TWI229957B - 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

1229957

FIELD OF THE INVENTION The present invention relates to a membrane electrode group structure of a fuel cell and a method for manufacturing beans, and more particularly, to a membrane electrode group suitable for a direct methanol fuel cell and an anode catalyst layer structure distributed in Zhejiang and the like. Manufacturing method: ^ 7 Prior art / ° Fuel cell (FC) is a power generation device that directly converts chemical energy into electrical energy. Compared with traditional power generation methods, fuel cells have low pollution, low noise, and high energy density. And high energy conversion efficiency and other advantages, it is a very forward-looking clean energy, the applicable range includes portable electronics, home power generation systems, transportation industry, military equipment, space industry, and large-scale power generation systems. field. The operating principle of fuel cells varies slightly according to their type. Proton exchange membrane fuel cells (protorl Exchange Membrane fuel ·

Cell (PEMFC) as an example. Hydrogen is oxidized in the anode catalyst layer to generate nitrogen ions (H +) and electrons (e-). Among them, hydrogen ions can be transferred via protons, the conductive membrane is transferred to the cathode, and electrons are passed through external circuits. After being transferred to the load for work, it is 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 a perspective exploded view of a conventional stacked ion exchange membrane fuel cell. Fig. 1B is a cross-sectional view of the membrane electrode group in Fig. 1A. As shown in Figure 1 and Figure 1β h, the traditional stacked fuel cell stack is composed of an anode catalyst electrode 121 and a proton conductive membrane 122 (Prouton Exchange).

Membrane (PEM) plus cathode catalyst electrode 丨 23 is a membrane electrode group 12 (Membrane Electrode Assembly, MEA), and a bipolar plate 12 is connected in series as an individual membrane electrode group 12 (β 丨 p〇 丨ar p 丨 ate) and both ends

0178-9190TWFl (Nl); 05-910044Jimy.ptc Page 6 1229957 Amendment ------ plug No. 5. Description of the invention (2) Pole: = group. In addition, the 'end electrode plate 11' and the dual flow channels ill and 131 serve as: in addition to the connection, a supply channel of ^ μ 冯 lice and lice * 1 is also designed inside. DMFC) is an alternative fuel cell Methan〇1 Fuel with 11 instead of liquid fuel fuel cells. It uses liquid methanol as the reactant in the anode reaction. Methanol is directly added as fuel, so it has great potential for generating electricity in portable batteries. Research on the production of methanol fuel cells, 'the structure of the anode and the design of the ion-exchange membrane fuel cell continue, but because Straight -1 ： ： ： 1 The media should be interrupted, resulting in poor reaction efficiency of the fuel cell. Therefore, the design of the transfer cell membrane electrode group is not entirely applicable to the direct methanol fuel cell system with Jia Yu Feng Ranyu. Earlier: Rentian t has a very small & on the surface of the ion-conducting membrane to pass: often cause: A i =: t has a very strong permeability '❿ the traditional direct methanol fuel electricity ϊ 1 ㈣ ss_) phenomenon' seriously affects The improvement of fuel power can make direct methanol fuel cells have better batteries. Content 2 Here, the purpose of the present invention is to provide a membrane electrode group for direct methanol office. Lifting the anode structure linear

0178-9l9 (mVFl (Nl); 05-910044-jimy.ptc Page 7 1229957 Amendment said-plug 9ll3812fi 5th, the description of the invention (3) the reaction efficiency of the methanol fuel cell. /, Person, the Another object of the invention is to reduce the reaction characteristics of the fuel cell designed by the anode structure of "a direct alcohol burner". The "blight effect" is used to maintain the material cost of the anode due to the metal contact in the fuel cell. "So, this hair = touch = more expensive in order to reduce the production cost of the membrane electrode group. The amount of heart catalyst used, material and electricity The present invention provides a kind of structure for a progressive membrane electrode group that is suitable for direct methanol operation, which includes A spelling, ... ,, cathode catalyst electrode and multiple layers of anode contacts ==,-have anode catalysts, and overlap each other and are set on protons: =: media = both include $ touch: each layer has multiple transmission channels ,, And the transmission pass: the positive electrode layer of each anode seeking = from the anode catalyst layer inwardly breaking the conductive film from the inside to the nearest from the anode to the cross-section width of 100nm to 1mm. In a preferred embodiment, the anode catalyst cloth is composed of the anode catalyst The anode that is closest to the proton conductive film on the anode conductive film is coated with the field catalyst content, and the conductive film can be layer-by-layer layered from the inside to the outside. (Pt / Ru) or external plating / ruthenium alloy W It is a uranium / ruthenium alloy, ▲ Meng αΈ / KU) carbon material. In the example of Li Fujia, in the proton transfer, the barrier layer, the alcohol barrier layer is a rust pot masonry * J ,. The surface has —Methanol

