TW200415823A - A catalyst electrode for a fuel cell, a fuel cell, a manufacturing method of a catalyst supporting particle for a fuel cell, and a manufacturing method of a catalyst electrode for a fuel cell - Google Patents

Abstract

A catalyst electrode for a fuel cell includes a base substrate which has an electronic conductivity; and a catalyst layer which is formed on the base substrate. The catalyst layer includes carbon particles which support a catalyst material of which an average diameter is in a certain range, and a polymer electrolyte material which is mixed with the carbon particles. The carbon particles include carbon nano horn aggregates to each of which a plurality of carbon nano horns are aggregated spherically. The carbon nano horn aggregates supports the catalyst material.

Description

V. Description of the invention (1) 1. [Technical field to which the invention belongs] The present invention relates to a fuel cell pool and a catalyst carrier particle for a fuel cell ::: Method for manufacturing a fuel electrode and a catalyst electrode . Clothing & method and for fuel cell 2. [Prior art] Electrode, 3 = The battery has an -electrode of a fuel electrode and an oxidant electrode Γ :: 1. The fuel is supplied to the fuel, and the lice are supplied to the geese ^ ^ to produce a dipole through an electrochemical reaction. In other words, when electrical energy is supplied to the oxidant electrode, hydrogen should be supplied to the fuel electrode, which should lead to the following reaction: The electrochemistry in the respective electrodes is at the fuel electrode terminal (positive electrode): Η2 2Η + + 2e ~ At the end of the oxidant electrode (negative electrode): 1/202 + 2H + + 2e- H2〇 For example, using + # in a battery, such as polymer electrolyte membranes such as ti ^ y ^ t films, can be obtained at normal temperature and pressure. 1A / cm2 or f according to the above f should be 'high output value, both electrodes need to be reached by the value ... The electrolytes and complex particles in a mixture of catalyst materials in Gansu are close to: ^ ΐ ΐ: ϊ ϊ ί Hydrogen is used as a fuel fuel cell. Natural research and smoke: The fuel cells for organic liquid fuels are already large. Nowadays, it is known that fuel power using organic liquid fuels is 200415823.

For example, the fuel cell He i se i should not be used as a surface area. It must be used to have carbon particles in it. In the end, the method is as follows: ΐ: Liquid fuel is another form of hydrogen as fuel. Case (JP_A- ^ ^ The direct use of methanol-type fuel cells, JL 1 2; = material transformation and direct supply to the fuel electrode = characteristics of the battery, we must increase the catalyst material 2 so increase in The catalytic activity of the catalyst electrode. For this purpose, five materials are used: the particle diameter of the particles is uniformly dispersed. For the conventional material of the interface. First, 'produce a metal plate with the catalyst; Then, a colloidal solution is made and used on carbon particles. The catalyst material is used to perform the reduction process of carbon particles. With this type of square catalyst material, carbon particles are carried. / This reduction process is usually at 400 ^ or higher in a hydrogen atmosphere. However, when a typical carbon material such as acetylene black is used to perform the reduction process at a temperature of 400 ° C, the average particle diameter & of the catalyst material increases to about 7 ~ 1 〇nm, and at this touch Cohesive force is generated in the particles. This causes a problem that the catalytic activity of the catalyst electrode is insufficient due to a decrease in the surface area of the catalyst material. The absorption material technology, the catalyst and the single-walled nanometer related to the above technology The catalyst carrier of the angular carbon particles has been disclosed in the Japanese published patent application (Jpt A 2 0 0 2 -1 5 9 8 5 1). The catalyst of the single-walled nano-horn-shaped rear particle of this technology provides a Oxidation catalyst for liquid phase reaction, the oxidation catalyst further includes single-walled nano-horn carbon particles aggregates whose single-walled nano-horn carbon poles are combined into a spherical shape. Single-walled technology of this technology Catalyst carrier for nano angular carbon particles

Page 9 200415823 V. Description of the invention (3) A carrier 'single-walled nano-angular carbon particles aggregate containing single-walled nano-angular carbon particles combined into a sphere and a metal catalyst on its surface . In this technology, the single-walled nano-angular carbon aggregates have the function of an oxidation catalyst (ethanol is decomposed into acetic acid and water, and acetic acid is decomposed into a chemical compound and methyl alcohol). By using a single-walled nano-angular carbon particle aggregate as a catalyst carrier ', the metal catalyst has a high catalyst dispersion and a high catalyst activity. The catalyst of the platinum group metal carried on the surface of the single-walled nano-angular carbon particle aggregate shows high catalytic activity (in the form of acid, ketone, carboxylic acid of alcohol oxidation reaction) reflected by its liquid phase. Three, [hairpin hairpin, which has a high cell and its hairpin hair media electrode, a good cell and its hairpin hair carrier particle diameter and its system for clarity] one of the purposes of the carbon particle Catalyst activity manufacturing method. Another purpose of the Ming is its highly scattered carbon particles manufacturing method. Mingzhi is another son ’which has a catalyst material manufacturing method. The invention is to provide a catalyst material for a fuel cell with a wide surface area and force; and the fuel cell using the catalyst electrode is to provide a catalyst activity for a fuel cell. And the fuel material using the above-mentioned catalyst electrode is to provide a high-level catalyst active force for a fuel cell, and it has a thin type for good uniform dispersion. In this embodiment, the present invention provides material 1

Page 10 200415823 V. Description of the invention (4) The catalyst electrode for β cell, which includes: a conductive layer and a catalyst layer on the substrate. The catalyst layer is more inclusive. Second, the carbon material of the catalyst material's average diameter of the catalyst material falls within two special touches; and-polymer electrolysis and intermixing with the carbon particles include: Muping The preparation of stone preparations is taken from Guangxi ^ ^ He Bei said that the Haishi stone granules are: "Jiaohuocai, ♦ also the body, in which a plurality of nano-horned stones are gathered in a spherical shape on each other. Together. The ^ -shaped body composes the catalyst material. The decagonal particles aggregate the catalyst electrode according to the present invention, and its specific interval is 0 · 5nm 0 · ⑽ ~ each = t: Ming's catalyst electrode, the plural The adjacent 7 π = 3 of the nano-angled carbon particles. A conical portion; and a tubular, side-cone portion connected to the conical portion is radiated from the center of the nano-angled interfering aggregates: the synapse The shape of the catalyst material is substantially that the catalyst material is uniformly dispersed in the catalyst material, and the catalyst material contains at least one catalyst electrode spherical shape according to the present invention. The catalyst electrode according to the present invention is a horny carbon particle aggregate. Gold: = contact 2 poles' ... The material contains at least one of two alloys, which Gold, and gold is at least doubled metals

Every-: ΐί, Mingzhi catalyst electrode, the mother of the plurality of nano-horn carbon particles is the early wall M㈣H every two: t !: catalyst electrode, the plurality of nano-horn carbon particles u are all early-layer (wall) type nano-angular graphite.

