JP2011096476A - Air-permeable porous electrode, air-permeable separator, fuel cell using them, manufacturing method of them, and vehicle using fuel cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an air-permeable porous electrode, an air-permeable porous spacer, a fuel cell using the air-permeable porous electrode and/or the air-permeable porous spacer, and a vehicle using that fuel cell. <P>SOLUTION: The fuel cell consists of: the air-permeable porous electrode directly coupled with an air-permeable base material surface having a through-hole formed by a process in which, on a porous base material surface having the through-hole to become a carrier, paste containing reactive metal particulates covered by the film formed of a compound to contain a reactive functional group on one end and a thiol group on the other end and a solvent is coated and cured; and the air-permeable porous spacer 13 directly coupled with the air-permeable porous electrode formed by coating and curing electric insulating particulate paste formed by a similar method on the air-permeable porous electrode. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a breathable porous electrode, a breathable separator, a fuel cell using them, a manufacturing method thereof, and a vehicle using the same.

  In particular, in the present invention, examples of the metal used as a gas-permeable porous electrode for a fuel cell include Pt, Pd, Ro, Ru, and V having catalytic action.

Conventionally, breathable porous electrodes and catalysts for fuel cells have been coated with catalyst metal fine particles on the surface of the support or mixed with catalyst metal fine particles in order to improve catalyst efficiency or reduce the amount used. Method is used.
For example, a technology for dispersing and fixing nanoscale-sized catalyst metal fine particles in an arbitrary shape on the surface of the support in an arbitrary shape, or a substrate made of resin on the surface, and provided on the substrate, and having an unsaturated bond portion There are the following patent documents relating to a technique in which a catalyst fine particle layer including a silane monomer and catalyst fine particles is fixed to a substrate by a chemical bond between an unsaturated bond portion of the silane monomer and the substrate.

JP 2003-80084 A JP 2008-161838 A

However, the method in which the catalytic metal fine particles are dispersed and fixed on the support has a problem that the ratio of the exposed catalyst is reduced and the utilization efficiency is poor.
Further, the method using dehydration condensation of a silane monomer has a problem that fine noble metal particles such as pure Pt having no hydroxyl group on the surface cannot be fixed.

In view of the above problems, the present invention
(1) Catalytic metal fine particles, a breathable base material (for example, a breathable solid polymer electrolyte) having a through-hole serving as a support for the catalytic metal fine particles, and a functional group reactive with the surface of the base material Using a substance having a functional group such as a thiol group that reacts with the surface of the catalytic metal fine particles,
A paste containing a reactive metal fine particle and a solvent covered with a film formed of a compound containing a reactive sensitive group at one end and a thiol group at the other end on the surface of a porous substrate having through-holes as a support. A breathable porous electrode directly bonded to a breathable substrate surface having a through-hole created by a coating step and a curing step;
(2) To provide a breathable porous separator directly bonded to a breathable porous electrode prepared by applying and curing an electrically insulating fine particle paste prepared by the same method on a breathable porous electrode.

further,
(3) Provide a fuel cell (FIG. 5) using the air-permeable porous electrode and / or air-permeable porous separator.
Furthermore, a vehicle using the fuel cell is provided.

  As described above, according to the present invention, there is an effect that an air permeable porous electrode, an air permeable separator, and a fuel cell using them can be formed using an application process and a curing process. In addition, there is an extraordinary effect that can provide a fuel cell using them at low cost.

FIG. 1 is an enlarged view up to the molecular level in order to conceptually explain the process of forming a monomolecular film having a functional group reactive with the surface of the support directly on the surface of the catalyst metal fine particles. Example 1

FIG. 2 (a) shows the application of a catalyst metal fine particle paste coated with a monomolecular film having a functional group reactive with the surface of the breathable solid polymer electrolyte on the surface of the breathable solid polymer electrolyte having active hydrogen. FIG. 3 is a conceptual cross-sectional view for explaining a curing step, in a state where a fine particle catalyst layer is formed. Moreover, FIG.2 (b) is sectional drawing which shows the state which laminated | stacked the spacer layer further. (Example 3)

FIG. 3A is a cross-sectional view of a breathable substrate (in this case, a breathable solid polymer electrolyte Nafion) containing active hydrogen on the surface. FIG. 3 (b) is an enlarged view of the portion ○ A of FIG. 2 to the molecular level, and a breathable catalytic metal fine particle layer bonded to the breathable solid polymer electrolyte surface is formed on the breathable solid polymer electrolyte surface. It is an enlarged view for demonstrating the process to form notionally. (Example 3)

