CN112928285A - Gas diffusion layer, preparation method thereof, fuel cell anode and fuel cell - Google Patents
Gas diffusion layer, preparation method thereof, fuel cell anode and fuel cell Download PDFInfo
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- CN112928285A CN112928285A CN202110259762.3A CN202110259762A CN112928285A CN 112928285 A CN112928285 A CN 112928285A CN 202110259762 A CN202110259762 A CN 202110259762A CN 112928285 A CN112928285 A CN 112928285A
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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
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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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
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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
Abstract
The invention relates to the technical field of fuel cells and discloses a gas diffusion layer and a preparation method thereof, a fuel cell anode and a fuel cell4O7At least one of powder and graphene nano-sheet. The gas diffusion layer is applied to the anode of the fuel cell, can effectively relieve the carbon corrosion of a microporous layer caused by insufficient hydrogen supply on the anode side in the prior art, and improves the anti-reversal capability of the anode side of the fuel cell.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a gas diffusion layer, a preparation method thereof, a fuel cell anode and a fuel cell.
Background
In the actual operation of the fuel cell stack, the shortage of hydrogen in the anode catalyst layer due to insufficient supply of external hydrogen, blockage of gas transmission channels by impurities, flooding, etc., causes the voltage of one or more cells to be negative, i.e., the so-called "reverse polarity" occurs. In order to maintain charge balance, water electrolysis and carbon corrosion occur in the anode catalytic layer at the time of reversal. Specifically, water is electrolyzed at the beginning, and after a certain period of time, the carbon support of the anode catalyst layer undergoes an oxidation reaction as the water content is greatly reduced. The corrosion of the carbon carrier of the anode catalyst layer can cause great irreversible damage to the performance of the battery, and the performance and the durability of the battery are seriously influenced. If the reverse polarity time is long enough, corrosion of carbon black may also occur in the microporous layer in the gas diffusion layer adjacent to the catalytic layer. In order to avoid carbon corrosion of the anode catalyst layer and the microporous layer, the water electrolysis catalytic capability of the battery anode needs to be improved, and the water electrolysis reaction time needs to be prolonged.
In order to address the reverse pole phenomenon, in the prior art, a reverse pole resistant active substance containing an iridium or ruthenium simple substance, an iridium or ruthenium simple substance oxide, and an iridium or ruthenium simple substance hydroxide is added to a catalytic layer, so that the water electrolysis catalytic capability of the catalytic layer is improved. However, in the prior art, the water electrolysis catalytic capability of the catalytic layer is improved only by adding the water electrolysis promoting catalyst to the carbon support corrosion of the catalytic layer. No corresponding solution has been proposed for corrosion of the carbon support of the microporous layer. Further, although the water electrolysis promoting catalyst such as iridium oxide can significantly prolong the time of the water electrolysis reaction, the oxidation reaction of the carbon support occurs eventually as the water content is gradually reduced. The reasons for this problem are: after water is fully electrolyzed, the carbon carrier-carbon black in the catalytic layer and the microporous layer is easy to generate oxidation reaction, so that platinum particles in the catalyst and polytetrafluoroethylene in the microporous layer are separated and agglomerated, and the electrochemical active area of the catalyst and the hydrophobicity of the microporous layer are reduced.
Disclosure of Invention
The invention provides a gas diffusion layer, a preparation method thereof, a fuel cell anode and a fuel cell.
In order to achieve the purpose, the invention provides the following technical scheme:
a gas diffusion layer comprising a substrate and a microporous layer formed on the substrate, the microporous layer comprising an electrically conductive material comprising multi-walled carbon nanotubes, Ti4O7At least one of powder and graphene nano-sheet.
Optionally, when the conductive material comprises the multi-walled carbon nanotubes, the diameter of the multi-walled carbon nanotubes is 10nm to 20nm, and the length of the multi-walled carbon nanotubes is 5 μm to 15 μm.
Optionally, when the conductive material comprises the Ti4O7When powdered, the Ti4O7The specific surface area of the powder was 50m2G to 70m2/g。
Optionally, when the conductive material includes the graphene nanoplatelets, the number of layers of the graphene nanoplatelets is greater than or equal to 10, the thickness of the graphene nanoplatelets is 5nm to 10nm, and the specific surface area of the graphene nanoplatelets is 80m2G to 100m2/g。
Optionally, when the conductive material only includes the multi-walled carbon nanotubes and graphene nanoplatelets, the mass ratio of the multi-walled carbon nanotubes to the graphene nanoplatelets is 2: 1.
