CN101000967A - Membrane electrode of protone exchange membrane fuel cell and preparation method thereof - Google Patents
Membrane electrode of protone exchange membrane fuel cell and preparation method thereof Download PDFInfo
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Abstract
This invention discloses a membrane electrode for PEMFC and its preparation method, which is made of three tiers. The middle layer is proton exchange membrane, and the two-side layers are porous cathode and porous anode catalyst-diffusion layer respectively which are both made of the catalyst, slurry and carbon fiber on the outer surface. The membrane electrode of this invention is obtained by using static flocking technology to implant the carbon fiber directly onto PEM with catalyst slurry and then drying. It simplifies the process of membrane electrode, reduces the contact resistance between layers, raises the capability of gas quick spreading and water timely discharge, and improves the electrochemical properties. When the current density is 200mA/cm2, the discharge power of battery increases 14~20%.
Description
Technical field:
The present invention relates to electrode of a kind of battery and preparation method thereof, particularly membrane electrode of a kind of used in proton exchange membrane fuel cell and preparation method thereof.
Background technology
(Proton Exchange Membrane Fuel Cell PEMFC) is the Blast Furnace Top Gas Recovery Turbine Unit (TRT) that Hydrogen Energy is changed into electric energy to Proton Exchange Membrane Fuel Cells.The PEMFC system is made of following several parts, and electrolyte is proton exchange membrane (PEM), Catalytic Layer (catalyst is that carbon carries Pt or carbon carries the Pt-Ru alloy), bipolar plates (graphite or the surface modification of metals plate that have gas and water flow channel).Owing to directly chemical energy is converted into electric energy, not limited by the Kano thermal cycle, so the energy conversion efficiency height is about 60%, be 2～3 times of internal combustion engine; And operating current is big, specific power is high.Electrolyte is a solid in addition, no electrolyte corrosion leakage phenomenon.So PEMFC is considered to the environmental protection power supply of field first-selections such as following electric automobile, electronic hybrid vehicle, electric bicycle, electric moving aid vehicle, the portable power supply of communication, distributing power station.
(Membrane Electrode Assembly MEA) is the critical component of PEMFC to the PEMFC membrane electrode, and its structure has crucial influence to the overall performance of Proton Exchange Membrane Fuel Cells.In the precious honest and clean work of clothing " fuel cell---principle technology an is used " book, introduced the structure of membrane electrode commonly used, as shown in Figure 1, be five-layer structure, constitute by fuel diffusion layer 4, porous anode Catalytic Layer 2, proton exchange membrane 1, porous cathode Catalytic Layer 3 and oxygen diffusion layer 5.Diffusion layer is generally carbon cloth or the carbon paper of handling through the polytetrafluoroethylene PTFE hydrophobic, and its significant feature is to support Catalytic Layer, stabilized electrodes structure, provide electronics, gas and drainage channel for electrode reaction.Catalytic Layer is the core of membrane electrode, is the place of cell reaction, is made up of catalyst and bonding agent.Bonding agent mainly adopts hydrophilic proton exchange resins solution and hydrophobic polytetrafluoroethylene (PTFE) emulsion, and proton exchange resins solution plays bonding after super-dry and effect proton conductive simultaneously.Catalyst is that particle diameter is that the Pt or the Pt alloying pellet of several nanometers is dispersed on the black carbon surface with high-specific surface area.Proton exchange membrane is delivered to the passage of negative electrode except proton can be provided from anode, also plays cathode and anode short circuit and the reaction gas effect of string mutually that prevents.The normal proton exchange membrane of using is a perfluorinated sulfonic acid type proton exchange membrane among the PEMFC at present.
In membrane electrode the performance of each several part material own, its structure with and preparation technology be key technology in the PEMFC research, determined chemical property and the practical process of PEMFC.
About membrane electrode preparation method, nowadays there is various method.A kind of general preparation method has been described among the Chinese patent CN1201270: catalyst and certain amount of solvent, binding agent and proton exchange resins are mixed together, after being uniformly dispersed through ultrasonic wave then, evenly be coated in catalyst pulp on the diffusion layer, carry out drying again, and then be coated with one deck proton exchange resins solution in catalyst layer surface.At last the diffusion layer of two composite catalysts is clamped a proton exchange membrane, MEA is made in hot pressing under certain temperature and pressure.
In addition, among the Chinese patent CN1471186 transfer printing membrane electrode preparation method has been described.At first catalyst and certain amount of solvent, binding agent and proton exchange resins are mixed, be coated in then on the thin slice of transfer printing, after treating the catalyst pulp drying, will be under high-temperature and high-pressure conditions with the thin slice and the proton exchange membrane pressing of Catalytic Layer, again thin slice is peeled off, catalyst is compound on the proton exchange membrane, then itself and diffusion layer hot pressing is made MEA.
