CN110459774A - A kind of preparation method of fuel cell membrane electrode - Google Patents
A kind of preparation method of fuel cell membrane electrode Download PDFInfo
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- CN110459774A CN110459774A CN201910740091.5A CN201910740091A CN110459774A CN 110459774 A CN110459774 A CN 110459774A CN 201910740091 A CN201910740091 A CN 201910740091A CN 110459774 A CN110459774 A CN 110459774A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000446 fuel Substances 0.000 title claims abstract description 24
- 210000000170 cell membrane Anatomy 0.000 title claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 72
- 239000012528 membrane Substances 0.000 claims abstract description 64
- 238000005507 spraying Methods 0.000 claims abstract description 43
- 238000007731 hot pressing Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000010023 transfer printing Methods 0.000 claims abstract description 10
- 238000012546 transfer Methods 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 238000005516 engineering process Methods 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229920000557 Nafion® Polymers 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 229910000765 intermetallic Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 230000000873 masking effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000007921 spray Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000002362 mulch Substances 0.000 abstract description 4
- 239000002985 plastic film Substances 0.000 abstract description 4
- 229920006255 plastic film Polymers 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 26
- 238000009792 diffusion process Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000006255 coating slurry Substances 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000000754 repressing effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Materials Engineering (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
The invention discloses a kind of preparation methods of fuel cell membrane electrode, comprising: the first catalyst pulp is sprayed to the face A of proton exchange membrane using spray coating method；Second catalyst pulp is coated on offset medium, and is dried；Offset medium after drying is bonded with the proton exchange membrane of the first catalyst pulp of spraying; wherein offset medium is coated with a face B not being sprayed-on facing towards proton exchange membrane of the second catalyst; protective film is covered in the face A that proton exchange membrane is sprayed-on the first catalyst pulp; offset medium, which is removed, using caloric transfer printing technology, after hot pressing obtains fuel cell membrane electrode.The present invention first sprays to transfer to avoid afterwards and is not easy to overturn plastic film mulch in single ultrasonic spray coating method, and proton exchange membrane is easy the problem of volume is stuck up, production efficiency is improved, Catalytic Layer and the larger problem of proton exchange membrane interface resistance in single transfer printing are avoided, reduces ohmage loss.
Description
Technical field
The present invention relates to a kind of preparation methods of fuel cell membrane electrode, belong to fuel cell membrane electrode technical field.
Background technique
Proton Exchange Membrane Fuel Cells (Proton Exchange Membrane Fuel Cells, PEMFC) in recent years
As a kind of novel clean energy resource, since its low pollution even nonstaining property is by global extensive concern.And the core of PEMFC
Component membrane electrode (Membrane Electrode Assembly, MEA) is that redox main field occurs for fuel cell
The emphasis of institute and researchers' research, especially to the research of its manufacture craft.
According to the different feature of structure, traditional method for preparing membrane electrode can be divided into GDE method (Gas Diffusion
Electrode, GDE) and CCM method (Catalyst Coated Membrane, CCM).So-called GDE method is mainly by catalyst
Slurry, which is coated on gas diffusion layers, forms catalyst layer, is then combined together GDE and proton exchange membrane by heat pressing process
MEA is made.But the membrane electrode interface resistance of technique preparation is larger, is unfavorable for proton conduction, and catalyst granules may
The hole in diffusion layer is blocked, the diffusion of gas is influenced, increases resistance to mass tranfer, to reduce battery performance.It generallys use at present
Be CCM method, i.e., catalyst layer is formed in proton exchange membrane, then MEA is formed in conjunction with gas diffusion layers.This method preparation
Membrane electrode porosity is larger, is conducive to gas diffusion, the catalyst layer and matter that the utilization rate of catalyst can be improved, and prepare
Proton exchange contact is close, to improve proton-conducting.