Optionally, when the conductive material comprises the multi-walled carbon nanotube and the Ti at the same time4O7Powder and the graphene nanoplatelets, the multiwalled carbon nanotube, the Ti4O7The mass ratio of the powder to the graphene nanosheets is 1:1: 1.
The invention also provides a preparation method of the gas diffusion layer, which is used for preparing the gas diffusion layer provided by the technical scheme and comprises the following steps:
mixing a conductive material, a polytetrafluoroethylene emulsion, deionized water, isopropanol and a surfactant according to a preset mass ratio, and ultrasonically stirring for a preset time to obtain uniformly dispersed microporous layer slurry;
coating the microporous layer slurry on the surface of a substrate;
performing a heat treatment on the microporous layer slurry coated on the substrate in an inert atmosphere to form a microporous layer;
removing residual isopropanol and surfactant and allowing the polytetrafluoroethylene in the microporous layer to be uniformly distributed;
wherein the conductive material comprises multi-walled carbon nanotubes and Ti4O7At least one of powder and graphene nano-sheet.
Optionally, the preset mass ratio is 3:4:7:25:1, and the preset time is 1 to 2 hours.
Optionally, heat treating the microporous layer slurry coated on the substrate in an inert atmosphere, comprising:
heat treatment is carried out in an inert atmosphere at 100 ℃ for 30min-60min, 200 ℃ for 1min-30min and 320 ℃ for 1min-10 min.
The invention also provides a fuel cell anode comprising any one of the gas diffusion layers provided in the above technical scheme.
The invention also provides a fuel cell, which comprises the fuel cell anode provided in the technical scheme.
By adopting the technical scheme of the embodiment of the invention, the beneficial effects are as follows:
in the gas diffusion layer provided by the embodiment of the invention, the conductive material can be multi-walled carbon nanotubes or Ti4O7At least one of powder and graphene nano-sheet, i.e. multi-walled carbon nanotube and Ti4O7At least one material of powder and graphene nano-sheet replaces the conductive material of microporous layer in the prior art, namely carbon black, multi-walled carbon nano-tube and Ti4O7The powder and the graphene nano-sheets have the characteristics of high conductivity, large specific surface area, mechanical strength and the like, can show good electrocatalytic performance, and the three materials are materials with high chemical stability and can be obviously usedAnd the oxidation resistance of the microporous layer in the reverse polarity is improved. The gas diffusion layer is applied to the anode of the fuel cell, so that the carbon corrosion of the microporous layer caused by insufficient hydrogen supply on the anode side in the prior art can be effectively relieved, the anti-reversal capability of the anode side of the fuel cell is improved, and the anti-reversal capability of the fuel cell can be obviously improved.
Drawings
FIG. 1 is a graph comparing the anti-reversal behavior of examples of the present invention and comparative examples.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that: in the present application, all embodiments and preferred methods mentioned herein can be combined with each other to form new solutions, if not specifically stated. In the present application, all the technical features mentioned herein as well as preferred features may be combined with each other to form new technical solutions, if not specifically stated. In the present application, percentages (%) or parts refer to percent by weight or parts by weight relative to the composition, unless otherwise specified. In the present application, the components referred to or the preferred components thereof may be combined with each other to form new embodiments, if not specifically stated. In this application, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "6-22" indicates that all real numbers between "6-22" have been listed herein, and "6-22" is only a shorthand representation of the combination of these numbers. The "ranges" disclosed herein may be in the form of lower limits and upper limits, and may be one or more lower limits and one or more upper limits, respectively. In the present application, the individual reactions or process steps may be performed sequentially or in sequence, unless otherwise indicated. Preferably, the reaction processes herein are carried out sequentially.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present application.
In a first aspect, embodiments of the present invention provide a gas diffusion layer, including a substrate and a microporous layer formed on one side of the substrate, where the microporous layer includes a conductive material, and the conductive material includes multi-walled carbon nanotubes (MWNTs), Ti4O7At least one of powder and Graphene Nanoplatelets (GNPs).
