TW200411972A - Structure of progressive-type membrane electrode assembly for direct methanol fuel cell and method for producing the same - Google Patents

Abstract

A structure of a progressive-type membrane electrode assembly for a direct methanol fuel cell includes: a proton transport membrane, a cathode catalyst, and a plurality of anode catalyst layers. The anode catalyst layers each contains an anode catalyst and are laminated on the proton transport membrane, in which the content of the anode catalyst in each anode catalyst layer increases monotonically from the inside to the outside. The surface of the proton transport membrane has a methanol barrier layer deposited on the dense anode catalyst particles on the surface of the proton transport membrane for reducing the crossover effect of methanol.

Description

200411972 V. Description of the invention (1) ----- TECHNICAL FIELD OF THE INVENTION The present invention relates to a membrane electrode group structure of a fuel cell and a manufacturing method thereof, and more particularly, to a direct methanol fuel cell having a progressive distribution. Membrane electrode group with anode catalyst layer structure and its method 4. The previous technology re- "method. Fuel cell (FC) is a kind of power generation device that directly converts chemical energy into electrical energy. Compared with traditional power generation methods, Fuel power ^: It has the advantages of low pollution, low voice, low energy density, and high energy conversion efficiency. 'It is a very forward-looking clean energy source. The applicable range includes portable electronics, home power generation systems, transportation The operating principles of various leading military fuel cells such as wheel equipment, space industry, and large-scale power generation systems vary slightly according to their types. Take Proton Exchange Membrane f / 'uel Cell (PEMFC) as an example. Hydrogen is oxidized in the anode catalyst layer to generate hydrogen ions (H +) and electrons (e-). The hydrogen ions can pass through Protons and conductive membranes are transferred to the cathode 'while electrons are transferred to the load through external circuits and then transferred to the cathode. At this time, the oxygen supplied to the cathode end will undergo a reduction reaction with hydrogen ions and electrons in the cathode catalyst layer and generate water. Fig. 1A is an exploded perspective view of a conventional stacked ion exchange membrane fuel cell, and Fig. 1B is a cross-sectional view of the membrane electrode group in Fig. 1A. As shown in Fig. 1 and Fig. 1B, the conventional stacked fuel cell stack 1 The composition includes a membrane electrode group 12 (Membrane Electrode Assembly, MEA) composed of an anode catalyst electrode 121, a proton conductive membrane i22 (Proton Exchange Membrane, PEM) and a cathode catalyst electrode 123, and as a

IH 0178-9190TWF (Nl); 05-910044; JIMY.ptd Page 6 200411972 V. Description of the invention (2) Bipolar plate 13 (Bip〇lar piate) with individual membrane electrode groups 12 connected in series and electrode plates 11 at both ends The assembled battery pack. In addition, the functions of the terminal electrode plate U and the bipolar plate 13 are not only connected in series as batteries, but also internally provided with flow channels 111 and 131 as supply channels for hydrogen and oxygen. Direct methanol fuel cell (DMFC) is another type of fuel cell using liquid fuel. It replaces the more dangerous hydrogen milk with liquid methanol as the reactant in the anode reaction. Because direct methanol fuel cells can directly add methanol as a fuel, they have a very large potential for development in portable electronics.

In the research of direct methanol fuel cells, most of the anode structure and manufacturing methods use the design of ion-exchange membrane fuel cells. However, because direct methanol fuel cells use methanol aqueous solution to conduct oxidation reaction in the anode catalyst layer, hydrogen is generated. Ions (H +), electrons (e ·), and carbon dioxide (c0), a large amount of carbon dioxide bubbles generated often occupy the anode catalyst surface, and the 1% of the catalyst reaction is interrupted, causing the fuel cell reaction efficiency is not Therefore, the design of traditional ion exchange membrane fuel cell membrane electrode group is not completely applicable to direct methanol fuel cell system using methanol as fuel.

