JP2006004787A - Gas diffusion membrane for solid polymer electrolyte fuel cell - Google Patents

Gas diffusion membrane for solid polymer electrolyte fuel cell Download PDF

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JP2006004787A
JP2006004787A JP2004180401A JP2004180401A JP2006004787A JP 2006004787 A JP2006004787 A JP 2006004787A JP 2004180401 A JP2004180401 A JP 2004180401A JP 2004180401 A JP2004180401 A JP 2004180401A JP 2006004787 A JP2006004787 A JP 2006004787A
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gas diffusion
membrane
fuel cell
recess
water
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Takashi Wano
隆司 和野
Tomoaki Uchiyama
智暁 内山
Masakatsu Urairi
正勝 浦入
Hiroyuki Higuchi
浩之 樋口
Noriyuki Kobayashi
宣之 小林
Harumichi Nakanishi
治通 中西
Keiichi Nakada
圭一 中田
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Nitto Denko Corp
Toyota Motor Corp
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Nitto Denko Corp
Toyota Motor Corp
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas diffusion membrane for a solid polyelectrolyte fuel cell which is superior in water management in a wide range of battery reaction ranging from a high electric current density area to a low electric current density area, and which does not obstruct a battery reaction, and in which permeation of the gas is uniform. <P>SOLUTION: In a gas diffusion membrane 10, a recess 13 is installed from the front surface toward the rear face of a hydrophobic porous membrane 12 formed of a hydrophobic binder resin and a conductive material. When this gas diffusion membrane 10 is positioned in the fuel cell so that its rear face will come to the electrode side, a superior water management capability is demonstrated. In other words, in the low electric current density area, the generated water is prevented from coming off since the porous membrane is hydrophobic and therefore the water is retained within the electrolyte membrane, while in the high electric current density area, the large quantity of generated water is evaporated, diffused through holes of the porous membrane, and condensed in the porous membrane, but the generated water is exhausted via the recess as a water passage. In addition, the battery reaction is not obstructed since the rear face contacting the electrode is flat and smooth and has a large contacting area with the electrode. Furthermore, since no penetration hole is installed in the porous membrane, the permeation of the gas also becomes uniformized. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、固体高分子電解質型燃料電池用ガス拡散膜に関する。   The present invention relates to a gas diffusion membrane for a solid polymer electrolyte fuel cell.

省エネルギーで環境にもやさしいという理由により、燃料電池が注目されており、自動車等で一部実用化されている。燃料電池は様々なタイプがあるが、図７に、固体高分子電解質型燃料電池の一例を示す。図示のように、この固体高分子電解質型燃料電池は、電解質膜（ＰＥＭ）６５、一対の電極６４、一対のガス拡散膜６３および一対のセパレータ６１を主要構成部材として、これらの部材で一つのセルが形成されている。前記ＰＥＭ６５は、プロトン伝導性を持ち、その外側に、貴金属を含む一対の電極６４が配置され、その一方がアノードに、他方がカソードになる。前記両電極６４のそれぞれの外側に、一対のガス拡散膜６３が配置されている。前記ガス拡散膜６３は、水素ガス、酸素（空気）を透過、拡散し、また生成した水を排水させ、且つ電極で発生した電子を集電、伝導する役割を果たす。さらに、前記ガス拡散膜６３のそれぞれの外側にガス流路６２が設けられたセパレータ６１が配置されている。前記固体高分子電解質型燃料電池において、アノードには水素が供給され、触媒によりプロトンが生成する。このプロトンは、電解質膜を通り、カソードに達し、電子と結合し、水が生成する。電解質膜のプロトンの伝導度は、膜内の水分によって変化し、水分量が多いと伝導度は上がり、水分量が少ないと伝導度は下がる。固体高分子電解質型燃料電池において、水分の管理は極めて重要であり、カソードでの水の排水および電解質膜の保水を両立させることが必要である。   Fuel cells are attracting attention because they are energy-saving and environmentally friendly, and are partially put into practical use in automobiles and the like. Although there are various types of fuel cells, FIG. 7 shows an example of a solid polymer electrolyte fuel cell. As shown in the figure, this solid polymer electrolyte fuel cell includes an electrolyte membrane (PEM) 65, a pair of electrodes 64, a pair of gas diffusion membranes 63, and a pair of separators 61 as main constituent members. A cell is formed. The PEM 65 has proton conductivity, and a pair of electrodes 64 including a noble metal are arranged on the outside thereof, one of which is an anode and the other is a cathode. A pair of gas diffusion films 63 are arranged on the outer sides of both electrodes 64. The gas diffusion film 63 plays a role of permeating and diffusing hydrogen gas and oxygen (air), draining generated water, and collecting and conducting electrons generated at the electrodes. Furthermore, a separator 61 provided with a gas flow path 62 is disposed outside each of the gas diffusion films 63. In the solid polymer electrolyte fuel cell, hydrogen is supplied to the anode, and protons are generated by the catalyst. The protons pass through the electrolyte membrane, reach the cathode, and combine with electrons to generate water. The proton conductivity of the electrolyte membrane varies depending on the moisture in the membrane, and the conductivity increases when the amount of moisture is large, and decreases when the amount of moisture is small. In a solid polymer electrolyte fuel cell, water management is extremely important, and it is necessary to achieve both water drainage at the cathode and water retention in the electrolyte membrane.