In the gas diffusion layer provided by the embodiment of the invention, the conductive material can be multi-walled carbon nanotubes or Ti4O7At least one of powder and graphene nano-sheet, i.e. multi-walled carbon nanotube and Ti4O7At least one material of powder and graphene nano-sheet replaces the conductive material of microporous layer in the prior art, namely carbon black, multi-walled carbon nano-tube and Ti4O7The powder and the graphene nanosheet have the characteristics of high conductivity, large specific surface area, mechanical strength and the like, and can show good electrocatalytic performance, and the three materials are high in chemical stability, so that the oxidation resistance of the microporous layer in the reverse polarity process can be obviously improved. The gas diffusion layer is applied to the anode of the fuel cell, so that the carbon corrosion of the microporous layer caused by insufficient hydrogen supply on the anode side in the prior art can be effectively relieved, the anti-reversal capability of the anode side of the fuel cell is improved, and the anti-reversal capability of the fuel cell can be obviously improved.
The conductive material is not limited to multi-walled carbon nanotubes (MWNTs) and Ti4O7At least one of the powder and the Graphene Nanoplatelets (GNPs) may be another material having electrical conductivity and high oxidation resistance.
In one possible embodiment, when the conductive material comprises multi-walled carbon nanotubes, the diameter of the multi-walled carbon nanotubes may be 10nm to 20nm and the length of the multi-walled carbon nanotubes may be 5 μm to 15 μm, which can improve the oxidation resistance of the microporous layer at the time of reverse polarity. For example, the diameter of the multi-walled carbon nanotube may be 10nm, 15nm, or 20nm, and the length of the multi-walled carbon nanotube may be 5 μm, 10 μm, or 15 μm.
In one possible embodiment, when the conductive material comprises Ti4O7When being powdered, Ti4O7The specific surface area of the powder was 50m2G to 70m2/g。
In one possible embodiment, when the conductive material includes graphene nanoplatelets, the number of layers of the graphene nanoplatelets may be greater than or equal to 10, the thickness of the graphene nanoplatelets may be 5nm to 10nm, and the specific surface area of the graphene nanoplatelets may be 80m2G to 100m2The oxidation resistance of the microporous layer in the reverse polarity can be improved.
In one possible embodiment, when the conductive material only comprises two materials of multi-wall carbon nanotubes and graphene nanoplatelets, the mass ratio of the multi-wall carbon nanotubes to the graphene nanoplatelets can be set to be 2:1, so that the oxidation resistance of the microporous layer in the reverse polarity can be improved.
In one possible embodiment, when the conductive material comprises both multi-walled carbon nanotubes, Ti4O7Powder and graphene nano-sheet, multi-walled carbon nanotube and Ti4O7The mass ratio of the powder to the graphene nanosheets can be 1:1:1, and the oxidation resistance of the microporous layer during reverse polarity can be improved.
It should be noted that the above mass ratio is only an exemplary one, and in the present application, the mass ratio of different materials in the conductive material includes, but is not limited to, the above ratio.
In a second aspect, an embodiment of the present invention further provides a preparation method of a gas diffusion layer, for preparing the gas diffusion layer provided in any one of the above technical solutions, where the preparation method includes the following steps:
step S11: mixing a conductive material, a Polytetrafluoroethylene (PTFE) emulsion, deionized water, isopropanol and a surfactant according to a preset mass ratio, and ultrasonically stirring for a preset time to obtain uniformly dispersed microporous layer slurry;
step S12: coating the microporous layer slurry on the surface of a substrate;
step S13: performing a heat treatment on the microporous layer slurry coated on the substrate in an inert atmosphere to form a microporous layer;
step S14: removing residual isopropanol and surfactant and allowing the polytetrafluoroethylene in the microporous layer to be uniformly distributed;
wherein the conductive material comprises multi-walled carbon nanotubes and Ti4O7At least one of powder and graphene nano-sheet.
The substrate may be a carbon paper substrate containing 20 wt.% of polytetrafluoroethylene, or may be other substrates, and is not limited herein.
In a possible embodiment, the predetermined mass ratio may be 3:4:7:25:1, and the predetermined time may be 1 to 2 hours.
In one possible embodiment, the heat treatment of the microporous layer slurry coated on the substrate in an inert atmosphere may include the steps of:
heat treatment is carried out in an inert atmosphere at 100 ℃ for 30min-60min, 200 ℃ for 1min-30min and 320 ℃ for 1min-10 min.