Because the PEMFC membrane electrode is a five-layer structure, cause the preparation process of membrane electrode loaded down with trivial details, increase the contact resistance between membrane electrode middle level and the layer, in the fuel cell use, easily cause Catalytic Layer and separating of diffusion layer to come off, reduce the time stability of membrane electrode, greatly influenced the chemical property and the life-span of fuel cell.In addition, the diffusion layer of membrane electrode all adopts carbon cloth or the carbon paper of handling through the polytetrafluoroethylene PTFE hydrophobic, though can guarantee to have enough intensity in the use, but owing to add more dielectric hydrophobic material, and then cause the diffused layer resistance rate big, porosity and unreasonable structure, the passage of omnidirectional draining and gas transmission has influenced fuel battery performance.
Static flocking technology is to utilize in the high-voltage electrostatic field, and two physical characteristics that the object same sex is repelled each other, there is a natural attraction between the sexes that have different electric charges realize.The high-voltage electrostatic field that electrostatic generator produces, one end is linked on the woven wire of villous fiber, and the other end is received on the metal plate of the flocked substrates that scribbles adhesive, because electrostatic effect, charged fiber can vertically be implanted on the flocked substrates that scribbles adhesive, forms stable fiber membrane.Introduced various active carbon fiber electrostatic spinning goods among the Chinese patent CN2344096, can use at aspects such as weaving face fabric, bag green wood material, air filting material, ornament materials.People such as Ji Tao are implanted in activated carbon fiber on common fabric or the polypropylene mesh by static flocking technology, make the filtration article (textile journal, 2004,10,109) that can be used for indoor air purification.
Summary of the invention
The object of the invention is to provide a kind of membrane electrode of used in proton exchange membrane fuel cell, reduces mea and becomes the number of plies, simplifies preparation technology, increases membrane electrode stability, makes the transmission channels that has unobstructed electronics, proton and liquid, gas in the diffusion layer simultaneously.
The membrane electrode of a kind of used in proton exchange membrane fuel cell of the present invention is formed by three layers, the intermediate layer is a proton exchange membrane, both sides are respectively porous cathode catalysis diffusion layer and porous anode catalysis diffusion layer: wherein proton exchange membrane is the perfluorinated sulfonic acid proton exchange membrane, thickness is 30～200 microns, and molal weight is 800～1300; Porous cathode catalysis diffusion layer and porous anode catalysis diffusion layer are 0.05～20 by mass ratio all: 1: 0.01～10 catalyst, binding agent and carbon fiber are formed, thickness is 10～5000 microns, outer surface all is that carbon fiber is formed, and thickness is 5～3000 microns; Carbon fiber is uniformly distributed in porous cathode catalysis diffusion layer and the porous anode catalysis diffusion layer or is distributed in top layer or surface; The volume parts of carbon fiber in porous cathode catalysis diffusion layer and porous anode catalysis diffusion layer is 1～90%; The carbon fiber of porous cathode catalysis diffusion layer and porous anode catalysis diffusion layer outer surface is the nonwoven carbon fiber or becomes 0～180 degree to arrange in order with membrane plane, and exists with porous form, and porosity is 1～95%.
The mass ratio that the catalyst that the present invention uses carries Pt catalyst or Pt and Ru as carbon is that 1: 0～2 carbon carries the Pt-Ru catalyst, and wherein to carry the content that Pt catalyst and carbon carries Pt in the Pt-Ru catalyst be 10～60wt% to carbon.
The binding agent that the present invention uses is the mixture of the ptfe emulsion of 60～80wt% as perfluorinated sulfonic acid proton exchange resins or perfluorinated sulfonic acid proton exchange resins and concentration, wherein the mass ratio of perfluorinated sulfonic acid proton exchange resins and ptfe emulsion is 1: 0～5, and perfluorinated sulfonic acid proton exchange resins molal weight is 800～1300.
The carbon fiber that the present invention uses is activated carbon fiber, celion, polyacrylonitrile-based carbon fibre or its mixture, and the distribution of lengths of carbon fiber is between 0.01～20 millimeter, and the diameter of carbon fiber is between 5～500 microns.
