CN114937799B - Membrane electrode, preparation method thereof and fuel cell - Google Patents
Membrane electrode, preparation method thereof and fuel cell Download PDFInfo
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- CN114937799B CN114937799B CN202210616757.8A CN202210616757A CN114937799B CN 114937799 B CN114937799 B CN 114937799B CN 202210616757 A CN202210616757 A CN 202210616757A CN 114937799 B CN114937799 B CN 114937799B
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- 239000000446 fuel Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 177
- 239000002574 poison Substances 0.000 claims abstract description 84
- 238000009792 diffusion process Methods 0.000 claims abstract description 75
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- 239000003054 catalyst Substances 0.000 claims description 133
- 239000002002 slurry Substances 0.000 claims description 78
- 229920000831 ionic polymer Polymers 0.000 claims description 59
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 55
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 47
- 229920000554 ionomer Polymers 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 230000001147 anti-toxic effect Effects 0.000 claims description 25
- 238000011068 loading method Methods 0.000 claims description 25
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000004806 packaging method and process Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium on carbon Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 229910002848 Pt–Ru Inorganic materials 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- 229910002835 Pt–Ir Inorganic materials 0.000 claims description 4
- 229910018879 Pt—Pd Inorganic materials 0.000 claims description 4
- 229910018967 Pt—Rh Inorganic materials 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- -1 polyethylene naphthalate Polymers 0.000 claims description 2
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
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- 238000012360 testing method Methods 0.000 description 34
- 238000002156 mixing Methods 0.000 description 15
- 229910052697 platinum Inorganic materials 0.000 description 15
- 238000000498 ball milling Methods 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
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- 230000010287 polarization Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000007731 hot pressing Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical group [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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Classifications
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- 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]
-
- 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
- H01M4/8605—Porous electrodes
-
- 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
-
- 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
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- 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
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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)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Inert Electrodes (AREA)
Abstract
The invention provides a membrane electrode and a preparation method thereof, and a fuel cell, wherein the membrane electrode comprises an anode gas diffusion layer, an anode anti-poison layer, an anode catalytic layer, a proton membrane, a cathode catalytic layer, a cathode gas diffusion layer and a sealing layer, the anode catalytic layer and the cathode catalytic layer are respectively arranged on two opposite surfaces of the proton membrane, the anode anti-poison layer is arranged on the anode catalytic layer, the sealing layer seals the side surfaces of the proton membrane, the anode catalytic layer, the cathode catalytic layer and the anode anti-poison layer, the anode gas diffusion layer is arranged on the anode anti-poison layer, and the cathode gas diffusion layer is arranged on the cathode catalytic layer. The membrane electrode has better CO poisoning resistance and can effectively prolong the service life of the fuel cell.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a membrane electrode, a preparation method thereof and a fuel cell.
Background
A hydrogen fuel cell is a cell that directly converts chemical energy into electrical energy by reacting hydrogen with oxygen. The proton exchange membrane fuel cell has the characteristics of low working temperature, quick start, high power density, mature application and the like, and is widely applied to automobiles.
At present, the maintenance amount of commercial vehicles in China only accounts for about 12% of the maintenance amount of the vehicles, but the maintenance amount of commercial vehicles in China leads to about 56% of the emission of CO 2 in road traffic. Thus, a hydrogen fuel cell would be an effective solution for commercial vehicles to achieve "carbon peak" and "carbon neutralization". At present, the service life of a fuel cell of a commercial vehicle is about 15000h, and the service life requirement of the commercial vehicle is not met with that of an internal combustion engine. Therefore, how to improve the service life is one of the most important problems in the popularization and application of the fuel cell of the commercial vehicle.
The membrane electrode is an important component of the fuel cell, is a place where electrochemical reaction occurs, and is compared with a chip of the fuel cell, and the cost thereof occupies more than 60% of the total cost of the fuel cell. Thus, the cost and lifetime of the membrane electrode directly determines the cost and lifetime of the fuel cell.
The working process of the membrane electrode is as follows: the high-purity hydrogen fuel from the hydrogen storage tank is decomposed into hydrogen protons and electrons under the action of the platinum catalyst when passing through the anode catalytic layer, the hydrogen protons are transferred to the cathode side through the proton membrane, the electrons are transferred to the cathode side through an external circuit, and when the electrons reach the cathode, the hydrogen fuel is combined with the protons and oxygen fuel from the ambient air under the action of the cathode platinum catalyst to generate water. The specific electrode reactions are as follows:
anode H 2→2H++2e- (1)
Cathode 1/2O 2+2H++2e-→H2 O (2)
The total reaction is H 2+1/2O2→H2 O
Even if high-purity hydrogen is used as the anode, trace CO still exists, and the CO reacts with the platinum catalyst in the catalytic layer to generate Pt-CO which is attached to the surface of the catalyst, so that the platinum catalyst is poisoned by CO carbon, the catalysis (1) can not be performed any more, and the service life of the battery is shortened. Therefore, how to improve the CO poisoning resistance of fuel cells has become an important point of commercial vehicle applications.
The methods mainly adopted at present are as follows: (1) purifying gas to remove CO; (2) Adding oxygen or air into raw material hydrogen to oxidize CO; (3) A binary, ternary or quaternary platinum ruthenium catalyst resistant to CO is adopted; (4) And (3) removing CO by using H 2O2 with a certain concentration as humidification liquid of the humidifier. However, in practical applications, the adoption of method (1) requires the addition of auxiliary equipment, and to achieve CO concentrations below 20ppm, significant increases in the complexity and cost of the vehicle system are required; the method (2) is troublesome in mixing hydrogen and air, and has a large safety risk; the method (3) adopts a platinum ruthenium system catalyst in the anode catalytic layer, has a certain CO resisting effect, but greatly reduces the reaction activity of the anode, so that the performance of the battery is obviously reduced; the addition of the method (4) H 2O2 can accelerate degradation of the proton membrane and dissolution and aggregation of the platinum catalyst, particularly in the processes of starting, stopping, idling and high-potential dynamic circulation of the vehicle, so that the durability of the fuel cell is seriously reduced.
Disclosure of Invention
Based on the above, it is necessary to provide a membrane electrode having a good CO poisoning resistance and capable of improving the service life of a fuel cell, a method for producing the same, and a fuel cell.
