CN114744219B - Preparation method of gas diffusion layer and gas diffusion layer - Google Patents
Preparation method of gas diffusion layer and gas diffusion layer Download PDFInfo
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- CN114744219B CN114744219B CN202210328727.7A CN202210328727A CN114744219B CN 114744219 B CN114744219 B CN 114744219B CN 202210328727 A CN202210328727 A CN 202210328727A CN 114744219 B CN114744219 B CN 114744219B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- 238000010438 heat treatment Methods 0.000 claims abstract description 44
- 238000002156 mixing Methods 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
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- 238000001035 drying Methods 0.000 claims abstract description 17
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- 239000007789 gas Substances 0.000 claims description 58
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
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- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
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- 235000021017 pears Nutrition 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
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- 239000000463 material Substances 0.000 abstract description 6
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
-
- 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
- H01M4/8647—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
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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- 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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- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention particularly relates to a preparation method of a gas diffusion layer and the gas diffusion layer, belonging to the technical field of proton exchange membrane fuel cells. A preparation method of a gas diffusion layer comprises the steps of mixing conductive carbon black, a water repellent, a dispersing agent and an anti-icing agent to obtain microporous layer slurry; obtaining a carbon paper substrate; and coating the microporous layer slurry on the surface of the carbon paper substrate, drying, and then carrying out heat treatment in an inert atmosphere to obtain the gas diffusion layer. The micron structure in the microporous layer of the gas diffusion layer prepared by the method has a continuous three-dimensional porous skeleton, has the structural characteristics of larger specific surface area, a large number of mesopores and the like, ensures that the gas diffusion layer can stably adsorb air, fills air on the surface of the material, reduces the free energy on the surface of the material, and ensures that the gas diffusion layer has excellent hydrophobicity and ice resistance.
Description
Technical Field
The invention belongs to the technical field of proton exchange membrane fuel cells, and particularly relates to a preparation method of a gas diffusion layer and the gas diffusion layer.
Background
The proton exchange membrane fuel cell generates water by the reaction of oxygen and hydrogen, and directly converts hydrogen energy into electric energy. The reaction component is formed by taking Pt/C as a catalyst and taking a Polymer Electrolyte Membrane (PEM) as a carrier for conducting protons. The electric energy efficiency is high (about 55%), the power density is high, the weight is light, the electric energy is simple and easy to use, the starting is rapid, and the like, so that the electric energy is an ideal choice in the fields of portable application, power stations, automobiles and the like.
The fuel cell mainly comprises a membrane electrode and a bipolar plate, wherein the membrane electrode comprises a catalytic layer and a gas diffusion layer. The gas diffusion layer is composed of a basal layer and a microporous layer, and has the main effects of transmitting reaction gas into the catalytic layer, timely discharging water generated by reaction, supporting the catalytic layer, timely radiating heat released by reaction and transmitting electrons. The gas diffusion layer acts as the primary site for gas and water transport and its degradation is one of the important factors affecting proton exchange membrane fuel cell life.
The gas diffusion layer has the characteristics of brittleness, easy breakage and the like, and the porous structure thereof makes it have a certain water-retaining property, and the internal pores thereof inevitably retain a certain amount of water. Under the working condition of the vehicle, the fuel cell inevitably needs to be subjected to low-temperature cold start, under the condition, water in the pores of the gas diffusion layer is easy to freeze, and a reaction gas transmission channel is blocked, so that the fuel cell fails to start. On the other hand, frost heaving stress generated by water solidification damages the gas diffusion layer and damages the carbon fiber structure, thereby degrading various performances such as drainage, gas transmission and the like of the gas diffusion layer, degrading the performance of the fuel cell and shortening the service life.
Disclosure of Invention
The utility model aims at providing a gas diffusion layer, it can solve among the prior art gas diffusion layer freezing resistance poor, can't realize cold start's technical problem.
The embodiment of the invention provides a preparation method of a gas diffusion layer, which comprises the following steps:
mixing conductive carbon black, a water repellent, a dispersing agent and an anti-icing agent to obtain microporous layer slurry;
obtaining a carbon paper substrate;
coating the microporous layer slurry on the surface of the carbon paper substrate, drying, and then carrying out heat treatment in an inert atmosphere to obtain the gas diffusion layer:
wherein: the molecular formula of the anti-icing agent is as follows: (Ni, co) - (CO) 3 ) 0.5 (OH) 0.11 H 2 O。
Optionally, the volume ratio of the anti-icing agent to the conductive carbon black is 1: (4-20).