Case number 9113812fi

1229957 V. Description of the invention (4) Dense anode catalyst particles on the surface of the membrane, using r In a preferred embodiment, the above two cathode catalyst electrodes are formed by hot dust, one of which is a membrane-like membrane electrode button structure. . The present invention also provides a direct nail transfer assembly structure, which includes a mass + conductive film and two anode catalyst layers. Within each anode / catalyst layer, 'AI = on the proton conductive membrane, wherein each anode is close to the anode catalyst layer of the proton conductive membrane. In a preferred embodiment, each of the holes in the anode catalyst layer contacts It gets bigger and bigger layer by layer inward and outward. After the anode touches a certain proportion of conductive particles, the layers are formed layer by layer. The above conductive particles are carbon material particles. The positive touch or the external uranium / ruthenium alloy (Pt / Ru) is better. In the embodiment, in the mass transfer barrier layer, the methanol barrier layer is a dense anode catalyst particle that penetrates the surface of the ion membrane. In a preferred embodiment, the above-mentioned cathodic cathode catalyst electrode is formed by hot dust. , A thin film-like membrane electrode group structure. Reduce the crossover effect of methanol). The catalyst layer, proton conductive membrane, and progressive membrane electrode suitable for direct methanol fuel cell battery cells. Cathode catalyst electrode and multiple layers of catalyst are placed on top of each other. The anode catalyst content of the layers gradually increases from the inside to the outside. The dielectric layer is porous, and the anode catalyst layers of the respective membranes are formed by mixing the anode catalyst with different proton conductive membranes, where the medium is surface / ruthenium alloy (Pt / Ru) particles. The surface of the conductive membrane has a methanol exchange method deposited on proton conduction to reduce the crossover effect of methanol. Catalyst layer, proton conductive membrane and direct methanol fuel cell suitable The present invention also provides a method for manufacturing a progressive membrane electrode group of a direct fuel cell. First, a proton conductive membrane is provided; then anode catalysts with different ratios and conductivity are used. The particles form multiple kinds of materials with the same proportion; and are coated on the proton conductive film layer by layer by the paddle with a small proportion of the anode catalyst in the above slurry.

0l78-9190TWFl (Nl); 05-910044Jimy.ptc 9th Tribute 1229957 Amendment f No. 9Π3812B V. Description of the invention (5) = Make the proton conductive membrane to form a plurality of anode catalysts. The cathode catalyst electrode, and then the anode side of the cathode catalyst electrode, and a plurality of anode catalyst layers and proton conduction pairs are formed by pressing to form a film-shaped membrane electrode group. In the example, the progressive membrane electrode: a manufacturing method, more m ^ ^ ^ ^ ^ m to reduce the crossover effect of methanol. The person then sequentially put various mixing ratios on the barrier layer. W water is coated on the methanol. In a preferred embodiment, the method for manufacturing a progressive membrane electrode group includes: · providing a hole-shaping agent · true w cut, Ran Fang; 喈 oblique Φ of different mixing ratios, According to the amount of the anode catalyst, according to Zhao Yi's predecessor μμ, such as 4 w < in the fruit capsule, the bucket card will be drawn in the heart, the proportion of the former is added to the hole shaping agent. What's the hole shaping agent can be ammonium oxalate) 4) 2 or ammonium carbonate (ΝΗ4) as the starting / in the case of a one-person car, the conductive particles are broken particles, the anode catalyst ^ "Gold (P " Ru ) Or the carbon material of Pt / Ru alloy is slightly obvious. Let it be made: 2 The above and other purposes, features, and advantages can be more easily understood; 'A preferred embodiment is given below. & In accordance with the accompanying drawings, 5 sheep gas is described as follows: Embodiment 2 Figure 2 is a schematic diagram of the reaction of a direct methanol fuel cell anode.

