ、ノズル５２から前記した第１の層２１ａを構成する触媒インク５３ａを、触媒インクを塗布している状態を示す触媒塗布装置の斜視図である図１１に示すように、固体高分子電解質膜１８の一面に吹き付ける。また、スプレー３３による触媒インク５３ａの吹き付け位置に応じて回転体４５を上下動させる。これにより、固体高０分子電解質膜１８のアクティブ領域全体に触媒インク５３ａが吹き付けられることになる。また、ドラム３０を回転させながら触媒インク５３ａを吹き付けると、遠心力によりＰｔなどの重い触媒はドラム内壁側へ移動し、固体高分子電解質膜１８側の触媒濃度が大きくなる。また、触媒インク５３に含まれた気泡が表面に浮き上がってくる。そして、触媒インク５３ａを塗布し終えたらドラム３０の回転動作および上下動動作を停止させる。   When the rotation of the drum 30 becomes constant, the spray 33 enters the center of the drum 30 and the catalyst ink 53a constituting the first layer 21a is applied from the nozzle 52 to the catalyst ink. As shown in FIG. 11 which is a perspective view of the catalyst coating apparatus showing the above, it is sprayed on one surface of the solid polymer electrolyte membrane 18. Further, the rotating body 45 is moved up and down according to the spraying position of the catalyst ink 53a by the spray 33. As a result, the catalyst ink 53a is sprayed over the entire active region of the solid high-molecular electrolyte membrane 18. When the catalyst ink 53a is sprayed while the drum 30 is rotated, a heavy catalyst such as Pt moves to the drum inner wall side by centrifugal force, and the catalyst concentration on the solid polymer electrolyte membrane 18 side increases. In addition, bubbles contained in the catalyst ink 53 float on the surface. When the application of the catalyst ink 53a is completed, the rotation operation and the vertical movement operation of the drum 30 are stopped.

なお、図１０（ｂ）は触媒インク塗布後の状態を示す、図５のＡ−Ａ線位置での断面図である。   FIG. 10B is a cross-sectional view taken along the line AA in FIG. 5, showing a state after the application of the catalyst ink.

そして、上記の第１の層２１ａの上に、第２の層２１ｂを、上記と同様にして塗布し、これにより、前記図３に示したように、固体高分子電解質膜１８上の触媒層２１は、固体高分子電解質膜１８側の触媒インク５３ａからなる第１の層２１ａと、この第１の層２１ａ上の触媒インク５３ｂからなる第２の層２１ａが順次形成された２層状態となる。   Then, the second layer 21b is applied on the first layer 21a in the same manner as described above, whereby the catalyst layer on the solid polymer electrolyte membrane 18 as shown in FIG. 21 is a two-layer state in which a first layer 21a made of the catalyst ink 53a on the solid polymer electrolyte membrane 18 side and a second layer 21a made of the catalyst ink 53b on the first layer 21a are sequentially formed. Become.

次に、塗布した触媒インク５３ａ，５３ｂが乾燥したところで、スプレー３３を待避させ、その代わりに、乾燥した触媒層の表面を削り滑らかにする加工を施す状態を示す斜視図である図１２に示すように、切削手段である筒状のヤスリ５５をドラム３０の中心に挿入させる。そして、駆動部４６を駆動してドラム３０を回転させながらヤスリ５５で触媒層２１の第２の層２１ｂの表面を削り、当該第２の層２１ｂの表面を滑らかにする。   Next, when the applied catalyst inks 53a and 53b are dried, the spray 33 is withdrawn, and instead, the surface of the dried catalyst layer is shaved and smoothed to show a state in which it is processed as shown in FIG. Thus, the cylindrical file 55 which is a cutting means is inserted into the center of the drum 30. Then, the surface of the second layer 21b of the catalyst layer 21 is shaved with a file 55 while the driving unit 46 is driven to rotate the drum 30 to smooth the surface of the second layer 21b.