Secondly, 'Because the surface of the ion-conducting membrane has very many micropores to transfer protons, but the permeability of methanol is very strong, and the traditional direct methanol fuel cell often seriously affects the characteristics of the fuel cell because of methanol's crossover phenomenon' The membrane electrode group of a traditional ion exchange membrane fuel cell must be appropriately modified in order for the direct methanol fuel cell to have better battery characteristics. Summary of the Invention

200411972 V. Description of the invention (3) Material and electricity The purpose of the present invention is to provide a direct methanol fueling methanol: material and electricity electrode group. Through the specially designed anode structure, the reaction efficiency of the direct-fired τ fresh-burning thorium battery is improved. The purpose of the Sun It is to provide a special design of the reaction characteristics of the fuel cell. Anode catalysts and cathode catalysts made from dimensional metal are mostly expensive to reduce the production cost of membrane electrode groups. In order to achieve the above object, the present invention provides a progressive membrane electrode group structure suitable for a battery, which includes a proton conduction electrode and a plurality of anode catalyst layers and a plurality of anode catalyst layers. The catalysts are placed on top of each other on the proton conductive medium. The layers have multiple transmission channels, and the transmission channels of the mesh 2 are close to the anode catalyst layer of the shell conductive film. In the embodiment, the cross-sectional width of the transmission channel is also increased layer by layer from the anode catalyst layer of the shell conductive film. * The cross-section width of the transmission channel is between 丨 ^ ⑽ to 丨 ^ 〆, the above

Mr. In a preferred embodiment, the anode catalyst layer is composed of a conductive thin :: yang: catalyst ', and the anode catalyst of each anode catalyst layer is overcoated. [Anode catalyst of sub-conductive film] The layers are processed layer by layer from the inside to the outside. The conductive film can be a carbon paper and the anode catalyst is platinum / ruthenium alloy.

200411972 V. Description of the invention (4) (Pt / Ru) or carbon material particles coated with platinum / ruthenium alloy (pt / Ru). In a preferred embodiment, on the barrier layer, the methanol barrier layer is a dense anode catalyst particle on the surface of a transparent membrane. In a preferred embodiment, the upper cathode catalyst electrode is a thin film formed by hot pressing. Electrode group structure The present invention further provides a direct group structure, which includes a proton conductive anode catalyst layer. Each anode catalyst layer is on a proton conductive membrane, wherein each anode is close to the anode catalyst of the proton conductive membrane. In a preferred embodiment, the pores of each anode catalyst layer become larger layer by layer from the nearest to the inside. In addition, after the conductive particles having an anode proportion, the conductive particles are layered one by one as carbon material particles or platinum / ruthenium alloy (Pt / Ru) plating. In a preferred embodiment, the methanol barrier layer is a barrier layer. Dense anode catalyst particles on the membrane surface. In a preferred embodiment, the upper cathode catalyst electrode is a thin film-shaped membrane electrode group structure formed by hot pressing. Proton conduction is used to reduce the crossover effect of methanol. The anode catalyst layer, the proton conductive film, and the formation of a progressive membrane electrode film suitable for a direct methanol fuel cell, a cathode catalyst electrode, and a plurality of layers containing an anode catalyst are arranged on top of each other to provide an anode catalyst layer. The anode catalyst content increases from the innermost layer to the inner layer. The anode catalyst layer is porous, and the anode catalyst layers of each proton conductive membrane are mixed from the anode catalyst and formed on the proton conductive membrane. The anode catalyst is a platinum / ruthenium alloy ( pt / Ru) carbon particles. The surface of the proton-conducting membrane has a methanol ion-exchange method deposited on the proton-conducting layer to reduce the crossover effect of methanol. Said anode catalyst layer, proton conductive membrane and formation of suitable direct methanol fuel cell