従来から、集電体となるカーボンペーパ等に層を設けたものを、ガス拡散膜とし、水分の制御が行われている（特許文献１参照）。図８に、前記ガス拡散膜の一例を示す。図示のように、このガス拡散膜７０は、カーボンペーパ７７と疎水層７６とで形成されている。前記カーボンペーパ７７は、基材としての役割を持つ。前記疎水層７６は、カーボンやそれに類似する導電性材料とポリテトラフルオロエチレン（ＰＴＦＥ）やテトラフルオロエチレン／パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）等の疎水性バインダー樹脂との混合ペーストを前記カーボンペーパ７７に塗布することで形成される。基材となるカーボンペーパ７７と疎水層７６を含めてガス拡散膜７０とし、疎水層の側に電極を配置して、固体高分子電解質型燃料電池の水分管理に用いている。図９に、前記ガス拡散膜７０を固体高分子電解質型燃料電池に適用した例を示す。図示のように、ＰＥＭ８５の外側には、電極（アノード若しくはカソード）８４が配置され、その外側にガス拡散膜７０が配置され、その外側にセパレータ８１が配置されている。ガス拡散膜７０は、その疎水層７６が電極８４側に位置し、かつその基材層７７がセパレータ８１側に位置する状態で、配置されている。しかしながら、前記導電性材料と疎水性バインダー樹脂との混合ペーストを塗布したガス拡散膜では、電池出力を上げた高電流密度域では、より多くの水が生成し、水の排水が不十分となり、カソード側のガス拡散膜内で凝縮した水がガス拡散を阻害し、急激に電池性能が低下するという問題があった。その一方で、低電流密度域では、少ない水の生成量に対して排水が良過ぎ、電解質膜が渇れてしまい、電池性能が低下するという問題があった。すなわち、この種のガス拡散膜では、高電流密度域から低電流密度域までの広範囲な電池反応で排水・保水の両立を達成するのが困難であった。また、混合ペーストを塗布する方法では、層厚みが一定にならず、水分管理が部分的に異なるため、電池反応が不均一に起こり、これに起因して電池性能が低下するという問題もあった。   Conventionally, water is controlled by using a carbon paper or the like as a current collector provided with a layer as a gas diffusion film (see Patent Document 1). FIG. 8 shows an example of the gas diffusion film. As shown in the figure, the gas diffusion film 70 is formed of a carbon paper 77 and a hydrophobic layer 76. The carbon paper 77 has a role as a base material. The hydrophobic layer 76 is formed by mixing a mixed paste of carbon or a conductive material similar thereto with a hydrophobic binder resin such as polytetrafluoroethylene (PTFE) or tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA). It is formed by applying to paper 77. A gas diffusion film 70 including a carbon paper 77 and a hydrophobic layer 76 as a base material is formed, and an electrode is disposed on the hydrophobic layer side, which is used for moisture management of the solid polymer electrolyte fuel cell. FIG. 9 shows an example in which the gas diffusion membrane 70 is applied to a solid polymer electrolyte fuel cell. As shown in the figure, an electrode (anode or cathode) 84 is disposed outside the PEM 85, a gas diffusion film 70 is disposed outside thereof, and a separator 81 is disposed outside thereof. The gas diffusion film 70 is disposed in a state where the hydrophobic layer 76 is located on the electrode 84 side and the base material layer 77 is located on the separator 81 side. However, in the gas diffusion film coated with the mixed paste of the conductive material and the hydrophobic binder resin, more water is generated in the high current density region where the battery output is increased, and the drainage of water becomes insufficient. There is a problem that the water condensed in the gas diffusion film on the cathode side hinders the gas diffusion and the battery performance is rapidly deteriorated. On the other hand, in the low current density region, there is a problem that drainage is too good for a small amount of generated water, the electrolyte membrane is exhausted, and the battery performance is lowered. That is, with this type of gas diffusion membrane, it has been difficult to achieve both drainage and water retention in a wide range of battery reactions from a high current density range to a low current density range. In addition, the method of applying the mixed paste has a problem that the layer thickness is not constant and the moisture management is partially different, so that the battery reaction occurs unevenly, resulting in a decrease in battery performance. .

そこで、前記導電性材料と疎水性バインダー樹脂との混合ペーストを膜状に成形し、貫通孔を形成し、ガス通路と水通路の区別を行い、スムーズにガス拡散と排水が行えるようにしたガス拡散膜が開発された（特許文献２参照）。図１０に、このガス拡散膜を固体高分子電解質型燃料電池に適用した例を示す。図示のように、この例では、ＰＥＭ９５の外側に、電極（アノード若しくはカソード）９４が配置され、その外側に、ガス拡散膜９０が配置され、その外側にセパレータ９１が配置されている。前記ガス拡散膜９０は、ガス拡散層９６と基材層９７とから形成され、ガス拡散層９６には、ガス透過孔９８と水透過孔９９が形成されている。そして、前記ガス拡散膜９０は、そのガス拡散層９６が電極９４側に位置し、かつその基材層９７がセパレータ９１側に位置する状態で配置されている。しかしながら、前記貫通孔を設けたガス拡散膜では、電極９４とガス拡散膜９６の接触面積が減少するため、電子移動が妨げられ、高電流密度域で電池反応が阻害されるという問題があった。さらに、貫通孔部分でガスが通りやすくなり、電極に供給されるガス量が部分的にばらつき、反応部位の差により熱分布が生じ、触媒の失活により電池寿命が短くなるという問題もあった。
特許第３３８２２１３号公報 特開２００３−１５１５８５号公報 Therefore, a mixed paste of the conductive material and the hydrophobic binder resin is formed into a film shape, a through hole is formed, the gas passage is distinguished from the water passage, and gas can be diffused and drained smoothly. A diffusion film has been developed (see Patent Document 2). FIG. 10 shows an example in which this gas diffusion membrane is applied to a solid polymer electrolyte fuel cell. As illustrated, in this example, an electrode (anode or cathode) 94 is disposed outside the PEM 95, a gas diffusion film 90 is disposed outside the PEM 95, and a separator 91 is disposed outside the PEM 95. The gas diffusion film 90 is formed of a gas diffusion layer 96 and a base material layer 97, and a gas permeation hole 98 and a water permeation hole 99 are formed in the gas diffusion layer 96. The gas diffusion film 90 is arranged with the gas diffusion layer 96 positioned on the electrode 94 side and the base material layer 97 positioned on the separator 91 side. However, the gas diffusion film provided with the through-hole has a problem in that the contact area between the electrode 94 and the gas diffusion film 96 is reduced, so that electron transfer is hindered and the cell reaction is inhibited in a high current density region. . Furthermore, there is a problem that gas easily passes through the through-hole portion, the amount of gas supplied to the electrode varies partially, heat distribution occurs due to the difference in reaction site, and battery life is shortened due to catalyst deactivation. .
Japanese Patent No. 3382213 JP 2003-151585 A

そこで、本発明の目的は、高電流密度域から低電流密度域までの広範囲な電池反応における水分管理に優れ、電池反応を阻害することなく、ガスの透過も均一である固体高分子電解質型燃料電池用ガス拡散膜を提供することである。   Accordingly, an object of the present invention is to provide a solid polymer electrolyte fuel that is excellent in moisture management in a wide range of battery reactions from a high current density region to a low current density region, and has uniform gas permeation without inhibiting the cell reaction The object is to provide a gas diffusion membrane for a battery.

前記目的を達成するために、本発明の固体高分子電解質型燃料電池用ガス拡散膜は、疎水性バインダー樹脂および導電性材料から形成された疎水性多孔質膜であり、この多孔質膜の表面から裏面に向かって凹部が形成されているガス拡散膜である。   In order to achieve the above object, the gas diffusion membrane for a polymer electrolyte fuel cell of the present invention is a hydrophobic porous membrane formed from a hydrophobic binder resin and a conductive material, and the surface of this porous membrane It is a gas diffusion film in which a recess is formed from the surface toward the back surface.