The IM methanol fuel cell uses an aqueous methanol solution (GMH + H2Q) to perform an emulsification reaction in the anode catalyst layer to generate hydrogen ions (6H +), electrons (60, and dioxination).

Page 10 〇178-9190TWFl (Nl): 05-910044; jimy.ptc 1229957 V. Description of the invention (6) Monthly correction of the stone counter (C02), as shown in Figure 2, if the anode is to be catalystized The product of the reaction must be continuously taken away from the anode, and the hydrogen ions produced by the lactation reaction and the surname of the dioxide, in other words, will not affect the opposition speed, and even make υ continue to be shifted in the battery reaction performance. Therefore, the present invention proposes a method for reducing the structure and reducing the structure, which helps the direct methanol fuel cell to form carbon dioxide on the surface of the highly-discharged anode catalyst, and the reaction efficiency. Figure 3 of the direct methanol fuel cell is a schematic diagram of the direct methanol structure of the present invention. As shown in Figure 3: the battery ’s progressive 臈 electrode group conductive film 21 and the plural Γ positive pole V; the heart cathode 22, a proton medium electrode through hot pressing and heat plant medium = 3 ′, two] ί ί 3 Λ Λ group structure. In order to simplify the illustration and the following embodiments, t it 1 ϋ® is a progressive% pole catalyst electrode with a thicker anode catalyst layer to form a membrane electrode group. 〆 9 The manufacturing method proposed by the invention, also Then it can be a progressive membrane electrode according to the present invention ;: A thin layer of anode catalyst layer above the first embodiment, as shown in FIG. 3, 'progressive membrane electrode group 2' 〇 It is touched by a proton conductive membrane The 'cavity 9' electrode 22 composed of the anode catalyst 22 and a plurality of anode contact layers 4 to 23 to 25 and the anode catalyst layers 23 to 25 are disposed opposite to the proton medium. Both sides' contain anode contacts in each of the anode catalyst layers 2 3 ~ 2 5

Page 11 1229957 Amendment --------- 91138126___ May 5, Invention Description (7) The reaction surface area is added to accelerate the elimination of an emulsified carbon after the oxidation reaction at the anode end. The catalyst layers 23 to 25 each have a plurality of M, 251 (Figure 3 is only a partial surface view), and the number of each layer is from the anode catalyst layer 23 closest to the proton conduction ㈣ ㈡ = layer is increasing 'and the transmission channel of each layer The wearing surface width also increases layer by layer from the inside to the outside of the anode catalyst layer 23 of the most conductive film 21. In order to prevent the carbon dioxide bubbles generated by the reaction from attaching to the anode contact, the anode catalyst cannot continue to react slightly, so the closer it is to ⑸, to help # ^ = 5 have more and larger transmission channels-guide Each anode catalyst layer of the anode catalyst electrodes 23 to 25 is composed of a thin electrode coated with an anode catalyst, and the anode catalyst content is from the closest to the proton pass, which is 23 to 25 from the inside to the outside. ， Zi Chuan Ling 膑 21% electrode catalyst layer 23: Canton's foreign policy layer is increased, so that most of the methanol aqueous solution is oxidized to emit carbon dioxide, which is ancient; Γ 70 becomes the anode catalyst electrode. It can effectively save the dangerous catalyst content in the writing stalk, and reduce the production cost. In this embodiment, the conductive film is a carbon paper or a carbon cloth, particles of If% alloy (Pt / RU) particles, or a carbon material coated with molybdenum / ruthenium alloy. The anode catalyst is added to the test solution and the solvent, and is prepared into a first and second anode = degree of incineration, and an appropriate proportion of the toner interface is added to the slurry of the pole catalyst concentration. The above different concentrations are applied to the conductive film. The preparation of each of the anode catalyst layers 2 3 to 25 is completed. Yoshiko 0178-919 (mVFl (NI); 05-91 (X) 44Jimy.ptc _Case No. 911381 Deng 1229957