FIG. 4 is an enlarged view of the portion B in FIG. 2 to the molecular level, and a step of forming a breathable catalytic metal fine particle layer bonded to the breathable solid polymer electrolyte surface on the breathable solid polymer electrolyte surface; FIG. 5 is an enlarged cross-sectional view for conceptually explaining a step of forming a breathable separator combined with the breathable catalytic metal fine particle layer. (Example 3)

FIG. 5 is a perspective view created for conceptually explaining the structure of the fuel cell of the present invention. (Example 3)

The present invention uses a substance having a functional group that reacts with the surface of the support and a functional group that reacts with the surface of the catalytic metal fine particles,
(1) A paste containing reactive metal fine particles covered with a film formed from a compound containing a reactive sensitive group at one end and a thiol group at the other end on the surface of a breathable porous substrate having through holes, and a solvent A breathable porous electrode is manufactured and provided by the step of applying and the step of curing.

  In the same manner, (2) an air-permeable porous spacer is manufactured and provided using electrically insulating fine particles instead of metal fine particles.

  At this time, the fine particle paste does not contain any binder component, and the fine particles are bonded and cured only through the reactive coatings on the surfaces of the fine particles that are in contact with each other.

  Furthermore, using a noble metal having a catalytic action, such as Pt, as the metal, and using the same technique as described above, (3) the breathable porous catalyst electrode and the breathable porous spacer are stacked on both sides of the solid polymer electrolyte. Thus, a fuel cell assembled in a stack structure is manufactured and provided by a step of producing a single fuel cell and a step of laminating and laminating a plurality of layers of the cells.

  When the plurality of fuel cells are stacked and heated by pressure bonding, since the functional groups reactive to each other remain on the surface of the air permeable porous spacer on the cell surface, the air permeable porous spacer can be simply heated. The battery cell can be bonded via

  Therefore, in the fuel cell of the present invention, the gas-permeable porous solid polymer electrolyte, the gas-permeable porous catalyst electrode layer, the gas-permeable porous spacer and the gas-permeable porous catalyst electrode layer are covalently bonded to each other. It is possible to provide a lightweight and compact fuel cell having high peelability, strong impact resistance, and high reliability.

  In order to increase the electromotive voltage, a single cell of a fuel cell (single cell) composed of a breathable porous solid polymer electrolyte, a breathable porous catalyst electrode layer, and a breathable porous spacer is provided for the required number of layers. A stack structure may be stacked and assembled.

  At this time, if the air-permeable porous catalyst electrode layer is made of nano metal particles, the metal fine particles are bonded and cured only through the reactive coatings on the surfaces of the fine particles that are in contact with each other. If a monomolecular film is used as the coating, the fine particles are only separated by an organic film having a thickness of 1 to 2 nm, electrons flow through a tunnel phenomenon, and the reaction gas can diffuse to the surface of the catalytic metal fine particles. Therefore, while being a gas permeable metal electrode, the conductivity can be as high as that of the bulk (about 70% of the bulk metal), and a gas permeable porous catalyst electrode layer with high catalyst utilization efficiency can be produced. Since this monomolecular film has a heat resistance up to about 300 ° C., there is no problem when it is used as a normal fuel cell.

  Furthermore, this manufacturing method can produce a stack-structured fuel cell by printing and pressure bonding, and thus can greatly reduce the manufacturing cost.

  Examples of the present invention will be described in detail below, but the present invention is not limited to these examples.

In the present invention, if it is a simple gas permeable electrode, the metal fine particles include conductive noble metal fine particles such as Au, Ag, Cu, Ni, and transparent conductive oxides such as ZnO, ITO, FTO, Alternatively, alloys containing them could be used. In addition, noble metal fine particles such as Pt, Pd, Ro, Ru, V, or alloys containing them could be used as gas permeable electrodes having a catalytic action.
Hereinafter, as a typical example, Pt (platinum) fine particles, which are noble metal fine particles having a catalytic action, will be described. However, the present invention is not limited to this.