Page 11 200415823

V. Description of the invention (5) The contact aggregation system according to the scope of the patent application 1 is supported on carbon fibers and electrodes, and it claims that there is at least one nano-horn carbon. ， Semi carbon fiber and nano carbon tube to reach the cost of the invention battery, which contains · a substrate with two electric characteristics at both ends of the electrolyte membrane; and-the layer contains: a one-touch electrode falling in a specific interval electrolysis液 材料。 Liquid material. In the carbon particle, a plurality of nano-horny carbon nano-horn-shaped aggregates are provided in accordance with the present invention, and the present invention provides a fuel ^ two-electrolyte membrane; and . The catalyst electrode further includes a catalyst layer once guided on the substrate. The carbon particles of the catalyst μ material are within the average of the catalyst material; and a polymer mixed with the carbon particles includes: nano-angular carbon particle aggregates whose particles are aggregated with each other in a spherical shape. Together. The composition of the catalyst material. The specific range of the battery cell is from lnra to 511111. ^ According to the fuel cell of the present invention, each of the plurality of nano-angled carbon particles includes: a conical portion; and a tubular 4 β-hine conical portion connected to the conical portion is composed of the nano-angled carbon. The center of the granular aggregates protrudes radially. According to the fuel cell of the present invention, the shape of the catalyst material is substantially spherical. According to the fuel cell of the present invention, the catalyst material is uniformly dispersed on the nano-angled carbon particle aggregates. 8. The fuel cell according to the present invention, the catalyst material comprises at least one cup i and a metal of one of the platinum group, and the alloy is an alloy of at least two of gold and platinum group metal.

200415823 V. Description of the invention (6) According to the fuel cell of the present invention, each of the plurality of nano-angular carbon particles is a single-walled nano-angular carbon particle. According to the fuel cell of the present invention, each of the plurality of nano-angular carbon particles is a single-layer (wall) type nano-angular graphite. The fuel cell according to the present invention, wherein the nano-angular carbon particle aggregate is supported on at least one of carbon fiber, nano-carbon fiber, and nano-carbon tube. In order to achieve another aspect of the present invention, the present invention provides a method for manufacturing a catalyst-carrying particle for a fuel cell. The steps include: (a) a metal salt solution of a catalyst metal material and a nanometer angle; The carbon particles aggregates are mixed, so that the catalyst metal of the catalyst metal material is attached to the nano-angle carbon particles aggregates to become metal particles. The nano-angle carbon particles aggregates include a plurality of spherical particles. Aggregated nano-sized carbon particles; then (b) performing a reduction procedure on the nano-shaped carbon particles aggregate, so that the catalyst metal is carried on the nano-shaped carbon particles aggregate. In order to achieve another aspect of the present invention, the present invention provides a method for manufacturing a catalyst electrode for a fuel cell, the steps including: (c) combining a metal salt solution of a catalyst metal material with nano-angle carbon The particle aggregates are mixed so that the catalyst metal of the catalytic metal material adheres to the nano-sized horny carbon particle aggregates to become metal particles. The nano-sized horny carbon particle aggregates include a plurality of spherical particles Together the nano-horn carbon particles; then (d) performing a reduction procedure on the nano-horn carbon particles aggregate, so that the catalyst metal is carried on the nano-horn carbon particles; and then (e) on the substrate A layer of paste is applied and allowed to dry, wherein the paste contains the nano-horned carbon particles aggregates