Alternatively, the raw materials of the anti-icing agent comprise CoCl 2 .6H 2 0、NiCl 2 .6H 2 O, urea and deionized water.
Optionally, the method further comprises the following steps:
CoCl is to be processed 2 .6H 2 0、NiCl 2 .6H 2 Mixing O, urea and deionized water under stirring to obtain a prefabricated liquid;
and (3) drying the prefabricated liquid in an oven to obtain the anti-icing agent.
Alternatively, coCl 2 .6H 2 0、NiCl 2 .6H 2 The mass ratio of O, urea and deionized water is (2-4) 1 (3-5):
(40-50)。
alternatively, coCl 2 .6H 2 0、NiCl 2 .6H 2 The mass ratio of O, urea and deionized water is 2:1:3:40.
Optionally, in the microporous layer slurry, the loading amount of the conductive carbon black on the surface of the carbon paper substrate is 1.0-2.5mg/cm 2 。
Optionally, in the microporous layer slurry, the mass fraction of the anti-icing agent is 5-20%.
Optionally, the conductive carbon Black comprises any one or more of acetylene Black, vulcan XC-72, black pears, carbon nanotubes, and graphene powder.
Optionally, the water repellent comprises any one or more of polytetrafluoroethylene, polyvinylidene fluoride, and copolymer of tetrafluoroethylene and ethylene.
Optionally, the dispersing agent comprises any one or more of ethanol, isopropanol, ethylene glycol and hexafluoroisopropanol.
Optionally, the mass ratio of the conductive carbon black to the dispersing agent is 1: (5-10).
Optionally, the mass percentage of the water repellent in the microporous layer slurry is 10-30%.
Optionally, the inert atmosphere is a nitrogen atmosphere.
Based on the same technical conception, the embodiment of the invention also provides a gas diffusion layer, which is prepared by adopting any one of the preparation methods of the gas diffusion layer.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
according to the preparation method of the gas diffusion layer, the micron structure in the microporous layer of the gas diffusion layer prepared by the preparation method has the structural characteristics of continuous three-dimensional porous frameworks, large specific surface area, a large number of mesopores and the like, the gas diffusion layer can stably adsorb air, the surface of the material is filled with air, the free energy of the surface of the material is reduced, and the gas diffusion layer has excellent hydrophobicity and ice resistance.
The foregoing description is only an overview of the present invention, and is intended to be implemented in accordance with the teachings of the present invention in order that the same may be more clearly understood and to make the same and other objects, features and advantages of the present invention more readily apparent.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a flow chart of a method provided by an embodiment of the present invention.
Detailed Description
The advantages and various effects of the present invention will be more clearly apparent from the following detailed description and examples. It will be understood by those skilled in the art that these specific embodiments and examples are intended to illustrate the invention, not to limit the invention.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning as commonly used in the art. Accordingly, 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. In case of conflict, the present specification will control. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention. For example, room temperature may refer to a temperature in the range of 10 to 35 ℃.
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.
The technical scheme of the embodiment of the application aims to solve the technical problems, and the overall thought is as follows:
according to an exemplary embodiment of the present invention, there is provided a method for manufacturing a gas diffusion layer, including the steps of:
s1, mixing conductive carbon black, a water repellent, a dispersing agent and an anti-icing agent to obtain microporous layer slurry.
S2, obtaining the carbon paper substrate.
And S3, coating the microporous layer slurry on the surface of the carbon paper substrate, drying, and then carrying out heat treatment in an inert atmosphere to obtain the gas diffusion layer.
Wherein: the molecular formula of the anti-icing agent is as follows: (Ni, co) - (CO) 3 ) 0.5 (OH) 0.11 H 2 O。
According to the preparation method of the gas diffusion layer, the micron structure in the microporous layer of the gas diffusion layer prepared by the preparation method has the structural characteristics of continuous three-dimensional porous frameworks, large specific surface area, a large number of mesopores and the like, the gas diffusion layer can stably adsorb air, the surface of the material is filled with air, the free energy of the surface of the material is reduced, and the gas diffusion layer has excellent hydrophobicity and ice resistance.
As an alternative embodiment, the volume ratio of the anti-icing agent to the conductive carbon black is 1: (4-20).