The membrane electrode preparation method of a kind of used in proton exchange membrane fuel cell of the present invention is as follows, below all represents with mass parts:
(1) under 150～300 ℃, the perfluorinated sulfonic acid proton exchange resins is dissolved in the solvent, obtain the resin solution that concentration is 5～15wt%, the mass ratio that respectively 0.5～300 part carbon is carried Pt catalyst or Pt and Ru then is that ptfe emulsion that 1: 0～2 carbon carries Pt-Ru catalyst and 0～100 part is put in 100 parts the resin solution, mix and make catalyst pulp, wherein carbon carries Pt catalyst and carbon and carries that Pt content is 10～60wt% in the Pt-Ru catalyst, catalyst pulp is passed through spraying respectively, dipping or sputtering method, be compound on perfluorinated sulfonic acid proton exchange membrane two-sided, drying is 10～120 minutes under 60～130 ℃, after the leveling again at the two-sided brushing catalyst pulp of perfluorinated sulfonic acid proton exchange membrane, brushing catalyst slurry thickness of feed layer is 1～50 micron, and the dead weight capacity of catalyst Pt on the perfluorinated sulfonic acid proton exchange membrane is 0.1～4.0mg/cm
2, obtain the perfluorinated sulfonic acid proton exchange membrane of brushing catalyst pulp;
(2) carbon fiber filament of diameter between 5～200 microns prescinded, make carbon fiber length between 0.01～10 millimeter, obtain carbon fiber; In the receiving screen and feed hopper that respectively the perfluorinated sulfonic acid proton exchange membrane and the carbon fiber of brushing catalyst pulp is placed into electrostatic flocking apparatus, carry out charged processing then, make both simultaneously charged, or the charged processing of substep, require both institutes electrically charged opposite; It is 4～100 kilovolts at voltage then, two electrode pads distances is under 2～30 centimetres the condition, utilize static flocking technology, the perfluorinated sulfonic acid proton exchange membrane that carbon fiber is implanted to the brushing catalyst pulp respectively is two-sided, obtain perfluorinated sulfonic acid proton exchange membrane with the catalysis diffusion layer, wherein the carbon fiber of Zhi Ruing can be by become 0～180 degree evenly to implant or unordered implantation with perfluorinated sulfonic acid proton exchange membrane plane, the volume parts of carbon fiber in the catalysis diffusion layer is 1～90%, the thickness of catalysis diffusion layer outer surface carbon fiber layer is 5～3000 microns, and porosity is between 1～95%;
(3) will dry 1～120 minute down at 60～150 ℃ with the perfluorinated sulfonic acid proton exchange membrane of catalysis diffusion layer, the carbon fiber of implantation is fixed in the catalysis diffusion layer, obtain a kind of membrane electrode of used in proton exchange membrane fuel cell.
The solvent that the present invention uses is 1: 1～10 the water and the mixed solvent of organic solvent as organic solvent or volume ratio, wherein organic solvent is methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, glycerol, N, dinethylformamide, N, N-dimethylacetylamide, dimethyl sulfoxide (DMSO), propene carbonate or its mixture.
The membrane electrode of a kind of used in proton exchange membrane fuel cell of the present invention has following advantage:
1. carbon fiber is implanted in the porous cathode diffusing catalyst layer and porous anode diffusing catalyst layer of membrane electrode, makes film
The diffusion layer of electrode and Catalytic Layer become unified whole, five traditional layer membrane electrode designs simplifications are become three-decker, Fig. 1 is existing membrane electrode of fuel batter with proton exchange film structural representation, wherein 1 is proton exchange membrane, 2 and 3 is Catalytic Layer, 4 and 5 is diffusion layers, the interface of Catalytic Layer and diffusion layer is obvious, easily cause producing bigger contact resistance between membrane electrode layer and the layer, Fig. 2 is a kind of membrane electrode of fuel batter with proton exchange film structural representation of the present invention, wherein 1 is proton exchange membrane, 2 and 3 is catalysis diffusion layers, because carbon fiber directly enters into the mixed layer inside of catalyst and binding agent composition, and then make the Catalytic Layer of membrane electrode and diffusion layer become unified integral body, thereby simplified the preparation technology of membrane electrode, improved the binding ability of membrane electrode Catalytic Layer and diffusion layer, having reduced the contact resistance between layer and the layer, improved the chemical property of membrane electrode, is 200mA/cm in current density
2Condition under, the discharge power of battery increases by 14～20%.
2. adopt carbon fiber to replace traditional carbon paper or carbon cloth as the membrane electrode diffusion layer material, and employing static flocking technology, directly be implanted on the membrane electrode by certain angle, make that the carbon fiber layer mesopore rate of membrane electrode outer surface is controlled, and structure with continuous, straight-through, directed liquids and gases transmission channels, and then having improved the gas rapid diffusion of membrane electrode and the ability that moisture is in time discharged, assurance gas rapid diffusion and moisture are in time discharged.
Membrane electrode of the present invention can be used for hydrogen/oxygen (sky) class Proton Exchange Membrane Fuel Cells, directly alcohol fuel battery, directly ethers fuel cell, the directly membrane electrode preparation of hydrazine types of fuel cells.