In a third aspect, the present invention also provides a fuel cell anode comprising any one of the gas diffusion layers provided in the above technical solutions.
In a fourth aspect, the present invention further provides a fuel cell, including the fuel cell anode provided in the above technical solution.
The gas diffusion layers of the examples of the present invention will be described in further detail with reference to examples and comparative examples.
Example 1:
preparation of a gas diffusion layer comprising the steps of:
step S11: mixing multi-walled carbon nanotubes (MWNTs), Polytetrafluoroethylene (PTFE) emulsion, deionized water, isopropanol and a surfactant according to a mass ratio of 3:4:7:25:1, and ultrasonically stirring for 1 hour to obtain uniformly dispersed microporous layer slurry;
step S12: coating the microporous layer slurry on the surface of a carbon paper substrate containing 20 wt.% PTFE;
step S13: sequentially carrying out heat treatment on the microporous layer slurry coated on the carbon paper substrate in an inert atmosphere at 100 ℃ for 30min, 200 ℃ for 5min and 320 ℃ for 3 min;
step S14: the residual isopropyl alcohol and surfactant were removed and PTFE in the microporous layer was uniformly distributed, resulting in a Gas Diffusion Layer (GDL).
Wherein, the multi-wall carbon nano-tube can be prepared by adopting a chemical vapor deposition method. For example, acetylene is used as a carbon source, and multi-wall carbon nanotubes are grown on a nickel sheet substrate at 550 ℃.
Example 2:
preparation of a gas diffusion layer comprising the steps of:
step S11: mixing Ti4O7Mixing the powder, Polytetrafluoroethylene (PTFE) emulsion, deionized water, isopropanol and surfactant according to the mass ratio of 3:4:7:25:1, and ultrasonically stirring for 2 hours to obtain uniformly dispersed microporous layer slurry;
step S12: coating the microporous layer slurry on the surface of a carbon paper substrate containing 20 wt.% PTFE;
step S13: sequentially carrying out heat treatment on the microporous layer slurry coated on the carbon paper substrate in an inert atmosphere at the temperature of 100 ℃ for 60min, 200 ℃ for 30min and 320 ℃ for 10 min;
step S14: the residual isopropyl alcohol and surfactant were removed and PTFE in the microporous layer was uniformly distributed, resulting in a Gas Diffusion Layer (GDL).
Wherein, Ti4O7The powder may be made up of TiO2Reduction reaction of the powder. For example, TiO is first2Heating the powder at 110 deg.C for 8-12H in atmospheric atmosphere, and then in H2Heating at 1050 deg.C for 4-6 h in atmosphere, and cooling to room temperature to obtain Ti4O7And (3) powder.
Example 3:
preparation of a gas diffusion layer comprising the steps of:
step S11: mixing graphene nanosheets, Polytetrafluoroethylene (PTFE) emulsion, deionized water, isopropanol and a surfactant according to a mass ratio of 3:4:7:25:1, and ultrasonically stirring for 1.5 hours to obtain uniformly dispersed microporous layer slurry;
step S12: coating the microporous layer slurry on the surface of a carbon paper substrate containing 20 wt.% PTFE;
step S13: sequentially carrying out heat treatment on the microporous layer slurry coated on the carbon paper substrate in an inert atmosphere at the temperature of 100 ℃ for 40min, 200 ℃ for 15min and 320 ℃ for 8 min;
step S14: the residual isopropyl alcohol and surfactant were removed and PTFE in the microporous layer was uniformly distributed, resulting in a Gas Diffusion Layer (GDL).
The graphene nanosheet can be prepared by adopting a redox method. For example, stirring the crystalline flake graphite in an oil bath at 50 ℃ for 40-60 min; then, an appropriate amount of H is added2O2Removing precipitate and color, washing with 5% dilute hydrochloric acid and deionized water to neutrality, filtering, and drying to obtain graphite oxide; then, placing the graphite oxide in a muffle furnace, and carrying out pyrolysis reduction at the high temperature of 600-900 ℃ to obtain expanded graphite; and finally, ultrasonically stripping for 4-5h in a mixed solvent of N-N, dimethylamide/deionized water in a certain proportion at 50 ℃ to obtain a GNPs suspension, centrifuging, performing suction filtration, and drying for 24h at 60 ℃ to obtain the graphene nanosheet.