Page 13 200415823 Fifth, the description of the invention (7) the body and the metal salt that is highly qualified as a fuel cell. The metal material is a metal particle aggregated in an aggregate, and the angular aggregate is dry. The collective end and the remanufacturing method of the high-electrolyte electrolyte material, the solution and the nano-corner catalyst metal are dependent on each other, and the nano-corner-like nano-line-shaped reduction process is performed, and then (h) in The paste contains this; (i) pressure is applied to the south molecular electromolecular electrolyte membrane and another embodiment is provided, the present invention provides-a kind of step = includes: (f) a catalyst metal-like carbon particle aggregate Mix so that the catalyst attaches to the nano-sized horny carbon particles aggregate to form a horn-shaped carbon particle aggregate containing a plurality of spherical carbon particles; then (g) the catalyst metal is then added to the nano-horned carbon particles. A layer of paste is coated on the nano substrate and dried nano-horn carbon particles aggregates and high-resolution nano-horn carbon particles containing the catalyst electrode are aggregated to dissolve a plasma membrane to support the catalyst. Each of the two ends of the medium electrode is connected. 、 The burning method of electric material, the electromagnetism of the electromagnetism of the electromagnetism and the electromagnetism of the electromagnetism of the electromagnetism and the elaboration of the electromagnetism. contact. Λ Λ Example 4 Ishi Shi ^ FIG. 1 shows a cross-sectional view schematically illustrating a structural example of a fuel cell according to this embodiment. The fuel cell 100 includes a catalyst high-resolution electrolyte membrane assembly 101. The catalyst polymer electrolyte membrane assembly 1 0j has "a fuel electrode 102, an oxidant electrode 108, and a polymer electrolytic J membrane U4. The fuel electrode 102 and the oxidant electrode are collectively referred to The catalyst is the second electrode of the catalyst. The fuel electrode 102 is composed of the substrate 104 and the catalyst layer 106. I surface Η Page 14 200415823 V. Description of the invention (8) The oxidant electrode 108 One U-field base pulls 1 Ϊ 〇 and one touch-pull JB 1 1 9 α z… or multiple catalyst electrodes polymer electrolysis; a membrane =: burning slanting snow; Chengba Gukou ... one shell The waist, and the e-pieces 101 are electrically connected through a fuel electrode terminal separator 120 and a ^ 7 Beilian assembly, and 122 are electrically connected. And the emulsifier electrode terminal separator 120 burns the battery 100. A fuel 124 separates the crying electrode 102 through the fuel electrode terminal. Moreover, the fuel electro-oxide 1 26 of the mono-oxide ⑺Λ electrolytic shell membrane assembly 101 is supplied to the catalyst electrode polymer electrolyte membrane group through the oxidant power ^ ^ 22 Pole 1 0 8. Poor ancestor 1 9 yl 丨, /, six 1 oxidant electricity 4 Ranke 124 with liquid organic fuel The alcohol 126 is an example of an oxygen-containing gas such as air and oxygen. The oxygen electrode, the fuel electrode 102, and the oxidant electrode 108 include a catalyst-supported bass and two molecules of electrolyte particles. Tapping sound J 〇6 ， 火 子 子 ^^ 104 2; ^ 1Π〇, Α „11 Λ L prepared * spiron increase 1 1 2 is also formed at the oxidant electrode 1 sequence 08. On the substrate 110. Waterproof process can be performed on the surfaces of the substrates 110 and 104. For example, porous substrates such as substrates 104 and 110 can copy paper and sintered metals. Take, for example, a procedure in which a waterproofing agent such as polytetrafluoroethylene can be used in the substrate ^ water ^ sequence. FIG. 2 shows a diagram illustrating an example of a structure of a catalyst layer of a catalyst electrode of the present invention. Here, the catalyst metal 40 5 is carried on the surface of the nano-corner agglomerates (aggregates) 401 and becomes carrier particles. In the graphene fuel cell 100, each of the catalyst layers 106 or 112 includes a polymer electrolyte 403 and a catalyst-carrying carbon particle having a structure shown in FIG. 2.丨 As shown in FIG. 2, the nano-horned carbon particles aggregated approximately in a spherical shape. Page 15 200415823 V. Description of the invention (9) 4 0 7 The horn-shaped carbon particles aggregate 4 0 1 is used for As a catalyst bitch. Here the nano-angular carbon particles 407 / charcoal particles. The case of making more spoon 2 does not mean that it is always an actual sphere; it also includes expanded circles, rings, and other various poly-n-nets. The cone-shaped component and the cone-shaped carbon particles aggregate and act on several nanometer corners of each circle, as if the nanometer is usually at 10nm. The angular carbon particle aggregates 401 are made of nanometer angular carbon particles 407. The poly-nano-angular carbon particles are a kind of nano-angular carbon tube, which comprises: a conical portion and a cylindrical (tubular) portion having a cylindrical shape and a cylindrical portion connected to each other. The nano-corner 401 is made up of a plurality of nano-horn-shaped carbon particles 407 gathered between cones of van der Waals. In this case, the compound carbon particles have a horn shape with a conical portion protruding from the surface thereof, and a tubular portion as a center. The diameter of the horny carbon particle aggregate 401 is guonm or less, and the diameter is 100 nm or less. Also, in each of the nano-angular carbon particles 407 constituting the nano-angular carbon particle aggregate 401, the diameter of the tubular portion is approximately 2 nm, and the length thereof is usually 30 nm to 50 nm. In the conical portion, the oblique angle on the cross section including the conical axis is about 20 on average. . Under this special structure, the nano-angular carbon particle aggregate 401 has a packed structure with a very large specific surface area. Nano horny carbon particle aggregates 40 1 can usually be produced by laser ablation, a solid single carbon material such as graphite is selected, and an inactive gas environment at room temperature and 1. 0 1 32 5 * 1 05 Pa Under production. In addition, the size of the pores between the nano-angular carbon particles 407 and the nano-angular carbon particles aggregate 401 can be determined by thunder.

Page 16 200415823 V. Description of the invention (ίο) The production status of the eliminant ^ and the oxidation process after production The application of rice horn-like slave aggregate 401 to the heart can be regarded as nano-horn Ⅱ. The carbon tube has a sphere like a football: like. However, it is not limited to the structure of the center. Moreover, its center can be regarded as empty. The charcoal particles t! 7V are regarded as 顶端 1 κ :: τ, Yoshiba, & Keyue b, which are apical (front edge, apex) closed. The conical apex at the end can end with a circle. As for the nano-angular carbon particles 407, which make up the nano-angular carbon particle aggregates 401, when the end of the conical wood ^ Qukoukan 4, do not say] when the cone-shaped apex is rounded to form the knot ' Then = see radial aggregation, so that part of the circular apex is still outside. Moreover, a part of the structure of the nano-angular carbon particles 407 may be incomplete and have minute holes. The nano horny carbon particle aggregate 40 j may further include the nano carbon tube. M / D ..., nano-angular carbon particles aggregate 401 can be assembled into single-walled nano-angular carbon particles. This assembly can improve the conductivity of the sons of nano-horny carbon particle aggregates 401. In addition, the nano-angular carbon particle aggregate 401 can also be assembled with a single-walled nano-angular carbon body composed of single-wide (wall) nano-angular graphite. This kind of assembly can improve the conductivity of nano-angular carbon particle aggregates 401. Therefore, 'when it is used as a catalyst electrode for a fuel cell,' bean soup 'is improved. The catalyst metal 405 can be used in the following cases, for example. Examples of the intermediate metal 405 include platinum, germanium, palladium, iridium, osmium, nails (platinum group metals), two silver (precious metal group including platinum group metals), thorium, nickel, cobalt, lithium, strontium, and yttrium. A single material or two or more of the above

415823 V. Description of the invention (11) Both combinations can be used. The above two or more alloys can also make the surface, as for the catalyst used for the fuel electrode 102 of the example of the oxidant electrode 08; "°: The catalyst similar to the above and the oxidant electrode 108 can be used ^ 1 One edge, the fuel electrode 102 may be the same as or different from the spider j. The diameter of the particles of the catalyst metal 405 is better. The diameter of the particles is very thin, such as $, or less than 5 nm. Because it becomes larger, it makes it contact Efficiency improvement of the catalyst: °: T The specific surface area of the catalyst becomes a very high reaction amount. When a small amount of catalyst can be used as the carbon particles, the carbon particles are aggregated by the aggregate 2 of the carbon particles 401. The amount is also very large ... from the large, and the unique three-dimensional structure of the catalyst material, the catalyzed carbon particles aggregate state 4 〇3 ^ ^ ^ φ # # ^ Λ; ^ hydrogen ion can be Effective transfer. Therefore, the catalyst electrode that is similar to the one used (fuel electrode 102 = the area where the fuel cell catalyst reacts on the sun and the moon is non-standard; the emulsifier electrode is used for its energy transmission. = Good so when it is used on a fuel cell = the average particle diameter of the material is preferably equal to or less than 2 Makes the specific surface area of the catalyst material larger. Therefore, the power output of the battery can be further improved. Incidentally, it needs to be specially limited. For example, it can be limited to 0.lnffi or more or less At 0.5nm or above. Such a limitation can obtain an electrode with excellent catalyst efficiency under good bioreleasability.% 疋 Catalyst electrodes for this fuel cell (fuel electrode 102 and oxidant