固体高分子電解質型燃料電池において、本発明のガス拡散膜を、その表面がセパレータ側に位置し、その裏面が電極側に位置するように配置すれば、高電流密度域から低電流密度域の広範囲の電池反応において、優れた水分管理能力を発揮する。すなわち、低電流密度域では、発生した水は、前記多孔質膜が疎水性であるため、その逸脱が防止されるから電解質膜の保水がよくなる。一方、高電流密度域では、大量に発生した水は、水蒸気となって前記多孔質膜の孔を通じて拡散し、かつ前記多孔質膜内で凝縮されるが、生じた水は、前記凹部を水路として外部に排出される。そして、本発明のガス拡散膜では、電極と接触する裏面は平滑であるため電極との接触面積が大きく、この結果、電池反応を阻害することがない。さらに、本発明のガス拡散膜において、前記多孔質膜に貫通孔を設けていないので、ガスの透過も均一となり、この結果、部分発熱も生じない。   In a solid polymer electrolyte fuel cell, if the gas diffusion membrane of the present invention is disposed so that the surface thereof is located on the separator side and the back surface thereof is located on the electrode side, the gas diffusion membrane from the high current density region to the low current density region is obtained. Exhibits excellent moisture management ability in a wide range of battery reactions. In other words, in the low current density region, the generated water is better retained in the electrolyte membrane because the porous membrane is hydrophobic and its deviation is prevented. On the other hand, in the high current density region, a large amount of generated water becomes water vapor and diffuses through the pores of the porous membrane, and is condensed in the porous membrane. Discharged to the outside. And in the gas diffusion film of this invention, since the back surface which contacts an electrode is smooth, a contact area with an electrode is large, As a result, a battery reaction is not inhibited. Further, in the gas diffusion membrane of the present invention, since the porous membrane is not provided with a through hole, gas permeation is uniform, and as a result, partial heat generation does not occur.

前述のように、本発明のガス拡散膜の凹部は、水の流路として機能するのが好ましい。高電流密度域で大量に発生した水を速やかに排水し、電池性能を維持できるからである。   As described above, the concave portion of the gas diffusion film of the present invention preferably functions as a water flow path. This is because a large amount of water generated in a high current density region can be quickly drained to maintain battery performance.

本発明のガス拡散膜の凹部の形状は特に制限されず、例えば、穴状でもよいし、溝状であってもよい。前記凹部の大きさも特に制限されず、穴状の場合、最大内径は、例えば、１０〜２０００μｍの範囲であり、好ましくは１０〜５００μｍの範囲であり、より好ましくは５０〜２００μｍの範囲であり、深さは、例えば、膜厚みの１０〜９０％の範囲であり、好ましくは３０〜８０％の範囲であり、より好ましくは４０〜８０％の範囲である。また、前記凹部が溝状の場合、その大きさは特に制限されず、最大幅は、例えば、１０〜５００μｍの範囲であり、好ましくは１０〜３００μｍの範囲であり、より好ましくは５０〜１００μｍの範囲であり、深さは、例えば、膜厚みの１０〜９０％の範囲であり、好ましくは３０〜８０％の範囲であり、より好ましくは４０〜８０％の範囲である。   The shape of the concave portion of the gas diffusion film of the present invention is not particularly limited, and may be, for example, a hole shape or a groove shape. The size of the recess is not particularly limited, and in the case of a hole shape, the maximum inner diameter is, for example, in the range of 10 to 2000 μm, preferably in the range of 10 to 500 μm, more preferably in the range of 50 to 200 μm. The depth is, for example, in the range of 10 to 90% of the film thickness, preferably in the range of 30 to 80%, and more preferably in the range of 40 to 80%. Moreover, when the said recessed part is groove shape, the magnitude | size is not restrict | limited in particular, The maximum width is the range of 10-500 micrometers, for example, Preferably it is the range of 10-300 micrometers, More preferably, it is 50-100 micrometers. For example, the depth is in the range of 10 to 90% of the film thickness, preferably in the range of 30 to 80%, and more preferably in the range of 40 to 80%.

本発明のガス拡散膜の凹部は、複数形成されているのが好ましい。より速やかに排水を行うことができるからである。前記凹部の個数は、特に制限されず、例えば、凹部の大きさ、燃料電池の規格等により適宜決定することができる。例えば、前記凹部の形状が穴状の場合、その個数は、例えば、１０〜２５０００個／ｃｍ2、好ましくは１０００〜２００００個／ｃｍ2、より好ましくは３０００〜１００００個／ｃｍ2であり、前記凹部の形状が溝状の場合、その個数は、例えば、５〜５０００個／ｃｍ2、好ましくは１００〜１０００個／ｃｍ2、より好ましくは２００〜５００個／ｃｍ2である。また、前記凹部は、多孔質膜表面に均一に形成してもよいし、一部に偏った状態で形成してもよい。 A plurality of recesses in the gas diffusion film of the present invention are preferably formed. This is because drainage can be performed more quickly. The number of the recesses is not particularly limited, and can be appropriately determined according to the size of the recesses, the standard of the fuel cell, and the like. For example, when the shape of the concave portion of the hole-shaped, and the number is, for example, 10 to 25,000 pieces / cm 2, preferably 1000 to 20,000 pieces / cm 2, more preferably 3,000 to 10,000 pieces / cm 2, wherein When the shape of the recess is a groove shape, the number thereof is, for example, 5 to 5000 / cm 2 , preferably 100 to 1000 / cm 2 , and more preferably 200 to 500 / cm 2 . Moreover, the said recessed part may be formed uniformly in the porous membrane surface, and may be formed in the state biased partially.

本発明のガス拡散膜において、前記疎水性バインダー樹脂は、特に制限されず、例えば、フッ素樹脂、ポリシロキサン、ポリイソブチレン等があり、この中でも、耐酸化性、耐水性に優れ、化学的に安定であるという理由により、フッ素樹脂が好ましい。フッ素樹脂としては、例えば、ＰＴＦＥ、ＰＦＡ、テトラフルオロエチレン／ヘキサフルオロプロピレン共重合体、ポリクロロトリフルオロエチレン、ポリフッ化ビニリデン、ポリフッ化ビニル、エチレン／テトラフルオロエチレン共重合体、エチレン／クロロトリフルオロエチレン共重合体等があるが、この中でもＰＴＦＥが好ましい。粒子間結着により強固な多孔構造をとるからである。   In the gas diffusion membrane of the present invention, the hydrophobic binder resin is not particularly limited, and examples thereof include fluororesin, polysiloxane, polyisobutylene, etc. Among them, excellent in oxidation resistance and water resistance, and chemically stable. For this reason, a fluororesin is preferred. Examples of the fluorine resin include PTFE, PFA, tetrafluoroethylene / hexafluoropropylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, ethylene / tetrafluoroethylene copolymer, and ethylene / chlorotrifluoro. There are ethylene copolymers, among which PTFE is preferred. This is because a strong porous structure is formed by interparticle bonding.

本発明のガス拡散膜において、前記導電性材料は、特に制限されないが、例えば、カーボンブラック粒子、グラファイト粒子および炭素繊維があげられ、これらは単独で使用してもよいし、２種類以上で併用してもよい。この中で好ましいのは、カーボンブラック粒子、グラファイト粒子であり、より好ましいのは、カーボンブラック粒子である。導電性に優れ、粒子径が小さいことから、水透過性にも優れるからである。   In the gas diffusion film of the present invention, the conductive material is not particularly limited, and examples thereof include carbon black particles, graphite particles, and carbon fibers, which may be used alone or in combination of two or more. May be. Among these, carbon black particles and graphite particles are preferable, and carbon black particles are more preferable. It is because it is excellent in electroconductivity and its particle diameter is small, it is also excellent in water permeability.