V. Description of the invention (8) The conductive channels 231, 241, and 251 in the anode catalyst layers 23 to 25 can be formed mechanically or by laser engraving, so that each anode catalyst ^ 23 ~ 25 The cross-section widths of the transmission channels 231, 241, and 251 are between 100 and 1 ππη ', which increases from the internal anode catalyst layer 2 3 to the external anode catalyst layer 2 5 layer by layer, and becomes larger by layer. Increase the reaction surface area and accelerate the elimination of carbon dioxide bubbles. 'In addition, in order to reduce the crossover effect of methanol, the anode side surface of the proton conductive membrane 21 of the progressive membrane electrode group 20 of the present invention has a methanol barrier layer, 2 1 1' δHydranol barrier layer 2 11 is The dense anode catalyst particle layer deposited on the surface of the proton-conducting membrane 21 by the ion exchange method is manufactured in the manner shown in Figures 4 and 8 and Figure 4B. Fig. 4A is a schematic diagram of the f method for preparing 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 this densely 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 fill the surface of the proton conductive membrane 2 1 In the micropores, the methanol that has penetrated into the pores is consumed to the full, avoiding the methanol to further cross into the cathode, forming a self-reaction (Sel f — reactio) in the local area, resulting in a decrease in the overall potential and discharge efficiency. And so on. The steps are as follows:

On page 13, first place the rafter conductive film 21 in the apparatus as shown in FIG. 4A, and fix it between the reaction tank 31 and the reduction tank 32 with 3 ^ 3 3; then, the anode to be deposited Pour the side of the catalyst into an aqueous solution of Pt (NH3) 4C12 and "" ㈨⑶%, (according to the Pt: Ru atomic ratio of 1: 1), and pour pure water on the other side, and leave it for a proper period of time; Add an appropriate amount of NaBH4 slowly to the one with pure water, stir and control the temperature, and avoid nitrogen bubbles on the surface to be deposited. As shown in Figure 4B, when hydrogen passes through the proton conductive membrane 21 V. Description of the invention (9) is transmitted to the left surface layer of the Japanese media. m 甲子 子 'effectively prevents the crossover effect of methanol. € -¾ ^ I ^ Fig. 3, the cathode catalyst electrode 22 of the present invention is made of one conductor and one electrode: this is a dipole catalyst. This conductive film can also be-carbon paper,-nickel-plated or gold-plated on the surface. The cathode catalyst for 八 · titanium, gold-plated copper, and surface-coated cathodes can be pt particles, and the proton conductive film can be: 2V2f //, Sizhi · —. When the above-mentioned multiple layers of anode catalyst Γ are completed, the number of Γ will be two = ', that is, the temperature of 130 ° c or higher can be taken under appropriate pressure = layer% pole catalyst layer 23 ~ 25, proton conductive film 21, and cathode catalyst electrode. J22 hot-pressed film-forming electrode group 20 ′ completes the present invention, which is suitable for a progressive film-electrode group for a battery. The second embodiment. The present invention also 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 and a cathode. The catalyst electrode 22 and a plurality of anode catalyst layers 23 to 25. Each of the anode catalyst layers 23 to 25 contains an anode catalyst and mutually weighs each other on the proton conductive film 21, and the anode 1 of each of the anode catalyst layers 23 to 25 contacts < the medium content from the closest to the proton conductive film 21 The anode catalyst layer 23 is gradually increased 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 and discharge the dioxide, and effectively save the amount of anode catalyst used.

1229957 Case number 91138126 V. Description of the invention (10) Reduce the production cost of membrane electrode group. In addition, in order to reduce the crossover effect of methanol, the anode side surface of the proton conductive membrane 21 of the membrane electrode group 20