According to one aspect of the present invention, there is provided a membrane electrode comprising an anode gas diffusion layer, an anode poison-resistant layer, an anode catalytic layer, a proton membrane, a cathode catalytic layer, a cathode gas diffusion layer and a sealing layer, wherein the anode catalytic layer and the cathode catalytic layer are respectively arranged on two opposite surfaces of the proton membrane, the anode poison-resistant layer is arranged on the anode catalytic layer, the sealing layer seals the side surfaces of the proton membrane, the anode catalytic layer, the cathode catalytic layer and the anode poison-resistant layer, the anode gas diffusion layer is arranged on the anode poison-resistant layer, and the cathode gas diffusion layer is arranged on the cathode catalytic layer.
In some of these embodiments, the anode anti-poison layer comprises a first ionomer and a first catalyst supported on the first ionomer; the main chain structure of the first ionic polymer is- (CF 2-CF)x(CF2-CF2)y -, wherein y/x is 5.8-7.0), and the side chain structure of the first ionic polymer is-O (CF 2)nSO3 H, wherein n is 2-4.
In some of these embodiments, the first ionomer has an EW value of 830g/eq to 1000g/eq.
In some of these embodiments, the first catalyst is one or more of a Pt-Ru/C catalyst, a Pt-Rh/C catalyst, a Pt-Pd/C catalyst, and a Pt-Ir/C catalyst.
In some of these embodiments, the anode antitoxic layer has a thickness of 1 μm to 3 μm.
In some of these embodiments, the sum of the loading of Ru, rh, pd, and Ir in the anode anti-poison layer is 0.02mg/cm 2～0.06mg/cm2.
In some embodiments, the mass percentage of Pt in the first catalyst is 20% to 60%.
In some of these embodiments, the anode catalytic layer comprises a second ionomer and a second catalyst supported on the second ionomer; the main chain structure of the second ionic polymer is- (CF 2-CF)x(CF2-CF2)y -, wherein y/x is 5.8-7.0), and the side chain structure of the second ionic polymer is-O (CF 2)nSO3 H, wherein n is 2-4.
In some of these embodiments, the second ionomer has an EW value of 830g/eq to 1000g/eq.
In some of these embodiments, the second catalyst is one or more of a Pt/C catalyst, a Pt-Co/C catalyst, a Pt-Ni/C catalyst.
In some embodiments, the mass percentage of Pt in the second catalyst is 20% -60%, and the loading of Pt in the anode catalytic layer is 0.05mg/cm 2～0.1mg/cm2.
In some of these embodiments, the cathode catalytic layer comprises a third ionomer and a third catalyst supported on the third ionomer; the main chain structure of the third ionic polymer is- (CF 2-CF)x(CF2-CF2)y - (wherein y/x is 4.2-6.0) and the side chain structure is-O (CF 2)nSO3 H wherein n is 1-3).
In some of these embodiments, the third ionomer has an EW value of 750g/eq to 860g/eq.
In some of these embodiments, the third catalyst is one or more of a Pt/C catalyst, a Pt-Co/C catalyst, a Pt-Ni/C catalyst.
In some embodiments, the mass percentage of Pt in the third catalyst is 40% -60%, and the loading of Pt in the cathode catalytic layer is 0.1mg/cm 2～0.35mg/cm2.
In some embodiments, the proton membrane is an enhanced composite sulfuric acid membrane, and the proton membrane has a thickness of 8 μm to 15 μm.
In some embodiments, the material of the sealing layer is polyethylene naphthalate or polyimide, and the thickness of the sealing layer is 45-75 μm.
In some of these embodiments, the thickness of the anode gas diffusion layer is greater than the thickness of the cathode gas diffusion layer.
In some of these embodiments, the sum of the thicknesses of the anode catalytic layer, the anode anti-poison layer, and the anode gas diffusion layer is less than the sum of the thicknesses of the cathode catalytic layer and the cathode gas diffusion layer.
According to another aspect of the present invention, there is provided a method for preparing a membrane electrode, comprising the steps of:
Respectively coating cathode catalytic layer slurry and anode catalytic layer slurry on two opposite surfaces of a proton membrane to respectively form a cathode catalytic layer and an anode catalytic layer;
coating anode anti-poison layer slurry on the anode catalytic layer to form an anode anti-poison layer;
Sealing the side surfaces of the proton membrane, the anode catalytic layer, the cathode catalytic layer and the anode antitoxic layer by adopting a sealing frame to form a sealing layer; and
And packaging an anode gas diffusion layer on the anode anti-poison layer, and packaging a cathode gas diffusion layer on the cathode catalytic layer.
In some of these embodiments, the anode catalytic layer slurry includes a second ionic polymer, a second catalyst, and a second solvent; the second solvent is one or more of water, isopropanol, n-propanol, ethanol and ethyl acetate; the mass ratio of the second catalyst to the second ionic polymer is (0.25-0.46): 1, wherein the solid content of the anode catalytic layer slurry is 1.0-1.5%.
In some of these embodiments, the cathode catalytic layer slurry includes a third ionic polymer, a third catalyst, and a third solvent; the third solvent is one or more of water, isopropanol, n-propanol and ethanol; the solid content of the cathode catalytic layer slurry is 1.8% -2.5%.
In some embodiments, the anode anti-poison layer slurry comprises a first ionic polymer, a first catalyst, and a first solvent, the first solvent is one or more of water, isopropanol, n-propanol, ethanol, and the solid content of the anode anti-poison layer slurry is 1.0% -1.5%.
According to another aspect of the present invention, there is provided a fuel cell including the membrane electrode described above.
Compared with the prior art, the invention has the following beneficial effects:
according to the membrane electrode, the anode anti-poisoning layer is arranged between the anode catalytic layer and the anode gas diffusion layer, so that the humidified water in the fuel can be rich in-OH, and the-OH can be exchanged with CO in CO-Pt to generate CO-OH, so that Pt is released, further, a Pt catalyst in the anode catalytic layer is prevented from being poisoned, the anti-poisoning capability of the anode catalytic layer is improved, and the service life of the fuel cell is prolonged. And, through setting up the positive pole antitoxic layer between positive pole catalysis layer and positive pole gas diffusion layer, promote the antitoxic ability of positive pole catalysis layer, can avoid causing adverse effect to other performances of membrane electrode.
In addition, the proton transfer rate in the anode catalytic layer is improved by regulating and controlling the molecular structure of the main chain of the ionic polymer and the molecular structure of the side chain sulfonic acid end in the anode catalytic layer; by regulating and controlling the main chain and side chain structure of the ionic polymer in the cathode catalytic layer, the permeability of oxygen in the cathode catalytic layer and the removal of generated water are obviously improved, and ohmic polarization and concentration polarization are reduced.