本発明のガス拡散膜は、補強等を目的として、その多孔質膜の表面に基材が配置されているのが好ましい。前記基材としては、導電性に優れるという理由から、カーボンペーパ、カーボンクロスおよびカーボンフェルトが好ましく、これらは単独で使用してもよいし、２種類以上で併用してもよい。   The gas diffusion membrane of the present invention preferably has a base material disposed on the surface of the porous membrane for the purpose of reinforcement or the like. As the base material, carbon paper, carbon cloth, and carbon felt are preferable because they are excellent in conductivity. These may be used alone or in combination of two or more.

つぎに、本発明のガス拡散膜の製造方法の一例について説明する。   Below, an example of the manufacturing method of the gas diffusion film of this invention is demonstrated.

本発明のガス拡散膜は、疎水性バインダー樹脂と導電性材料との混合ペーストを多孔質膜構造に成形し、前記多孔質膜の表面から裏面に向かって凹部を設けることで製造される。   The gas diffusion film of the present invention is produced by forming a mixed paste of a hydrophobic binder resin and a conductive material into a porous film structure and providing a recess from the surface of the porous film toward the back surface.

前記疎水性バインダー樹脂の材質は、前述のとおりである。   The material of the hydrophobic binder resin is as described above.

前記導電性材料の材質は、前述のとおりである。前記導電性材料の平均粒子径は、例えば、２０ｎｍ〜５０μｍの範囲であり、好ましくは４０ｎｍ〜１０μｍの範囲である。   The material of the conductive material is as described above. The average particle diameter of the conductive material is, for example, in the range of 20 nm to 50 μm, and preferably in the range of 40 nm to 10 μm.

つぎに、前記疎水性バインダー樹脂と導電性材料とを混合する。混合比率は、前記両材料の合計重量中（固形分換算）、導電性材料が４０〜９５％、好ましくは５０〜９０％、疎水性バインダー樹脂が５〜６０％、好ましくは１０〜５０％の範囲である。混合方法としては、例えば、ＰＴＦＥファインパウダーとカーボンブラック粒子をドライ状態でヘンシェルミキサー等で混合する方法、水若しくは有機溶剤にカーボンブラック粒子を攪拌しながら投入し、さらにＰＴＦＥディスパージョンを滴下する方法等が挙げられる。必要に応じて、界面活性剤を投入してもよい。液媒体で混合した場合、乾燥等を行って溶剤を除去し、粉体を得る。   Next, the hydrophobic binder resin and the conductive material are mixed. The mixing ratio is 40 to 95%, preferably 50 to 90% for the conductive material, 5 to 60% for the hydrophobic binder resin, and preferably 10 to 50% in the total weight of both materials (in terms of solid content). It is a range. As a mixing method, for example, a method of mixing PTFE fine powder and carbon black particles in a dry state with a Henschel mixer or the like, a method of adding carbon black particles to water or an organic solvent while stirring, and a method of adding PTFE dispersion dropwise, etc. Is mentioned. If necessary, a surfactant may be added. When mixed in a liquid medium, the solvent is removed by drying or the like to obtain a powder.

つぎに、前記混和物に成形助剤を加えた後、予備成形を行う。前記成形助剤としては、特に制限されず、例えば、ナフサ、ホワイトオイル、流動パラフィン、トルエン、キシレン等の炭化水素油や、アルコール類、ケトン類およびエステル類の有機溶剤等を使用できる。また、これらは、単独で使用してもよく、若しくは二種類以上を併用してもよい。環境保護の点から、直鎖状炭化水素系で低沸点の溶剤を用いるのが好ましい。予備成形の方法は、特に制限されないが、例えば、ドラムミキサーや回転体上で容器ごと回す方法、成形助剤を噴霧しながら攪拌する方法等が挙げられる。ダマを作らず、疎水性バインダー樹脂の繊維化を極力起こさないように予備成形するのが好ましい。   Next, a molding aid is added to the mixture, followed by preforming. The molding aid is not particularly limited, and examples thereof include hydrocarbon oils such as naphtha, white oil, liquid paraffin, toluene, xylene, and organic solvents such as alcohols, ketones, and esters. Moreover, these may be used independently or may use 2 or more types together. From the viewpoint of environmental protection, it is preferable to use a linear hydrocarbon-based low-boiling solvent. The preforming method is not particularly limited, and examples thereof include a method of rotating the entire container on a drum mixer or a rotating body, a method of stirring while spraying a molding aid, and the like. It is preferable to pre-mold so as not to cause lumps and to make the hydrophobic binder resin fiber as much as possible.

つぎに、前記予備成形物をシート状に成形する。前記成形方法としては、例えば、前記予備成形物をロッド状に押し出した後、対になったロールにより圧延する圧延法や、板状に押し出してシート状にする押し出し法が挙げられる。また、前記両方の方法を組み合わせてもよい。前記シートを乾燥し、成形助剤を除去して多孔質膜を得る。前記乾燥方法としては、加熱法または抽出法等が挙げられる。前記抽出法に使用する溶媒は、特に制限されないが、例えば、ノルマルデカン、ドデカン、ナフサ、ケロシン、スモイル等が挙げられる。前記多孔質膜の膜厚は、２０〜３００μｍの範囲にあるのが好ましく、また、孔径は、例えば、１〜３０μｍの範囲であり、好ましくは２〜２０μmの範囲であり、より好ましくは５〜１５μｍの範囲である。なお、本発明における前記多孔質膜は、前述の製造方法に制限されず、他の製造方法で製造されてもよい。   Next, the preform is formed into a sheet shape. Examples of the forming method include a rolling method in which the preform is extruded into a rod shape and then rolled with a pair of rolls, and an extrusion method in which the preform is extruded into a sheet shape to form a sheet. Moreover, you may combine both the said methods. The sheet is dried and the molding aid is removed to obtain a porous film. Examples of the drying method include a heating method and an extraction method. The solvent used in the extraction method is not particularly limited, and examples thereof include normal decane, dodecane, naphtha, kerosene, and sumoyl. The thickness of the porous membrane is preferably in the range of 20 to 300 μm, and the pore diameter is, for example, in the range of 1 to 30 μm, preferably in the range of 2 to 20 μm, more preferably in the range of 5 to 5 μm. The range is 15 μm. In addition, the said porous membrane in this invention is not restrict | limited to the above-mentioned manufacturing method, You may manufacture with another manufacturing method.