There is a methanol barrier layer 211 ′, and the methanol barrier layer ′ is: J 于 于: On: The dense anode catalyst particles 212 layer on the surface of the sub-conducting film 21, and the clothing method is as described above, which is not repeated here. The difference from the first embodiment is that each of the anode catalyst layers 23 to 25 in the case of 篦 .9Q, JJ is known as porous, and each of the anode catalyst layers 23 to 25 The pores become larger layer by layer from the anode catalyst layer 2 3 closest to the conductive film 21, so the anode catalyst layer 25 closer to the anode end surface has larger through holes, which can help to discharge carbon dioxide gas. . Secondly, the anode catalyst layers 23 to 25 are formed by mixing the anode catalyst with conductive particles of different proportions, and then forming the anode catalyst layer by layer on the proton conductive film 21. The conductive particles are carbon material particles, and the anode catalyst is platinum / ruthenium alloy (Pt / Ru) or carbon material particles plated with platinum / ruthenium alloy. The manufacturing methods of the nano-anode catalyst used in this embodiment are described as follows: First, ‘H2PtCl6 · 6Η20 and RUC13 (according to the pt: Ru atomic ratio of 1: 1)

Dissolve in an appropriate amount of deionized water, neutralize to neutrality with Na2CO3, add an appropriate amount of NaHS03 and stir to promote the reaction to complete, and then add an appropriate amount of Na / O3 to obtain a dark precipitate; then The precipitate was filtered off and mixed into deionized water, and then an appropriate ion exchange resin (Ion_Exchange was added).

Resin, Dowex 50WX4, 100 ~ 200 mesh); Finally, the suspended ion exchange resin was filtered to obtain a platinum / ruthenium suspension solution. Next, if you want to make it, add the appropriate amount of H2 02 directly to the pt / Ru suspension solution, stir and heat for one hour. Then, wait for the solution

0178-919〇rrWFl (Nl); 05-910044uimy.ptc Page 15 _ Case No. 91138126 1229957

V. Description of the invention (11) After cooling, filter through a porous ceramic funnel to obtain a black powder and dry in a vacuum oven to obtain a platinum / ruthenium alloy (Pt / Ru). Suffering == 0 ° C of carbon / fine particles of ruthenium alloy, need to be suspended and dissolved in Pt / Rll. Medium, 'Add to the toner to evenly disperse after shaking, and then add an appropriate amount of ^^ 0', or cook with ultrasound for 1 hour; then, 'After the solution cools, it will turn black after adding more and more buckets. Place the powder in 110. (: In the vacuum oven ^ dry holes ^ raw ceramics leaked carbon particles of externally plated button / ruthenium alloy. Finally, the platinum / Shuhe 0 gold is obtained or externally plated carbon material particles of platinum / ruthenium alloy into After the tube type high temperature expansion i / t) gas is heated to 250 ° C as a protective atmosphere, it is switched into hydrogen exhaustion = diplexing with argon

、， 付> 上 一 小 一 小 IV on the two small watch IV, and then use argon as the protective atmosphere to reduce the temperature to normal temperature, that is, the platinum / ruthenium alloy (Pt / Ru) or platinum / jade contact particles used in the wood medium. ] The method of preparing the slurry used in this example is as follows. Two slurry (INK) with different composition ratios, the slurry preparation steps are as follows: " " 5 weeks Nano anode catalyst mixed into a small amount of water

For example, the proton exchange solution (Nafion® Solution 1 100 e \ V), Tongcheng ★ a slurry of anode catalyst concentration. Then, with the concentration of the first anode catalyst " degree-then, add the appropriate proportion of carbon powder (1: 2) to make the slurry of the second and third anode catalyst concentrations to complete three For the anode catalyst concentration slurry connector, 'In order to make each anode catalyst layer 2 3 ~ 2 5 have a porous structure, and the pores of each of the 1% anode catalyst layers 23 ~ 25 are closest to the proton conductive membrane? !! The anode catalyst layer 23 becomes larger layer by layer from the inside to the outside. So the first to third sun