Furthermore, the fuel cell has smaller ohmic loss, concentration loss and activation loss and higher power density through the coupling anchoring between the cathode catalytic layer and the anode catalytic layer; by anchoring and interlocking the thicknesses of the film layers, water generated on the cathode side can be permeated to the anode side, the amount of-OH generated on the anode anti-poison layer is increased, the ohmic polarization and concentration polarization of the battery are further reduced, and the power density and durability of the battery are remarkably improved.
Drawings
FIG. 1 is a schematic cross-sectional view of a membrane electrode according to an embodiment of the invention;
fig. 2 is a schematic cross-sectional structure of a membrane electrode according to another embodiment of the invention.
Reference numerals illustrate:
10. A membrane electrode; 11. an anode gas diffusion layer; 12. an anode antitoxic layer; 13. an anode catalytic layer; 14. a proton membrane; 15. a cathode catalytic layer; 16. a cathode gas diffusion layer; 17. and (3) a sealing layer.
Detailed Description
The detailed description of the present invention will be provided to make the above objects, features and advantages of the present invention more obvious and understandable. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, whereby the invention is not limited to the specific embodiments disclosed below.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Referring to fig. 1 and 2, an embodiment of the present invention provides a membrane electrode 10, wherein the membrane electrode 10 includes an anode gas diffusion layer 11, an anode anti-poison layer 12, an anode catalyst layer 13, a proton membrane 14, a cathode catalyst layer 15, a cathode gas diffusion layer 16 and a sealing layer 17.
Wherein the anode catalytic layer 13 and the cathode catalytic layer 15 are respectively arranged on two opposite surfaces of the proton membrane 14; the anode antitoxic layer 12 is arranged on the anode catalytic layer 13; the sealing layer 17 seals the sides of the proton membrane 14, the anode catalytic layer 13, the cathode catalytic layer 15 and the anode anti-poison layer 12; an anode gas diffusion layer 11 is provided on the anode anti-poison layer 12, and a cathode gas diffusion layer 16 is provided on the cathode catalyst layer 15.
In the membrane electrode 10, an anode anti-poison layer 12 is arranged between an anode catalytic layer 13 and an anode gas diffusion layer 11, and the anode anti-poison layer 12 is sealed by covering the edge of the anode anti-poison layer 12 by a sealing layer 17; through the anode anti-poison layer 12, the humidified water in the fuel can generate rich-OH structure, and the-OH can exchange with CO in CO-Pt to generate CO-OH, so that Pt is released, further, the Pt catalyst in the anode catalytic layer 13 is not poisoned, the anti-poison capability of the anode catalytic layer 13 is improved, and the service life of the fuel cell is prolonged.
In addition, by providing the anode catalyst layer 13 and the cathode catalyst layer 15 on the opposite surfaces of the proton membrane 14, respectively, the power density of the fuel cell can be remarkably improved by the coupling anchoring between the anode catalyst layer 13 and the cathode catalyst layer 15.
In some of these embodiments, the anode anti-poison layer 12 comprises a first ionomer and a first catalyst supported on the first ionomer; the main chain structure of the first ionic polymer is- (CF 2-CF)x(CF2-CF2)y - (wherein y/x is 5.8-7.0), the side chain structure of the first ionic polymer is-O (CF 2)nSO3 H, wherein n is 2-4), the EW value (equivalent specific gravity) of the first ionic polymer is 830-1000 g/eq, and the first catalyst is one or more of Pt-Ru/C catalyst, pt-Rh/C catalyst, pt-Pd/C catalyst and Pt-Ir/C catalyst.
Specifically, the thickness of the anode antitoxic layer 12 is 1 μm to 3 μm. The sum of the loading of Ru, rh, pd and Ir in the anode anti-poison layer 12 was 0.02mg/cm 2～0.06mg/cm2. The mass percentage content of Pt in the first catalyst in the anode antitoxic layer 12 is 20% -60%.
In some of these embodiments, the anode catalytic layer 13 includes a second ionomer and a second catalyst supported on the second ionomer; the main chain structure of the second ionic polymer is- (CF 2-CF)x(CF2-CF2)y - (wherein y/x is 5.8-7.0), the side chain structure of the second ionic polymer is-O (CF 2)nSO3 H wherein n is 2-4), the EW value of the second ionic polymer is 830-1000 g/eq, and the second catalyst is one or more of Pt/C catalyst, pt-Co/C catalyst and Pt-Ni/C catalyst.
By forming the anode catalytic layer 13 by using the second ionic polymer having the above-described main chain molecular structure and side chain sulfonic acid end molecular structure, the proton transfer rate in the anode catalytic layer 13 can be effectively improved, thereby improving the performance of the fuel cell.
In some specific examples, the mass percentage content of Pt in the second catalyst of the anode catalytic layer 13 is 20% to 60%, and the loading amount of Pt in the anode catalytic layer 13 is 0.05mg/cm 2～0.1mg/cm2.
In some of these embodiments, the cathode catalytic layer 15 includes a third ionomer and a third catalyst supported on the third ionomer; the main chain structure of the third ionic polymer is- (CF 2-CF)x(CF2-CF2)y - (wherein y/x is 4.2-6.0), the side chain structure is-O (CF 2)nSO3 H, wherein n is 1-3), the EW value of the third ionic polymer is 750-860 g/eq, the third catalyst is one or more of Pt/C catalyst, pt-Co/C catalyst and Pt-Ni/C catalyst, the mass percentage of Pt in the third catalyst is 40-60%, and the loading amount of Pt in the cathode catalytic layer 15 is 0.1mg/cm 2～0.35mg/cm2.
By forming the cathode catalytic layer 15 by using the third ionic polymer having the main chain molecular structure and the side chain sulfonic acid end molecular structure, the permeability of oxygen and the transmission rate of generated water in the cathode catalytic layer 15 can be effectively improved, and the performance of the fuel cell can be further improved.
Referring to fig. 1, in one specific example, a sealing layer 17 covers at a lower surface edge of the anode anti-poison layer 12 and at an upper surface edge of the cathode catalyst layer 15, and the sealing layer 17 is capable of sealing sides of the proton membrane 14, the anode catalyst layer 13, the cathode catalyst layer 15, and the anode anti-poison layer 12. The anode gas diffusion layer 11 covers the end of the anode anti-poison layer 12 and the seal layer 17; the cathode gas diffusion layer 16 covers the end of the cathode catalytic layer 15 and the sealing layer 17.