Membrane electrode is prepared using direct spraying method, spray efficiency is low, and preparation time is long, and for relatively thin proton exchange
Film is easy fold after removing protective layer, and the plastic film mulch before spraying spends the time longer, so spray coating method is only used for small rule at present
The production and research and development of mould, are unfavorable for mass production.In addition, the Catalytic Layer of spray coating method preparation is more loose, with membrane electrode
It uses, Catalytic Layer is easy to fall off, and seriously affects the service life of battery.Membrane electrode, Catalytic Layer and proton are prepared using transfer printing
Exchange membrane interface resistance is larger, and hot repressing can make Catalytic Layer more densely cross-linked after coating drying, reduce the hole of catalyst layer
Gap rate, and then influence the performance of membrane electrode.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies of existing technologies, a kind of fuel cell membrane electrode is provided
Preparation method, first sprays to transfer to avoid afterwards and is not easy to overturn plastic film mulch in single ultrasonic spray coating method and proton exchange membrane is easy volume
The problem of sticking up improves production efficiency, avoids in single transfer printing Catalytic Layer and proton exchange membrane interface resistance is biggish asks
Topic reduces ohmage loss.
In order to solve the above technical problems, the present invention provides a kind of preparation method of fuel cell membrane electrode, characterized in that packet
It includes:
First catalyst pulp is sprayed to the face A of proton exchange membrane using spray coating method；
Second catalyst pulp is coated on offset medium, and is dried；
Offset medium after drying is bonded with the proton exchange membrane of the first catalyst pulp of spraying, wherein offset medium is coated with
The face B that the one of second catalyst is not sprayed-on facing towards proton exchange membrane is sprayed-on the first catalyst pulp in proton exchange membrane
The face A be covered with protective film, remove offset medium using caloric transfer printing technology, after hot pressing and obtain fuel cell membrane electrode.
Further, the preparation method of first catalyst pulp is: catalyst, deionized water, 5%Nafion is molten
Liquid and solvent mixing, wherein mass ratio is 1: 1 ~ 20 between catalyst, deionized water, 5%Nafion solution and solvent:
2~15 : 20~50；0.5 ~ 1 h, which is handled, by ultrasonic shear obtains the first required catalyst pulp.
Further, the preparation method of second catalyst pulp is: by catalyst, dispersing agent, 5%Nafion solution
With binder mix, wherein between catalyst, dispersing agent, 5%Nafion solution and binder mass ratio be 1: 1 ~ 12: 2 ~
15 : 0.2~5；The second required catalyst pulp is obtained by 1 ~ 16 h of ultrasonic agitation processing.
Further, the catalyst in first catalyst pulp and the second catalyst pulp be Pt, Ru, Ir, Pd,
The alloy or intermetallic compound that one of Co, Ni, Fe, Mn or various metals are formed, the carrier of the catalyst are charcoal
One of black, active carbon, graphene are a variety of.
Further, the solvent is one of methanol, ethyl alcohol, isopropanol, glycerol or a variety of.
Further, the dispersing agent is one of methanol, ethyl alcohol, isopropanol or a variety of, and the binder is second two
One of alcohol, glycerine, polyethylene glycol, butyl acetate are a variety of.
Further, the equipment for spraying the first catalyst pulp is ultrasonic spraying apparatus, the carrying capacity of the first catalyst pulp
For 0.05 ~ 0.70 mg/cm2, the face spray-coating surface A is anode or cathode.
Further, the second catalyst pulp is coated on offset medium through silk-screen printing, blade coating or slit
The method of coating, the carrying capacity of the second catalyst pulp are 0.05 ~ 0.70 mg/cm2。
Further, the offset medium is one of polytetrafluoroethylene film, release film, polyimide film, masking foil.
Further, the drying temperature is 60 ~ 140 DEG C, and drying time is 10 ~ 180 min, and thermal transfer temperature is
80 ~ 150 DEG C, hot pressing time is 1 ~ 5 min, and hot pressing pressure is 50 ~ 140 Kg/cm2。
Advantageous effects of the invention:
It is not easy to overturn plastic film mulch in single ultrasonic spray coating method and proton exchange membrane is easy volume and sticks up 1. first spraying and transferring to avoid afterwards
The problem of, improve production efficiency.