  First, platinum fine particles 1 having a size of about 100 nm were prepared and dried well. Here, in addition to platinum, noble metal fine particles having catalytic action of Pd, Ro, Ru, V, etc., or alloys thereof could be used. Further, the smaller the particle size, the larger the surface area per unit weight and the higher the catalyst efficiency, but it is preferably nanometers to several tens of microns. If it is larger than this, the surface area per unit weight will be reduced, and the catalyst utilization efficiency will be worsened. On the other hand, if it is smaller than this, the breathability of oxygen and hydrogen is deteriorated.

  Next, 1 wt% of a chemical adsorbent having a thiol group at one end and a reactive functional group at the other end, for example, a chemical represented by the following chemical formula (Chemical Formula 1) (preferably the concentration of the chemical adsorbent is 0. The chemical adsorption solution was prepared by dissolving in ethanol.

The adsorbed liquid was mixed with the fine platinum particles 1 of about 100 nm and stirred, and reacted in ordinary air (relative humidity was 45%, but lower humidity is better) for about 2 hours. At this time, since the surface of the platinum fine particle directly thiolates 2 with the thiol group of the drug, it is covered with a reactive monomolecular film having the -Si (OCH ₃ ) group of the chemical adsorbent as a surface.

  After that, when the mixture was placed in ethanol and washed with stirring, the excess adsorbent could be removed, and the monomolecular film-like reactive coating 3 represented by the following chemical formula (Chemical Formula 2) could be formed to cover the platinum fine particles. . (Fig. 1 (b))

  In this treatment, the coating film was extremely thin with a film thickness of nanometer level, so that the particle shape was not impaired. Further, even if this film is left as it is, oxygen or hydrogen gas can freely pass between the film molecules, and the catalytic action of the base particles was not impaired.

On the other hand, if it is taken out into the air without washing, the reactivity is almost unchanged, but the chemical adsorbent remaining on the platinum particle surface partially reacts with moisture in the air on the particle surface due to evaporation of the solvent, and the particle surface. Fine particles on which an ultrathin polymer film made of the chemical adsorbent was formed were obtained.
In this case, since the film thickness is about several tens of nanometers, the catalytic action of the base fine particles is reduced as it is, but in order to increase the heat resistance, the fine particles of the breathable porous catalyst electrode are fused or sintered. In this case, there was no problem in the catalytic action because it could be decomposed and removed.

Next, the fine particles were dispersed in a non-aqueous organic solvent (for example, octane) to prepare a platinum fine particle paste having a reactive surface. In addition to the non-aqueous organic solvent, alcohol, an aqueous solvent, or water could be used as the paste solvent.
Further, the paste viscosity can be easily controlled by adjusting the concentration, and therefore, the paste viscosity may be appropriately adjusted in accordance with a coating printing apparatus such as an ink jet printer, a screen printing apparatus, or a gravure printing apparatus.

Furthermore, as shown in FIG. 2 (a), the surface of the porous substrate having through holes, for example, a breathable solid electrolyte film 11 (Nafion ^R manufactured by DuPont, etc.) can be several microns on both sides. When coating is performed with a film thickness (the coating thickness can be arbitrarily adjusted according to the required performance), the organic solvent is evaporated and reacted with moisture in the air. Then, as shown in the chemical formula (Chemical Formula 3), it was cross-linked and cured to form a gas-permeable catalyst fine particle film 12.

At this time, as shown in FIG. 3 (a), since the surface of the solid electrolyte film 21 (11 in FIG. 2 (a)) also contains a large number of hydroxyl groups 22 derived from sulfonic acid groups, a dealcoholization reaction occurs. Thus, a bond 23 of the chemical formula (Chemical Formula 4) is generated, and the platinum (catalyst metal) fine particles 24 are bonded via the covalent bond 23 without impairing the air permeability of the air-permeable solid electrolyte film 21 (for example, Nafion). It was cured and bonded and fixed to the surface of the solid electrolyte film 21 to form the catalyst fine particle layer 25 . (Fig. 3 (b))

  In addition, the monomolecular film on the surface of the platinum fine particle 24 in a non-contact portion was subjected to a dealcoholization reaction with moisture in the air, and changed to a hydrophilic hydroxyl group as represented by the chemical formula (Formula 5).

In this case, since the platinum fine particles 24 are only covered with a coating of about 1 nanometer, the air gap 26 can be secured without damaging the particle gaps, and the water vapor generated by the reaction can freely pass through the fine particle gaps. Was able to pass through.
Here, the size of the through hole 27 is preferably smaller than the size of the fine particles, but is not limited thereto.