The reason for controlling the mass fraction of the anti-icing agent is that: excessive mass fraction of the anti-icing agent leads to excessive holes on the surface and inside of the microporous layer, and reduces the conductivity of the gas diffusion layer; the mass fraction of the anti-icing agent is too low, a large number of holes cannot be formed in the microporous layer and the inside, and the cold start resistance of the gas diffusion layer cannot be realized.
As an alternative embodiment, the starting material for the anti-icing agent comprises CoCl 2 .6H 2 0、NiCl 2 .6H 2 O, urea and deionized water.
As an alternative embodiment, the method further comprises the steps of:
s0.1, coCl 2 .6H 2 0、NiCl 2 .6H 2 And mixing O, urea and deionized water under stirring to obtain the prefabricated liquid.
S0.2, placing the prefabricated liquid into an oven for drying to obtain the anti-icing agent.
As an alternative embodiment, coCl 2 .6H 2 0、NiCl 2 .6H 2 The mass ratio of O, urea and deionized water is (2-4) 1 (3-5) 40-50.
Preferably, coCl 2 .6H 2 0、NiCl 2 .6H 2 The mass ratio of O, urea and deionized water is 2:1:3:40.
As an alternative embodiment, the loading of the conductive carbon black on the surface of the carbon paper substrate in the microporous layer slurry is 1.0-2.5mg/cm 2 。
As an alternative embodiment, the mass fraction of the anti-icing agent in the microporous layer slurry is 5-20%.
As an alternative embodiment, the conductive carbon Black includes any one or more of acetylene Black, vulcan XC-72, black pears, carbon nanotubes, and graphene powder.
As an alternative embodiment, the water repellent comprises any one or more of polytetrafluoroethylene, polyvinylidene fluoride, and copolymers of tetrafluoroethylene and ethylene.
As an alternative embodiment, the dispersant includes any one or more of ethanol, isopropanol, ethylene glycol, hexafluoroisopropanol, and combinations thereof.
As an alternative embodiment, the mass ratio of the conductive carbon black to the dispersant is 1: (5-10).
As an alternative embodiment, the mass percentage of the water repellent in the microporous layer slurry is 10-30%.
As an alternative embodiment, the inert atmosphere is a nitrogen atmosphere.
According to another exemplary embodiment of the present invention, there is provided a gas diffusion layer, which is prepared by using any one of the above methods for preparing a gas diffusion layer.
The present application will be described in detail with reference to examples, comparative examples and experimental data.
Example 1
The embodiment provides a method for preparing a gas diffusion layer, which comprises the following steps:
s0.1, 2g CoCl 2 .6H 2 0、1gNiCl 2 .6H 2 Magnetically stirring and mixing O, 3g of urea and 40g of deionized water for 30min to obtain a prefabricated liquid;
s0.2, placing the prefabricated liquid into an oven for drying to obtain the anti-icing agent, wherein the molecular formula of the anti-icing agent is as follows: (Ni, co) - (CO) 3 ) 0.5 (OH) 0.11 H 2 O。
S1, mixing conductive carbon black, a water repellent, a dispersing agent and the anti-icing agent to obtain microporous layer slurry.
S1.1, selecting isopropanol as a dispersing agent, mixing the isopropanol with water, and then adding an anti-icing agent to obtain slurry A.
S1.2, mixing ethanol with water, selecting Vulcan XC-72 as conductive carbon black, and adding the Vulcan XC-72 into an ethanol solution to obtain slurry B.
S1.3, respectively carrying out magnetic stirring and ultrasonic dispersion on the slurry A and the slurry B, then mixing, selecting 60% polytetrafluoroethylene as a water repellent, adding polytetrafluoroethylene into the mixed slurry of the slurry A and the slurry B, and carrying out magnetic stirring and autumn final mixing to obtain the microporous layer slurry.
Wherein:
the mass fraction of the anti-icing agent in the microporous layer slurry is 12%; the volume ratio of the anti-icing agent to the conductive carbon black is 1:4.
S2, obtaining the commercial carbon paper substrate.
And S3, coating the microporous layer slurry on the surface of the carbon paper substrate, drying, and then carrying out heat treatment in an inert atmosphere to obtain the gas diffusion layer.
Wherein:
the loading of the conductive carbon black on the surface of the carbon paper substrate is 1.0mg/cm 2 。
The inert atmosphere is selected from nitrogen atmosphere.
The heat treatment comprises first heating and second heating, wherein the temperature of the first heating is 60 ℃, and the time of the first heating is 2 hours; the temperature of the second heating was 200℃and the time of the second heating was 4 hours.