ヤスリ掛けが終了したらドラム３０を装着部４４から取り外し、図８（ｂ）で示すように、ドラム３０を開いて触媒層２１が片面に形成された固体高分子電解質膜１８を内壁面３９から取り外す。次に、この触媒層２１を貼り付け面として内壁面３９に固体高分子電解質膜１８を貼り付ける。このとき、内壁面３９には静電防止処理と撥水処理が施されているので、塗布済みの触媒粉末が内壁面３９に付着してドラム３０と導通するのが防止される。   When the file is finished, the drum 30 is removed from the mounting portion 44. As shown in FIG. 8B, the drum 30 is opened and the solid polymer electrolyte membrane 18 having the catalyst layer 21 formed on one side is removed from the inner wall surface 39. . Next, the solid polymer electrolyte membrane 18 is attached to the inner wall surface 39 using the catalyst layer 21 as an attachment surface. At this time, since the inner wall surface 39 has been subjected to antistatic treatment and water repellent treatment, the coated catalyst powder is prevented from adhering to the inner wall surface 39 and being electrically connected to the drum 30.

以下、同様の工程を行い固体高分子電解質膜１８の他方の面にも触媒インク５３ａ，５３ｂを塗布して、第１の層２３ａ，第２の層２３ｂからなる２層構造の触媒層２３を形成する。   Thereafter, the same process is performed to apply the catalyst inks 53a and 53b to the other surface of the solid polymer electrolyte membrane 18, so that the catalyst layer 23 having a two-layer structure including the first layer 23a and the second layer 23b is formed. Form.

上記した第１の実施形態によれば、固体高分子電解質膜１８側に位置する第１の層２１ａ，２３ａからなる触媒インク５３ａは、第２の層２１ｂ，２３ｂからなる触媒インク５３ｂに比較して、触媒担持カーボン粒子の触媒担持率が高く、電解質の量が多く、触媒担持カーボン粒子の粉砕度合いが大きく（粒径が小さく）なっている。   According to the first embodiment described above, the catalyst ink 53a composed of the first layers 21a and 23a located on the solid polymer electrolyte membrane 18 side is compared with the catalyst ink 53b composed of the second layers 21b and 23b. Thus, the catalyst supporting rate of the catalyst supporting carbon particles is high, the amount of the electrolyte is large, and the degree of pulverization of the catalyst supporting carbon particles is large (the particle size is small).

ここで、例えば触媒担持カーボンの触媒担持率が高いと触媒濃度が高くなり、また吸水性の高い電解質の量が多いと、多量の電解質によって液水を保持しやすく、さらに触媒担持カーボンの粉砕度合いが大きいことからカーボン表面積が大きくなって触媒濃度も高くなる。   Here, for example, if the catalyst loading rate of the catalyst-carrying carbon is high, the catalyst concentration becomes high, and if the amount of the electrolyte having high water absorption is large, liquid water can be easily held by a large amount of electrolyte, and the degree of pulverization of the catalyst-carrying carbon Is large, the carbon surface area is increased and the catalyst concentration is also increased.

この結果、このような触媒インク５３ａは、固体高分子電解質膜１８と馴染みやすく、触媒濃度が高いことから反応性が良好となって、発電性が重視されたものとなり、燃料電池の出力向上に寄与することができる。   As a result, such a catalyst ink 53a is easy to become familiar with the solid polymer electrolyte membrane 18, and since the catalyst concentration is high, the reactivity becomes good and power generation is emphasized, and the output of the fuel cell is improved. Can contribute.

一方、第１の層２１ａ，２３ａからなる触媒インク５３ａに比較して、触媒担持カーボン粒子の触媒担持率が低く、電解質の量が少なく、触媒担持カーボンの粉砕度合いが小さい（粒径が大きい）第２の層２１ｂ，２３ｂからなる触媒インク５３ｂは、触媒担持カーボン粒子の触媒担持率が低いことから触媒濃度が低く、また電解質の量が少ないことから、液水を保持しにくく、さらに触媒担持カーボンの粉砕度合いが小さいことから、カーボン表面積が小さくなって触媒濃度も低くなる。   On the other hand, compared with the catalyst ink 53a composed of the first layers 21a and 23a, the catalyst supporting carbon particles have a lower catalyst supporting rate, the amount of electrolyte is small, and the degree of pulverization of the catalyst supporting carbon is small (the particle size is large). The catalyst ink 53b composed of the second layers 21b and 23b has a low catalyst concentration because the catalyst-carrying carbon particles have a low catalyst-carrying rate, and also has a small amount of electrolyte, so that it is difficult to hold liquid water. Since the degree of pulverization of carbon is small, the carbon surface area is reduced and the catalyst concentration is also reduced.