Description of drawings
Fig. 1 is existing membrane electrode of fuel batter with proton exchange film structural representation.
Fig. 2 is a kind of membrane electrode of fuel batter with proton exchange film structural representation of the present invention.
Embodiment:
Following examples are that the present invention will be further described, but are not limited to scope of the present invention.
The perfluorinated sulfonic acid proton exchange membrane that following examples are used has the CHFM1150 film of Donggue Shenzhou New Material Co., Ltd., Shandong, and its thickness is 50 microns, and molal weight is 1100; The perhaps CHFM10125 film of Donggue Shenzhou New Material Co., Ltd., Shandong, its thickness is 125 microns, molal weight is 1000; The perhaps Nafion112 film of du pont company, its thickness is about 50 microns, and molal weight is 1100.
The perfluorinated sulfonic acid proton exchange resins that following examples are used has the CHF1000 resin of Donggue Shenzhou New Material Co., Ltd., Shandong, and its molal weight is 1000; The perhaps Nafion resin of du pont company, its molal weight is 1100.
(1) under 200 ℃, the CHF1000 resin dissolves is arrived N, in the dinethylformamide, obtain the resin solution that concentration is 5wt%, then 1 part carbon being carried the Pt catalyst puts in 100 parts the resin solution, mix and make catalyst pulp, wherein carbon carries that Pt content is 20wt% in the Pt catalyst, catalyst pulp is passed through spraying method, be compound on CHFM1150 film two-sided, drying is 60 minutes under 80 ℃, and again at the two-sided brushing catalyst pulp of CHFM1150 film, the dead weight capacity of catalyst Pt on the CHFM1150 film is 1.0mg/cm after the leveling
2, obtain the CHFM1150 film of brushing catalyst pulp;
(2) the activated carbon fiber long filament of diameter between 50～100 microns prescinded, make activated carbon fiber length between 0.01～5 millimeter, obtain carbon fiber; In the receiving screen and feed hopper that the CHFM1150 film and the carbon fiber of brushing catalyst pulp is placed into electrostatic flocking apparatus, carry out charged processing respectively, make both charged simultaneously, and the CHFM1150 film positively charged of brushing catalyst pulp, the carbon fiber tape negative electricity; Be that 60 kilovolts, two electrode pads distances are under 12 centimetres the condition at voltage then, utilize static flocking technology, the CHFM1150 film that carbon fiber is implanted to the brushing catalyst pulp respectively is two-sided, obtain CHFM1150 film with the catalysis diffusion layer, wherein the carbon fiber of Zhi Ruing is by become 60 degree evenly to implant with the CHFM1150 membrane plane, carbon fiber is 75% in the volume parts of catalysis diffusion layer, and the thickness of catalysis diffusion layer outer surface carbon fiber layer is 200～500 microns, and porosity is 90%;
(3) will dry 10 minutes down at 80 ℃ with the CHFM1150 film of catalysis diffusion layer, the carbon fiber of implantation is fixed in the catalysis diffusion layer, obtain a kind of membrane electrode of used in proton exchange membrane fuel cell.
(1) under 200 ℃, 's 1: 5 water and N with the CHF1000 resin dissolves to volume ratio, in the dinethylformamide mixed solvent, obtain the resin solution that concentration is 5wt%, then 5 parts carbon being carried the Pt catalyst puts in 100 parts the resin solution, mix and make catalyst pulp, wherein carbon carries that Pt content is 20wt% in the Pt catalyst, catalyst pulp is passed through spraying method, be compound on CHFM1150 film two-sided, drying is 60 minutes under 80 ℃, and again at the two-sided brushing catalyst pulp of CHFM1150 film, the dead weight capacity of catalyst Pt on the CHFM1150 film is 1.0mg/cm after the leveling
2, obtain the CHFM1150 film of brushing catalyst pulp;
(2) the celion long filament of diameter between 50～100 microns prescinded, make celion length between 0.01～5 millimeter, obtain carbon fiber; In the receiving screen and feed hopper that the CHFM1150 film and the carbon fiber of brushing catalyst pulp is placed into electrostatic flocking apparatus, carry out charged processing respectively, make both charged simultaneously, and the CHFM1150 film positively charged of brushing catalyst pulp, the carbon fiber tape negative electricity; Be that 60 kilovolts, two electrode pads distances are under 12 centimetres the condition at voltage then, utilize static flocking technology, the CHFM1150 film that carbon fiber is implanted to the brushing catalyst pulp respectively is two-sided, obtain CHFM1150 film with the catalysis diffusion layer, wherein the carbon fiber of Zhi Ruing is by become 90 degree evenly to implant with the CHFM1150 membrane plane, carbon fiber is 75% in the volume parts of catalysis diffusion layer, and the thickness of catalysis diffusion layer outer surface carbon fiber layer is 200～500 microns, and porosity is 85%;
(3) will dry 10 minutes down at 80 ℃ with the CHFM1150 film of catalysis diffusion layer, the carbon fiber of implantation is fixed in the catalysis diffusion layer, obtain a kind of membrane electrode of used in proton exchange membrane fuel cell.