1229957

Case No. 5. Description of the invention (12) The slurry with extremely high catalyst concentration should be used in accordance with an existing agent, such as: oxalic acid 4) 2c2 04 or carbonic acid pores: to form the anode catalyst layer 25 No. 1—Anode-forming pore-forming agent, used to form anode catalyst layer. The slurry with more curvature contains appropriate hole-forming agent, which is used to shape the “three anode catalyst concentration cracks with full catalyst system”. When the material contains fewer pores, the first anode catalyst layer 23 of the second catalyst layer 23, when the agent precipitates to form the porous layer expanded from the inner layer layer by layer required by the invention; Take a look! Figure 3 In the second embodiment, when various forging materials are blended (Decal is repeated-coated) and the transfer process is ^ Π Γ, d) 51 ^ ep ^ ^ (Die- Coating) f ^ formula weights slurry with different% electrode catalyst concentration,-^ 2 Π # ^ ^ ^ 'Λ; 302 32: sub-degree Λ will rent multiple anode catalyst layers under appropriate pressure 2, ΛΛ Λ21 and cathode catalyst electrode 22 are hot-pressed into a membrane electrode. The cost of the invention is suitable for direct methanol fuel cell. The relationship between the electromotive force and the current density when the electrode group and the traditional membrane electrode group are reacted; 5B === The membrane electrode group and the traditional membrane electrode group are in a 10% methanol aqueous solution. Structure of the membrane electrode group under pure methanol environment

0178-9190rnVFl (Nl); 〇5-910〇44〇imy.ptc Page 17 Degree and current density pass θ t: Cross-Relation diagram '5C picture is power density 4 * The strange picture is from 5 A ~ The experimental data in the 5C chart can be 1229957 to amend case number 911381, Deng Wu, Invention Note (13). Although the electromotive force is slightly smaller than the traditional membrane electrode group, the progressive anode structure can be quickly excluded from the anode catalyst surface. The reaction efficiency of the formed carbon dioxide gas j, k fuel cell, so the progressive membrane electrode group of the present invention has a higher output voltage under the center of higher current density, and the output of this Maoming progressive membrane electrode group The power density is also much higher than the membrane electrode group of traditional fuel cells (Figure 5C). From the above-mentioned "the membrane electrode group of the direct methanol fuel cell of the present invention has a progressive anode structure", its transmission channel is enlarged from the proton conductive membrane from the inside to the f layer, which helps the direct methanol fuel cell to discharge at a high level. In order to improve the anode milk bubbles on the anode and reduce the reaction efficiency of the mass transfer fuel cell, the rate of indirect increase of the direct methanol can be effectively eliminated. The anode catalyst particles reduce the anode contact force one by one from the outer layer to the inner layer " stability of the battery. And the use of catalyst, reducing direct methanol fuel = degree 'can effectively reduce the anode and greatly increase the possibility of commercialization. ..., ', the manufacturing cost of the battery, so although the present invention has been limited to the present invention by a preferred embodiment, anyone skilled in the art is as above, but it is not intended to be used within the scope. 2. The door shall not deviate from the spirit scope of the present invention as the oblique scope of the attached patent application. Therefore, the protection of the present invention shall prevail. 1229957 ΜΆ ^ 91138126 Brief description of the drawing Figure 1 A is a traditional stacked figure. < Dimensional exploded view of the ion-exchange membrane fuel cell is a sectional view of the membrane electrode group in the Uth figure. II: Schematic of the reaction of the direct methanol fuel cell anode. ®: Schematic diagram of the structure of the direct methanol fuel pool membrane of the present invention. 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. Figure 4B is an enlarged schematic view of the range 34 in Figure 4A of the present invention. Figure 5A is a graph of the relationship between electromotive force and current density when the progressive membrane electrode group of the present invention and a conventional membrane electrode group react in pure methyl alcohol. Fig. 5B is a graph showing the relationship between voltage and current density when the progressive membrane electrode group of the present invention and a conventional membrane electrode group are reacted in a 10% methanol aqueous solution. Fig. 5C is a graph showing the relationship between power density and current density when the progressive membrane electrode group of the present invention and a conventional membrane electrode group are reacted in a 10% methanol aqueous solution. DESCRIPTION OF SYMBOLS 10 Conventional ion exchange membrane fuel cell 11 Terminal electrode plate 111 Flow channel 12 Membrane electrode group 12 1 Anode catalyst electrode 12 2 Proton conductive membrane

0178-9190TWFl (Nl); 05-910044Jimy.ptc page 19 1229957 case number 91138126

0178-9190TWFl (Nl); 05-910044; jimy.ptc Page 20

Claims (1)