2. the present invention is relative to single ultrasonic spray coating method, when spraying, transfer reduces spraying number, and then reduces
Because catalyst pulp caused by sputtering wastes in spraying process, production cost is reduced.
3. the membrane electrode catalyst granules arrangement of spray coating method preparation is loose, with the use of membrane electrode, Catalytic Layer is easy de-
It falls.Heat pressing process is used in CCM preparation process of the present invention, first sprays the Catalytic Layer transferred afterwards so that on spraying after hot pressing more
Be it is close, avoid the generation of the above problem.
4. the present invention avoids Catalytic Layer and proton exchange membrane circle using spray coating method relative to single thermal transfer, cathode
The larger problem of surface resistance reduces ohmage loss.
Detailed description of the invention
Fig. 1 is the performance of the membrane electrode assembling monocell of embodiment 1, embodiment 2, comparative example 1, comparative example 2 and comparative example 3
Compare figure.
Specific embodiment
The invention will be further described below in conjunction with the accompanying drawings.Following embodiment is only used for clearly illustrating the present invention
Technical solution, and not intended to limit the protection scope of the present invention.
The preparation of first catalyst pulp: a certain amount of Pt/C catalyst is weighed in the first beaker, wherein Pt mass contains
Amount is 60%, and deionized water is then added.A certain amount of 5% Nafion solution is weighed in the second beaker, and (Du Pont company is raw
Produce) and aqueous isopropanol the solution in the second beaker is added dropwise to dropwise in the first beaker, most under ice-water bath ultrasound condition
Constant volume is carried out with isopropanol afterwards.Then ultrasound is carried out, high speed shear and clasmatosis respectively handle 10 min, wherein urges in slurry
Mass ratio is 1:8:50 between agent, 5%Nafion solution and solvent.
The preparation of second catalyst pulp: weighing a certain amount of Pt/C catalyst, and wherein Pt mass content is 40%, by it
It is placed in deionized water, 5% Nafion solution (production of Du Pont company) and aqueous isopropanol is then added, is placed in ice-water bath
Then middle ultrasonic 30 mim adds ethylene glycol, 6 h of mechanical stirring.Wherein catalyst, isopropanol, 5%Nafion solution and
Mass ratio is 1:6:10:4 between ethylene glycol.
[embodiment 1]:
Spray coating method prepares CCM cathode: cutting sizeable proton exchange membrane, spraying is placed in the heating of ultrasound spraying instrument up
On platform, vacuum pump is opened by the smooth absorption of proton exchange membrane, then sprays the first catalyst pulp, control Pt carrying capacity is 0.48
mg/cm2, only carry out the spraying of proton exchange membrane single side.
Blade coating: taking the PTFE film of 50 μ m-thicks, before coating slurry, is cleaned with dehydrated alcohol to offset medium.
Offset medium is adsorbed on vacuum platform after having cleaned drying, and is coated the second catalyst pulp using blade coating equipment
Onto offset medium, coating machine scraper coating thickness and coating speed, which is arranged, makes the control of Pt carrying capacity in 0.20 mg/cm2, coated
It is dried after.
Transfer printing prepares CCM anode: by offset medium and the proton exchange membrane of above-mentioned spraying one side of the coating after dry
Fitting, wherein offset medium has an one side not sprayed facing towards proton exchange membrane of catalyst layer, sprays in proton exchange membrane
Be covered with protective film on one side.3 min of hot-pressing processing is carried out under 120 DEG C, 10 Mpa of pressure, removes offset medium after cooling,
Obtain CCM.Gas diffusion layers and proton exchange membrane are finally subjected to second of hot-pressing processing, obtain membrane electrode.