The embodiment also provides a gas diffusion layer which is prepared by adopting the preparation method.
Example 2
The embodiment provides a method for preparing a gas diffusion layer, which comprises the following steps:
s0.1, 2g CoCl 2 .6H 2 0、1gNiCl 2 .6H 2 Magnetically stirring and mixing O, 3g of urea and 40g of deionized water for 30min to obtain a prefabricated liquid;
s0.2, placing the prefabricated liquid into an oven for drying to obtain the anti-icing agent, wherein the molecular formula of the anti-icing agent is as follows: (Ni, co) - (CO) 3 ) 0.5 (OH) 0.11 H 2 O。
S1, mixing conductive carbon black, a water repellent, a dispersing agent and the anti-icing agent to obtain microporous layer slurry.
S1.1, selecting isopropanol as a dispersing agent, mixing the isopropanol with water, and then adding an anti-icing agent to obtain slurry A.
S1.2, mixing ethanol with water, selecting Vulcan XC-72 as conductive carbon black, and adding the Vulcan XC-72 into an ethanol solution to obtain slurry B.
S1.3, respectively carrying out magnetic stirring and ultrasonic dispersion on the slurry A and the slurry B, then mixing, selecting 60% polytetrafluoroethylene as a water repellent, adding polytetrafluoroethylene into the mixed slurry of the slurry A and the slurry B, and carrying out magnetic stirring and autumn final mixing to obtain the microporous layer slurry.
Wherein: in the microporous layer slurry, the mass fraction of the anti-icing agent is 5%; the volume ratio of the anti-icing agent to the conductive carbon black is 1:20.
S2, obtaining the commercial carbon paper substrate.
And S3, coating the microporous layer slurry on the surface of the carbon paper substrate, drying, and then carrying out heat treatment in an inert atmosphere to obtain the gas diffusion layer.
Wherein:
the loading of the conductive carbon black on the surface of the carbon paper substrate is 2.5mg/cm 2 。
The inert atmosphere is selected from nitrogen atmosphere.
The heat treatment comprises first heating and second heating, wherein the temperature of the first heating is 60 ℃, and the time of the first heating is 2 hours; the temperature of the second heating was 200℃and the time of the second heating was 4 hours.
Example 3
The embodiment provides a method for preparing a gas diffusion layer, which comprises the following steps:
s0.1, 2g CoCl 2 .6H 2 0、1gNiCl 2 .6H 2 Magnetically stirring and mixing O, 3g of urea and 40g of deionized water for 30min to obtain a prefabricated liquid;
s0.2, placing the prefabricated liquid into an oven for drying to obtain the anti-icing agent, wherein the molecular formula of the anti-icing agent is as follows: (Ni, co) - (CO) 3 ) 0.5 (OH) 0.11 H 2 O。
S1, mixing conductive carbon black, a water repellent, a dispersing agent and the anti-icing agent to obtain microporous layer slurry.
S1.1, selecting isopropanol as a dispersing agent, mixing the isopropanol with water, and then adding an anti-icing agent to obtain slurry A.
S1.2, mixing ethanol with water, selecting Vulcan XC-72 as conductive carbon black, and adding the Vulcan XC-72 into an ethanol solution to obtain slurry B.
S1.3, respectively carrying out magnetic stirring and ultrasonic dispersion on the slurry A and the slurry B, then mixing, selecting 60% polytetrafluoroethylene as a water repellent, adding polytetrafluoroethylene into the mixed slurry of the slurry A and the slurry B, and carrying out magnetic stirring and autumn final mixing to obtain the microporous layer slurry.
Wherein: in the microporous layer slurry, the mass fraction of the anti-icing agent is 8%; the volume ratio of the anti-icing agent to the conductive carbon black is 1:10.
S2, obtaining the commercial carbon paper substrate.
And S3, coating the microporous layer slurry on the surface of the carbon paper substrate, drying, and then carrying out heat treatment in an inert atmosphere to obtain the gas diffusion layer.
Wherein:
the ice-resistant agent loading on the surface of the carbon paper substrate is 2.5mg/cm 2 。
The inert atmosphere is selected from nitrogen atmosphere.
The heat treatment comprises first heating and second heating, wherein the temperature of the first heating is 60 ℃, and the time of the first heating is 2 hours; the temperature of the second heating was 200℃and the time of the second heating was 4 hours.