  Furthermore, although the system which reacts directly with the film surface is used here, even if the film surface is covered in advance with a coating containing another functional group that reacts directly or indirectly with the reactive group, the other The film coating on the surface of the reactive fine particle and the film surface are subjected to a crosslinking reaction directly or via a multi-functional cross-linking agent to bond and fix the fine particles to the film surface, further improving the peel resistance of the air-permeable catalyst fine particle layer. did it.

  Furthermore, after the formation of the air-permeable catalyst fine particle layer, once again, a reaction solution containing a substance containing a fluorocarbon group at one end and methoxysilyloxy at the other end, for example, a substance represented by the chemical formula (Formula 6) When applied to the surface of the air-permeable catalyst fine particle layer and reacted, a water-repellent monomolecular film can be formed only on the surface of fine particles near the surface, and the catalyst fine particles on the side close to the solid electrolyte film, that is, on the side close to the solid electrolyte film Since the surface of the catalyst has many hydroxyl groups as shown in the chemical formula (Chemical Formula 5), it remains hydrophilic, and only the outer catalyst particles far from the solid electrolyte film can be processed to be water-repellent, and the water generated by the reaction in the catalyst particle film It was possible to prevent backflow.

  Next, electrically insulating silica fine particles 28 having a reactivity on the order of several tens of microns serving as spacers prepared by the same method as described above (preferably the fine particles have a size of several hundreds of nanometers to several hundreds of microns. In this case, since the silica surface does not react with the thiol group, a functional group that reacts with a hydroxyl group on the silica surface, such as a trimethoxysilyl group or a chlorosilyl group, instead of the thiol group described above. The other end was replaced with a reactive group such as an epoxy group or an amino group (for example, a chemical represented by the chemical formula (Chemical Formula 7 or 8) could be used). A porous spacer layer (13 in FIG. 2 (b) and 29 in FIG. 4) can be formed by creating a paste of insulating fine particles and applying it to form a breathable and insulating spacer layer on both sides. The

When the terminal was coated with a monomolecular film having an epoxy group, the fine particles could be efficiently crosslinked and cured using a multi-sensitive crosslinking agent such as triazole.
The material of the fine particles may be either an inorganic material or an organic material as long as it is electrically insulating and has a hydrophilic surface.
Furthermore, this spacer layer is preferably applied on both sides in order to increase the ease of assembly into the stack structure in the subsequent process and increase the air flow rate, but it may be applied on one side as required.

  In this case, the ventilation route 26 'can be secured in the same manner as described above. (Fig. 4)

Finally, as shown in FIG. 5, the required number of single cells 33 from which positive and negative lead wires 31 and 32 are drawn are stacked, combined in a stack structure, and heat-pressed, and the air inlet 34 and hydrogen gas (direct In the case of a methanol-type fuel cell, methanol) When the other layer end surfaces were sealed while leaving the layer end surface of the blow-in port 35 and the reacted water intake port 36, a lightweight and small stacked fuel cell 37 could be produced by printing. .

  At this time, silanol groups similar to the chemical formula (Chemical Formula 4) or similar to the chemical formula (Chemical Formula 4) remain on the surface of each fine particle film. Therefore, the dealcoholization reaction occurred at the contact point only by pressure heating, and single cells could be bonded and laminated. In addition, since such adhesive layers are bonded to each other through a covalent bond, they were not easily peeled between single cells and between the respective layers even when a reaction gas was injected from the end face.

Here, the shape of the catalyst metal fine particles and the spacer particles may be mixed with fine particles having different sizes. In this case, there is an effect that the fine particle density can be improved and the aeration speed can be reduced.
On the other hand, if a foaming agent is mixed in the coated fine particle paste in advance and foamed at the time of curing, and the fine particles are bonded and fixed in a state including voids larger than the fine particles, the airflow resistance can be reduced and the flow rate can be increased. It becomes.

Furthermore, as a fine particle, a large metal fine particle previously covered with a small metal fine particle is prepared in the same manner, and even if it is used, it is possible to increase the gap, reduce the airflow resistance, and increase the flow velocity. Become. In particular, when forming a catalytic metal layer, catalytic metal fine particles fixed on the surface of large fine particles of different materials are used. For example, using inorganic fine particles such as low-cost silica for large particles and using fine particles such as platinum for small particles has an effect of reducing the catalyst usage fee.
Here, it is preferable that the large fine particles are 500 to 1 micron and the size of the small metal fine particles is 1/5 to 1/100 of the large fine particles.