(1) under 200 ℃, the CHF1000 resin dissolves is arrived N, in the N-dimethylacetylamide, obtain the resin solution that concentration is 5wt%, then 200 parts carbon being carried the Pt catalyst puts in 100 parts the resin solution, mix and make catalyst pulp, wherein carbon carries that Pt content is 40wt% in the Pt catalyst, catalyst pulp is passed through spraying method, be compound on CHFM10125 film two-sided, drying is 60 minutes under 80 ℃, and again at the two-sided brushing catalyst pulp of CHFM10125 film, the dead weight capacity of catalyst Pt on the CHFM10125 film is 1.0mg/cm after the leveling
2, obtain the CHFM10125 proton exchange membrane of brushing catalyst pulp;
(2) the activated carbon fiber long filament of diameter between 50～100 microns prescinded, make activated carbon fiber length between 0.01～5 millimeter, obtain carbon fiber; In the receiving screen and feed hopper that the CHFM10125 film and the carbon fiber of brushing catalyst pulp is placed into electrostatic flocking apparatus, carry out charged processing respectively, make both charged simultaneously, and the CHFM10125 film positively charged of brushing catalyst pulp, the carbon fiber tape negative electricity; Be that 60 kilovolts, two electrode pads distances are under 15 centimetres the condition at voltage then, utilize static flocking technology, the CHFM10125 film that carbon fiber is implanted to the brushing catalyst pulp respectively is two-sided, obtain CHFM10125 film with the catalysis diffusion layer, wherein the carbon fiber of Zhi Ruing is by become 90 degree evenly to implant with the CHFM10125 membrane plane, carbon fiber is 80% in the volume parts of catalysis diffusion layer, and the thickness of catalysis diffusion layer outer surface pure carbon fiber layer is 200～500 microns, and porosity is 86%;
(3) will dry 10 minutes down at 80 ℃ with the CHFM10125 film of catalysis diffusion layer, the carbon fiber of implantation is fixed in the catalysis diffusion layer, obtain a kind of membrane electrode of used in proton exchange membrane fuel cell.
(1) under 200 ℃, with the Nafion resin dissolves in dimethyl sulfoxide (DMSO), obtain the resin solution that concentration is 5wt%, be respectively that 1: 1 the carbon ptfe emulsion that to carry Pt-Ru catalyst and 2.5 parts of concentration be 70wt% is put in 100 parts the resin solution then with the mass ratio of 15 parts of Pt and Ru, mix and make catalyst pulp, wherein carbon carries that Pt content is 40wt% in the Pt-Ru catalyst, catalyst pulp is passed through spraying method, be compound on Nafion112 film two-sided, drying is 60 minutes under 80 ℃, again at the two-sided brushing catalyst pulp of Nafion112 film, the dead weight capacity of catalyst Pt on the Nafion112 film is 0.5mg/cm after the leveling
2, obtain the Nafion112 film of brushing catalyst pulp;
(2) the polyacrylonitrile-based carbon fibre long filament of diameter between 50～100 microns prescinded, make polyacrylonitrile-based carbon fibre length between 0.01～5 millimeter, obtain carbon fiber; In the receiving screen and feed hopper that the Nafion112 film and the carbon fiber of brushing catalyst pulp is placed into electrostatic flocking apparatus, carry out charged processing respectively, make both charged simultaneously, and the Nafion112 film positively charged of brushing catalyst pulp, the carbon fiber tape negative electricity; Be that 60 kilovolts, two electrode pads distances are under 18 centimetres the condition at voltage then, utilize static flocking technology, the Nafion112 film that carbon fiber is implanted to the brushing catalyst pulp respectively is two-sided, obtain Nafion112 film with the catalysis diffusion layer, wherein the carbon fiber of Zhi Ruing is by become 90 degree evenly to implant with the proton exchange membrane plane, carbon fiber is 82% in the volume parts of catalysis diffusion layer, and the thickness of catalysis diffusion layer outer surface pure carbon fiber layer is 200～500 microns, and porosity is 84%;
(3) will dry 10 minutes down at 80 ℃ with the Nafion112 film of catalysis diffusion layer, the carbon fiber of implantation is fixed in the catalysis diffusion layer, obtain a kind of membrane electrode of used in proton exchange membrane fuel cell.