この結果、このような触媒インク５３ｂは、カーボン粒子周囲の液水が少なくなり、燃料電池スタック１の起動停止による触媒・カーボンの腐食が抑制され、またカーボン表面積が小さく触媒濃度が低いことから反応ガスと接触しにくく、燃料電池スタック１の起動停止によるカーボンの腐食が抑制され、耐久性が重視されたものとなり、燃料電池の耐久性向上に寄与することができる。   As a result, the catalyst ink 53b reacts because the liquid water around the carbon particles is reduced, the catalyst / carbon corrosion due to the start and stop of the fuel cell stack 1 is suppressed, and the carbon surface area is small and the catalyst concentration is low. It is difficult to come into contact with gas, carbon corrosion due to the start and stop of the fuel cell stack 1 is suppressed, and durability is emphasized, which can contribute to improving the durability of the fuel cell.

さらに、触媒担持カーボン粒子の粉砕度合いが小さいために、粉砕後の触媒担持カーボン粒子相互間の隙間が大きくなり、反応ガスや液水の拡散性が向上する。   Further, since the degree of pulverization of the catalyst-carrying carbon particles is small, the gap between the crushed catalyst-carrying carbon particles is increased, and the diffusibility of the reaction gas and liquid water is improved.

したがって、上記したような発電性を重視した触媒インク５３ａを固体高分子電解質膜１８側に塗布し、一方耐久性を重視した触媒インクと５３ｂを、固体高分子電解質膜１８側とは反対のガス拡散層２２，２４側に、互いに別々の層となるよう塗り分けして塗布することで、燃料電池スタック１の発電性および耐久性を共に高めて良好な燃料電池性能を確保することができる。   Therefore, the above-described catalyst ink 53a focusing on power generation is applied to the solid polymer electrolyte membrane 18 side, while the catalyst ink 53b focusing on durability and 53b are gas opposite to the solid polymer electrolyte membrane 18 side. By separately coating the diffusion layers 22 and 24 so as to be separate layers, it is possible to improve both the power generation performance and durability of the fuel cell stack 1 and to ensure good fuel cell performance.

また、電解質は、触媒担持カーボン粒子の粉砕後に、この粉砕した触媒担持カーボン粒子が混入する溶媒中に投入し分散させている。このため、電解質は、過剰に分散されることを回避して過剰な水分保持を防止し、燃料電池スタック１の起動停止操作時での水と触媒層中のカーボンとの反応を防止して、起動停止時での耐久性を高めることができる。   Further, after the catalyst-carrying carbon particles are pulverized, the electrolyte is charged and dispersed in a solvent in which the pulverized catalyst-carrying carbon particles are mixed. For this reason, the electrolyte avoids excessive water retention by avoiding excessive dispersion, prevents reaction between water and carbon in the catalyst layer during the start / stop operation of the fuel cell stack 1, The durability at the time of starting and stopping can be improved.

さらに、触媒インクの固体高分子電解質膜１８への塗布は、遠心力を利用して行うことで、比重の大きい触媒担持カーボン粒子が固体高分子電解質膜１８側に寄せられ、固体高分子電解質膜１８側の触媒濃度が高くなるような触媒濃度勾配を形成でき、発電性能を高めることができる。   Furthermore, application of the catalyst ink to the solid polymer electrolyte membrane 18 is performed using centrifugal force, so that the catalyst-carrying carbon particles having a large specific gravity are brought closer to the solid polymer electrolyte membrane 18 side, and the solid polymer electrolyte membrane is thus obtained. A catalyst concentration gradient that increases the catalyst concentration on the 18th side can be formed, and power generation performance can be improved.