  Furthermore, when a film of a compound containing a reactive sensitive group at one end and a thiol group at the other end is formed on the surface of the reactive catalytic metal fine particle, a reactive sensitive group at one end and a thiol at the other end If a compound containing a group and a compound containing a fluorocarbon group at one end and a thiol group at the other end are mixed at an arbitrary ratio, the film is covered with a reactive and moderately water-repellent coating. It was possible to create fine particles and to improve the water separation of the generated water.

Furthermore, when another layer of metal fine particles is used as a simple electrode, conductive Au, Ag, Cu, Ni or transparent conductive ZnO, ITO, FTO fine particles are applied to the catalyst metal surface. However, in the case of a fuel cell, it is more convenient to use Pt, Pd, Ro, Ru, V having a catalytic action, or an alloy containing them, because it can also be used as an electrode.
In this case, the conductivity of the air-permeable electrode depends on the bulk conductivity of the conductive fine particles to be used, but about 70% of the bulk conductivity can be secured if it is made well.

In addition, about the chemical | medical agent used, instead of the compound containing the thiol group of (Chemical Formula 1), the chemical substance represented by the following general chemical formula (9) could be used.
(Chemical 9)
_{(AO) 3 Si- (CH 2} ) n -T

Specifically, compounds represented by the following chemical formulas (11) to (18) could be used.
_{(11) H 2 N- (CH} 2) n -T
_{(12) HOOC- (CH 2)} n -T
(13) EP- (CH ₂ ) _n -T
_{(14) (AO) 3 Si-} (CH 2) n -T
_{(15) HS- (CH 2)} n -T
_{(16) HO- (C 6 H} 4) -T
_{(17) H 2 N- (C} 6 H 4) -T
_{(18) HS- (C 6 H} 4) -T
Here, in the compounds of (11) to (18),
T represents a functional group containing an SH group such as a triazine thiol (following chemical formula 19) group or a triazole thiol (following chemical formula 20) group including an SH group.
N is an integer of 0 to 16, A is an alkyl group, and EP represents the following chemical formula (21) or (22).

In the above embodiment uses a _{CF 3 (CF 2) 7 (} CH 2) 2 SiSi (OCH 3) 3 as a fluorocarbon chemical adsorbent, besides those mentioned above, the following (31) The substances shown in (42) were available.
(31) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(32) CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(33) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(34) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(35) CF ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(36) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
(37) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(38) CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(39) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃
(40) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃
(41) CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(42) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃

Furthermore, instead of (Chemical Formula 7) or (Chemical Formula 6) containing an epoxy group or an amino group, a substance represented by the following general chemical formulas (51 to 66) could be used.
_{(51) (CH 2 OCH)} CH 2 O (CH 2) 7 Si (OCH 3) 3
_{(52) (CH 2 OCH)} CH 2 O (CH 2) 11 Si (OCH 3) 3
_{(53) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 2 Si (OCH 3) 3
_{(54) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 4 Si (OCH 3) 3
_{(55) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 6 Si (OCH 3) 3
_{(56) (CH2OCH) CH 2} O (CH 2) 7 Si (OC 2 H 5) 3
_{(57) (CH 2 OCH)} CH 2 O (CH 2) 11 Si (OC 2 H 5) 3
_{(58) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 2 Si (OC 2 H 5) 3
_{(59) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 4 Si (OC 2 H 5) 3
_{(60) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 6 Si (OC 2 H 5) 3
(61) H ₂ N (CH ₂ ) ₅ Si (OCH ₃ ) ₃
(62) H ₂ N (CH ₂ ) ₇ Si (OCH ₃ ) ₃
(63) H ₂ N (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(64) H ₂ N (CH ₂ ) ₅ Si (OC ₂ H ₅ ) ₃
(65) H ₂ N (CH ₂ ) ₇ Si (OC ₂ H ₅ ) ₃
(66) H ₂ N (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃

Here, the (CH ₂ OCH) group represents a functional group represented by the chemical formula (Chemical Formula 21), and the (CH ₂ CHOCH (CH ₂ ) ₂ ) CH group is represented by the chemical formula (Chemical Formula 22). Represents a functional group.