[embodiment 2]:
Spray coating method prepares CCM anode: cutting sizeable proton exchange membrane, spraying is placed in the heating of ultrasound spraying instrument up
On platform, vacuum pump is opened by the smooth absorption of proton exchange membrane, then sprays the first catalyst pulp, control Pt carrying capacity is 0.24
mg/cm2, only carry out the spraying of proton exchange membrane single side.
Blade coating: taking the PTFE film of 50 μ m-thicks, before coating slurry, is cleaned with dehydrated alcohol to offset medium.
Offset medium is adsorbed on vacuum platform after having cleaned drying, and is coated the second catalyst pulp using blade coating equipment
Onto offset medium, coating machine scraper coating thickness and coating speed, which is arranged, makes the control of Pt carrying capacity in 0.48 mg/cm2, coated
It is dried after.
Transfer printing prepares CCM cathode: by offset medium and the proton exchange membrane of above-mentioned spraying one side of the coating after dry
Fitting, wherein offset medium has an one side not sprayed facing towards proton exchange membrane of catalyst layer, sprays in proton exchange membrane
Be covered with protective film on one side.3 min of hot-pressing processing is carried out under 120 DEG C, 10 Mpa of pressure, removes offset medium after cooling,
Obtain CCM.Gas diffusion layers and proton exchange membrane are finally subjected to second of hot-pressing processing, obtain membrane electrode.
[comparative example 1]:
Sizeable proton exchange membrane is cut, spraying is placed in up on the heating platform of ultrasound spraying instrument, opens vacuum pump
By the smooth absorption of proton exchange membrane, the first catalyst pulp is then sprayed, control Pt carrying capacity is 0.48 mg/cm2。
Proton exchange membrane is overturn after the completion of spraying and carries out another side spraying, it is same to spray the first catalyst pulp, control
Pt carrying capacity is 0.24 mg/cm2To get the CCM for arriving fuel cell membrane electrode.Finally by gas diffusion layers and proton exchange membrane into
Second of hot-pressing processing of row, obtains membrane electrode.
[comparative example 2]:
CCM prepared by comparative example 1 carries out 3 min of hot-pressing processing under 120 DEG C, 10 Mpa of pressure, then by gas diffusion layers
Second of hot-pressing processing is carried out with proton exchange membrane, obtains membrane electrode.
[comparative example 3]:
The PTFE film for taking 50 μ m-thicks cleans offset medium with dehydrated alcohol before coating slurry.After having cleaned drying
Offset medium is adsorbed on vacuum platform, and the second catalyst pulp is coated to by offset medium using blade coating equipment
On, coating machine scraper coating thickness and coating speed are set to control Pt carrying capacity, cathode carrying capacity is 0.48 mg/cm2, anode load
Amount is 0.24 mg/cm2, it is dried after the completion of coating.
The two panels PTFE film for being coated with anode and cathode difference carrying capacity is respectively placed in the two sides of proton exchange membrane, at 120 DEG C,
3 min of hot-pressing processing is carried out under 10 Mpa of pressure, is then removed the PTFE film of two sides, is obtained completely being catalyzed layer film.Finally
Gas diffusion layers and proton exchange membrane are subjected to second of hot-pressing processing, obtain membrane electrode.
From embodiment 1 in Fig. 1 it can be found that the CCM after spraying passes through certain temperature compared with comparative example 1 and comparative example 2
After degree and pressure hot pressing, performance is not changed significantly, but catalyst layer is not easily to fall off after hot pressing.Embodiment 1 and right
Ratio 3 can be seen that the present invention and prepare cathode catalyst layer using first spray coating method, then prepares anode using transfer printing process again and urges
The membrane electrode performance of agent layer preparation is substantially better than the membrane electrode of transfer printing preparation, especially in ohmic polarization region.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvement and deformations can also be made, these improvement and deformations
Also it should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of fuel cell membrane electrode, characterized in that include:
First catalyst pulp is sprayed to the face A of proton exchange membrane using spray coating method；
Second catalyst pulp is coated on offset medium, and is dried；
Offset medium after drying is bonded with the proton exchange membrane of the first catalyst pulp of spraying, wherein offset medium is coated with
The face B that the one of second catalyst is not sprayed-on facing towards proton exchange membrane is sprayed-on the first catalyst pulp in proton exchange membrane
The face A be covered with protective film, remove offset medium using caloric transfer printing technology, after hot pressing and obtain fuel cell membrane electrode.