つぎに、前記多孔質膜の表面から裏面に向かって凹部を設ける。前記多孔質膜の表面に、内径１０μｍ〜２ｍｍの凹部を深さ１０μｍ刻みで設ける。なお、凹部形成の際には、裏面まで貫通しないようにする。前記凹部の加工方法は、特に制限されず、先端の鋭い針等を使用したり、エキシマレーザ、ＹＡＧレーザまたは超短パルスレーザ等のレーザを使用したりして、加工することができる。   Next, a recess is provided from the front surface to the back surface of the porous film. On the surface of the porous membrane, concave portions having an inner diameter of 10 μm to 2 mm are provided at a depth of 10 μm. It should be noted that when the recess is formed, it does not penetrate to the back surface. The method for processing the recess is not particularly limited, and can be processed by using a needle having a sharp tip, or using a laser such as an excimer laser, a YAG laser, or an ultrashort pulse laser.

前記凹部の形状は、前述のとおり、特に制限されず、穴状や溝状であってもよいし、その他の形状であってもよい。前記穴状の凹部は、円形や楕円形であってもよいし、その他の形状であってもよい。長径と短径の差が大きい形状の場合には、長径を、直線状だけでなく、曲線状や折れ曲がり線状の形状とすることもできる。また、柱状や錐状の凹部であってもよいし、螺旋状に加工してもよい。また、凹部の加工点の配列は、特に制限されず、例えば、図３に示すように格子状に配列してもよいし、図４に示すように千鳥状に配列してもよい。また、前記凹部は、図５に示すような溝状の加工としてもよい。凹部が溝状の場合、図５に示すように、寸法の長い方向の寸法Ｌ1を「長さ」、短い方向の最大寸法Ｌ2を「最大幅」とする。 As described above, the shape of the concave portion is not particularly limited, and may be a hole shape or a groove shape, or may be another shape. The hole-shaped recess may be circular or elliptical, or may have other shapes. In the case of a shape having a large difference between the major axis and the minor axis, the major axis can be not only a straight line but also a curved line or a bent line. Further, it may be a columnar or conical recess, or may be processed into a spiral. Further, the arrangement of the processing points of the recesses is not particularly limited, and for example, the processing points may be arranged in a lattice pattern as shown in FIG. 3, or in a staggered pattern as shown in FIG. Further, the concave portion may be formed into a groove shape as shown in FIG. When the recess has a groove shape, as shown in FIG. 5, the dimension L 1 in the long direction is the “length” and the maximum dimension L 2 in the short direction is the “maximum width”.

前記凹部の加工には、微細な加工が可能な点から、エキシマレーザ、ＹＡＧレーザまたは超短パルスレーザ等のレーザが好ましく用いられ、中でも紫外線波長領域〜近赤外線波長領域の波長を有する、パルス幅が１０-6秒以下のフェムト秒パルスレーザが特に好ましく用いられる。フェムト秒パルスレーザを用いると、パルスエネルギーが高いので、多光子吸収過程を利用したレーザ加工を行うことが可能で、その尖塔のパワーにより、波長より短い幅の微細加工を行うことができるようになる。例えば、最小の径又は幅が２００μｍ以下である微小凹部（特に、短径が０．０５〜２００μｍであり、且つ長径が０．０５μｍ以上（例えば、０．０５〜１０００００μｍ）である微小凹部）を形成できるようになる。レーザ照射時に焦点距離を変えることにより、照射径が変わり、その結果、形成される凹部の径も変わる。また、レーザによる加工では、加工時に高温になることで、凹部表面の官能基が減少し、疎水性が高まり、撥水性が向上する。なお、レーザは、その照射方向に対して垂直な方向に、且つ前記多孔質膜の表面に対して平行な方向に、レーザの焦点を移動させながら照射するのが好ましい。 A laser such as an excimer laser, a YAG laser, or an ultrashort pulse laser is preferably used for processing the concave portion because it can be finely processed. Among these, a pulse width having a wavelength in the ultraviolet wavelength region to the near infrared wavelength region is used. Is particularly preferably a femtosecond pulse laser having a duration of 10 −6 seconds or less. When using a femtosecond pulse laser, the pulse energy is high, so it is possible to perform laser processing using a multiphoton absorption process, and the power of the spire allows fine processing with a width shorter than the wavelength. Become. For example, a minute recess having a minimum diameter or width of 200 μm or less (particularly, a minute recess having a minor axis of 0.05 to 200 μm and a major axis of 0.05 μm or more (for example, 0.05 to 100,000 μm)). It becomes possible to form. By changing the focal length at the time of laser irradiation, the irradiation diameter changes, and as a result, the diameter of the formed recess also changes. Further, in the processing by laser, the functional group on the concave surface is reduced, the hydrophobicity is increased, and the water repellency is improved due to the high temperature during processing. The laser is preferably irradiated while moving the focal point of the laser in a direction perpendicular to the irradiation direction and in a direction parallel to the surface of the porous film.

以上のようにして、本発明のガス拡散膜を製造できる。図１に、本発明のガス拡散膜の一例を示す。図示のとおり、本発明のガス拡散膜１０は、疎水性バインダー樹脂と導電性材料から形成された多孔質膜１２の表面から裏面に向かって凹部１３が設けられている。   As described above, the gas diffusion film of the present invention can be manufactured. FIG. 1 shows an example of the gas diffusion film of the present invention. As shown in the figure, the gas diffusion film 10 of the present invention is provided with a recess 13 from the front surface to the back surface of a porous film 12 formed of a hydrophobic binder resin and a conductive material.