1229957 Case No. 91138126 Amendment 6. Scope of patent application1. A progressive membrane electrode group of a direct methanol fuel cell with the surname of hibiscus, including: 、, 冉 Ran-proton conductive membrane 'has a first surface; multiple anode catalyst layers The anode catalyst is contained and is overlapped and disposed on one surface of the proton-conducting membrane, wherein the anode catalyst layers each have a plurality of transmission channels, and the number of the transmission channels in the anode catalyst layers is arrogant. The anode catalyst layer of the sin conductive film is increased layer by layer from the inside to the outside; and θ a cathode catalyst electrode is disposed on one side of the proton conductive film opposite to the anode catalyst layers. /, 2 · As for the direct methanol fuel cell described in item 1 of the scope of the patent application, the membrane electrode group structure, wherein the cross-section width of the transmission channels also starts from the anode catalyst layer closest to the proton conductive membrane. Progressively from the inside to the outside, 3. The progressive membrane electrode group structure of the direct methanol fuel cell as described in the scope of the patent application, wherein the cross-sectional width of the transmission channels is between 100 nm and 1 mm. Again, 4. The S-type T of the direct methanol fuel cell as described in item 1 of the scope of the patent application, in which the anode structure of the anode catalyst layer of the anode catalyst layer, the anode is close to the anode contact of the proton conductive film The catalyst layer is pushed from the inside to the bottom. Ten: The direct methanol fuel cell progressive membrane electrode group structure of item 4 of the patent scope is requested. The anode catalyst layer is coated on the anode 1 film with the anode contact. Media. 1229957 ^ MM 9113819R VI. Scope of Patent Application Month Amendment I. 6. ^ Progressive membrane electrode group structure of direct methanol fuel cell as described in item 5 of the scope of patent application, wherein the conductive film is a carbon paper. 7. Progressive membrane electrode group structure of direct methanol fuel cell as described in item 1 of the scope of patent application, wherein the anode catalyst is platinum / ruthenium alloy (Pt / Ru) 〇, 8 The structure of the progressive membrane electrode group of the direct methanol fuel cell according to the item, wherein the anode catalyst is carbon material particles of platinum / ruthenium alloy (Pt / Ru). "9. The progressive j-membrane electrode structure of a direct methanol fuel cell as described in item 1 of the scope of patent application, wherein the first surface of the proton conductive membrane has a methanol barrier layer, and the methanol barrier layer is made of a dense The anode catalyst is formed.,, 1. The progressive methanol electrode structure of the direct methanol fuel cell as described in item 9 of the scope of the patent application, wherein the methanol barrier layer is deposited on the first by an ion-exchange method. The surface of the surface. U • The progressive membrane electrode group structure of a direct methanol fuel cell as described in item 1 of the scope of the patent application, wherein the anode catalyst layer, the proton conductive membrane, and the cathode catalyst electrode are hot-pressed. Shaped to form a thin film structure. 12 · —A progressive membrane electrode group structure for a direct methanol fuel cell, including: a proton conductive film with a first surface; a plurality of anode catalyst layers containing anode catalysts and mutually Overlaid on one side of the proton conductive membrane, wherein the anode catalyst content of the anode catalyst layers is from the anode catalyst layer closest to the proton transfer membrane from the inside to the outside. 0178-91 WIAVF1 (N1), () 5-91 (X) 44; ji my. Ptc page 22 1229957 --1 ^ JU38126 6. The scope of patent application is increasing layer by layer; and ^ ___ A amendment A cathode catalyst electrode is disposed on one side of the proton conductive film opposite to the anode catalyst layer. /, 1 3 · The progressive membrane electrode group structure of the direct methanol fuel cell as described in item 2 of the patent application range, 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 13 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. The inner layer and the outer layer become larger and larger by 15. The progressive membrane electrode group structure of the direct methanol fuel cell described in item 12 of the patent application scope, wherein the anode catalyst layers are mixed by the anode catalyst in different proportions. After the conductive particles are formed layer by layer on the first surface of the quality inspection film. 16 · The progressive membrane electrode group structure of a direct methanol fuel cell as described in item 15 of the scope of patent application, wherein the conductive particles are carbon material particles. 