Referring to fig. 2, in another specific example, a sealing layer 17 covers the side of the anode anti-poison layer 12 and covers the upper surface edge of the cathode catalyst layer 15, and the sealing layer 17 can seal the side of the proton membrane 14, the anode catalyst layer 13, the cathode catalyst layer 15, and the anode anti-poison layer 12. The anode gas diffusion layer 11 covers the end of the anode anti-poison layer 12 and the seal layer 17; the cathode gas diffusion layer 16 covers the end of the cathode catalytic layer 15 and the sealing layer 17.
In some specific examples, the proton membrane 14 is a polymeric proton membrane, specifically a reinforced composite sulfuric acid membrane, and the proton membrane 14 has a thickness of 8 μm to 15 μm. The sealing layer 17 is made of polyethylene naphthalate (PEN) or Polyimide (PI), and the thickness of the sealing layer 17 is 45-75 μm. By the sealing layer 17 of the above-described material and thickness, the side surfaces of the plasma membrane 14, the anode catalyst layer 13, the cathode catalyst layer 15, and the anode anti-poison layer 12 can be effectively sealed.
In some of these embodiments, the thickness of the anode gas diffusion layer 11 in the membrane electrode 10 is greater than the thickness of the cathode gas diffusion layer 16; the sum of the thicknesses of the anode catalytic layer 13, the anode poison resistant layer 12 and the anode gas diffusion layer 11 is smaller than the sum of the thicknesses of the cathode catalytic layer 15 and the cathode gas diffusion layer 16.
In the above manner, the thickness of the anode gas diffusion layer 11, the thickness of the anode catalytic layer 13, the thickness of the cathode catalytic layer 15, the thickness of the anode anti-poison layer 12 and the thickness of the cathode gas diffusion layer 16 are anchored and interlocked; the water generated on the cathode side of the membrane electrode 10 can permeate to the anode side, the-OH amount in the anode anti-poison layer 12 can be increased, and the three-phase interface structure optimization of the catalyst in the anode catalytic layer 13, the proton membrane 14 and the fuel is facilitated, so that the ohmic polarization and concentration polarization of the fuel cell are reduced, and the power density and durability of the fuel cell are remarkably improved.
Compared with the traditional commercial membrane electrode, the membrane electrode 10 has the initial power density of 2200mA/cm 2 @0.67V under the simulated anode hydrogen composition of 99.99% +100ppm CO, and has the voltage attenuation of only 25mV and the ECSA attenuation of only 28% under the 2.0A/cm 2 after the durability test of a 6000q carrier; after the catalyst is durable by 50000q, the voltage attenuation at 0.8A/cm 2 is 20mV, and the ECSA attenuation is 35%, so that the battery performance and durability performance are better. The membrane electrode 10 is applied to a proton membrane fuel cell, can obviously improve the CO adaptability of the fuel cell, and meets the requirements of commercial vehicles on dynamic property and durability.
The membrane electrode 10 of the present invention can be prepared by the following method:
Preparing anode catalytic layer slurry: the anode catalytic layer slurry comprises a second ionic polymer, a second catalyst, and a second solvent; wherein the second solvent is one or more of water, isopropanol, n-propanol, ethanol and ethyl acetate; the mass ratio of the second catalyst to the second ionic polymer is (0.25-0.46): 1, the solid content of the anode catalytic layer slurry is 1.0-1.5%.
Preparing cathode catalytic layer slurry: the cathode catalytic layer slurry comprises a third ionic polymer, a third catalyst, and a third solvent; wherein the third solvent is one or more of water, isopropanol, n-propanol and ethanol; the solid content of the cathode catalytic layer slurry is 1.8% -2.5%.
Preparing anode anti-poison layer slurry: the anode anti-poison layer slurry comprises a first ionic polymer, a first catalyst and a first solvent, wherein the first solvent is one or more of water, isopropanol, n-propanol and ethanol, and the solid content of the anode anti-poison layer slurry is 1.0-1.5%.
Coating the cathode catalytic layer slurry and the anode catalytic layer slurry on two opposite surfaces of the proton membrane 14 respectively to form a cathode catalytic layer 15 and an anode catalytic layer 13 respectively; coating anode anti-poison layer slurry on the anode catalytic layer 13 to form an anode anti-poison layer 12; sealing the side surfaces of the proton membrane 14, the anode catalytic layer 13, the cathode catalytic layer 15 and the anode anti-poison layer 12 by adopting a sealing frame to form a sealing layer 17; an anode gas diffusion layer 11 is encapsulated on the anode anti-poison layer 12, and a cathode gas diffusion layer 16 is encapsulated on the cathode catalytic layer 15; thereby forming the membrane electrode 10 of the present invention.
Specifically, the cathode catalytic layer slurry, the anode catalytic layer slurry and the anode anti-poison layer slurry can be respectively coated on the corresponding film layers in an ultrasonic spraying mode; the anode gas diffusion layer 11 and the cathode gas diffusion layer 16 may be encapsulated on the respective film layers by a thermocompression encapsulation method. The anode gas diffusion layer 11 and the cathode gas diffusion layer 16 may be conventional gas diffusion layers.
The present invention will be further described with reference to specific examples and comparative examples, which should not be construed as limiting the scope of the invention.
Example 1:
the preparation method of the membrane electrode 10 according to an embodiment of the present invention includes the following steps:
Anode catalytic layer 13 slurry configuration: 0.4g of Pt/C catalyst with the mass fraction of 40%; 1.0g of water; a second ionomer having y/x of 5.8, n of 2, and an EW value of 1000 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain anode catalytic layer 13 slurry; wherein the main chain structure of the second ionic polymer is- (CF 2-CF)x(CF2-CF2)y - (CF 2)nSO3 H; the side chain structure is-O;
Cathode catalytic layer 15 slurry configuration: 0.4g of Pt-Ni/C catalyst with the mass fraction of 52 percent; 1.0g of water; a third ionomer having y/x of 4.2, n of 1, and an EW value of 750 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain cathode catalytic layer 15 slurry; wherein the third ionic polymer has a main chain structure of- (CF 2-CF)x(CF2-CF2)y) -and a side chain structure of-O (CF 2)nSO3 H;
Anode antitoxic layer 12 slurry configuration: 0.4g of Pt-Ru/C catalyst with the mass fraction of 20 percent; 1.0g of water; a first ionomer having y/x of 7.0, n of 4, and an EW value of 1000 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain anode antitoxic layer 12 slurry; wherein the main chain structure of the first ionic polymer is- (CF 2-CF)x(CF2-CF2)y -) and the side chain structure is-O (CF 2)nSO3 H.