また、上記のように遠心力を利用して触媒インクを塗布することで、触媒インク中の泡が触媒層２１，２３の表面に浮き上がり、表面を、乾燥後に研磨することで平滑化しやすくなる。   In addition, by applying the catalyst ink using centrifugal force as described above, bubbles in the catalyst ink float on the surfaces of the catalyst layers 21 and 23, and the surfaces are easily smoothed by polishing after drying.

上述の実施形態では、触媒塗布手段としてスプレー３３による塗布として例示したが、図１３に示すように、ダイヘッド５８をドラム３０の内側（中心）に挿入し、そのダイヘッド５８から触媒インク５３ａ，５３ｂを固体高分子電解質膜１８に塗布するようにしてもよい。   In the above-described embodiment, the application by the spray 33 is exemplified as the catalyst application unit. However, as shown in FIG. 13, the die head 58 is inserted into the inside (center) of the drum 30, and the catalyst inks 53 a and 53 b are discharged from the die head 58. It may be applied to the solid polymer electrolyte membrane 18.

また、上述の実施形態では、吸引手段によってドラム３０の内壁面３９に固体高分子電解質膜１８を吸着保持させたが、静電気により固体高分子電解質膜１８を内壁面３９に固定させてもよい。   In the above-described embodiment, the solid polymer electrolyte membrane 18 is adsorbed and held on the inner wall surface 39 of the drum 30 by the suction means. However, the solid polymer electrolyte membrane 18 may be fixed to the inner wall surface 39 by static electricity.

また、上述の実施形態では、筒状のヤスリ５５を使用したが、図１４に示すように、棒５９の先端部のみにヤスリ６０が形成された切削手段を使用してもよい。   In the above-described embodiment, the cylindrical file 55 is used. However, as shown in FIG. 14, a cutting means in which a file 60 is formed only at the tip of the rod 59 may be used.

また、上述の実施形態では、乾燥後の触媒層２１，２３の表面をヤスリ５５，６０で削って滑らかにするようにしたが、図１５に示すように、回転軸６１の先端に設けた圧延ローラ６２を触媒層２１，２３に押し付けて当該触媒層２１，２３の表面を平坦にするようにしてもよい。   In the above-described embodiment, the surfaces of the dried catalyst layers 21 and 23 are smoothed by the files 55 and 60. However, as shown in FIG. The roller 62 may be pressed against the catalyst layers 21 and 23 to flatten the surfaces of the catalyst layers 21 and 23.

本発明の第２の実施形態として、固体高分子電解質膜１８上に形成する触媒層２１，２３を、互いに別々の層となるよう塗り分ける際に、図１６に示すように、燃料電池の発電性、特に初期発電性を重視した前記触媒インク５３ａからなる第１の層２１α（２３α）と、燃料電池の耐久性を重視した前記触媒インク５３ｂからなる第２の層２１β（２３β）とを、交互に塗り分けるようにしている。   As a second embodiment of the present invention, when the catalyst layers 21 and 23 formed on the solid polymer electrolyte membrane 18 are separately applied to be separate layers, as shown in FIG. The first layer 21α (23α) made of the catalyst ink 53a focusing on the performance, particularly the initial power generation property, and the second layer 21β (23β) made of the catalyst ink 53b focused on the durability of the fuel cell, I try to paint them alternately.

その際、第１，第２の各層２１α（２３α），２１β（２３β）の長手方向が、図１７（ａ）に示すように、矢印Ｇで示す反応ガスの流れ方向と交差していてもよく、また図１７（ｂ）に示すように、矢印Ｇで示す反応ガスの流れ方向に沿っていてもよい。   At that time, the longitudinal direction of each of the first and second layers 21α (23α) and 21β (23β) may intersect the flow direction of the reaction gas indicated by the arrow G as shown in FIG. Also, as shown in FIG. 17 (b), it may be along the flow direction of the reaction gas indicated by the arrow G.

上記のようにして触媒インク５３ａ，５３ｂを塗布する作業は、例えばスクリーン印刷装置を用いて行うことができる。   The operation of applying the catalyst inks 53a and 53b as described above can be performed using, for example, a screen printing apparatus.