17 · The structure of a progressive membrane electrode assembly for a direct methanol fuel cell as described in item 16 of the scope of patent application, wherein the anode catalyst is platinum / ruthenium alloy (Pt / Ru). ’,,’ 18 · The structure of a progressive membrane electrode assembly for direct methanol fuel cell as described in item 16 of the scope of patent application, wherein the anode catalyst is carbon material particles plated with platinum / pair gold (Pt / Ru). 19 · The progressive membrane electrode group structure of direct methanol fuel power as described in item 12 of the scope of the patent application, wherein the first-side of the proton-conducting membrane is further provided with a methylated barrier layer, and the methanol barrier layer Formed by the dense medium. $ 0178-9190 Monk coffee 1 910044 Fine y.ptc Page 23 1229957 Year—Case No. 911 1? R VI. Patent Application Range 20 · The structure of a progressive membrane electrode group for a direct methanol fuel cell as described in item 9 of the patent application scope, wherein the methanol barrier layer is ion-exchange Deposited on the first surface. ° '2 1 · As described in the patent application scope of item 12 of the direct methanol fuel cell, and also a progressive membrane electrode group structure, wherein the anode catalyst layer, the proton conductive membrane and the 4 cathode catalyst electrode system By hot pressing, a thin film front is formed. 22 · —Progressive membrane electrode assembly manufacturing method for direct methanol fuel cells' includes: · Providing a proton conductive membrane; forming a plurality of non-comparable slurries with different proportions of anode catalyst and conductive particles; from these slurries The slurry with a small proportion of the anode catalyst 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 cathode catalyst electrode is provided The anode catalyst layers are placed on the opposite sides of the anode catalyst layers, and the anode catalyst layers, the proton conductive film, and the cathode catalyst electrodes are thermoformed to form a thin film structure. 23. The method for manufacturing a progressive membrane electrode assembly for a direct methanol fuel cell as described in item 22 of the scope of the patent application, further comprising: forming a methanol barrier layer on one side of the proton conductive membrane by an ion exchange method, wherein the methanol The barrier layer is a uniform dense anode catalyst layer, and the slurry is coated on the methanol barrier layer. 24. Direct methanol fuel cell as described in item 22 of the scope of patent application Amendment No. 1229957 Case No. 911381? .R 6. The method of manufacturing a progressive membrane electrode group for which the scope of the patent application includes the provision of a hole-shaping agent; and in these pastes, according to the amount of the anode catalyst according to a Add the hole shaping agent. 25. The direct methanol fuel cell as described in item 24 of the scope of patent application = progressive membrane electrode assembly manufacturing method, wherein the hole shaping agent is oxalic acid. 0 2 6 · As described in item 22 of the scope of patent application A method for manufacturing a progressive membrane electrode group of a direct methanol fuel cell, wherein the conductive particles are carbon material particles. 27. The method for manufacturing a progressive membrane electrode group of a direct methanol fuel cell as described in item 22 of the scope of the patent application, wherein the anode catalyst is platinum / human gold (Pt / Ru). 28. According to the method for manufacturing a progressive membrane electrode group of a direct methanol fuel cell as described in item 22 of the scope of the patent application, the anode catalyst is carbon particles of outer platinum platinum ruthenium alloy (Pt / RU). ’, Again, · 0178-9190WFl (Nl); 05-910044; jimy.ptc Members are kindly requested to indicate the Schematic Correction Page of Ι2299ΪΤ · 138126. Date of revision: 93.2.10 After the amendment of this case, whether to change the original ο Electromotive force 丨 V) Quality content 〇 〇 〇 ′ 一 〇 〇 to ο ο * 4 ^ 〇ι Ο α \ ο ο 铖 5Α 涵 100 150 (# ^^^ (mA / cnf) 200 ό 1229957 Schematic revision page No. 91138126 Date of revision: 93.2.10 Voltage ο ο 〇 〇 〇 〇 Kj ο ο Private ο 50 濉 5Β 涵 100 150 200 tsl ^ m ^ (mA / cn ^) 250 300 -Ο- ^ 声 ^^^ 征 虫 苏 1229957 Schematic revision page 91138126 Revised date: 93.2.10 〇 Power density 〇mW / cm2) ^ U) 〇 〇 〇 〇 〇 〇 50 濉 5C culvert 00 150 200 csl ^ m ^ (mA / cnf) 250 300 ilfMO