なお、本発明のガス拡散膜は、必要に応じて、撥水処理剤でコーティングしてもよい。前記撥水処理剤としては、特に制限されず、市販の撥水処理剤を使用できる。例えば、各種のフッ素系撥水処理剤を用いることができ、中でもパーフルオロアルキル基を有する撥水処理剤がより好ましい。パーフルオロアルキル基を有する撥水処理剤としては、例えば、ダイキン社製商品名ユニダイン、セイミケミカル社製商品名エスエフコートシリーズ、信越化学社製商品名Ｘ−７０−０２９等がある。また、それ以外の撥水処理剤としては、例えば、住友スリーエム社製スコッチガード、旭硝子社製商品名アサヒガード、信越化学社製商品名ＫＰ−８０１Ｍ等がある。撥水処理剤による処理方法は、特に制限されず、例えば、撥水処理剤溶液へ浸漬し、その後乾燥する方法、撥水処理剤溶液を塗布し、その後乾燥する方法等がある。前記撥水処理溶液の濃度は、１〜５重量％とするのが好ましい。前記撥水処理剤溶液に使用する溶媒は、例えば、シンナー等がある。浸漬処理の条件は、例えば、温度１５〜３５℃、浸漬時間２〜１０分であり、好ましくは、温度２０〜２５℃、浸漬時間２〜３分である。前記塗布の方法は、特に制限されず、例えば、スプレー法、スピンコート法、ディッピング法、ロールコータ法等がある。また、浸漬若しくは塗布後の乾燥は、特に制限されないが、例えば、８０〜１２０℃の温度雰囲気下で２〜１０分程度加熱乾燥するのが好ましい。加熱乾燥することで、撥水処理剤を溶融固化させ、ガス拡散膜との結合を強くすることができる。   In addition, you may coat the gas diffusion film of this invention with a water-repellent processing agent as needed. The water repellent treatment agent is not particularly limited, and a commercially available water repellent treatment agent can be used. For example, various fluorine-based water repellent treatment agents can be used, and among them, a water repellent treatment agent having a perfluoroalkyl group is more preferable. Examples of the water-repellent treatment agent having a perfluoroalkyl group include Daikin's trade name Unidyne, Seimi Chemical's trade name SF Coat Series, Shin-Etsu Chemical's trade name X-70-029, and the like. Other water repellent treatment agents include, for example, Sumitomo 3M Scotch Guard, Asahi Glass trade name Asahi Guard, Shin-Etsu Chemical trade name KP-801M, and the like. The treatment method using a water repellent treatment agent is not particularly limited, and examples thereof include a method of immersing in a water repellent treatment solution and then drying, a method of applying a water repellent treatment agent solution, and then drying. The concentration of the water repellent treatment solution is preferably 1 to 5% by weight. Examples of the solvent used in the water repellent solution include thinner. The conditions for the immersion treatment are, for example, a temperature of 15 to 35 ° C. and an immersion time of 2 to 10 minutes, and preferably a temperature of 20 to 25 ° C. and an immersion time of 2 to 3 minutes. The coating method is not particularly limited, and examples thereof include a spray method, a spin coating method, a dipping method, and a roll coater method. Moreover, although the drying after immersion or application | coating is not restrict | limited, For example, it is preferable to heat-dry about 2 to 10 minutes in 80-120 degreeC temperature atmosphere. By drying by heating, the water repellent agent can be melted and solidified, and the bond with the gas diffusion film can be strengthened.

本発明のガス拡散膜は、その多孔質膜の表面に基材を配置して使用してもよい。前記基材の材質は、前述のとおりである。また、前記基材と多孔質膜は、加圧または加熱加圧により一体化してもよい。この際の条件は、適宜設定できるが、通常、温度２０〜１００℃、圧力０．５〜２０ＭＰａ、加圧時間２〜６０分である。   The gas diffusion membrane of the present invention may be used with a substrate disposed on the surface of the porous membrane. The material of the base material is as described above. The base material and the porous membrane may be integrated by pressurization or heating and pressurization. The conditions at this time can be set as appropriate, but are usually a temperature of 20 to 100 ° C., a pressure of 0.5 to 20 MPa, and a pressurization time of 2 to 60 minutes.

本発明のガス拡散膜は、固体高分子電解質型燃料電池用ガス拡散膜として使用される。使用に際しては、電解質膜を介して一対の電極を配置し、前記電極のそれぞれの外側に、本発明のガス拡散膜およびセパレータを配置して、固体高分子電解質型燃料電池を形成する。電極およびセパレータについては、従来公知のものを用いればよい。   The gas diffusion membrane of the present invention is used as a gas diffusion membrane for a solid polymer electrolyte fuel cell. In use, a pair of electrodes is disposed via an electrolyte membrane, and the gas diffusion membrane and separator of the present invention are disposed outside each of the electrodes to form a solid polymer electrolyte fuel cell. Conventionally known electrodes and separators may be used.

つぎに、本発明の実施例について、比較例と併せて説明する。   Next, examples of the present invention will be described together with comparative examples.

図３に示すような穴状の凹部（穴状の凹部は楕円形）が格子状に配列された構造のガス拡散膜を作製した。すなわち、まず、ＰＴＦＥディスパージョン（ダイキン社製商品名Ｄ２Ｅ）２０重量部とカーボンブラック粒子（東海カーボン社製商品名＃４５００）８０重量部を水媒体で２分間混合した。前記混合液をメタノール中に投入、凝析させ混合物を得た。さらに濾過を行い、１００℃の温度雰囲気下で２時間加熱乾燥し、溶媒を除去した。これに成形助剤（ノルマルドデカン）を重量分率で５５重量％になるよう配合し、金属製の筒に充填して、０．２ＭＰａで加圧成形することで予備成形物を得た。ついで、予備成形物をラム押出し機（ＲＲ＝５０）にて押出し、直径２０ｍｍ、長さ１０ｍの丸棒状押出し物を得た。前記丸棒状押出し物を金属ロール間で圧延し、厚さ０．２ｍｍ、巾１００ｍｍのシートを得た。前記シートを１５０℃の炉内で乾燥し、成形助剤を除去し、厚さ０．１９ｍｍ、巾９０ｍｍの多孔質膜を得た。前記多孔質膜に、照射波長７８０ｎｍ、パルス幅１４０フェムト秒、パルス繰り返し１ｋＨｚのチタン・サファイア・フェムト秒パルスレーザを、照射出力３０ｍＷ、照射径２０μｍ、移動速度５００μｍ／ｓで走査させながら、１秒ごとにシャッターの開閉を繰り返し行って、レーザ照射し、表面から裏面に向かって凹部を形成した。その後、純水中で超音波洗浄を行って、本発明のガス拡散膜３０を得た。   A gas diffusion film having a structure in which hole-shaped concave portions (hole-shaped concave portions are oval) as shown in FIG. That is, first, 20 parts by weight of PTFE dispersion (trade name D2E manufactured by Daikin) and 80 parts by weight of carbon black particles (trade name # 4500 manufactured by Tokai Carbon Co., Ltd.) were mixed in an aqueous medium for 2 minutes. The mixture was poured into methanol and coagulated to obtain a mixture. Further, filtration was performed, followed by heating and drying in a temperature atmosphere of 100 ° C. for 2 hours to remove the solvent. A molding aid (normal dodecane) was added to this so as to have a weight fraction of 55% by weight, filled into a metal cylinder, and pressure-molded at 0.2 MPa to obtain a preform. Subsequently, the preform was extruded with a ram extruder (RR = 50) to obtain a round bar-shaped extrudate having a diameter of 20 mm and a length of 10 m. The round bar-shaped extrudate was rolled between metal rolls to obtain a sheet having a thickness of 0.2 mm and a width of 100 mm. The sheet was dried in a furnace at 150 ° C., and the molding aid was removed to obtain a porous film having a thickness of 0.19 mm and a width of 90 mm. While scanning the porous film with a titanium / sapphire / femtosecond pulse laser with an irradiation wavelength of 780 nm, a pulse width of 140 femtoseconds, and a pulse repetition of 1 kHz at an irradiation output of 30 mW, an irradiation diameter of 20 μm, and a moving speed of 500 μm / s for 1 second. Each time the shutter was opened and closed repeatedly, laser irradiation was performed to form a recess from the front surface to the back surface. Thereafter, ultrasonic cleaning was performed in pure water to obtain the gas diffusion film 30 of the present invention.