2. a kind of preparation method of fuel cell membrane electrode according to claim 1, characterized in that first catalyst
The preparation method of slurry is: catalyst, deionized water, 5%Nafion solution and solvent being mixed, wherein catalyst, deionization
Mass ratio is 1:1 ~ 20:2 ~ 15:20 ~ 50 between water, 5%Nafion solution and solvent；By ultrasonic shear processing 0.5 ~ 1
H obtains the first required catalyst pulp.
3. a kind of preparation method of fuel cell membrane electrode according to claim 1, characterized in that second catalyst
The preparation method of slurry is: by catalyst, dispersing agent, 5%Nafion solution and binder mix, wherein catalyst, dispersing agent,
Mass ratio is 1:1 ~ 12:2 ~ 15:0.2 ~ 5 between 5%Nafion solution and binder；It is obtained by 1 ~ 16 h of ultrasonic agitation processing
The second required catalyst pulp.
4. a kind of preparation method of fuel cell membrane electrode according to claim 2 or 3, characterized in that described first urges
Catalyst in agent slurry and the second catalyst pulp is one of Pt, Ru, Ir, Pd, Co, Ni, Fe, Mn or a variety of gold
Belong to the alloy or intermetallic compound formed, the carrier of the catalyst is one of carbon black, active carbon, graphene or more
Kind.
5. a kind of preparation method of fuel cell membrane electrode according to claim 2, characterized in that the solvent is first
One of alcohol, ethyl alcohol, isopropanol, glycerol are a variety of.
6. a kind of preparation method of fuel cell membrane electrode according to claim 3, characterized in that the dispersing agent is first
One of alcohol, ethyl alcohol, isopropanol are a variety of, and the binder is ethylene glycol, in glycerine, polyethylene glycol, butyl acetate
It is one or more.
7. a kind of preparation method of fuel cell membrane electrode according to claim 1, characterized in that the first catalyst of spraying
The equipment of slurry is ultrasonic spraying apparatus, and the carrying capacity of the first catalyst pulp is 0.05 ~ 0.70 mg/cm2, the face spray-coating surface A is
Anode or cathode.
8. a kind of preparation method of fuel cell membrane electrode according to claim 1, characterized in that by the second catalyst slurry
Material is coated to the method for passing through silk-screen printing, blade coating or slot coated on offset medium, the carrying capacity of the second catalyst pulp
For 0.05 ~ 0.70 mg/cm2。
9. a kind of preparation method of fuel cell membrane electrode according to claim 1, characterized in that the offset medium is
One of polytetrafluoroethylene film, release film, polyimide film, masking foil.