  Further, fine filaments and fibers could be used as the shapes of the catalyst metal fine particles and the spacer fine particles. The material of the spacer is preferably an electrically insulating granular silica, alumina, ceramics, an inorganic material such as glass, or an organic material, but is not limited thereto.

  In this state, the heat resistance is about 300 ° C. Therefore, when higher temperature heat resistance is required, the organic coating is oxidized or decomposed and removed by heating at a temperature lower than the melting temperature of the catalyst metal fine particles or spacer particles and higher than the temperature at which the organic membrane decomposes. The heat resistance can be improved to below the melting temperature of the catalyst metal fine particles and spacer particles.

In addition, since this fuel cell is extremely light and compact, it is an energy supply device that replaces the gasoline of a vehicle that is required to reduce the CO ₂ load and improve the energy utilization efficiency of a mobile phone that can be used for a long time. If it is incorporated, the maximum effect can be demonstrated.

  In the above embodiment, the fuel cell using a gas permeable catalyst electrode has been described. However, the gas permeable porous electrode of the present invention is not limited to the catalyst electrode. It can be used in any field as long as it requires a porous electrode.

  The air-permeable spacer can also be used as a liquid-permeable or ion-permeable spacer that requires electrical insulation.

  In particular, since the fuel cell of the present invention is extremely light and compact, it can be used for a mobile device requiring a power source, such as a mobile phone or a vehicle.

DESCRIPTION OF SYMBOLS 1 Platinum fine particle 2 Thiolate bond 3 Reactive film 11 Breathable solid electrolyte film 12 Platinum fine particle
13 Porous Spacer Layer 21 Solid Electrolyte Film 22 Hydroxyl 23 Bond 24 Platinum Fine Particle
25 catalyst fine particle layer 26, 26 ′ vent route 27 through hole 28 electrically insulating silica fine particle 29 porous spacer layer 31 positive lead wire 32 negative lead wire 33 single cell 34 air inlet 35 air hydrogen gas inlet Mouth 36 water intake
37 fuel cell

Claims (34)

Reactive metal fine particles covered with a coating formed of a compound containing a reactive sensitive group at one end and a thiol group at the other end are bonded and fixed to the surface of a breathable substrate having a through-hole through the coating. A breathable porous electrode characterized by comprising: The breathable porous electrode according to claim 1, wherein fine particles having different sizes are mixed and used as the reactive metal fine particles. The breathable porous electrode according to claim 1, wherein the reactive metal fine particles are bonded and fixed in a state including a void larger than the fine particles. 2. The breathable porous electrode according to claim 1, wherein large metal fine particles covered with small metal fine particles are used as the reactive metal fine particles. 2. The breathable porous electrode according to claim 1, wherein metal fine particles fixed in advance on the surface of large fine particles of different materials are used as the reactive metal fine particles. The surface of the reactive fine metal particles is covered with a mixed film of a compound containing a reactive sensitive group at one end and a thiol group at the other end and a compound containing a fluorocarbon group at one end and a thiol group at the other end. The water / oil repellent breathable porous electrode according to claim 1, wherein the porous electrode is water repellent and oil repellent. The water / oil / oil repellent porous electrode according to claim 1, wherein the coating is directly bonded to the surface of the metal fine particles via sulfur of the compound. The water / oil / oil repellent porous electrode according to claim 1, wherein the coating is a monomolecular film. The metal fine particles are conductive Au, Ag, Cu, Ni, transparent conductive ZnO, ITO, FTO, catalytic Pt, Pd, Ro, Ru, V, or an alloy containing them. The breathable porous electrode according to any one of claims 1 to 8. The breathable porous electrode according to any one of claims 1 to 9, wherein the metal fine particles have a size of nanometers to several hundreds of microns. The breathable porous electrode according to any one of claims 1, 2, and 4 to 10, wherein the size of the through hole is smaller than the size of the fine particles. Applying a paste containing reactive metal fine particles covered with a film formed of a compound containing a reactive sensitive group at one end and a thiol group at the other end to a porous substrate surface having a through-hole, and a solvent; The manufacturing method of the air permeable porous electrode characterized by including the process to harden | cure. The method for producing a breathable porous electrode according to claim 13, wherein fine particles having different sizes are mixed and used as the reactive metal fine particles. The method for producing a breathable porous electrode according to any one of claims 12 and 13, wherein a foaming agent is mixed in the paste and heated and foamed during curing. The method for producing a breathable porous electrode according to any one of claims 12 to 14, wherein large metal fine particles previously covered with small metal fine particles are used as the reactive metal fine particles. The method for producing a breathable porous electrode according to any one of claims 12 to 15, wherein metal fine particles fixed on the surface of large fine particles of different materials in advance are used as the reactive metal fine particles. Covering the surface of reactive metal fine particles with a mixture of a compound containing a reactive sensitive group at one end and a thiol group at the other end and a compound containing a fluorocarbon group at one end and a thiol group at the other end The method for producing a water / oil repellent breathable porous electrode according to any one of claims 12 to 16. The method for producing a water- and oil-repellent and air-permeable porous electrode according to any one of claims 12 to 17, wherein the coating is directly bonded to the surface of the metal fine particle through sulfur of the compound. The compound represented by any one of the following chemical formulas (11) to (18) is used as the compound containing a thiol group, The water / oil / oil repellent ventilation according to any one of claims 12 to 18 Of manufacturing porous porous electrode.
_{(11) H 2 N- (CH} 2) n -T
_{(12) HOOC- (CH 2)} n -T
(13) EP- (CH ₂ ) _n -T
_{(14) (AO) 3 Si-} (CH 2) n -T
_{(15) HS- (CH 2)} n -T
_{(16) HO- (C 6 H} 4) -T
_{(17) H 2 N- (C} 6 H 4) -T
_{(18) HS- (C 6 H} 4) -T
In the chemical formulas (11) to (18),
T represents an SH group, a triazine thiol (following chemical formula 19) group, or a triazole thiol (following chemical formula 20) group.
N is an integer from 0 to 16,
A is an alkyl group,
EP represents the following chemical formula 3 or 4.