第２の実施形態においては、燃料電池の発電性、特に初期発電性を重視した前記触媒インク５３ａからなる第１の層２１α（２１β）と、燃料電池の耐久性を重視した前記触媒インク５３ｂからなる第２の層２１β（２３β）を、固体高分子電解質膜１８上に形成しているので、従来のように、燃料電池の初期発電性および耐久性のいずれにおいても中間程度の性能を維持する触媒インクを使用する場合に比較して、燃料電池の発電性および耐久性を共に高めて良好な燃料電池性能を確保することができる。   In the second embodiment, from the first layer 21α (21β) made of the catalyst ink 53a that emphasizes the power generation performance of the fuel cell, particularly the initial power generation performance, and the catalyst ink 53b that emphasizes the durability of the fuel cell. Since the second layer 21β (23β) to be formed is formed on the solid polymer electrolyte membrane 18, the intermediate performance is maintained in both the initial power generation performance and durability of the fuel cell as in the prior art. Compared with the case where catalyst ink is used, both the power generation performance and durability of the fuel cell can be enhanced to ensure good fuel cell performance.

燃料電池スタックの全体構成図である。1 is an overall configuration diagram of a fuel cell stack. 図１の燃料電池スタックにおける燃料電池単セルの拡大断面図である。It is an expanded sectional view of the fuel cell single cell in the fuel cell stack of FIG. 本発明の第１の実施形態に係わる固体高分子電解質膜上に触媒層を形成した状態を示す側面図である。It is a side view which shows the state which formed the catalyst layer on the solid polymer electrolyte membrane concerning the 1st Embodiment of this invention. （ａ）は、第１の層を形成する触媒インクの調整工程図、（ｂ）は、第２の層を形成する触媒インクの調整工程図である。(A) is the adjustment process figure of the catalyst ink which forms a 1st layer, (b) is the adjustment process figure of the catalyst ink which forms a 2nd layer. 触媒インクを固体高分子電解質膜上に塗布する触媒塗布装置の斜視図である。It is a perspective view of the catalyst coating device which coats catalyst ink on a solid polymer electrolyte membrane. 図５の触媒塗布装置の分解斜視図である。It is a disassembled perspective view of the catalyst coating apparatus of FIG. 図５の触媒塗布装置の平面図である。It is a top view of the catalyst coating apparatus of FIG. 図５の触媒塗布装置におけるドラムの平面図であり、（ａ）は高分子電解質膜をドラムに装着する前の状態、（ｂ）は高分子電解質膜に触媒インクを塗布後の状態である。FIG. 6 is a plan view of a drum in the catalyst coating apparatus of FIG. 5, (a) is a state before the polymer electrolyte membrane is mounted on the drum, and (b) is a state after the catalyst ink is applied to the polymer electrolyte membrane. （ａ）は図５のＡ−Ａ線断面図、（ｂ）は図５のＢ−Ｂ線断面図である。(A) is the sectional view on the AA line of FIG. 5, (b) is the sectional view on the BB line of FIG. （ａ）は高分子電解質膜をドラムの内壁面に装着させた状態を示す図５のＡ−Ａ線位置での断面図、（ｂ）は触媒インク塗布後の状態を示す図５のＡ−Ａ線位置での断面図である。5A is a cross-sectional view taken along the line AA in FIG. 5 showing a state in which the polymer electrolyte membrane is attached to the inner wall surface of the drum, and FIG. 5B is a cross-sectional view taken after application of the catalyst ink in FIG. It is sectional drawing in the A line position. 触媒インクを塗布している状態を示す触媒塗布装置の斜視図である。It is a perspective view of the catalyst application apparatus which shows the state which has apply | coated the catalyst ink. 乾燥後の触媒層をヤスリで削って表面を滑らかにする工程を示す斜視図である。It is a perspective view which shows the process of shaving off the catalyst layer after drying, and smoothing the surface. ダイヘッドを使用して触媒インクを固体高分子電解質膜に塗布する例を示す図である。It is a figure which shows the example which apply | coats catalyst ink to a solid polymer electrolyte membrane using a die head. 先端部のみにヤスリが形成された切削手段を使用した例を示す図である。It is a figure which shows the example using the cutting means in which the file was formed only in the front-end | tip part. 圧延ローラを触媒層に押し付けて表面を平坦にする例を示す図である。It is a figure which shows the example which presses a rolling roller against a catalyst layer, and makes the surface flat. 本発明の第２の実施形態に係わる固体高分子電解質膜上に触媒層を形成した状態を示す平面図である。It is a top view which shows the state which formed the catalyst layer on the solid polymer electrolyte membrane concerning the 2nd Embodiment of this invention. 第２の実施形態における固体高分子電解質膜上に触媒層を形成した状態を示す平面図で、（ａ）は第１，第２の各層の長手方向が、反応ガスの流れ方向と交差していている状態、（ｂ）は第１，第２の各層の長手方向が、反応ガスの流れ方向に沿っている状態を示す。It is a top view which shows the state which formed the catalyst layer on the solid polymer electrolyte membrane in 2nd Embodiment, (a) is the longitudinal direction of each 1st, 2nd layer crossing the flow direction of a reactive gas. (B) shows the state where the longitudinal direction of each of the first and second layers is along the flow direction of the reaction gas.