Comparative Examples 1
Adopt traditional transfer film electrode preparation method as a comparison case.At first 5 parts carbon is carried the N of the 5wt%Nafion of Pt catalyst and 100 parts, the N-dimethylacetamide solution mixes and obtains catalyst pulp, wherein carbon carries that Pt content is 40wt% in the Pt catalyst, then catalyst pulp is coated on the ptfe sheet of transfer printing, treat that catalyst pulp is at room temperature after the drying, at 100 ℃, to close with the thin slice and the Nafion112 mould of Catalytic Layer under the condition of 5MPa, again thin slice is peeled off, make Catalytic Layer be compound to Nafion112 film surface, repeat above step then, Catalytic Layer is compound to the another side of Nafion112 film, obtain the Nafion112 film with Catalytic Layer, the dead weight capacity of catalyst Pt on the Nafion112 film is 1.0mg/cm
2, the carbon paper that will handle through polytetrafluoroethylene is as diffusion layer material then, and it is made membrane electrode with the Nafion112 film of band Catalytic Layer hot pressing 80s under 130 ℃, the condition of 8MPa.
The membrane electrode of embodiment 1, embodiment 2, embodiment 3 and Comparative Examples 1 preparation and the collector plate of the graphite cake material that a side has parallel groove are assembled into monocell, carry out performance test.The effective area of membrane electrode test is 25cm
2The test operation condition: battery temperature is 80 ℃, H
2Humidification temperature is 85 ℃, O
2Humidification temperature is 90 ℃, H
2Pressure is 10Psi, O
2Pressure is 15Psi, H
2And O
2Flow control be 200mA/cm at operating current
2Under the state, stoichiometric proportion is 1: 1.5.Test result sees the following form:
Table 1
| Membrane electrode | Voltage (mV) | Power density (mW/cm 2) |
| |
450 | 90 |
| |
485 | 97 |
| |
500 | 100 |
| |
480 | 96 |
| Comparative Examples 1 | 420 | 84 |
Above-mentioned membrane electrode The performance test results shows that the chemical property of the membrane electrode of used in proton exchange membrane fuel cell of the present invention is apparently higher than the chemical property of conventional film electrode.
Claims (6)
1. the membrane electrode of a used in proton exchange membrane fuel cell is characterized in that structure is as follows:
Form by three layers, the intermediate layer is a proton exchange membrane, and both sides are respectively porous cathode catalysis diffusion layer and porous anode catalysis diffusion layer; Wherein proton exchange membrane is the perfluorinated sulfonic acid proton exchange membrane, and thickness is 30～200 microns, and molal weight is 80～1300; Porous cathode catalysis diffusion layer and porous anode catalysis diffusion layer are 0.05～20 by mass ratio all: 1: 0.01～10 catalyst, binding agent and carbon fiber are formed, thickness is 10～5000 microns, outer surface all is that carbon fiber is formed, and thickness is 5～3000 microns; Carbon fiber is uniformly distributed in porous cathode catalysis diffusion layer and the porous anode catalysis diffusion layer or is distributed in top layer or surface; The volume parts of carbon fiber in porous cathode catalysis diffusion layer and porous anode catalysis diffusion layer is 1～90%; The carbon fiber of porous cathode catalysis diffusion layer and porous anode catalysis diffusion layer outer surface is the nonwoven carbon fiber or becomes 0～180 degree to arrange in order with membrane plane, and exists with porous form, and porosity is 1～95%.
2. the membrane electrode of a kind of used in proton exchange membrane fuel cell according to claim 1, it is characterized in that catalyst is that mass ratio that carbon carries Pt catalyst or Pt and Ru is that 1: 0～2 carbon carries the Pt-Ru catalyst, wherein to carry the content that Pt catalyst and carbon carries Pt in the Pt-Ru catalyst be 10～60wt% to carbon.
3. the membrane electrode of a kind of used in proton exchange membrane fuel cell according to claim 1, it is characterized in that binding agent is that perfluorinated sulfonic acid proton exchange resins or perfluorinated sulfonic acid proton exchange resins and concentration are the mixture of the ptfe emulsion of 60～80wt%, wherein the mass ratio of perfluorinated sulfonic acid proton exchange resins and ptfe emulsion is 1: 0～5, and perfluorinated sulfonic acid proton exchange resins molal weight is 800～1300.
4. the membrane electrode of a kind of used in proton exchange membrane fuel cell according to claim 1, it is characterized in that carbon fiber is activated carbon fiber, celion, polyacrylonitrile-based carbon fibre or its mixture, the distribution of lengths of carbon fiber is between 0.01～20 millimeter, and the diameter of carbon fiber is between 5～500 microns.