The cathode catalyst layer 15 slurry and the anode catalyst layer 13 slurry disposed as described above are applied to the opposite surfaces of the proton membrane 14 by ultrasonic spraying. Wherein the thickness of the cathode catalytic layer 15 is 15 μm and the platinum loading is 0.2mg/cm 2; the anode catalytic layer 13 had a thickness of 5 μm and a platinum loading of 0.05mg/cm 2.
The anode anti-poison layer 12 slurry is coated on the anode catalytic layer 13 by adopting an ultrasonic spraying mode, the thickness of the anode anti-poison layer 12 is 2 mu m, and the Ru loading capacity is 20 mu g/cm 2.
Sealing frames made of PEN with the thickness of 45 μm are respectively sealed at the edges of the anode anti-poison layer 12 and the cathode catalytic layer 15 to form a sealing layer 17. And the sealing layer 17 seals the sides of the proton membrane 14, the anode catalytic layer 13, the cathode catalytic layer 15 and the anode anti-poison layer 12.
And respectively hot-pressing and packaging an anode gas diffusion layer 11 with the thickness of 251 mu m and a cathode gas diffusion layer 16 with the thickness of 248 mu m on the anode anti-poison layer 12 and the cathode catalytic layer 15 to obtain the membrane electrode 10.
The membrane electrode 10 prepared in example 1 was assembled into a fuel cell, and a single cell test was performed. Wherein, table 1 is the endurance test conditions of the 6000-turn carrier of the battery; table 2 shows the durability test results of 6000-cycle battery carriers; table 3 is the battery 50000 cycle carrier durability test conditions; table 4 shows the test results of the 50000-cycle carrier durability test of the battery.
Table 1 6000 ring carrier durability test conditions
Table 2 6000 ring carrier durability test results
Table 3 50000 circles of catalyst durability test conditions
Table 4 50000 results of catalyst durability test
As can be seen from the data in tables 2 and 4, the fuel cell obtained by using the membrane electrode 10 prepared in example 1 of the present invention has higher initial performance, after 50000 cycles of endurance test, the 0.68V performance decay is only 6%, the electrochemical active area ECSA decay is only 28.2%, and excellent adaptability to CO and endurance performance are exhibited. Can meet the use requirement of commercial vehicles on durability. Exhibits excellent adaptability to CO and durability.
Example 2:
the preparation method of the membrane electrode 10 according to an embodiment of the present invention includes the following steps:
Anode catalytic layer 13 slurry configuration: 0.4g of Pt/C catalyst with mass fraction of 20%; 1.0g of water; a second ionomer having y/x of 7.0, n of 4, and an EW value of 830 g/eq; 30g of normal propyl alcohol is mixed, dispersed for 15 minutes in Primix dispersing equipment at a peripheral speed of 15m/s and a rotating speed of 7000rpm, and the temperature of a cooler is 5 ℃ to obtain slurry of the anode catalytic layer 13; wherein the main chain structure of the second ionic polymer is- (CF 2-CF)x(CF2-CF2)y - (CF 2)nSO3 H; the side chain structure is-O;
Cathode catalytic layer 15 slurry configuration: 0.4g of Pt-Co/C catalyst with the mass fraction of 52 percent; 1.0g of water; a third ionomer having y/x of 4.2, n of 1, and an EW value of 750 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain cathode catalytic layer 15 slurry; wherein the third ionic polymer has a main chain structure of- (CF 2-CF)x(CF2-CF2)y) -and a side chain structure of-O (CF 2)nSO3 H;
Anode antitoxic layer 12 slurry configuration: 0.4g of Pt-Rd/C catalyst with mass fraction of 20%; 1.0g of water; a first ionomer having y/x of 6, n of 3, and an EW value of 1000 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain anode antitoxic layer 12 slurry; wherein the main chain structure of the first ionic polymer is- (CF 2-CF)x(CF2-CF2)y -) and the side chain structure is-O (CF 2)nSO3 H.
The slurry of the cathode catalyst layer 15 and the slurry of the anode catalyst layer 13, which were disposed as described above, were coated on the opposite surfaces of the proton membrane 14 having a thickness of 15 μm by slit extrusion. Wherein the thickness of the cathode catalytic layer 15 is 12 μm and the platinum loading is 0.15mg/cm 2; the anode catalytic layer 13 had a thickness of 5 μm and a platinum loading of 0.06mg/cm 2.
The anode anti-poison layer 12 slurry is coated on the anode catalytic layer 13 by adopting an ultrasonic spraying mode, the thickness of the anode anti-poison layer 12 is 3 mu m, and the Pd loading capacity is 40 mu g/cm 2.
Sealing frames with the thickness of 45 mu m and PI are respectively sealed at the edges of the anode anti-poison layer 12 and the cathode catalytic layer 15 to form a sealing layer 17. And the sealing layer 17 seals the sides of the proton membrane 14, the anode catalytic layer 13, the cathode catalytic layer 15 and the anode anti-poison layer 12.
And respectively hot-pressing and packaging an anode gas diffusion layer 11 with the thickness of 180 mu m and a cathode gas diffusion layer 16 with the thickness of 178 mu m on the anode anti-poison layer 12 and the cathode catalytic layer 15 to obtain the membrane electrode 10.
The membrane electrode 10 prepared in example 2 was assembled into a fuel cell, and a single cell test was performed. Wherein, table 5 is a battery 6000-turn carrier endurance test result, and test conditions are the same as example 1 (as shown in table 1); table 6 shows the results of the 50000-cycle endurance test of the battery, and the test conditions were the same as in example 1 (shown in Table 3).
Table 5 results of 6000-turn carrier durability test
Table 6 50000 results of catalyst durability test
As can be seen from the data in tables 5 and 6, the fuel cell obtained by using the membrane electrode 10 prepared in example 2 of the present invention has higher initial performance, after 50000 cycles of endurance test, the 0.68V performance decay is only 3%, the electrochemical active area ECSA decay is only 29.2%, and excellent adaptability to CO and endurance performance are exhibited. Can meet the use requirement of commercial vehicles on durability.