Page 18 200415823 V. Description of the invention (12) Electrode 108) In the middle, the catalyst material is preferably spherical in nature. Here, "substantially spherical" means that the ratio of the long diameter to the short diameter of the catalyst particle ^ $ average is equal to or less than 3. This design can make the shape of the catalyst metal 405 more consistent. Well, the specific surface area 7 of the catalyst metal 405 can be increased. And the catalyst metal 405 is preferably uniformly dispersed in the nano-angled carbon particles 401. Here, "uniform sentence dispersion" means Because the formation of cohesives and secondary particles is inhibited, the catalyst metal 405 can be uniformly dispersed on the surface of the nano-angular carbon particle aggregate 401. This setting = makes contact Also: "Yes" 2 The area is more increased. Therefore, when it is used in Ertunchi, the monthly output of b $ can be improved. f, the polymer electrolyte 403 also plays a role of electrically connecting the two break-up genus two membranes i1 10: 4 to the surface of the catalyst electrode holding the two: the angle of the carbon particle aggregate 401, It also has the role of the fuel 124 in contact with the surface of the catalyst metal 405. Due to: characteristics. Therefore, for: ': electrode 108 needs to have excellent chloride ion transport with oxygen transmission ;; = ;: 403, the material is preferably with solid, the organic polymer (guba ^ organic liquid fuel transmission Characteristics. The strong acid groups, discic acid groups or the like are weak acid groups with polar groups, such as sulfur compounds. 7 Strong groups, and such as carboxylic acid groups and similar organic high eight groups Examples of perfluorocarbon compounds (such as ^ knives) include: JVAF ION (product 200415823, invention description (13) name) made by DuPont, containing sulfonic acid, registered trademark, ASHlpLEX (product name, manufactured by Asahi Kasei Corporation) )) ·, Perfluorocarbon compounds containing carboxyl groups (for example, 跗 丨 ⑽s membrane (trade name): registered trademark, manufactured by Asahi Soko Corporation); polystyrenesulfonic acid copolymer, benzenesulfonic acid copolymer, cross-linked alkane Copolymers of sulfonic acid derivatives, fluorene-containing polymers, etc .; Propane is a copolymer obtained by copolymerizing propylene amines of acid and n-butyl methylpropionate. Sundial — ^ 4 is a polymer having a polar group as a target. In addition to the above, for example, polybenzimidazole derivatives, polybenzimidazole-derived polyethyleneimine cross-linking materials f, and the like may be used. Polyresin, (Polysuamine) derivatives, such as polydiethylamine ethyl H = poly, phenethyl, such as diethylamine ethyl polymethacrylic acid t [propylene s Polypropylene-based resins containing warp-based groups represented by silanols and hydroxyethyl polymethyl acrylates; ^ Warp-based polybenzyl resins represented by fines; 卩 and its analogs: B In addition, a cross-linking substituent may be appropriately implanted into the above-mentioned polymer: I:: it 'For example, vinyl, epoxy, propenyl, methacrylic clay, clay Sik group, hydroxymethyl , Azido and naphthoquinone. 4 (Π β μ μ at the fuel electrode 102 and the oxidant electrode 108 polymer electrolyte 40 3 may be the same or different from each other. Zui Cheng obliquely consider the polymer electrolyte 'in Figure 2' The description of 403 is only: Yes: It is formed and connected to a part of the nano-horn carbon aggregates 401. It can also be formed and connected to the entire nano-horn carbon aggregates 40 1

200415823

★ It requires t ^ media layers 106 and 112, and for fuel cell electrodes ^, it is necessary to guide the catalyst t and catalysts: and high permeability of materials / oxidants to reach-extravagant. The catalyst metal 40 5 of Dali is composed of nano-angular carbon particle aggregates 4 0 1 of the catalyst metal 4 5 which is used to promote effective catalyst reaction. It has a very large electrical conductivity. In addition, because it has an angular structure protruding radially from the center of the nano-horn aggregates 401, the fuel / oxygen can reach the catalyst metal & 5 through the grooves between the corners in winter. 1 port > It has many angular structures that protrude radially from the center of the material, z. The surface area is not large and it can carry a large amount of catalyst metal 405. In addition to this, since the tip of the corner portion contacts the polymer electrolyte 403 or the adjacent corner portion, ions and electrons can be easily transferred. In other words, the nano-angular anaerobic granules collectively 401 are very suitable and effective as a carrier of the catalyst metal 405 of the catalyst layer 106 and U2. In the fuel cell 100, the polymer electrolyte membrane 114 plays a role of separating the fuel electrode 102 from the oxidant electrode 108 and pushing hydrogen ions and water molecules therebetween. Therefore, in the polymer electrolyte membrane 114, it is preferred that the thin, membrane has good hydrogen ion conductivity. In addition, it is preferred to have chemical properties and strong mechanical strength. As a material constituting the South Molecular Electrolyte Membrane 114, a strong acid group such as a gallic acid group, a phosphonic acid group, a phosphonic acid group, and a phosphonic group is preferable, and an organic polymer containing a polar group that is a weak acid group is preferred. As organic polymers such as $, for example: sulfonated poly (4-phenoxybenzophenyl- 丨, 4— ^ building (4 ~ phenoxybenzoyl_1,4-phenylene), paraffin yellowing polybenzomide σ South molecule of Fangxiang family, polystyrene lutein acid copolymer, poly'benzene