前記ガス拡散膜３０を光学顕微鏡で観察したところ、短径２０μｍ、長径５００μｍ、深さ１３０μｍの穴状の凹部３３が等間隔に形成されており、裏面への貫通は見られなかった。なお、凹部３３の間隔は、長径方向５００μｍ、短径方向３００μｍで、その個数は、３００個／ｃｍ2であった。このガス拡散膜３０を用いて燃料電池評価を行った。燃料電池評価に際して、図２の構造の燃料電池セルを作製した。すなわち、０．４ｍｇ／ｃｍ2の触媒活性物質が１０μｍの厚みで担持された電解質膜（デュポン社製商品名Ｎａｆｉｏｎ＃１１７）１５を介して一対の電極１４を、前記電極１４のそれぞれの外側に、裏面が前記電極１４に接するように前記ガス拡散膜３０を、さらにそのそれぞれの外側にカーボンペーパ（東レ製商品名ＴＧＨ−０６０、厚さ２４０μｍ）１６およびセパレータ１１を配置した。なお、電極面積は１２．９６ｃｍ2であり、電池反応評価は、セル温度８０℃、水素ガス０．５リットル／分、０．１５ＭＰａ、空気ガス１．０リットル／分、０．１５ＭＰａの条件で行い、東洋テクニカ株式会社製燃料電池評価装置にて電流密度と電圧との関係を調べた。 When the gas diffusion film 30 was observed with an optical microscope, hole-shaped concave portions 33 having a minor axis of 20 μm, a major axis of 500 μm, and a depth of 130 μm were formed at equal intervals, and no penetration to the back surface was observed. The intervals between the recesses 33 were 500 μm in the major axis direction and 300 μm in the minor axis direction, and the number thereof was 300 / cm 2 . Fuel cell evaluation was performed using this gas diffusion membrane 30. When evaluating the fuel cell, a fuel cell having the structure of FIG. 2 was produced. That is, a pair of electrodes 14 are placed on the outer sides of the electrodes 14 via an electrolyte membrane (trade name Nafion # 117, manufactured by DuPont) 15 in which 0.4 mg / cm 2 of a catalytically active substance is supported in a thickness of 10 μm. The gas diffusion film 30 was disposed so that the back surface was in contact with the electrode 14, and the carbon paper (trade name TGH-060 manufactured by Toray Industries, Inc., thickness 240 μm) 16 and the separator 11 were further disposed on the outer sides thereof. The electrode area was 12.96 cm 2 and the battery reaction was evaluated under the conditions of a cell temperature of 80 ° C., hydrogen gas of 0.5 liter / minute, 0.15 MPa, air gas of 1.0 liter / minute, and 0.15 MPa. The relationship between current density and voltage was examined using a fuel cell evaluation device manufactured by Toyo Technica Co., Ltd.

実施例１のガス拡散膜を、ダイキン社製商品名ユニダインＴＧ−７１５を信越化学者社製商品名ＦＲシンナーで３重量％に希釈した撥水処理溶液に浸漬し、その後、ガス拡散膜の外周に付着した余分な撥水処理溶液を濾紙にて除去し、１２０℃の温度雰囲気下で５分間乾燥することで、撥水処理剤でコーティングした。前記撥水処理剤でコーティングしたガス拡散膜を用い、実施例１と同様にして燃料電池評価を行った。   The gas diffusion membrane of Example 1 was immersed in a water repellent treatment solution obtained by diluting Daikin TG-715 (trade name, manufactured by Daikin Co., Ltd.) to 3% by weight with trade name FR thinner (trade name, Shin-Etsu Chemical Co., Ltd.) The excess water-repellent treatment solution adhering to the film was removed with a filter paper, and dried at 120 ° C. for 5 minutes to coat with a water-repellent treatment agent. The fuel cell was evaluated in the same manner as in Example 1 using the gas diffusion film coated with the water repellent agent.

サファイア・フェムト秒パルスレーザの照射径を１００μｍ、移動速度を１００μｍ／ｓとしたこと以外は、実施例１と同様にしてガス拡散膜を作製した。形成された穴状の凹部は、最大内径１００μｍの円形で、その深さは、１７０μｍ、間隔は、１００μｍ、個数は、１２００個／ｃｍ2であった。なお、凹部の配列は、図４に示すような千鳥状であった。前記ガス拡散膜を用い、実施例１と同様にして燃料電池評価を行った。 A gas diffusion film was produced in the same manner as in Example 1 except that the irradiation diameter of the sapphire femtosecond pulse laser was 100 μm and the moving speed was 100 μm / s. The formed hole-shaped recesses were circular with a maximum inner diameter of 100 μm, the depth was 170 μm, the interval was 100 μm, and the number was 1200 / cm 2 . In addition, the arrangement | sequence of a recessed part was zigzag shape as shown in FIG. Using the gas diffusion membrane, a fuel cell was evaluated in the same manner as in Example 1.

チタン・サファイア・フェムト秒パルスレーザを、速度１００μｍ／ｓで円移動させるように走査したこと以外は、実施例１と同様にしてガス拡散膜を作製した。形成された穴状の凹部は、最大内径１０００μｍの円形で、その深さは、４０μｍ、間隔は、１０００μｍ、個数は、２５個／ｃｍ2であった。なお、凹部の配列は、図４に示すような千鳥状であった。前記ガス拡散膜を用い、実施例１と同様にして燃料電池評価を行った。 A gas diffusion film was produced in the same manner as in Example 1 except that the titanium / sapphire / femtosecond pulse laser was scanned so as to move circularly at a speed of 100 μm / s. The formed hole-shaped recesses were circular with a maximum inner diameter of 1000 μm, the depth was 40 μm, the interval was 1000 μm, and the number was 25 / cm 2 . In addition, the arrangement | sequence of a recessed part was zigzag shape as shown in FIG. Using the gas diffusion membrane, a fuel cell was evaluated in the same manner as in Example 1.

（比較例１）
実施例１の多孔質膜に、レーザ加工により膜の厚み方向に孔径１００μｍの貫通孔を１ｍｍ間隔であけたものについて、実施例１と同様にして燃料電池評価を行った。 (Comparative Example 1)
Fuel cell evaluation was performed in the same manner as in Example 1 on the porous membrane of Example 1 having through-holes with a pore diameter of 100 μm formed at intervals of 1 mm in the thickness direction of the membrane by laser processing.

（比較例２）
実施例１の多孔質膜（凹部形成無し）について、実施例１と同様にして燃料電池評価を行った。 (Comparative Example 2)
Fuel cell evaluation was performed in the same manner as in Example 1 for the porous membrane of Example 1 (no recess formation).

前記実施例１，２および比較例１，２の燃料電池評価結果を図６のグラフに示す。   The fuel cell evaluation results of Examples 1 and 2 and Comparative Examples 1 and 2 are shown in the graph of FIG.

図６に示したとおり、実施例では、比較例より、より高い電流密度まで電圧の落ち込みが見られず、より広い電流密度域で高い電池性能が維持できている。   As shown in FIG. 6, in the example, no voltage drop is observed up to a higher current density than in the comparative example, and high battery performance can be maintained in a wider current density region.