200411972 V. Description of the invention (5) The present invention also provides a gradual group manufacturing method of a direct methanol fuel cell. First, a proton conductive film is provided; and then, a plurality of different ratios of destruction are formed by a non-f membrane electrode catalyst and conductive particles. For example, a slurry having a small proportion of anode catalyst in the anode slurry was applied layer by layer on the proton field traces to form a plurality of anode catalyst layers on the proton conductive film. Connect a 1-film cathode catalyst electrode, and then place the cathode catalyst electrode on the anode catalyst reed β supply side. The anode catalyst layer, the proton conductive film, and the cathode are formed by hot pressing to form a thin film. Membrane electrode group structure. In a preferred embodiment, in the method for manufacturing a progressive membrane electrode group, a sub-exchange method is used to deposit a dense proton on the surface of a proton-conducting membrane as a methanol barrier layer 1 to reduce the crossover effect of methanol, and then sequentially The slurry in various mixing ratios is coated on the broadcast blocking layer. ^ In a preferred embodiment, the method for manufacturing a progressive membrane electrode assembly further includes: providing a hole-shaping agent; and then adding the holes into the hole in a predetermined proportion according to the amount of the anode catalyst in the slurry of different mixing ratios. Shaper. In the above, the hole shaping agent may be ammonium oxalate (NH4) 2C204 or ammonium carbonate (NQ4) 2. 〇 3 〇 In a preferred embodiment, the conductive particles are carbon material particles, and the anode catalyst is a self / ruthenium alloy (Pt / Ru) or a platinum / ruthenium alloy plated carbon material particle. The aB bottle allows the above and other objects, features, and advantages of the present invention to be more >, ...,. A preferred embodiment is given below, and in conjunction with the accompanying drawings, the detailed description is as follows:

200411972 V. Description of the invention (6) Embodiment Figure 2 is a schematic diagram of the reaction of a direct methanol fuel cell anode. The direct methanol fuel cell uses an aqueous methanol solution (CH30H + H20) to perform an oxidation reaction in the anode catalyst layer to generate nitrogen ions (6H +), electrons (6e_), and carbon dioxide (COP). As shown in Figure 2, if the anode is to be contacted with If the medium continues to work, the products of the oxidation reaction must be continuously removed from the surface of the anode catalyst; in other words, the hydrogen ions, electrons and carbon dioxide produced by the oxidation reaction must be continuously removed, so as not to affect the opposition rate or even the oxidation. The reaction is interrupted, which reduces the reaction efficiency of the battery. Therefore, the present invention proposes a progressive anode structure which helps direct alcohol fuel cells to quickly eliminate carbon dioxide bubbles formed on the anode catalyst surface under high discharge, and reduce Mass transfer hinders the use of anode catalysts on the anode and improves the reaction efficiency of direct methanol fuel cells.

Fig. 3 is a schematic diagram of the structure of a progressive membrane electrode and an assembly of a direct methanol fuel cell according to the present invention. As shown in FIG. 3, the anode catalyst electrode formed by a cathode catalyst electrode 22, a proton conductive film 21, and a plurality of anode catalyst layers 23, 24, 25 is hot-pressed and hot-pressed to form a suitable direct methanol. A thin film membrane electrode group structure for a fuel cell. In order to simplify the illustration and the following description of the embodiment, 'Figure 3 only uses three thick anode catalyst layers to form a progressive electrode catalyst electrode of a membrane electrode group, but in actual implementation, it can also be in accordance with the present invention. The proposed manufacturing method uses three or more thin anode catalyst layers to form the progressive membrane electrode group of the present invention.

0178.9190TWF (Nl); 05-910044; JIMY.ptd

200411972 V. Description of the invention (7) As shown in FIG. 3 of the first embodiment, the progressive membrane electrode group 20 is composed of a proton conductive membrane 21, a cathode catalyst 22, and a plurality of anode catalyst layers 23 to 25. The cathode The catalyst electrodes 2 2 and the anode catalyst layers 23 to 25 are arranged oppositely to the protons |