Page 21 200415823 V. Description of the invention (15) Copolymers of sulfonic acid copolymers, cross-linked alkane sulfonic acid derivatives, fluororesin frameworks and fluorinated polymers composed of sulfonic acid; Propylamine 2-methylpropyl A copolymer obtained by copolymerizing sulfonamides and butyl methacrylates together with acrylic esters; perfluorocarbon compounds containing sulfonic acid groups (for example, Shanbang Company Na fi on (trade name) 'Aciplex (trade name) manufactured by Asahi Kasei Corporation; perfluorocarbon compounds containing a radical (for example, F 丨 em 丨 on S membrane (trade name) manufactured by Asahi Glass Co.). Choose a sulfonated poly (4-phenoxybenzophenyl-1,4-phenylene), burnt stone yellowing polybenzo, and wait for the aromatic polymer It can suppress the penetration of liquid organic fuel, and suppress the decrease of battery efficiency caused by staggering phenomenon. Gaseous fuel or liquid fuel can be used as fuel 1 2 4. For example, when using gaseous fuel, hydrogen can be used. And when When a liquid fuel is used, organic compounds that can be used in the fuel 1 2 4 include alcohols such as methanol, ethanol, and propanol, ethers such as methyl ether, and cycloalkanes such as cyclohexane. Hydrophilic group-containing cycloalkanes such as hydroxyl, carboxyl, amine, and amido groups, and mono- or di-substituents of cycloalkanes, but not necessarily limited thereto. Here, the cycloalkanes may be cycloalkanes Substituents thereof or substances other than aromatic compounds may be used. The method of manufacturing the fuel cell 100 is explained below. The method of manufacturing the fuel cell 100 is not particularly limited. For example, the following methods may be used. Come to manufacture., NW knife into head The method of Figure 3 shows an electrode catalyst of a process - producing first described.

Page 22 200415823 V. Description of the invention (16) The figure illustrates an example of a manufacturing method of the catalyst electrode of the present invention. The catalyst metal 405 can be carried in the corner aggregate 401 by using a typical injection method. The method includes the following steps: First, the catalyst material containing catalyst metal 4 to I is dissolved or dispersed in a solvent to obtain a colloidal / valley solution SO 1); The colloidal solution and nano-horny carbon particles aggregated 401 to this. In order to attach the catalyst material to the nano-angular carbon particle aggregate 4 01. (Step S02); Next, a reduction sequence is performed on the nano-angled carbon particle aggregates 401 so that the catalyst material is supported on the nano-angled carbon particle aggregates => step 803), and then , Dispersing the polymer electrolyte (particles) and the nano-horn-shaped carbon particle aggregates 4 〇 ^ supported on the catalyst material 4 in a solvent = producing a paste (step s〇4); finally, This paste is applied onto the substrate 110 and dried (step S 0 5). Finally, the touch :: :( 102 ′ 1〇8) can be obtained. With this method, the catalyst material can be supported on the nano-sized carbon particles aggregate 401 (carbon particles). ιη〇Γ, the reduction procedure is carried out at a low temperature from room temperature to 100 ° C, for example, at too high temperature: = T 0 0 c or below. By this method, the average particle diameter of such a very small or larger particle that supports the catalytic metal 40 5 in the carbon particle aggregate 40 may be less than or equal to 5⑽, such as 1 «嗲 is too & Or smaller. In addition, the catalyst metal 405 can be uniformly dispersed in the mouth-water-like angular carbon particles 407. In the straight scales Lt, S04, the particle set of the polymer electrolyte 403 in the paste is 100.511 or more of 401 and 1 or less and 1 or less. Nano horny carbon particles are polymerized, and the weight ratio of the zirconia to the molecular electrolyte 403 is between, for example,

Page 23 200415823 V. Description of the invention (17) 2 Stomach · 1 and 40: 1 range. The weight ratio of water to solution in the paste is, for example, between about 2: 1 and 10: 1. Incidentally, the nano-angular carbon particle aggregates 401 can be used in carbon fibers, nano-carbon fibers, nano-carbon tubes, or the like through thermal processes to support the two-phase carbon fibers, nano-carbon fibers, nano-carbon The 2 meter horny carbon particles aggregate 401 in the rice carbon tube or the like is used for the nano horny carbon particles in step s02 to collectively 401. Therefore, the microstructures of the catalyst layer 106 and the catalyst layer 12 can be arbitrarily adjusted. The method for applying the paste on the substrates 104 and 110 is not particularly limited. For example, methods such as bristle coating, spray coating, and screen printing can be used. The paste is applied at a thickness of about ˜1 m to 2 mm. After the paste is applied, it is heated in accordance with the heating temperature and heating time of the fluororesin used for the substrate 104 and 10 and / or the paste to prepare a fuel electrode 102 and an oxidant electrode 108. Heating temperature and heating time, select appropriate conditions according to the materials used, such as heating temperature 10 (TC ~ 250 it, heating time 30 seconds to 30 minutes 0

By using the catalyst electrode generated by the above method, the fuel cell 100 can be generated as described below. Fig. 4 shows a flowchart illustrating an example of a method for manufacturing a fuel cell of the present invention. X The polymer electrolyte membrane 114 can be formed by using an appropriate method and depending on the material used (step S11). For example, when the polymer electrolyte membrane 1 j 4 is made of organic molecules (polymers), it can dissolve or disperse the liquid after dissolving the organic polymer materials in the solvent, and peelable sheets such as polytetrafluoroethylene. It is obtained by casting on top.

Page 24 200415823 V. Description of the invention (18) The catalyst electrode (the fuel electrode 02 and the oxidant electrode 108) can be formed by the method of steps S01 to S05 described above (step S12). After that, the obtained polymer electrolyte membrane 4 is sandwiched between the fuel electrode 102 and the oxidant electrode 108 and is subjected to a hot pressing process to form a catalyst electrode-polymer electrolyte membrane assembly 101 (step S13). At this time, the surface of the catalyst layer 106 is directly facing one surface of the polymer electrolyte membrane 114, and the surface of the catalyst layer 112 is facing the other surface of the polymer electrolyte membrane 114. The condition of the hot pressing process also varies depending on the material. For example, when the polymer electrolyte membrane ι14 and the polymer electrolyte 403 on the surface of the catalyst electrode (102, 108) are made of an organic polymer having a softening point temperature and a glass transition temperature, its heat-pressing treatment The temperature can be set higher than the softening point temperature and glass transition temperature of the polymer. Actually, for example, the temperature is 10025 ° C and the pressure is 1 to 100 kg / cm2, and the time is 10 seconds to 300 seconds. In the fuel cell 100 thus obtained, the nano-horn carbon particles aggregate 401 is used as a catalyst to support carbon particles, and the nano-horn carbon particles are aggregated on the surface of the body 401 to form a spherical shape. The average particle diameter of the catalyst metal 40 5 is ^ m ′ or less, and the catalyst metal 40 5 is uniformly dispersed therein. Therefore, it has high catalyst use efficiency and excellent battery characteristics. .... The use range of the fuel cell of this embodiment is not particularly limited. For example, it can be used in a portable electronic device, such as a mobile phone, a personal computer, a PDA (personal digital secretary), various cameras, a navigation system, a portable music reproduction player, or the like. μ '' `` Example ''