Example 4
The embodiment provides a method for preparing a gas diffusion layer, which comprises the following steps:
s0.1, 4g CoCl 2 .6H 2 0、1gNiCl 2 .6H 2 Magnetically stirring and mixing O, 5g of urea and 50g of deionized water for 30min to obtain a prefabricated liquid;
s0.2, placing the prefabricated liquid into an oven for drying to obtain the anti-icing agent, wherein the molecular formula of the anti-icing agent is as follows: (Ni, co) - (CO) 3 ) 0.5 (OH) 0.11 H 2 O。
S1, mixing conductive carbon black, a water repellent, a dispersing agent and the anti-icing agent to obtain microporous layer slurry.
S1.1, selecting isopropanol as a dispersing agent, mixing the isopropanol with water, and then adding an anti-icing agent to obtain slurry A.
S1.2, mixing ethanol with water, selecting Vulcan XC-72 as conductive carbon black, and adding the Vulcan XC-72 into an ethanol solution to obtain slurry B.
S1.3, respectively carrying out magnetic stirring and ultrasonic dispersion on the slurry A and the slurry B, then mixing, selecting 60% polytetrafluoroethylene as a water repellent, adding polytetrafluoroethylene into the mixed slurry of the slurry A and the slurry B, and carrying out magnetic stirring and autumn final mixing to obtain the microporous layer slurry.
Wherein: in the microporous layer slurry, the mass fraction of the anti-icing agent is 20%; the volume ratio of the anti-icing agent to the conductive carbon black is 1:4.
S2, obtaining the commercial carbon paper substrate.
And S3, coating the microporous layer slurry on the surface of the carbon paper substrate, drying, and then carrying out heat treatment in an inert atmosphere to obtain the gas diffusion layer.
Wherein:
the loading of the conductive carbon black on the surface of the carbon paper substrate is 2.5mg/cm 2 。
The inert atmosphere is selected from nitrogen atmosphere.
The heat treatment comprises first heating and second heating, wherein the temperature of the first heating is 60 ℃, and the time of the first heating is 2 hours; the temperature of the second heating was 200℃and the time of the second heating was 4 hours.
The embodiment also provides a gas diffusion layer which is prepared by adopting the preparation method.
Example 5
The embodiment provides a method for preparing a gas diffusion layer, which comprises the following steps:
s0.1, 3g CoCl 2 .6H 2 0、1gNiCl 2 .6H 2 Magnetically stirring and mixing O, 4g of urea and 45g of deionized water for 30min to obtain a prefabricated liquid;
s0.2, placing the prefabricated liquid into an oven for drying to obtain the anti-icing agent, wherein the molecular formula of the anti-icing agent is as follows: (Ni, co) - (CO) 3 ) 0.5 (OH) 0.11 H 2 O。
S1, mixing conductive carbon black, a water repellent, a dispersing agent and the anti-icing agent to obtain microporous layer slurry.
S1.1, selecting isopropanol as a dispersing agent, mixing the isopropanol with water, and then adding an anti-icing agent to obtain slurry A.
S1.2, mixing ethanol with water, selecting Vulcan XC-72 as conductive carbon black, and adding the Vulcan XC-72 into an ethanol solution to obtain slurry B.
S1.3, respectively carrying out magnetic stirring and ultrasonic dispersion on the slurry A and the slurry B, then mixing, selecting 60% polytetrafluoroethylene as a water repellent, adding polytetrafluoroethylene into the mixed slurry of the slurry A and the slurry B, and carrying out magnetic stirring and autumn final mixing to obtain the microporous layer slurry.
Wherein: in the microporous layer slurry, the mass fraction of the anti-icing agent is 10%; the volume ratio of the anti-icing agent to the conductive carbon black is 1:15.
S2, obtaining the commercial carbon paper substrate.
And S3, coating the microporous layer slurry on the surface of the carbon paper substrate, drying, and then carrying out heat treatment in an inert atmosphere to obtain the gas diffusion layer.
Wherein:
the loading of the conductive carbon black on the surface of the carbon paper substrate is 1.5mg/cm 2 。
The inert atmosphere is selected from nitrogen atmosphere.
The heat treatment comprises first heating and second heating, wherein the temperature of the first heating is 60 ℃, and the time of the first heating is 2 hours; the temperature of the second heating was 200℃and the time of the second heating was 4 hours.
The embodiment also provides a gas diffusion layer which is prepared by adopting the preparation method.