10. a kind of preparation method of fuel cell membrane electrode according to claim 1, characterized in that the drying temperature
It is 60 ~ 140 DEG C, drying time is 10 ~ 180 min, and thermal transfer temperature is 80 ~ 150 DEG C, and hot pressing time is 1 ~ 5
Min, hot pressing pressure are 50 ~ 140 Kg/cm2。
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910740091.5A CN110459774A (en) | 2019-08-12 | 2019-08-12 | A kind of preparation method of fuel cell membrane electrode |
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| CN201910740091.5A CN110459774A (en) | 2019-08-12 | 2019-08-12 | A kind of preparation method of fuel cell membrane electrode |
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| CN110459774A true CN110459774A (en) | 2019-11-15 |
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| CN201910740091.5A Pending CN110459774A (en) | 2019-08-12 | 2019-08-12 | A kind of preparation method of fuel cell membrane electrode |
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| CN111129530A (en) * | 2019-12-31 | 2020-05-08 | 一汽解放汽车有限公司 | Catalytic slurry, membrane electrode, preparation method and application thereof |
| CN111244480A (en) * | 2020-01-21 | 2020-06-05 | 福建卓翼能源科技发展有限公司 | Carbon-supported palladium-based alloy fuel cell membrane electrode and preparation method thereof |
| CN111740120A (en) * | 2020-06-30 | 2020-10-02 | 武汉理工新能源有限公司 | Membrane electrode, preparation method thereof and fuel cell |
| CN112531188A (en) * | 2020-12-08 | 2021-03-19 | 安徽枡水新能源科技有限公司 | Preparation method of fuel cell membrane electrode |
| CN112599796A (en) * | 2020-12-14 | 2021-04-02 | 中国科学院大连化学物理研究所 | Batch production method and equipment for high-yield and antipole-resistant catalytic electrode of fuel cell |
| CN112599793A (en) * | 2020-12-14 | 2021-04-02 | 中国科学院大连化学物理研究所 | CCM coating process for realizing anti-swelling by using protective back membrane |
| CN112599791A (en) * | 2020-12-14 | 2021-04-02 | 中国科学院大连化学物理研究所 | High-yield fuel cell catalytic electrode coating production method and equipment thereof |
| CN112701337A (en) * | 2020-12-28 | 2021-04-23 | 南京大学昆山创新研究院 | Device and method for continuously preparing fuel cell CCM (continuous charge-transfer membrane) by recycling transfer medium |
| CN112838237A (en) * | 2021-01-22 | 2021-05-25 | 中汽创智科技有限公司 | Battery membrane electrode and preparation process thereof |
| CN112980247A (en) * | 2019-12-14 | 2021-06-18 | 中国科学院大连化学物理研究所 | High-stability ink-jet printing ink for fuel cell and preparation and application thereof |
| CN113517459A (en) * | 2021-09-14 | 2021-10-19 | 山东华滋自动化技术股份有限公司 | Process for producing membrane electrode |
| CN113991128A (en) * | 2021-10-27 | 2022-01-28 | 中汽创智科技有限公司 | Method and equipment for mass production of membrane electrode assembly |
| CN114204052A (en) * | 2021-12-03 | 2022-03-18 | 中国科学院大连化学物理研究所 | High-uniformity CCM (continuous coating) process for fuel cell |
| CN114220978A (en) * | 2021-12-20 | 2022-03-22 | 鸿基创能科技(佛山)有限公司 | CCM preparation method for hydrogen production by water electrolysis, CCM and membrane electrode |
| CN115064715A (en) * | 2022-06-28 | 2022-09-16 | 浙江锋源氢能科技有限公司 | Membrane electrode CCM (continuous current mode) and preparation method thereof, membrane electrode assembly MEA (membrane electrode assembly) and fuel cell |
| CN115472847A (en) * | 2022-09-21 | 2022-12-13 | 北京化工大学 | Preparation method of high-efficiency proton exchange membrane fuel cell membrane electrode |
| CN116230970A (en) * | 2023-01-18 | 2023-06-06 | 江苏擎动新能源科技有限公司 | Membrane electrode and preparation method thereof |
| CN116759590A (en) * | 2023-08-17 | 2023-09-15 | 安徽明天新能源科技有限公司 | Preparation method of composite CCM with high durability and low activation time and different catalytic layers |