符号の説明Explanation of symbols

１８ 固体高分子電解質膜（電解質膜）
２１，２３ 触媒層
２１ａ，２３ａ 第１の層（別々の層）
２１ｂ，２３ｂ 第２の層（別々の層）
２１α，２３α 第１の層（別々の層）
２１β，２３β 第２の層（別々の層）
２８ 溶媒
２９Ａ，２９Ｂ 触媒担持カーボン粒子
５３ａ，５３ｂ 触媒インク
１００ 電解質
２９０Ａ，２９０Ｂ 粉砕後の触媒担持カーボン粒子 18 Solid polymer electrolyte membrane (electrolyte membrane)
21, 23 Catalyst layers 21a, 23a First layer (separate layers)
21b, 23b Second layer (separate layers)
21α, 23α First layer (separate layers)
21β, 23β Second layer (separate layers)
28 Solvent 29A, 29B Catalyst-supported carbon particles 53a, 53b Catalyst ink 100 Electrolyte 290A, 290B Catalyst-supported carbon particles after pulverization

Claims (9)

触媒担持カーボン粒子と、電解質と、溶媒とを混合、分散させて触媒インクとし、この触媒インクを電解質膜に塗布する際に、前記触媒担持カーボン粒子の触媒担持率と、前記電解質の量と、前記触媒担持カーボン粒子の粉砕度合いとの少なくとも一つの条件が異なる複数種類の触媒インクを製造し、この複数種類の触媒インクを、前記電解質膜に互いに別々の層となるよう塗り分けして塗布する燃料電池の電極用触媒層の形成方法であって、前記複数種類の触媒インクの前記三つの条件すべてを異なるものとし、この三つの条件すべてが大となる触媒インクが、前記電解質膜側となるよう前記触媒インクを前記電解質膜に塗布することを特徴とする燃料電池の電極用触媒層の形成方法。   The catalyst-supporting carbon particles, the electrolyte, and the solvent are mixed and dispersed to form a catalyst ink, and when the catalyst ink is applied to the electrolyte membrane, the catalyst-supporting rate of the catalyst-supporting carbon particles, the amount of the electrolyte, A plurality of types of catalyst inks having at least one condition different from the degree of pulverization of the catalyst-carrying carbon particles are manufactured, and the plurality of types of catalyst inks are separately applied to the electrolyte membrane so as to form separate layers. A method for forming a catalyst layer for an electrode of a fuel cell, wherein all three conditions of the plurality of types of catalyst inks are different, and a catalyst ink in which all three conditions are large is on the electrolyte membrane side. A method for forming a catalyst layer for an electrode of a fuel cell, wherein the catalyst ink is applied to the electrolyte membrane. 前記複数種類の触媒インクを、前記電解質膜の互いに異なる面上に塗り分けして塗布することを特徴とする請求項１に記載の燃料電池の電極用触媒層の形成方法。 2. The method for forming a catalyst layer for an electrode of a fuel cell according to claim 1, wherein the plurality of types of catalyst inks are applied separately on different surfaces of the electrolyte membrane. 前記三つの条件すべてを異なるものとし、この三つの条件すべてが大となる触媒インクと、同小となる触媒インクとを、前記電解質膜の互いに異なる面上に塗り分けして塗布することを特徴とする請求項２に記載の燃料電池の電極用触媒層の形成方法。 The three conditions are all different, and the catalyst ink that is large for all three conditions and the catalyst ink that is small for the three conditions are separately applied onto different surfaces of the electrolyte membrane. The method for forming a catalyst layer for an electrode of a fuel cell according to claim 2 . 前記三つの条件すべてが大となる触媒インクと、同小となる触媒インクとを、前記電解質膜上に交互に塗り分けして塗布することを特徴とする請求項３に記載の燃料電池の電極用触媒層の形成方法。 