On both sides of the conductive film 21, an anode catalyst I is contained in each of the anode catalyst layers 23 to 25. In order to increase the reaction surface area and accelerate the elimination of carbon dioxide generated after the oxidation reaction at the anode end, each anode catalyst layer 23 to 25 has a plurality of transmission channels 231, 241, 251 (Figure 3 is only a partial cross-section / figure ), The number of transmission channels of each layer is from the anode catalyst layer 23 closest to the proton conductive film 21 ^ increasing from the inside to the outside, and the cross-section width of each layer of transmission channels is also from the anode catalyst layer closest to the shellfish conductive film 21 Starting from 23, it increases layer by layer from the inside to the outside. In other words, in order to prevent carbon dioxide bubbles generated by the reaction from adhering to the surface of the anode catalyst particles, the anode catalyst particles cannot continue to react. Therefore, the anode catalyst layer 25 closer to the anode end surface has more and larger transmission channels 2 5 1. To help expel carbon dioxide.

—Stomach The anode catalyst layers forming the anode catalyst electrodes 23 to 25 according to the present invention are composed of an anode catalyst coated with an electrical thin film, and the catalyst content of each anode catalyst layer 23 to 25 is closest to the proton conductive membrane. The anode catalyst layer of 21 ... Large = layer by layer, so that the methanol aqueous solution can be used on the one hand. The surface layer is finished] The carbon dioxide is oxidized and the carbon dioxide is discharged. In addition, it can also effectively save the energy. " Anode catalyst content reduces production costs. In this implementation, the Mg thin film is a carbon paper or carbon. The anode contact is made of uranium / ruthenium alloy (Pt / Ru) particles or a carbon material coated with platinum / ruthenium alloy.

200411972 V. Description of the invention (8), κτ f: The operation is to first add the anode catalyst to A proton exchange solution (Nafion® Solution) »Outer gold 丨 丄 ^ ^ ^ M and / or cereals, and prepare a first An anode catalyst is a coating for the anode catalyst layer 25 on the surface of the anode. Then, the first material is added with an appropriate proportion of carbon powder to prepare a second-order coating slurry, and the slurry of different concentrations is applied to each anode catalyst to complete each anode contact. Preparation of dielectric layers 23-25. In the manufacture of the conductive channels 231, 241, and 251, S \ is formed by laser engraving, so that the cross-sectional width of each anode catalyst I ,, 231, 241, 251 is between 1011111%, Γ @ «Λ, which changes from the internal anode catalyst layer 23 to the external anode catalyst layer = layer boost: layer by layer, which increases the reaction surface area and accelerates the elimination of slave dioxide bubbles. In addition, in order to reduce the crossover effect of methanol, an anode barrier layer 211 is provided on the anode side surface of the progressive electrode group 20 of the present invention > subconducting film 21, and the methanol barrier layer 211 is deposited on the proton conduction by ion exchange method. The dense anode catalyst particle layer on the surface of the film 21 is manufactured as shown in Figs. 4A and 4B. FIG. 4A is a schematic diagram of a method for manufacturing a methanol barrier layer by an ion exchange method according to the present invention, and FIG. 4B is an enlarged schematic diagram of a range 34 thereof. The purpose of making the chic and deposited catalyst layer is to provide the last line of defense for the anode catalyst to oxidize methanol. Dense anode catalyst particles 2 1 2 are deposited on the proton conductive membrane 21, which can be filled in the proton conductive membrane 21 In the micropores on the surface, the alcohol which penetrates into the micropores is consumed to the full, avoiding the further crossover of methanol to the poles to form a local self-reaction (Self-reaction), which leads to the integration