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| CN112980247A (en) * | 2019-12-14 | 2021-06-18 | 中国科学院大连化学物理研究所 | High-stability ink-jet printing ink for fuel cell and preparation and application thereof |
| CN111129530A (en) * | 2019-12-31 | 2020-05-08 | 一汽解放汽车有限公司 | Catalytic slurry, membrane electrode, preparation method and application thereof |
| CN111244480A (en) * | 2020-01-21 | 2020-06-05 | 福建卓翼能源科技发展有限公司 | Carbon-supported palladium-based alloy fuel cell membrane electrode and preparation method thereof |
| CN111244480B (en) * | 2020-01-21 | 2022-05-24 | 福建卓翼能源科技发展有限公司 | Carbon-supported palladium-based alloy fuel cell membrane electrode and preparation method thereof |
| CN111740120A (en) * | 2020-06-30 | 2020-10-02 | 武汉理工新能源有限公司 | Membrane electrode, preparation method thereof and fuel cell |
| CN112531188A (en) * | 2020-12-08 | 2021-03-19 | 安徽枡水新能源科技有限公司 | Preparation method of fuel cell membrane electrode |
| CN112599791A (en) * | 2020-12-14 | 2021-04-02 | 中国科学院大连化学物理研究所 | High-yield fuel cell catalytic electrode coating production method and equipment thereof |
| CN112599793A (en) * | 2020-12-14 | 2021-04-02 | 中国科学院大连化学物理研究所 | CCM coating process for realizing anti-swelling by using protective back membrane |
| CN112599796A (en) * | 2020-12-14 | 2021-04-02 | 中国科学院大连化学物理研究所 | Batch production method and equipment for high-yield and antipole-resistant catalytic electrode of fuel cell |
| CN112701337A (en) * | 2020-12-28 | 2021-04-23 | 南京大学昆山创新研究院 | Device and method for continuously preparing fuel cell CCM (continuous charge-transfer membrane) by recycling transfer medium |
| CN112838237A (en) * | 2021-01-22 | 2021-05-25 | 中汽创智科技有限公司 | Battery membrane electrode and preparation process thereof |
| CN113517459A (en) * | 2021-09-14 | 2021-10-19 | 山东华滋自动化技术股份有限公司 | Process for producing membrane electrode |
| CN113991128A (en) * | 2021-10-27 | 2022-01-28 | 中汽创智科技有限公司 | Method and equipment for mass production of membrane electrode assembly |
| CN114204052A (en) * | 2021-12-03 | 2022-03-18 | 中国科学院大连化学物理研究所 | High-uniformity CCM (continuous coating) process for fuel cell |
| CN114204052B (en) * | 2021-12-03 | 2023-11-10 | 中国科学院大连化学物理研究所 | Continuous coating process for high-uniformity CCM of fuel cell |
| CN114220978A (en) * | 2021-12-20 | 2022-03-22 | 鸿基创能科技(佛山)有限公司 | CCM preparation method for hydrogen production by water electrolysis, CCM and membrane electrode |
| CN115064715A (en) * | 2022-06-28 | 2022-09-16 | 浙江锋源氢能科技有限公司 | Membrane electrode CCM (continuous current mode) and preparation method thereof, membrane electrode assembly MEA (membrane electrode assembly) and fuel cell |
| CN115064715B (en) * | 2022-06-28 | 2023-10-27 | 浙江锋源氢能科技有限公司 | Membrane electrode CCM and preparation method thereof, membrane electrode assembly MEA and fuel cell |
| CN115472847A (en) * | 2022-09-21 | 2022-12-13 | 北京化工大学 | Preparation method of high-efficiency proton exchange membrane fuel cell membrane electrode |
| CN116230970A (en) * | 2023-01-18 | 2023-06-06 | 江苏擎动新能源科技有限公司 | Membrane electrode and preparation method thereof |
| CN116230970B (en) * | 2023-01-18 | 2024-01-19 | 江苏擎动新能源科技有限公司 | Membrane electrode and preparation method thereof |
| CN116759590A (en) * | 2023-08-17 | 2023-09-15 | 安徽明天新能源科技有限公司 | Preparation method of composite CCM with high durability and low activation time and different catalytic layers |
| CN116759590B (en) * | 2023-08-17 | 2023-10-31 | 安徽明天新能源科技有限公司 | Preparation method of multi-layer catalytic layer structure CCM |
| CN117594811A (en) * | 2023-11-16 | 2024-02-23 | 安徽明天新能源科技有限公司 | Hot-pressing auxiliary reinforced fuel cell membrane electrode and preparation method thereof |
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