Example 3:
the preparation method of the membrane electrode 10 according to an embodiment of the present invention includes the following steps:
Anode catalytic layer 13 slurry configuration: 0.4g of Pt-Co/C catalyst with the mass fraction of 40 percent; 1.0g of water; a second ionomer having y/x of 6.0, n of 3, and an EW value of 850 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain anode catalytic layer 13 slurry; wherein the main chain structure of the second ionic polymer is- (CF 2-CF)x(CF2-CF2)y - (CF 2)nSO3 H; the side chain structure is-O;
cathode catalytic layer 15 slurry configuration: 0.4g of Pt-Co/C catalyst with the mass fraction of 52 percent; 1.0g of water; a third ionomer having y/x of 4.8, n of 2, and an EW value of 800 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain cathode catalytic layer 15 slurry; wherein the third ionic polymer has a main chain structure of- (CF 2-CF)x(CF2-CF2)y) -and a side chain structure of-O (CF 2)nSO3 H;
anode antitoxic layer 12 slurry configuration: 0.4g of Pt-Rh/C catalyst with the mass fraction of 20%; 1.0g of water; a first ionomer having y/x of 6.7, n of 4, and an EW value of 850 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain anode antitoxic layer 12 slurry; wherein the main chain structure of the first ionic polymer is- (CF 2-CF)x(CF2-CF2)y -) and the side chain structure is-O (CF 2)nSO3 H.
The cathode catalyst layer 15 slurry and the anode catalyst layer 13 slurry disposed as described above are applied to the opposite surfaces of the proton membrane 14 by ultrasonic spraying. Wherein the thickness of the cathode catalytic layer 15 is 15 μm and the platinum loading is 0.1mg/cm 2; the anode catalytic layer 13 had a thickness of 5 μm and a platinum loading of 0.08mg/cm 2.
The anode anti-poison layer 12 slurry is coated on the anode catalytic layer 13 by adopting an ultrasonic spraying mode, the thickness of the anode anti-poison layer 12 is 1 mu m, and the Ru loading capacity is 20 mu g/cm 2.
Sealing frames made of PEN with the thickness of 45 μm are respectively sealed at the edges of the anode anti-poison layer 12 and the cathode catalytic layer 15 to form a sealing layer 17. And the sealing layer 17 seals the sides of the proton membrane 14, the anode catalytic layer 13, the cathode catalytic layer 15 and the anode anti-poison layer 12.
And respectively hot-pressing and packaging an anode gas diffusion layer 11 with the thickness of 251 mu m and a cathode gas diffusion layer 16 with the thickness of 248 mu m on the anode anti-poison layer 12 and the cathode catalytic layer 15 to obtain the membrane electrode 10.
The fuel cell obtained by using the membrane electrode 10 prepared in example 3 of the present invention exhibited excellent adaptability to CO and durability.
Example 4:
the preparation method of the membrane electrode 10 according to an embodiment of the present invention includes the following steps:
Anode catalytic layer 13 slurry configuration: 0.4g of Pt-Ni/C catalyst with the mass fraction of 40 percent; 1.0g of water; a second ionomer having y/x of 6.0, n of 2, and an EW value of 900 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain anode catalytic layer 13 slurry; wherein the main chain structure of the second ionic polymer is- (CF 2-CF)x(CF2-CF2)y - (CF 2)nSO3 H; the side chain structure is-O;
Cathode catalytic layer 15 slurry configuration: 0.4g of Pt/C catalyst with the mass fraction of 52%; 1.0g of water; a third ionomer having y/x of 5.0, n of 3, and an EW value of 820 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain cathode catalytic layer 15 slurry; wherein the third ionic polymer has a main chain structure of- (CF 2-CF)x(CF2-CF2)y) -and a side chain structure of-O (CF 2)nSO3 H;
Anode antitoxic layer 12 slurry configuration: 0.4g of Pt-Pd/C catalyst with the mass fraction of 20%; 1.0g of water; a first ionomer having y/x of 5.8, n of 2, and an EW value of 880 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain anode antitoxic layer 12 slurry; wherein the main chain structure of the first ionic polymer is- (CF 2-CF)x(CF2-CF2)y -) and the side chain structure is-O (CF 2)nSO3 H.
The cathode catalyst layer 15 slurry and the anode catalyst layer 13 slurry disposed as described above are applied to the opposite surfaces of the proton membrane 14 by ultrasonic spraying. Wherein the thickness of the cathode catalytic layer 15 is 15 μm and the platinum loading is 0.3mg/cm 2; the anode catalytic layer 13 had a thickness of 5 μm and a platinum loading of 0.1mg/cm 2.
The anode anti-poison layer 12 slurry is coated on the anode catalytic layer 13 by adopting an ultrasonic spraying mode, the thickness of the anode anti-poison layer 12 is 2 mu m, and the Ru loading capacity is 20 mu g/cm 2.
Sealing frames made of PEN with the thickness of 45 μm are respectively sealed at the edges of the anode anti-poison layer 12 and the cathode catalytic layer 15 to form a sealing layer 17. And the sealing layer 17 seals the sides of the proton membrane 14, the anode catalytic layer 13, the cathode catalytic layer 15 and the anode anti-poison layer 12.
And respectively hot-pressing and packaging an anode gas diffusion layer 11 with the thickness of 251 mu m and a cathode gas diffusion layer 16 with the thickness of 248 mu m on the anode anti-poison layer 12 and the cathode catalytic layer 15 to obtain the membrane electrode 10.
The fuel cell obtained by using the membrane electrode 10 prepared in example 4 of the present invention exhibited excellent adaptability to CO and durability.
Example 5:
the preparation method of the membrane electrode 10 according to an embodiment of the present invention includes the following steps:
Anode catalytic layer 13 slurry configuration: 0.4g of Pt-Ni/C catalyst with the mass fraction of 40 percent; 1.0g of water; a second ionomer having y/x of 6.5, n of 3, and an EW value of 980 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain anode catalytic layer 13 slurry; wherein the main chain structure of the second ionic polymer is- (CF 2-CF)x(CF2-CF2)y - (CF 2)nSO3 H; the side chain structure is-O;
Cathode catalytic layer 15 slurry configuration: 0.4g of Pt-Ni/C catalyst with the mass fraction of 52 percent; 1.0g of water; a third ionomer having y/x of 5.2, n of 3, and an EW value of 860 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain cathode catalytic layer 15 slurry; wherein the third ionic polymer has a main chain structure of- (CF 2-CF)x(CF2-CF2)y) -and a side chain structure of-O (CF 2)nSO3 H;
Anode antitoxic layer 12 slurry configuration: 0.4g of Pt-Ru/C catalyst with the mass fraction of 20 percent; 1.0g of water; a first ionomer having y/x of 6.8, n of 4, and an EW value of 900 g/eq; mixing 30g of n-propanol, and dispersing in ball milling equipment for 8 hours to obtain anode antitoxic layer 12 slurry; wherein the main chain structure of the first ionic polymer is- (CF 2-CF)x(CF2-CF2)y -) and the side chain structure is-O (CF 2)nSO3 H.