200411972 V. Description of the invention (9) Cases of decreased body potential and decreased discharge efficiency. The manufacturing steps are as follows: First, the proton conductive membrane 21 is placed in an apparatus as shown in FIG. 4A, and is fixed between the reaction tank 31 and the reduction tank 32 with a clamp 33; then, the side on which the anode catalyst is to be deposited Pour into? 1; (〇3) 4 (: 12 and paragraph 11 (1 ^ 0) (1 ^ 03) 3 (according to Pt: Ru atomic ratio of 1: 1)), the other side is poured into pure water only and left to stand For a suitable period of time, slowly add an appropriate amount of NaBH4 to the side with only pure water, and stir and control the temperature to avoid generating hydrogen bubbles on the surface to be deposited. As shown in Figure 4B, when hydrogen passes through When the proton-conducting membrane 21 is transferred to the left surface, a dense catalyst layer can be formed on the surface of the proton-conducting membrane 2 丨. If the reaction time is sufficient and the temperature is controlled properly, the particle size of the anode catalyst particles 212 is about a few Between nanometers and tens of nanometers, the methanol that penetrates into the micropores can be fully consumed, effectively blocking the crossover effect of methanol. 凊 Referring to FIG. 3 again, the cathode catalyst electrode 22 of the present invention is composed of an electricity: The film is coated with a cathode catalyst. This conductive film can also be a carbon paper, a mesh metal ... titanium, gold-plated copper, and #coated with metal. The cathode catalyst electrode 22, * The medium can be platinum (Pt) particles, and the proton conducting membrane 21 can be used, for example, by STafion® by DuPont. A ~ Upper layer 23 ~ 25 After that, the temperature of the plurality of anode catalyst layers 130 ^ can be thermoformed into a film by an appropriate pressure d electrode 22 under the above-mentioned plurality of anode catalyst layers; =, 21; / tai \ conductive film 21 And cathode catalyst ^ battery progressive battery electrode plant. Where the cost of the invention is applicable to direct methanol combustion

200411972 V. Description of Invention (ίο) Second Embodiment

The present invention further provides a method for manufacturing a progressive membrane electrode group. Please refer to FIG. 3. As described in the first embodiment, the progressive membrane electrode group 20 includes a proton conductive film 21, a cathode catalyst electrode 22, and a plurality of cathode electrode groups. Layer anode catalyst layers 23-25. Each of the anode catalyst layers 23 to 25 contains an anode catalyst and is overlapped with each other and is disposed on the proton conductive film 21. The anode catalyst content of each of the anode catalyst layers 23 to 25 is from the anode catalyst layer closest to the proton conductive film 21. From 23, layer by layer from the inside to the outside, so that the methanol solution at the anode end can complete most of the oxidation reaction at the surface layer to discharge carbon dioxide, and effectively save the amount of anode catalyst used, reduce the production cost of the membrane electrode group. To reduce the crossover effect of methanol, the anode side surface of the proton conductive membrane 21 of the vaneless membrane electrode group 20 in this embodiment also has a methanol barrier layer 211 similar to the first embodiment. The methanol barrier layer 211 is The dense anode catalyst particles 212 layer deposited on the surface of the proton conductive membrane 21 by the two-exchange method is manufactured as described above, and is not repeated here. The difference from the first embodiment is that the anode interrogation layers 23 to 25 in the second embodiment are porous, and the holes of the anode catalyst layers 23 to 25 are porous.

The anode catalyst layer 23 near the proton conductive membrane 21 becomes larger layer by layer from the inside to the outside. The anode catalyst layer 25, which is closer to the anode end surface, has larger through holes, which helps to discharge carbon dioxide gas. Secondly, the "anode catalyst layer 23:25 is a mixture of conductive particles with different proportions of the catalyst, and then is formed layer by layer on the protons.) The two conductive particles are carbon particles. The anode catalyst is platinum / ruthenium alloy (Pt / RU) or It is a carbon material particle coated with platinum / ruthenium alloy. The manufacturing methods of the nano anode catalyst used in this embodiment are respectively

200411972 V. Description of the invention (11) As follows ^ First, H2PtCl6 · 6H20 and RuC13 (based on the Pt: Ru atomic ratio of 1: 1) f in an appropriate amount of deionized water, neutralize to neutral with Na2C03, and add an appropriate amount NaHS〇3 and stir to promote the reaction to complete, and then add an appropriate amount of NazC03 to obtain a dark precipitate; then filter the precipitate and mix it into deionized water, and then add an appropriate amount of ion exchange resin (Ion_Exchange Resin, Dowex 50WX4, 100 ~ 2002 ") and stir it; finally, the suspended ion exchange resin was filtered to obtain a platinum / ruthenium suspension solution.