本発明のガス拡散膜は、固体高分子電解質型燃料電池用ガス拡散膜として利用可能である。   The gas diffusion membrane of the present invention can be used as a gas diffusion membrane for a solid polymer electrolyte fuel cell.

本発明のガス拡散膜の一例の模式断面図である。It is a schematic cross section of an example of the gas diffusion film of the present invention. 本発明のガス拡散膜を用いた固体高分子電解質型燃料電池の一例の模式断面図である。It is a schematic cross section of an example of a solid polymer electrolyte fuel cell using the gas diffusion membrane of the present invention. 本発明における穴状の凹部の加工点の配列の一例の模式図である。It is a schematic diagram of an example of the arrangement | sequence of the processing point of the hole-shaped recessed part in this invention. 本発明における穴状の凹部の加工点の配列のその他の例の模式図である。It is a schematic diagram of the other example of the arrangement | sequence of the processing point of the hole-shaped recessed part in this invention. 本発明における溝状の凹部の形状の一例の模式図である。It is a schematic diagram of an example of the shape of the groove-shaped recessed part in this invention. 本発明のガス拡散膜を用いた固体高分子電解質型燃料電池の一例の電流密度に対する電圧の変化を示したグラフである。It is the graph which showed the change of the voltage with respect to the current density of an example of the solid polymer electrolyte fuel cell using the gas diffusion membrane of this invention. 固体高分子電解質型燃料電池の一例の模式断面図である。It is a schematic cross section of an example of a solid polymer electrolyte fuel cell. 従来の固体高分子電解質型燃料電池用ガス拡散膜の一例の模式断面図である。It is a schematic cross section of an example of a conventional gas diffusion membrane for a polymer electrolyte fuel cell. 従来のガス拡散膜を用いた固体高分子電解質型燃料電池の一例の模式断面図である。It is a schematic cross section of an example of a solid polymer electrolyte fuel cell using a conventional gas diffusion membrane. 従来のガス拡散膜を用いた固体高分子電解質型燃料電池のその他の例の模式断面図である。It is a schematic cross section of the other example of the solid polymer electrolyte fuel cell using the conventional gas diffusion membrane.

符号の説明Explanation of symbols

１０、３０、４０、５０、６３、７０、９０、９６ ガス拡散膜
１１、６１、８１、９１ セパレータ
１２、３２、４２、５２ 多孔質膜
１３、３３、４３、５３ 凹部
１４、６４、８４、９４ 電極
１５、６５、８５、９５ 電解質膜
１６、７７、９７ 基材
６２、９８ ガス通路
７６ 疎水層
９９ 水通路 10, 30, 40, 50, 63, 70, 90, 96 Gas diffusion film 11, 61, 81, 91 Separator 12, 32, 42, 52 Porous film 13, 33, 43, 53 Recess 14, 14, 64, 84, 94 Electrode 15, 65, 85, 95 Electrolyte membrane 16, 77, 97 Base material 62, 98 Gas passage 76 Hydrophobic layer 99 Water passage

Claims (13)

固体高分子電解質型燃料電池用のガス拡散膜であって、前記ガス拡散膜は、疎水性バインダー樹脂および導電性材料から形成された疎水性多孔質膜であり、この多孔質膜の表面から裏面に向かって凹部が形成されているガス拡散膜。 A gas diffusion membrane for a solid polymer electrolyte fuel cell, wherein the gas diffusion membrane is a hydrophobic porous membrane formed from a hydrophobic binder resin and a conductive material, and the front surface to the back surface of the porous membrane A gas diffusion film in which a recess is formed toward the surface. 前記凹部が、水の流路として機能する請求項１記載のガス拡散膜。 The gas diffusion film according to claim 1, wherein the recess functions as a water flow path. 前記凹部の形状が、穴状である請求項１または２記載のガス拡散膜。 The gas diffusion film according to claim 1 or 2, wherein the recess has a hole shape. 前記穴状の凹部において、その最大内径が１０〜２０００μｍの範囲であり、深さが膜厚みの１０〜９０％の範囲である請求項３記載のガス拡散膜。 The gas diffusion film according to claim 3, wherein the hole-shaped recess has a maximum inner diameter in the range of 10 to 2000 µm and a depth in the range of 10 to 90% of the film thickness. 前記凹部の形状が、溝状である請求項１または２記載のガス拡散膜。 The gas diffusion film according to claim 1 or 2, wherein the recess has a groove shape. 前記溝状の凹部において、その最大幅が１０〜５００μｍの範囲であり、深さが膜厚みの１０〜９０％の範囲である請求項５記載のガス拡散膜。 The gas diffusion film according to claim 5, wherein the groove-shaped recess has a maximum width in the range of 10 to 500 µm and a depth in the range of 10 to 90% of the film thickness. 前記凹部が複数形成されている請求項１から６のいずれかに記載のガス拡散膜。 The gas diffusion film according to any one of claims 1 to 6, wherein a plurality of the recesses are formed. 前記疎水性バインダー樹脂が、フッ素樹脂である請求項１から７のいずれかに記載のガス拡散膜。 The gas diffusion membrane according to any one of claims 1 to 7, wherein the hydrophobic binder resin is a fluororesin. 前記フッ素樹脂が、ポリテトラフルオロエチレンである請求項８記載のガス拡散膜。 The gas diffusion membrane according to claim 8, wherein the fluororesin is polytetrafluoroethylene. 前記導電性材料が、カーボンブラック粒子、グラファイト粒子および炭素繊維からなる群から選択された少なくとも一つである請求項１から９のいずれかに記載のガス拡散膜。 The gas diffusion film according to any one of claims 1 to 9, wherein the conductive material is at least one selected from the group consisting of carbon black particles, graphite particles, and carbon fibers. 前記多孔質膜の表面に基材が配置されている請求項１から１０のいずれかに記載のガス拡散膜。 The gas diffusion membrane according to any one of claims 1 to 10, wherein a base material is disposed on a surface of the porous membrane. 前記基材が、カーボンペーパ、カーボンクロスおよびカーボンフェルトからなる群から選択された少なくとも一つである請求項１１記載のガス拡散膜。 The gas diffusion film according to claim 11, wherein the base material is at least one selected from the group consisting of carbon paper, carbon cloth, and carbon felt. 電解質膜を介して一対の電極が配置され、前記電極のそれぞれの外側に、一対のガス拡散膜が配置された固体高分子電解質型燃料電池であって、前記ガス拡散膜が、請求項１から１２のいずれかに記載のガス拡散膜である固体高分子電解質型燃料電池。 A solid polymer electrolyte fuel cell in which a pair of electrodes are arranged via an electrolyte membrane, and a pair of gas diffusion membranes are arranged outside each of the electrodes, wherein the gas diffusion membrane is from A solid polymer electrolyte fuel cell, which is the gas diffusion membrane according to any one of 12.
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