The cathode catalyst layer 15 slurry and the anode catalyst layer 13 slurry disposed as described above are applied to the opposite surfaces of the proton membrane 14 by ultrasonic spraying. Wherein the thickness of the cathode catalytic layer 15 is 15 μm and the platinum loading is 0.35mg/cm 2; the anode catalytic layer 13 had a thickness of 5 μm and a platinum loading of 0.09mg/cm 2.
The anode anti-poison layer 12 slurry is coated on the anode catalytic layer 13 by adopting an ultrasonic spraying mode, the thickness of the anode anti-poison layer 12 is 2 mu m, and the Ru loading capacity is 20 mu g/cm 2.
Sealing frames made of PEN with the thickness of 45 μm are respectively sealed at the edges of the anode anti-poison layer 12 and the cathode catalytic layer 15 to form a sealing layer 17. And the sealing layer 17 seals the sides of the proton membrane 14, the anode catalytic layer 13, the cathode catalytic layer 15 and the anode anti-poison layer 12.
And respectively hot-pressing and packaging an anode gas diffusion layer 11 with the thickness of 251 mu m and a cathode gas diffusion layer 16 with the thickness of 248 mu m on the anode anti-poison layer 12 and the cathode catalytic layer 15 to obtain the membrane electrode 10.
The fuel cell obtained by using the membrane electrode 10 prepared in example 5 of the present invention exhibited excellent adaptability to CO and durability.
Comparative example 1:
a method of producing a membrane electrode 10, which is substantially the same as in example 1, differs from example 1 only in that: an anode antitoxic layer 12 is not provided between the anode catalytic layer 13 and the anode gas diffusion layer 11.
The membrane electrode 10 prepared in comparative example 1 was assembled into a fuel cell, and a single cell test was performed. Wherein, table 7 is a battery 6000-turn carrier endurance test result, and test conditions are the same as example 1 (as shown in table 1); table 8 shows the results of the 50000-cycle endurance test of the battery, and the test conditions were the same as in example 1 (shown in Table 3).
TABLE 7 results of 6000-turn Carrier durability test
Table 8 50000 results of catalyst durability test
As can be seen from the data in tables 7 and 8, the fuel cell obtained using the membrane electrode 10 prepared in comparative example 1, in which the anode anti-poison layer 12 was omitted, had little initial performance change under the idle operating condition of 0.8V, but had greatly reduced initial performance under the rated operating condition of 0.68V. The open circuit voltage performance variation is not obvious. The idle speed working condition and the rated working condition after 50000 circles of acceleration have large performance attenuation amplitude, and the performance attenuation amplitude is reduced by 12.5 percent, so that the requirements of commercial vehicles on long service life cannot be met.
Comparative example 2:
A method of producing a membrane electrode 10, which is substantially the same as in example 1, differs from example 1 only in that: the thickness relationship between the anode gas diffusion layer 11 and the cathode gas diffusion layer 16 is different; the thickness relationship among the anode catalytic layer 13, the anode poison resistant layer 12, the anode gas diffusion layer 11, the cathode catalytic layer 15, and the cathode gas diffusion layer 16 is different.
Specifically, the thickness of the anode gas diffusion layer 11 in comparative example 2 was 168 μm, the thickness of the cathode gas diffusion layer 16 was 172 μm, and the thickness of the anode gas diffusion layer 11 was smaller than the thickness of the cathode gas diffusion layer 16; the thickness of the anode catalytic layer 15 was 5 μm; the sum of the thicknesses of the anode catalytic layer 13, the anode anti-poison layer 12 and the anode gas diffusion layer 11 is 176 μm, which is greater than 175 μm of the sum of the thicknesses of the cathode catalytic layer 15 and the cathode gas diffusion layer 16.
The membrane electrode 10 prepared in comparative example 2 was assembled into a fuel cell, and a single cell test was performed. Wherein, table 9 is a battery 6000-turn carrier endurance test result, and test conditions are the same as example 1 (as shown in table 1); table 10 shows the results of the 50000-cycle endurance test of the battery, and the test conditions were the same as in example 1 (see Table 3).
Table 9 6000 ring carrier durability test results
Table 10 50000 results of catalyst durability test
As can be seen from the data in tables 9 and 10, the fuel cell obtained using the membrane electrode 10 prepared in comparative example 2 had little initial performance change at 0.8V at idle, but had a significant decrease in initial performance at 0.68V at rated. The open circuit voltage performance variation is not obvious. The idle speed working condition and the rated working condition after 50000 circles of acceleration have large performance attenuation amplitude, the attenuation amplitude is reduced by 11%, and the requirement of the commercial vehicle on long service life cannot be met.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (13)
1. The membrane electrode is characterized by comprising an anode gas diffusion layer, an anode anti-poison layer, an anode catalytic layer, a proton membrane, a cathode catalytic layer, a cathode gas diffusion layer and a sealing layer, wherein the anode catalytic layer and the cathode catalytic layer are respectively arranged on two opposite surfaces of the proton membrane, the anode anti-poison layer is arranged on the anode catalytic layer, the sealing layer seals the side surfaces of the proton membrane, the anode catalytic layer, the cathode catalytic layer and the anode anti-poison layer, the anode gas diffusion layer is arranged on the anode anti-poison layer, and the cathode gas diffusion layer is arranged on the cathode catalytic layer;
The anode antitoxic layer comprises a first ionic polymer and a first catalyst supported on the first ionic polymer; the main chain structure of the first ionic polymer is- (CF 2-CF）x（CF2-CF2）y -, wherein y/x is 5.8-7.0; the side chain structure of the first ionic polymer is-O (CF 2）nSO3 H, wherein n is 2-4; and the EW value of the first ionic polymer is 830 g/eq-1000 g/eq;
The first catalyst is one or more of a Pt-Ru/C catalyst, a Pt-Rh/C catalyst, a Pt-Pd/C catalyst and a Pt-Ir/C catalyst; the sum of the loading amounts of Ru, rh, pd and Ir in the anode antitoxic layer is 0.02 mg/cm 2~0.06 mg/cm2; the mass percentage of Pt in the first catalyst is 20% -60%;
The thickness of the anode gas diffusion layer is greater than the thickness of the cathode gas diffusion layer;
The sum of the thicknesses of the anode catalytic layer, the anode anti-poison layer, and the anode gas diffusion layer is less than the sum of the thicknesses of the cathode catalytic layer and the cathode gas diffusion layer.