Next, if you want to make, directly add the appropriate H2O2 'to the Pt / Ru suspension solution, stir and heat it for one hour; then, after the solution is cooled, filter through a porous ceramic funnel to obtain a black powder. Put it in a vacuum oven and dry to get platinum / ruthenium alloy (pt / Ru). If you want to make carbon particles of external plating / ruthenium alloy, you need to add high graphitized carbon powder treated with hot acid reflux in Pt / RlI suspension solution, and stir it vigorously or excite the carbon powder with ultrasonic waves. Disperse evenly, then add an appropriate amount of h2O2, and heat and boil for one hour after mixing; then, after the solution is cooled, filter through a porous ceramic funnel to obtain a black powder, and place it in 110. (:: Dry in a vacuum oven to obtain platinum / ruthenium alloy plated carbon material particles. Finally, send the platinum / ruthenium alloy (p or external bell molybdenum / ruthenium alloy carbon material particles to a tube-type high temperature furnace) After heating to 250 ° C with nitrogen as the protective atmosphere, switch to hydrogen and maintain the temperature for more than two hours, and then reduce the temperature to normal temperature with argon and fluorine as the protective gas to obtain the platinum / ruthenium used in the anode and pole catalysts of this example. Alloy (Pt / Ru) or carbon plated with platinum / ruthenium alloy. The preparation method of the slurry used in this example is described below.

200411972

Mixing slurry with different ingredients (! NK), the slurry preparation steps are as follows: firstly mix the nano anode catalyst mentioned above into a small amount of water, and then add a proton exchange solution (Nafion® Solution 1100 EW) in a proper proportion, A slurry having a first anode catalyst concentration is formed. Then, using the slurry of the first anode catalyst concentration, adding the appropriate proportion of carbon powder (1: 2) to prepare the slurry of the second and third anode catalyst concentrations to complete three types of slurry with no anode catalyst . ^ Next, in order to produce a porous structure for each of the anode catalyst layers 23 to 25, and the pores of each of the anode catalyst layers 23 to 25 are enlarged from the anode catalyst layer 23 closest to the proton conductive film 21 layer by layer from the inside to the outside. . Therefore, the above-mentioned slurry of the first to third anode catalyst concentrations need to be added with a hole-forming agent according to a predetermined ratio, such as: ammonium oxalate (leg 4) 2 (: 2 04 or ammonium carbonate (NH 4) 2C03. The slurry used to form the first anode catalyst concentration of the anode catalyst layer 25 contains more pores / co-plastics. 'The second anode catalyst used to form the anode catalyst layer 24 is concentrated in the second anode catalyst. The hole shaping agent is used to form the anode catalyst layer 23. The slurry of the anode catalyst concentration contains less hole shaping agent. Therefore, when each of the anode catalyst layers 23 to 25 is formed, after the solvent evaporates, As a result of the pore-forming agent being precipitated, the porous junction required by the present invention to be expanded layer by layer from the inner layer is formed. Please refer to FIG. 3 again. In the second embodiment, the coating method can be repeated after various pastes are formulated ( Repeat_c〇at), transfer process (Decal-transferred), or die coating method (Die-coating) method, the slurry of different anode catalyst concentrations are overlapped to form a proton conductive membrane.