200415823 V. Description of the invention (19) The following will further illustrate the catalyst electrode for a fuel cell according to the present invention and its fuel cell by using examples. However, the present invention is not limited to this. [First Example] The nano-angular carbon particle aggregate 401 was produced by a laser ablation method. That is, a sintered round carbon rod as a solid carbon material is contained in a vacuum container, and the container has been vacuumized to 10 · 2Pa. After that, argon gas was introduced so as to generate an atmospheric pressure of 1 · 0 1 325 * 105 Pa. Next, the solid carbon material was irradiated with carbon dioxide laser light with a high power output for 30 minutes at room temperature. The irradiation is performed with a laser output of 100 W and a continuous vibration with a pulse width of 20 ms, and the surface of the solid carbonaceous material is ≧ 20. Angle to complete. When the soot material thus obtained was observed with a transmission electron microscope (TEM), it was confirmed that it was a nanohorn-shaped carbon particle aggregate structure. The obtained soot was further subjected to four ultrasonic procedures (400 kΗz and 60 minutes) in ethanol and decanted. Therefore, nano-angular carbon particle aggregates composed of single or multiple particles can be obtained. Taking the TEM for particle observation, the particle diameters of the obtained nano-horn carbon aggregates were all between 1 nm and 100 nm. The nano-angular carbon particle aggregation system thus obtained is used to generate a catalyst carrying carbon particles. 10 g of nano horny carbon particles aggregates were mixed into a 500 wt.% Solution containing 3 wt% of dinitrodiamine platinum nitrate as a catalyst and shaken. Then ‘6 8 & 1 9 8 v / v% ethanol aqueous solution was added as a reduction

Page 26 200415823 V. Description of the invention (20) Agent. The dispersed solution was mixed at about 95 ° C, and the platinum particles used as a catalyst material were stirred for 8 hours and collectively. The horny π f nanometer horny carbon particles loaded with platinum particles were aggregated and performed at room temperature (20 t) for 5 hours. The anti-granular aggregates were in a hydrogen flow &, π # 杜士 山 、 藏 孝B_ and the reduction process, you can take the catalyst that holds the carbon particles. The amount of platinum particles carried in the nano-corner is about 50% of its own weight. " Wood By using this TEM to observe the obtained catalysts holding carbon particles, the following matters can be confirmed. In other words, 'Ming carried on the nano-angular carbon particles aggregate has an average particle diameter of 1 to 2 nm, and the ratio of the long diameter to the short diameter of the particles is about 1, which is spherical and uniform. Scattered in nano-horned stones. And, even if the reduction procedure is operated at 6 and § 〇 respectively, the openings > shape and size of the turned particles are substantially the same as when the reduction procedure is operated at room temperature. Incidentally, when the reduction procedure is at 400. (At 3 times, the average particle diameter of the platinum particles is about 5ηιη, and it is still spherical. Therefore, using nano-horned carbon particle aggregates as the carbon material, and the reduction process at low temperature can make the The catalyst material is uniformly dispersed on the surface of the nano-angled carbon particle aggregates, and the average particle diameter can be extremely thinned to 1 nm to 2 nm. [First Comparative Example] Acetylene black (manufactured by Denki Kagakusha) is used here ) As a carbon material, and the catalyst metal is carried therein in a manner similar to the first embodiment. When using the TEM as in the first embodiment to observe the acquired country, page 27, 200415823 V. Description of the invention (21) When the catalyst of carbon particles is loaded, the average particle diameter is supported. JL "Hei: ff ^ Black platinum has about 7-flat to glued-on. By the way, it is inconsistent. Many particles At the time of the program, the position i B ′ :: mention: when the typical reduction, the average particle diameter of the δH catalyst metal is about 10 nm at 40 ° c. Therefore, we can 4rr ± k , Mm, 47, -T ^ 4, and the reduction process is performed at low k, that is, The effect of miniaturizing the particles on the catalyst can still be produced by using the black block. [Second Embodiment] The catalyst holding carbon particles produced in the first embodiment is used to produce fuel cells. Catalyst electrodes and fuel cells.

…, A 5% NAFION solution manufactured by ARUDORICH Chemical Co., Ltd is used as a methanol solution for a polymer electrolyte. This solution was mixed with n-butyl acetate and stirred so that the mass density of the polymer electrolyte became 0.1 to 0.4 mg / cm3, and a colloidal dispersion solution of the polymer electrolyte was produced. By adding the nano-sized horny carbon particles aggregate powder holding platinum in the first embodiment to the colloidal dispersion solution of the polymer electrolyte, the colloidal substance is replaced by the nano-sized horny carbon particles aggregate. Absorbed on the surface. The dispersion solution thus obtained is made into a paste through an ultrasonic dispersion unit. This paste was applied to carbon paper by screen printing as a substrate (a gas diffusion layer). Then, it is heated and dried to form an electrode for a fuel cell of a high-molecular electrolyte type. The substrate was a carbon paper (manufactured by Toray Industries, Inc.) having a thickness of 0.19 mm. The catalyst electrode for the fuel cell thus obtained was manufactured by hot pressing at du pont κ · κ · at 120 ° C ~ 200 ° C and a pressure of 50 ~ 100kg / ⑽2.