2. The membrane electrode of claim 1, wherein the anode antitoxic layer has a thickness of 1 μm to 3 μm.
3. The membrane electrode of claim 1, wherein the anode catalytic layer comprises a second ionomer and a second catalyst supported on the second ionomer; the main chain structure of the second ionic polymer is- (CF 2-CF）x（CF2-CF2）y -, wherein y/x is 5.8-7.0), the side chain structure of the second ionic polymer is-O (CF 2）nSO3 H, wherein n is 2-4, and the EW value of the second ionic polymer is 830 g/eq-1000 g/eq.
4. The membrane electrode according to claim 3, wherein the second catalyst is one or more of Pt/C catalyst, pt-Co/C catalyst, pt-Ni/C catalyst; the mass percentage of Pt in the second catalyst is 20% -60%, and the loading amount of Pt in the anode catalytic layer is 0.05 mg/cm 2~0.1 mg/cm2.
5. The membrane electrode of claim 1, wherein the cathode catalytic layer comprises a third ionomer and a third catalyst supported on the third ionomer; the main chain structure of the third ionic polymer is- (CF 2-CF）x（CF2-CF2）y -, wherein y/x is 4.2-6.0), the side chain structure is-O (CF 2）nSO3 H, wherein n is 1-3, and the EW value of the third ionic polymer is 750 g/eq-860 g/eq.
6. The membrane electrode according to claim 5, wherein the third catalyst is one or more of Pt/C catalyst, pt-Co/C catalyst, pt-Ni/C catalyst; the mass percentage of Pt in the third catalyst is 40% -60%, and the loading amount of Pt in the cathode catalytic layer is 0.1 mg/cm 2~0.35 mg/cm2.
7. The membrane electrode of claim 1, wherein the proton membrane is an enhanced composite sulfuric acid membrane, and the thickness of the proton membrane is 8-15 μm.
8. The membrane electrode according to claim 1, wherein the material of the sealing layer is polyethylene naphthalate or polyimide, and the thickness of the sealing layer is 45 μm to 75 μm.
9. The preparation method of the membrane electrode is characterized by comprising the following steps:
Respectively coating cathode catalytic layer slurry and anode catalytic layer slurry on two opposite surfaces of a proton membrane to respectively form a cathode catalytic layer and an anode catalytic layer;
coating anode anti-poison layer slurry on the anode catalytic layer to form an anode anti-poison layer;
Sealing the side surfaces of the proton membrane, the anode catalytic layer, the cathode catalytic layer and the anode antitoxic layer by adopting a sealing frame to form a sealing layer; and
Packaging an anode gas diffusion layer on the anode anti-poison layer, and packaging a cathode gas diffusion layer on the cathode catalytic layer;
Wherein the anode antitoxic layer comprises a first ionic polymer and a first catalyst supported on the first ionic polymer; the main chain structure of the first ionic polymer is- (CF 2-CF）x（CF2-CF2）y -, wherein y/x is 5.8-7.0; the side chain structure of the first ionic polymer is-O (CF 2）nSO3 H, wherein n is 2-4; and the EW value of the first ionic polymer is 830 g/eq-1000 g/eq;
The first catalyst is one or more of a Pt-Ru/C catalyst, a Pt-Rh/C catalyst, a Pt-Pd/C catalyst and a Pt-Ir/C catalyst; the sum of the loading amounts of Ru, rh, pd and Ir in the anode antitoxic layer is 0.02 mg/cm 2~0.06 mg/cm2; the mass percentage of Pt in the first catalyst is 20% -60%;
The thickness of the anode gas diffusion layer is greater than the thickness of the cathode gas diffusion layer;
The sum of the thicknesses of the anode catalytic layer, the anode anti-poison layer, and the anode gas diffusion layer is less than the sum of the thicknesses of the cathode catalytic layer and the cathode gas diffusion layer.
10. The method of producing a membrane electrode according to claim 9, wherein the anode catalytic layer slurry includes a second ionic polymer, a second catalyst, and a second solvent; the second solvent is one or more of water, isopropanol, n-propanol, ethanol and ethyl acetate; the mass ratio of the second catalyst to the second ionic polymer is (0.25-0.46): 1, wherein the solid content of the anode catalytic layer slurry is 1.0% -1.5%.
11. The method of producing a membrane electrode according to claim 9, wherein the cathode catalytic layer slurry comprises a third ionic polymer, a third catalyst, and a third solvent; the third solvent is one or more of water, isopropanol, n-propanol and ethanol; the solid content of the cathode catalytic layer slurry is 1.8% -2.5%.
12. The method for preparing a membrane electrode according to claim 9, wherein the anode anti-poison layer slurry comprises a first ionic polymer, a first catalyst and a first solvent, the first solvent is one or more of water, isopropanol, n-propanol and ethanol, and the solid content of the anode anti-poison layer slurry is 1.0% -1.5%.
13. A fuel cell comprising the membrane electrode according to any one of claims 1 to 8 or comprising the membrane electrode produced by the production method according to any one of claims 9 to 12.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104205458A (en) * | 2011-12-20 | 2014-12-10 | Ucl商业有限公司 | Fuel cell |
| CN112751045A (en) * | 2019-10-31 | 2021-05-04 | 现代自动车株式会社 | Fuel cell catalyst composite and method of manufacturing electrode including the same |
| CN114420944A (en) * | 2022-01-19 | 2022-04-29 | 一汽解放汽车有限公司 | Fuel cell membrane electrode, preparation method thereof and fuel cell |
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| CN100592563C (en) * | 2003-09-26 | 2010-02-24 | 保罗·谢勒学院 | Membrane electrode assembly (MEA), method for its preparation, and method for the preparation of membranes to be assembled into the MEA |
| JP2019518306A (en) * | 2016-05-02 | 2019-06-27 | サイモン フレーザー ユニバーシティー | Energy conversion device containing stable ionene |
| CN110600755B (en) * | 2019-09-06 | 2021-03-19 | 宁波柔创纳米科技有限公司 | A kind of coating method and battery of carbon support material loaded with metal catalyst |
| KR20210124780A (en) * | 2020-04-07 | 2021-10-15 | 현대자동차주식회사 | Polymer electrolyte membrane for fuel cell and method of manufacturing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104205458A (en) * | 2011-12-20 | 2014-12-10 | Ucl商业有限公司 | Fuel cell |
| CN112751045A (en) * | 2019-10-31 | 2021-05-04 | 现代自动车株式会社 | Fuel cell catalyst composite and method of manufacturing electrode including the same |
| CN114420944A (en) * | 2022-01-19 | 2022-04-29 | 一汽解放汽车有限公司 | Fuel cell membrane electrode, preparation method thereof and fuel cell |
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