The method for producing a breathable porous electrode according to any one of claims 12 to 19, wherein a monomolecular film is used as the coating. As the metal fine particles, conductive Au, Ag, Cu, Ni, transparent conductive ZnO, ITO, FTO, catalytic Pt, Pd, Ro, Ru, V, or an alloy containing them is used. The method for producing a breathable porous electrode according to any one of claims 12 to 20. The method for producing a breathable porous electrode according to any one of claims 12 to 121, wherein the metal fine particles have a size of nanometers to several hundreds of microns. The method for producing a breathable porous electrode according to any one of claims 12 to 22, wherein a non-aqueous organic solvent, an aqueous solvent, or water is used as a solvent for the paste. 24. The breathable porous electrode according to any one of claims 12 to 23, wherein a substrate containing a functional group that reacts directly or indirectly with the reactive group is used on the surface of the porous substrate. Production method. 25. The production of a breathable porous electrode according to any one of claims 12 to 24, wherein the surface of the porous substrate having through holes and the reactive group on the surface of the fine particles are reacted directly or indirectly. Method. It is characterized by forming large metal particles covered with small metal particles by forming films with different reactive groups on the surfaces of large particles and small particles and reacting them directly or indirectly with each other. The manufacturing method of the air permeable porous electrode of Claim 15. 27. The production of a breathable porous electrode according to claim 26, wherein the large fine particles are 500 to 1 micron, and the size of the small metal fine particles is 1/5 to 1/100 of the large fine particles. Method. 12. The breathable porous spacer according to claim 1, wherein alkoxysilylki is used in place of the thiol group, and electrically insulating fine particles are used in place of the metal fine particles. The breathable porous spacer according to claim 28, wherein the electrically insulating fine particles are silica or alumina. 29. The method for producing a breathable porous spacer according to claim 12, wherein alkoxysilylki is used instead of the thiol group, and electrically insulating fine particles are used instead of the metal fine particles. The method for producing a breathable porous spacer according to claim 30, wherein the electrically insulating fine particles are silica or alumina. A fuel cell comprising the air permeable porous electrode according to claim 1 and / or the air permeable porous spacer according to claim 28 or 29. A method for producing a fuel cell, wherein the method for producing a breathable porous electrode according to claims 12 to 27 and / or the method for producing a breathable porous spacer according to claims 31 and 32 is used. A vehicle equipped with a fuel cell manufactured by using any one of claims 1 to 33.