5. the membrane electrode preparation method of a kind of used in proton exchange membrane fuel cell as claimed in claim 1 is characterized in that the preparation method is as follows, below all represents with mass parts:
(1) under 150～300 ℃, the perfluorinated sulfonic acid proton exchange resins is dissolved in the solvent, obtain the resin solution that concentration is 5～15wt%, the mass ratio that respectively 0.5～300 part carbon is carried Pt catalyst or Pt and Ru then is that ptfe emulsion that 1: 0～2 carbon carries Pt-Ru catalyst and 0～100 part is put in 100 parts the resin solution, mix and make catalyst pulp, wherein carbon carries Pt catalyst and carbon and carries that Pt content is 10～60wt% in the Pt-Ru catalyst, catalyst pulp is passed through spraying respectively, dipping or sputtering method, be compound on perfluorinated sulfonic acid proton exchange membrane two-sided, drying is 10～120 minutes under 60～130C, after the leveling again at the two-sided brushing catalyst pulp of perfluorinated sulfonic acid proton exchange membrane, brushing catalyst slurry thickness of feed layer is 1～50 micron, and the dead weight capacity of catalyst Pt on the perfluorinated sulfonic acid proton exchange membrane is 0.1～4.0mg/cm
2, obtain the perfluorinated sulfonic acid proton exchange membrane of brushing catalyst pulp;
(2) carbon fiber filament of diameter between 5～200 microns prescinded, make carbon fiber length between 0.01～10 millimeter, obtain carbon fiber; In the receiving screen and feed hopper that respectively the perfluorinated sulfonic acid proton exchange membrane and the carbon fiber of brushing catalyst pulp is placed into electrostatic flocking apparatus, carry out charged processing then, make both simultaneously charged, or the charged processing of substep, require both institutes electrically charged opposite; It is 4～100 kilovolts at voltage then, two electrode pads distances is under 2～30 centimetres the condition, utilize static flocking technology, the perfluorinated sulfonic acid proton exchange membrane that carbon fiber is implanted to the brushing catalyst pulp respectively is two-sided, obtain perfluorinated sulfonic acid proton exchange membrane with the catalysis diffusion layer, wherein the carbon fiber of Zhi Ruing can be by become 0～180 degree evenly to implant or unordered implantation with perfluorinated sulfonic acid proton exchange membrane plane, the volume parts of carbon fiber in the catalysis diffusion layer is 1～90%, the thickness of catalysis diffusion layer outer surface carbon fiber layer is 5～3000 microns, and porosity is between 1～95%;
(3) will dry 1～120 minute down at 60～150 ℃ with the perfluorinated sulfonic acid proton exchange membrane of catalysis diffusion layer, the carbon fiber of implantation is fixed in the catalysis diffusion layer, obtain a kind of membrane electrode of used in proton exchange membrane fuel cell.
6. the membrane electrode preparation method of a kind of used in proton exchange membrane fuel cell according to claim 5, it is characterized in that solvent is that organic solvent or volume ratio are 1: 1～10 the water and the mixed solvent of organic solvent, wherein organic solvent is methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, glycerol, N, dinethylformamide, N, N-dimethylacetylamide, dimethyl sulfoxide (DMSO), propene carbonate or its mixture.