200411972 V. Description of Invention (13)

After the anode catalyst layers are dried on Jiazhi barrier layer 2 11, a plurality of anode catalyst layers 23 to 25, proton conductive film 21 and cathode catalyst can be applied at a temperature of igQ ° C or higher under appropriate pressure. The electrode 22 is hot-pressed into a membrane electrode group 20 to complete the progressive membrane electrode group applicable to the direct methanol fuel cell of the present invention. The membrane electrode group of the direct methanol fuel cell of the present invention has a progressive anode structure, and its transmission channels become larger layer by layer from the proton conductive film from the inside to the outside, which helps the direct methanol fuel cell to quickly exclude the anode under high discharge. Carbon dioxide bubbles formed on the surface of the catalyst, and reduce the mass transfer obstacle, in order to improve the utilization rate of the anode catalyst on the anode, and indirectly improve the reaction efficiency of the direct methanol fuel cell. Secondly, having dense anode catalyst particles on the surface of the ion-conducting membrane can effectively reduce the crossover phenomenon of methanol and can also increase the stability of the battery. The decrease in the smooth catalyst density from the outer layer to the inner layer can effectively reduce the amount of anode catalyst used, reduce the manufacturing cost of direct methanol fuel cells, and greatly increase the possibility of commercialization. Although the present invention has been disclosed in the preferred embodiment as above, it is not used: Gen ^ Invention: Anyone skilled in this art will not depart from the spirit of the present invention I: 5 H Two may: a little change and retouch, so the present invention The protection scope shall be determined by the scope of the attached patent application.

200411972 A brief description of the diagram Figure Chuan is a perspective view of a conventional reactor-type ion exchange membrane fuel cell. Figure 1B is a cross-sectional view of the membrane electrode group in Figure 1A. Fig. 2 is a graph showing the reaction of a direct methanol fuel cell anode. Fig. 3 is a progressive graph of a direct f alcohol fuel cell according to the present invention. Schematic. Armoured membrane electrode Figure 4A is a schematic diagram of a method for manufacturing a methanol barrier layer by an ion exchange method according to the present invention. FIG. 4B is an enlarged schematic view of a range 34 in FIG. 4A of the present invention. DESCRIPTION OF SYMBOLS 10 Conventional ion exchange membrane 11 End electrode plate 111 Flow path 12 Membrane electrode group 121 Anode catalyst electrode 122 Proton conductive membrane 123 Cathode catalyst electrode 13 Bipolar plate 131 Flow channel 20 Progressive membrane electrode group 21 Proton conductive membrane 211 Methanol barrier layer 212 Anode catalyst particles Page 19 0178-9190TW (Nl); 05-910044; JIMY.ptd 200411972 Simple illustration of the diagram 22 Cathode catalyst electrode 23 First anode catalyst layer 24 Second m-pole catalyst layer 25 The first anode catalyst layer 231, 241. 251 Pass 31 Reaction tank 32 Reduction tank 33 Clamping device 34 Magnification range%

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Claims (1)