Page 28 200415823 V. Description of the invention (22) NAFI0N115 is formed on both surfaces to form the catalyst electric hammer-decomposed membrane assembly. This is used to measure the fuel cell: tritium molecular electricity. The output characteristics of the battery are measured by supplying hydrogen (room temperature tritium device. 1. 〇 1 325 * 1 〇5pa) to the battery. The obtained junction pressure is characteristic of power output. The possible reasons should be as follows. Ϊ: The platinum of the media material is located on the surface of the nano-horned carbon particles aggregate: Ϊ: The surface area promoted by the catalyst reaction is larger. + Ju Power, and F. Chu Yifang Comparative Example "Actually named i: The acetylene black powder carrying platinum in the comparative example is similar to the second material battery i series used to manufacture and evaluate the catalyst electrode of the fuel cell. And the example produced by the fuel plant using δH loaded with diethyl black, after the reduction at 400 ° C, the energy output of acetylene t is 0.60w. However, using the same surface-loaded ^ black example, the energy output after reduction at room temperature is J.b5W. This is the improvement that can be achieved by the energy rotation of the C particle sequence at low temperature when a catalyst carrying carbon particles is generated. However, compared with the carbon material, the horned carbon aggregates of Muxing Ethereum are still relatively low in energy output.笛 笛 一… The second embodiment ”The medium gold uses a method similar to the first embodiment, that is, the catalyst is an alloy of surface and ruthenium. The catalyst metal is made of vaporized platinum. And gasification

Page 29 200415823

: == > Generated by cleavage, and further supported by the nano-horn carbon aggregates. : Walk through the original sequence at room temperature under an argon stream containing 4wt% hydrogen. When Tian used TEM to observe the platinum and ruthenium alloy on the catalyst holding broken particles as in the first embodiment, the following matters were confirmed. That is, the average particle diameter of the catalyst metal is 1 to 2 nm, and the ratio of the long diameter to the short diameter is about 1, and it is spherical and uniformly dispersed on the nanohornite inverse particles. . Therefore, even if the catalyst metal is an alloy of platinum and ruthenium, by using nano-horned carbon particle aggregates as the carbon material and performing the reduction process at room temperature, the particle diameter of the catalyst metal can also be reduced. It is thinned and uniformly dispersed on the surface of the nano-angled carbon particle aggregate.

[Third Comparative Example] Here, acetylene black (manufactured by Denki Kagakusha) was used as the carbon material, and the catalyst metal was configured similarly to the third embodiment.

When the TEM was used as in the first embodiment to observe that the catalyst Nishou 'holding carbon particles, the average particle diameter of the Fan and Shu alloy carried on the E-fast black was about 7 nm. Moreover, the shape of the catalyst metal is irregular, and many particles are even glued together. Incidentally, the average particle diameter of the catalyst metal located on the second fast black when the typical reduction procedure is performed at a temperature of 400 ° C is about 10 nm. Therefore, it can be seen that the reduction process performed at a low temperature will cause the effect of miniaturization of the particles on the catalyst even if the fast black is used. [Fourth embodiment] The carbon particles carried in the second embodiment (nano-angled carbon particles gather)

Page 30 200415823 V. Description of the invention (24) Collective) The catalyst is the same as the second embodiment, which is used to manufacture the fuel cell. 10v / v% methanol and 1.0 · 1 325 * 1 05Pa oxygen were respectively supplied to the fuel electrode and the oxidant electrode of the obtained battery, thereby defining the direct methanol-based pear of the fuel cell, and this energy output characteristic was also Measured at room temperature. As a result, the result of this energy output characteristic was also determined to improve 0.20 W. [Fourth Comparative Example] The powder of acetylene black carrying platinum in the third comparative example is used here to produce and measure a catalyst electrode for a fuel cell and the fuel cell as in the fourth embodiment.

These two batteries, which are used in the case of acetylene black loaded with the acetylene black, can be reduced to 0.15W at room temperature and 400 ° C. Therefore, compared with the case of using nano-horn carbon aggregates as the carbon material, the two energy output characteristics are still low. The surface aggregates of the catalyst metal come collectively from this month. This embodiment is on the particles that are feasible when oxygen is used as the metal. Inventions that are not manufactured are not isolated. For example, as a fuel, the catalyst is at a low temperature and the fuel is not limited to this invention. However, the reduction is performed evenly under the extremely useful catalyst, and the use of the energy-carrying tank under the spirit of the above implementation is used in the embodiment, and even the carbon-carrying process can be performed on the nano-catalyst. example. What I have done is to improve the use of nano-horned carbon particles to aggregate particles in the battery system, and it is possible to reduce the thickness of the nano-horned carbon particles aggregates that are already supported, and it has excellent performance. People should understand that the above-mentioned actual technical changes and modifications all use hydrogen-oxygen and methanol ~ hydrogen as fuel.

200415823 Oil and similar as oxidant. According to the present invention, the average grain of the nano-angle material has a catalyst reaction carried at this degree. In addition, according to the fuel cell, the catalyst-carrying particles for the fuel-electric cell are obtained in a uniformly dispersed state, and the fuel cell can use the empty carbon particle-like carbon particles to set the diameter of the carbon. The invention of fuel-electricity on the surface of the pellet, also in which the contact is held, the thin electrode made of the contact electrode used in the pool, and the description of the invention (25), such as natural gas, light t Double-particle aggregates, and its catalysts can obtain surface area and high surface area and its fuel cell < simple media electrode and J suppression because of ith t ′, and are often clever. It is also possible that the catalyst M for fuel cells in this manner is uniformly dispersed to be used as a nano-angle to gather in a spherical shape at 5 nm or less. The catalyst electrode for a wide pool of catalyst material can obtain the cohesive force of the fuel cell medium material, and its catalyst activity force is non-media-carrying particles, and the manufacturing method. The force is very high. Page 32 200415823 Brief description of the drawings 5. [Simplified description of the drawings] FIG. 1 shows a cross-sectional view schematically illustrating a structural example of the fuel cell of the present invention. FIG. 2 shows a diagram illustrating an example of a structure of a catalyst layer of a catalyst electrode of the present invention. Fig. 3 shows a flowchart illustrating an example of a method for manufacturing a catalyst electrode of the present invention. Fig. 4 shows a flowchart illustrating an example of a method for manufacturing a fuel cell of the present invention.