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| CN106784948A (en) * | 2017-03-21 | 2017-05-31 | 北京化工大学 | A kind of polymer dielectric film fuel cell based on Electrostatic Absorption |
| CN108140846A (en) * | 2015-09-24 | 2018-06-08 | 可隆工业株式会社 | Membrane-membrane electrode for fuel cell component and its manufacturing method and the fuel cell system including the component |
| CN108898667A (en) * | 2018-06-22 | 2018-11-27 | 同济大学 | A kind of carbon paper morphological parameters extracting method based on X-ray CT three-dimensionalreconstruction |
| CN109888302A (en) * | 2019-02-25 | 2019-06-14 | 成都新柯力化工科技有限公司 | A kind of method that scale continuously prepares membrane electrode ordering Catalytic Layer |
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| CN113270593A (en) * | 2021-04-22 | 2021-08-17 | 上海唐锋能源科技有限公司 | Membrane electrode for proton exchange membrane fuel cell and preparation method thereof |
| CN113410496A (en) * | 2021-06-16 | 2021-09-17 | 东北大学秦皇岛分校 | All-solid-state trace water-containing low-temperature applicable proton exchange membrane and preparation method thereof |
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| CN102142572B (en) * | 2010-01-28 | 2013-11-06 | 南亚电路板股份有限公司 | Direct methanol fuel cell structure and manufacturing method thereof |
| US10336874B2 (en) * | 2011-12-19 | 2019-07-02 | National Research Council Of Canada | Co-extruded ultra thin films |
| US10868311B2 (en) | 2015-09-24 | 2020-12-15 | Kolon Industries, Inc. | Membrane-electrode assembly for fuel cell, method for manufacturing same, and fuel cell system comprising same |
| CN108140846A (en) * | 2015-09-24 | 2018-06-08 | 可隆工业株式会社 | Membrane-membrane electrode for fuel cell component and its manufacturing method and the fuel cell system including the component |
| CN108140846B (en) * | 2015-09-24 | 2021-07-16 | 可隆工业株式会社 | Membrane electrode assembly for fuel cell, method of manufacturing the same, and fuel cell system including the same |
| CN106784948A (en) * | 2017-03-21 | 2017-05-31 | 北京化工大学 | A kind of polymer dielectric film fuel cell based on Electrostatic Absorption |
| CN106784948B (en) * | 2017-03-21 | 2023-03-21 | 北京化工大学 | Polymer electrolyte membrane fuel cell based on electrostatic adsorption |
| CN108898667A (en) * | 2018-06-22 | 2018-11-27 | 同济大学 | A kind of carbon paper morphological parameters extracting method based on X-ray CT three-dimensionalreconstruction |
| CN108898667B (en) * | 2018-06-22 | 2020-11-27 | 同济大学 | Carbon paper morphological parameter extraction method based on X-ray CT three-dimensional reconstruction |
| CN109888302A (en) * | 2019-02-25 | 2019-06-14 | 成都新柯力化工科技有限公司 | A kind of method that scale continuously prepares membrane electrode ordering Catalytic Layer |
| CN112310420A (en) * | 2019-07-29 | 2021-02-02 | 上海济平新能源科技有限公司 | Electrode for fuel cell, membrane electrode assembly, chip, catalyst layer, catalyst dispersion liquid, and method for producing same |
| CN110808392A (en) * | 2019-10-25 | 2020-02-18 | 东莞市魔方新能源科技有限公司 | Fuel cell membrane electrode and preparation process thereof |
| CN111244478A (en) * | 2020-01-20 | 2020-06-05 | 鸿基创能科技(广州)有限公司 | Method for preparing crack-free catalyst coating film, catalyst coating film and membrane electrode |
| CN111549573A (en) * | 2020-05-09 | 2020-08-18 | 中国科学院山西煤炭化学研究所 | Carbon paper for proton exchange membrane hydrogen fuel cell and preparation method thereof |
| CN112083041B (en) * | 2020-09-15 | 2021-06-01 | 中国科学院大连化学物理研究所 | Online testing method for resin content of catalyst layer of fuel cell |
| CN112083041A (en) * | 2020-09-15 | 2020-12-15 | 中国科学院大连化学物理研究所 | Online testing method for resin content of catalyst layer of fuel cell |
| CN112615018A (en) * | 2020-12-21 | 2021-04-06 | 上海电气集团股份有限公司 | Cathode catalyst layer, preparation method thereof, membrane electrode and fuel cell |
| CN112687903A (en) * | 2020-12-28 | 2021-04-20 | 武汉理工氢电科技有限公司 | Catalyst layer, membrane electrode assembly, fuel cell and preparation method |
| CN113270593A (en) * | 2021-04-22 | 2021-08-17 | 上海唐锋能源科技有限公司 | Membrane electrode for proton exchange membrane fuel cell and preparation method thereof |
| CN113410496A (en) * | 2021-06-16 | 2021-09-17 | 东北大学秦皇岛分校 | All-solid-state trace water-containing low-temperature applicable proton exchange membrane and preparation method thereof |
| CN114122415A (en) * | 2021-11-24 | 2022-03-01 | 西安交通大学 | Cathode structure catalyst layer of proton exchange membrane fuel cell and preparation method and application thereof |
| CN114122415B (en) * | 2021-11-24 | 2024-05-24 | 西安交通大学 | Cathode sequential catalytic layer of proton exchange membrane fuel cell, and preparation method and application thereof |
| CN114583187A (en) * | 2022-03-02 | 2022-06-03 | 大连理工大学 | Preparation method and application of ordered multi-layer cathode catalyst layer membrane electrode |
| CN114899416A (en) * | 2022-04-22 | 2022-08-12 | 中国科学院大连化学物理研究所 | Fuel cell catalyst layer and preparation method thereof |
| CN114899416B (en) * | 2022-04-22 | 2023-11-03 | 中国科学院大连化学物理研究所 | Fuel cell catalytic layer and preparation method thereof |
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