4. The fuel cell electrode according to claim 3 , wherein a catalyst ink having a large value for all three conditions and a catalyst ink having a small value are applied separately on the electrolyte membrane. 5. For forming a catalyst layer for use. 前記電解質は、前記触媒担持カーボン粒子の粉砕後に、この粉砕した触媒担持カーボン粒子が混入する前記溶媒中に投入することを特徴とする請求項１ないし４のいずれか１項に記載の燃料電池の電極用触媒層の形成方法。 The electrolyte, after the grinding of the catalyst-carrying carbon particles, the fuel cell according to any one of claims 1 to 4, characterized in that introducing in the solvent that the crushed catalyst carrying carbon particles are mixed Method for forming electrode catalyst layer. 触媒担持カーボン粒子と、電解質と、溶媒とを混合、分散させて触媒インクとし、この触媒インクが電解質膜に塗布された燃料電池の電極用触媒層において、前記触媒担持カーボン粒子の触媒担持率と、前記電解質の量と、前記触媒担持カーボン粒子の粉砕度合いとの少なくとも一つの条件が異なる複数種類の触媒インクを製造し、この複数種類の触媒インクが、前記電解質膜に互いに別々の層となるよう塗り分けして塗布されていて、前記複数種類の触媒インクの前記三つの条件すべてを異なるものとし、この三つの条件すべてが大となる触媒インクが、前記電解質膜側となるよう前記電解質膜に塗布されていることを特徴とする燃料電池の電極用触媒層。   In the catalyst layer for a fuel cell electrode in which catalyst-supported carbon particles, an electrolyte, and a solvent are mixed and dispersed to form a catalyst ink, and this catalyst ink is applied to the electrolyte membrane, And producing a plurality of types of catalyst inks having different conditions of at least one of the amount of the electrolyte and the degree of pulverization of the catalyst-carrying carbon particles, and the plurality of types of catalyst inks form separate layers on the electrolyte membrane. The electrolyte membrane is applied in such a manner that all three conditions of the plurality of types of catalyst inks are different, and the catalyst ink in which all three conditions are large is on the electrolyte membrane side. A catalyst layer for an electrode of a fuel cell, which is coated on the electrode. 前記複数種類の触媒インクが、前記電解質膜の互いに異なる面上に塗り分けして塗布されていることを特徴とする請求項６に記載の燃料電池の電極用触媒層。 The catalyst layer for an electrode of a fuel cell according to claim 6 , wherein the plurality of types of catalyst inks are applied separately on different surfaces of the electrolyte membrane. 前記三つの条件すべてが大きい触媒インクと、同小さい触媒インクとを、前記電解質膜の互いに異なる面上に塗り分けして塗布されていることを特徴とする請求項７に記載の燃料電池の電極用触媒層。 8. The electrode of a fuel cell according to claim 7 , wherein a catalyst ink having a large size for all three conditions and a catalyst ink having the same small size are applied separately on different surfaces of the electrolyte membrane. Catalyst layer. 前記三つの条件すべてが大となる触媒インクと、同小となる触媒インクとが、前記電解質膜上に交互に塗り分けして塗布されていることを特徴とする請求項８に記載の燃料電池の電極用触媒層。 9. The fuel cell according to claim 8 , wherein a catalyst ink having a large value for all three conditions and a catalyst ink having a small value for the three conditions are alternately applied separately on the electrolyte membrane. The electrode catalyst layer.
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