200411972 6. The scope of the patent application includes a kind of indirect membrane electrode group structure for direct methanol fuel cells, including a proton conductive membrane, which has a number of anode catalyst layers on the first side, which contains anode catalyst on one side of the membrane. The anode catalyst layers "have a plurality of 2 delivery channels, and the number of the transmission channels in the anode catalyst layers increases from the inner layer starting from the anode catalyst layer near the proton conducting membrane 2; and = cathode catalyst The electrode is disposed on one side of the depolarization catalyst layer on the proton conductive membrane. The transmission channels in the structure of the membrane electrode group of the direct methanol fuel cell as described in the first patent application scope of gradual and 隹 2+ The cross-sectional width also starts from the anode catalyst layer of the proton-conducting membrane to 3 amines layer by layer from the inside to the outside: the gradual rigidity of the direct methanol fuel cell described in the scope of the patent application-2 between the 4 transmission channels The cross-section width ranges from progressive 4- ^: Γ The structure of the direct methanol fuel cell described in the first item of the patent consumption range ^ ^ group structure, in which the anode catalyst layers of the anode catalyst layer are gradually increased # Nearly 5 Haibei conduction 臈The anode catalyst layer gradually increases from the inside to the outside 2 Bt: Please refer to the electrode group structure of the direct methanol fuel cell described in the first item of the patent scope. The anode catalyst layers are coated with the anode catalyst on a conductive film Media. 21st stomach ZAjyjil ly / z 200411972 6. The scope of patent application is increased layer by layer; and a cathode catalyst electrode is disposed on one side of the proton conductive film opposite to the anode catalyst layers. 13. The structure of a progressive membrane electrode assembly for a direct methanol fuel cell as described in item 12 of the scope of the patent application, wherein the anode catalyst layers are porous. 1 4 · The progressive membrane electrode group structure of a direct methanol fuel cell as described in item 3 of the scope of the patent application, wherein the holes of the anode catalyst layer start from the anode catalyst layer closest to the proton conductive film. It grows layer by layer from the inside out. 1 5 · Progressive membrane electrode group structure of direct methanol fuel cell as described in item 2 of the patent application scope, wherein the anode catalyst layers are mixed with conductive particles of different proportions by the anode catalyst, and then layer by layer. It is formed on the first surface of the proton conductive membrane. 16 · The progressive membrane electrode group structure of a direct methanol fuel cell as described in item 5 of the patent application scope, wherein the conductive particles are carbon material particles. 1 7 The progressive membrane electrode group structure of direct methanol fuel cell and battery as described in item 6 of the patent application scope, wherein the anode catalyst is Pt / Ru. ',% 18 · The structure of the progressive membrane electrode group of the direct methanol fuel cell as described in item 6 of the patent application range, wherein the anode catalyst is carbon material particles plated with platinum / ruthenium alloy (Pt / Ru). · 19 · According to the structure of the progressive membrane electrode group of the direct methanol fuel cell described in item 2 of the patent application scope, wherein the first surface of the proton conductive membrane further has a methanol barrier layer, and the methanol barrier layer is composed of The dense anode catalyst is formed. 0178-9190TWF (Nl); 05-910044; JIMY.ptd page 23 200411972 VI. Application for patent scope 20 · The structure of the progressive membrane electrode group of the direct methanol fuel cell as described in item 19 of the patent scope for application, wherein the methanol The barrier layer is deposited on the first surface by an ion exchange method. 21. The progressive membrane electrode group structure of a direct methanol fuel cell as described in item 12 of the scope of the patent application, wherein the anode catalyst layer, the proton conductive film, and the cathode catalyst electrode are formed by hot pressing to form a Thin film structure D 22 · —A method for manufacturing a progressive membrane electrode group of a direct methanol fuel cell 'includes: providing a proton conductive film; forming a plurality of different ratios of slurry with different proportions of anode catalyst and conductive particles; The slurry having a small proportion of the anode catalyst in the same slurry is coated on the proton conductive film layer by layer, so that a plurality of anode catalyst layers are formed on the proton conductive film; a cathode catalyst electrode is provided; The catalyst electrodes are placed on the opposite sides of the anode catalyst layers. The anode catalyst layers, the proton conductive film, and the cathode catalyst electrodes are formed by hot pressing to form a thin film structure. 2 3 · The method for manufacturing a progressive membrane electrode assembly of a direct methanol fuel cell as described in item 22 of the scope of patent application, further comprising: forming a methanol barrier layer on one surface of the proton conductive membrane by an ion exchange method, wherein the The methanol barrier layer is a uniform dense anode catalyst layer, and the polymers are coated on the methanol barrier layer. 24 · Direct methanol fuel cell as described in item 22 of the scope of patent application 200411972 6. The method for manufacturing a progressive membrane electrode group with patent application scope, further includes: providing a hole-shaping agent; and adding the hole-shaping agent to the slurry in accordance with a predetermined ratio according to the amount of the anode catalyst. 25. The method of manufacturing a progressive membrane electrode assembly for a direct methanol fuel cell as described in item 24 of the scope of the patent application, wherein the hole shaping agent is oxalic acid. 26. The direct methanol fuel cell as described in item 22 of the scope of the patent application The method for manufacturing a progressive membrane electrode group, wherein the conductive particles are carbon material particles. 2 7 · The method for manufacturing a progressive membrane electrode assembly of a direct methanol fuel cell as described in item 22 of the scope of patent application, wherein the anode catalyst is platinum / ruthenium alloy (Pt / Ru) 〇 28 · If the scope of patent application is The method for manufacturing a progressive membrane electrode group for a direct methanol fuel cell according to item 22, wherein the anode catalyst is carbon material particles of an outer recording surface / nail alloy (Pt / Ru). 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