Comparative example 1
The only difference from example 1 is that:
(1) The microporous layer slurry is different;
(2) The preparation method of the microporous layer slurry is different, and specifically comprises the following steps: 1g of commercial graphene oxide was weighed into a beaker, added with 3g of deionized water for wetting, and then added with 4g of ethanol for dispersion. After the dispersion was completed, 1g of polytetrafluoroethylene as a water repellent and 0.6g of one of polyvinylidene fluoride, KH-550, and orthosilicate were added to a beaker, followed by ultrasonic dispersion with power set at 500w and dispersion time at 30min, to obtain a microporous layer slurry.
Experimental example 1
The freezing time performance of the gas diffusion layers prepared in examples 1 to 3 and comparative example 1, respectively, was examined, and the results are shown in Table 1.
TABLE 1 freezing time of each sample
As can be seen from Table 1, the anti-freezing time of the gas diffusion layers provided in examples 1 to 3 of the present application is significantly improved by 3 times compared with that of comparative example 1, and the gas diffusion layers have obvious advantages.
Experimental example 2
The gas diffusion layers prepared in examples 1 to 3 and comparative example 1 were examined for ice nucleation, respectively, and the results are shown in Table 2.
TABLE 2 nucleation temperature of various ices
As can be seen from table 2, the gas diffusion layers provided in examples 1 to 3 of the present application have significantly improved ice nucleation temperatures compared to comparative example 1, and have significant advantages.
Experimental example 3
Contact angles of the gas diffusion layers prepared in examples 1 to 3 and comparative example 1 were measured, respectively, and the results are shown in Table 3.
TABLE 3 contact angle data for each sample
As can be seen from Table 3, the contact angles of the gas diffusion layers provided in examples 1 to 3 of the present application are also improved to some extent as compared with comparative example 1.
Experimental example 4
The results of the conductivity measurements of the gas diffusion layers prepared in examples 1 to 3 and comparative example 1, respectively, are shown in Table 4.
TABLE 4 conductivity data for each sample
As can be seen from Table 4, the conductivities of the gas diffusion layers provided in examples 1-3 of the present application were substantially equivalent to those of comparative example 1, and were able to meet the standard of normal use.
Finally, it is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (12)
1. A method of making a gas diffusion layer comprising the steps of:
mixing conductive carbon black, a water repellent, a dispersing agent and an anti-icing agent to obtain microporous layer slurry;
obtaining a carbon paper substrate;
coating the microporous layer slurry on the surface of the carbon paper substrate, drying, and then carrying out heat treatment in an inert atmosphere to obtain the gas diffusion layer;
the preparation method of the anti-icing agent comprises the following steps:
CoCl is to be processed 2 ·6H 2 O、NiCl 2 ·6H 2 Mixing O, urea and deionized water under stirring to obtain a prefabricated liquid;
drying the prefabricated liquid in an oven to obtain the anti-icing agent;
wherein, coCl 2 ·6H 2 O、NiCl 2 ·6H 2 The mass ratio of O, urea and deionized water is (2-4) 1 (3-5) 40-50.
2. The method of claim 1, wherein the volume ratio of the anti-icing agent to the conductive carbon black is 1: (4-20).
3. The process according to claim 1, wherein CoCl 2 ·6H 2 O、NiCl 2 ·6H 2 The mass ratio of O, urea and deionized water is 2:1:3:40.
4. The method of claim 1, wherein the conductive carbon black loading on the surface of the carbon paper substrate in the microporous layer slurry is 1.0-2.5mg/cm 2 。
5. The method of claim 1, wherein the mass fraction of the anti-icing agent in the microporous layer slurry is 5-20%.
6. The method of claim 1, wherein the conductive carbon Black comprises any one or more of acetylene Black, vulcan XC-72, black pears, carbon nanotubes, graphene powder.
7. The method of claim 1, wherein the water repellent comprises any one or more of polytetrafluoroethylene, polyvinylidene fluoride, and copolymers of tetrafluoroethylene and ethylene.
8. The method of claim 1, wherein the dispersant comprises any one or more of ethanol, isopropanol, ethylene glycol, hexafluoroisopropanol.
9. The preparation method according to claim 1, wherein the mass ratio of the conductive carbon black to the dispersant is 1: (5-10).
10. The method of claim 1, wherein the mass percentage of the water repellent in the microporous layer slurry is 10-30%.
11. The method of claim 1, wherein the inert atmosphere is a nitrogen atmosphere.
12. A gas diffusion layer prepared by the method of any one of claims 1 to 11.
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