Component symbol description: 1 0 0 fuel cell 1 0 1 catalyst polymer electrolyte membrane assembly 1 0 2 fuel electrode 1 0 4 substrate 1 0 6 catalyst layer I 0 8 oxidant electrode II 0 substrate

11 2 Catalyst layer 11 4 Polymer electrolyte membrane 1 2 0 Fuel electrode terminal separator 1 2 2 Oxidant electrode terminal separator 124 Fuel

Page 33 200415823

Page 34

Claims (1)

200415823 6. Scope of patent application 1. A catalyst electrode for a fuel cell, including: a) a substrate having conductivity; b) a catalyst layer formed on the substrate, wherein the catalyst layer It further includes: b · 1) · carbon particles containing a catalyst material, wherein the average diameter of the catalyst material falls within a specific interval; and b. 2).-Polymer electrolyte material, and the carbon particles Mixed with each other; wherein the carbon particles further comprise: i. Nano-horn carbon particles aggregate, wherein a plurality of nano-horn carbon particles are aggregated together in a spherical shape; With this catalyst material. 2. The catalyst electrode for a fuel cell as described in the first patent application, wherein the specific interval is 0.1 nm to 5 nm. 3. The catalyst electrode for a fuel cell according to item 1 of the patent application scope, wherein each of the plurality of nano-angled carbon particles includes: a) a cone portion; and b) a connection to The tubular portion of the conical portion; wherein the conical portion protrudes radially from the center of the nano-angled carbon particle aggregate. 4. The catalyst electrode for a fuel cell as described in the first patent application, wherein the shape of the catalyst material is substantially spherical. 5. The catalyst electrode for a fuel cell according to item 1 of the patent application scope, wherein the catalyst material is uniformly dispersed on the nano-angular carbon particle aggregate. 6. The catalyst electrode for fuel cell, such as the scope of patent application item 1, where Page 35 200415823 6. Scope of patent application The catalyst metal includes at least one of an alloy, gold, and a group of metals. The alloy is an alloy composed of at least two of gold and a group of metals. 7. The catalyst electrode for a fuel cell according to item 1 of the patent application, wherein each of the plurality of nano-angled carbon particles belongs to a single-walled nano-angled carbon particle. 8. The catalyst electrode for a fuel cell according to item 1 of the patent application, wherein each of the plurality of nano-angular carbon particles is a single-walled nano-angular graphite. 9. The catalyst electrode for a fuel cell according to item 1 of the patent application, wherein the nano-angular carbon particle aggregation system is supported on at least one of carbon fiber, nano-carbon fiber and nano-carbon tube. 1 0. A fuel cell comprising: a) a polymer electrolyte membrane; b) two catalyst electrodes at two ends of the polymer electrolyte membrane, wherein the catalyst electrode further comprises: b. 1) -A conductive substrate; b · 2) ·-a catalyst layer formed on the substrate; wherein the catalyst layer further comprises: i. Carbon particles carrying a catalyst metal, an average diameter of the catalyst metal Falls in a specific interval; i i. A polymer electrolyte material mixed with the carbon particles; wherein the carbon particles further include: i ii nano-angled carbon particle aggregates, wherein a plurality of nano-particles Page 36 200415823 6. Scope of patent application The angular carbon particles are aggregated in a spherical shape; the nano-horn carbon particle aggregates contain the catalyst material. 1 1. The fuel cell according to item 10 of the patent application, wherein the specific interval is from 0.1 nm to 5 nm 〇1 2. The fuel cell according to item 10 of the patent application, wherein the plurality of nano-angles Each of the shaped disks includes: c) a cone portion; and d) a tubular portion connected to the cone portion; wherein the cone portion is radial from the center of the nano-angled carbon particle aggregate 12. The fuel cell according to item 10 of the patent application scope, wherein the shape of the catalyst material is substantially spherical. 14. The fuel cell according to item 10 of the patent application scope, wherein the catalyst material is uniformly dispersed on the nano-angled carbon particle aggregates. 15. The fuel cell according to item 10 of the patent application scope, wherein the catalyst metal includes at least one of an alloy, gold, and a group of metals, and the alloy is composed of at least two of gold and platinum group metals Alloy. 16. The fuel cell according to item 10 of the patent application scope, wherein each of the plurality of nano-horn carbon particles belongs to a single-walled nano-horn carbon particle. 1 7. The fuel cell according to item 10 of the patent application scope, wherein each of the plurality of nano-angular carbon particles belongs to a single-walled nano-angular graphite. 18. The fuel cell according to item 10 of the patent application scope, wherein the nano-angled carbon particle aggregation system is supported on at least one of carbon fiber, nano-carbon fiber and nano-carbon tube. Page 37 200415823 VI. Scope of patent application 1 9. A method for manufacturing catalyst-carrying particles for fuel cells, the steps include: a). A metal salt solution of a catalyst metal material and nano-angle carbon particles The aggregates are mixed, so that the catalyst metal of the catalyst metal material can be attached to the nano-horn carbon particles aggregates to become metal particles. The nano-horn carbon particles aggregates include a plurality of spherical aggregates. The nano-horn carbon particles together; b). The nano-horn carbon particles aggregates are subjected to a reduction procedure to enable the catalyst metal to be supported on the nano-horn carbon particles aggregates. 2 0. A method for manufacturing a catalyst electrode for a fuel cell, the steps include: c) mixing a metal salt solution of a catalyst metal material with nano-sized horny carbon particles to enable the catalyst The catalytic metal of metallic material is attached to the nano-sized horny carbon particles aggregate to become metal particles, wherein the nano-shaped horny carbon particle aggregates include a plurality of nano-sized horny $ anti-particles that are gathered together in a spherical shape; d) performing a reduction procedure on the nano-angled carbon particle aggregates to enable the catalyst metal to be supported on the nano-angled aggregates; then e) coating a layer of paste on a substrate and It is allowed to dry, wherein the paste contains the nano-horn carbon aggregates and a polymer electrolyte material. 2 1. A method for manufacturing a fuel cell, the steps include: f) mixing a metal salt solution of a catalyst metal material with nano-sized horny carbon particles aggregates to enable the catalyst of the catalyst metal material to be made Metal attachment 200415823 6. The scope of the patent application is to form metal particles on aggregates of nano-sized carbon particles, wherein the aggregates of nano-sized carbon particles include a plurality of nano-sized carbon particles aggregated in a spherical shape; g) Performing a reduction procedure on the nano-angled carbon particle aggregates to enable the catalyst metal to be supported on the nano-angled aggregates; h) coating a layer of paste on a substrate and allowing it to dry , Wherein the paste contains the nano-horn carbon aggregates and a polymer electrolyte material; and i) Pressure is applied to one end of the nano-horn-shaped carbon particle aggregate containing the catalyst electrode to the polymer electrolyte membrane, and each end of the catalyst electrode is connected to each end of the polymer electrolyte membrane. Page 39