Example 4:
preparation of a gas diffusion layer comprising the steps of:
step S11: mixing a multi-walled carbon nanotube, a graphene nanosheet, a Polytetrafluoroethylene (PTFE) emulsion, deionized water, isopropanol and a surfactant according to a mass ratio of 2:1:4:7:25:1, and ultrasonically stirring for 2 hours to obtain uniformly dispersed microporous layer slurry;
step S12: coating the microporous layer slurry on the surface of a carbon paper substrate containing 20 wt.% PTFE;
step S13: sequentially carrying out heat treatment on the microporous layer slurry coated on the carbon paper substrate in an inert atmosphere at 100 ℃ for 30min, 200 ℃ for 10min and 320 ℃ for 8 min;
step S14: the residual isopropyl alcohol and surfactant were removed and PTFE in the microporous layer was uniformly distributed, resulting in a Gas Diffusion Layer (GDL).
Example 5:
preparation of a gas diffusion layer comprising the steps of:
step S11: mixing multi-wall carbon nanotube and Ti4O7Mixing the powder, the graphene nanosheets, Polytetrafluoroethylene (PTFE) emulsion, deionized water, isopropanol and a surfactant according to a mass ratio of 1:1:1:4:7:25:1, and ultrasonically stirring for 2 hours to obtain uniformly dispersed microporous layer slurry;
step S12: coating the microporous layer slurry on the surface of a carbon paper substrate containing 20 wt.% PTFE;
step S13: sequentially carrying out heat treatment on the microporous layer slurry coated on the carbon paper substrate in an inert atmosphere at the temperature of 100 ℃ for 40min, 200 ℃ for 20min and 320 ℃ for 5 min;
step S14: the residual isopropyl alcohol and surfactant were removed and PTFE in the microporous layer was uniformly distributed, resulting in a Gas Diffusion Layer (GDL).
Comparative example 1:
preparation of a gas diffusion layer comprising the steps of:
step S11: mixing carbon black, Polytetrafluoroethylene (PTFE) emulsion, deionized water, isopropanol and a surfactant according to a mass ratio of 3:4:7:25:1, and ultrasonically stirring for 1-2 hours to obtain uniformly dispersed microporous layer slurry;
step S12: coating the microporous layer slurry on the surface of a carbon paper substrate containing 20 wt.% PTFE;
step S13: sequentially carrying out heat treatment on the microporous layer slurry coated on the carbon paper substrate for 30-60 min at 100 ℃, 1-30 min at 200 ℃ and 1-10 min at 320 ℃ in an inert atmosphere;
step S14: the residual isopropyl alcohol and surfactant were removed and PTFE in the microporous layer was uniformly distributed, resulting in a Gas Diffusion Layer (GDL).
Comparative example 2:
preparation of a gas diffusion layer comprising the steps of:
step S11: mixing carbon black, a multi-walled carbon nanotube, a Polytetrafluoroethylene (PTFE) emulsion, deionized water, isopropanol and a surfactant according to a mass ratio of 2:1:4:7:25:1, and ultrasonically stirring for 1-2 hours to obtain uniformly dispersed microporous layer slurry;
step S12: coating the microporous layer slurry on the surface of a carbon paper substrate containing 20 wt.% PTFE;
step S13: sequentially carrying out heat treatment on the microporous layer slurry coated on the carbon paper substrate for 30-60 min at 100 ℃, 1-30 min at 200 ℃ and 1-10 min at 320 ℃ in an inert atmosphere;
step S14: the residual isopropyl alcohol and surfactant were removed and PTFE in the microporous layer was uniformly distributed, resulting in a Gas Diffusion Layer (GDL).
In the above examples 1 to 5, taking example 1 as an example, the gas diffusion layer prepared in example 1 was added to the anode of the fuel cell as the anti-reversal gas diffusion layer, and when the hydrogen supply to the anode of the fuel cell was insufficient, the anode anti-reversal behavior was examined as shown in fig. 1. In fig. 1, curve a is a curve obtained by adding the gas diffusion layer prepared in example 1 as the anti-reverse electrode gas diffusion layer to the anode of the fuel cell, i.e., the conductive material includes only carbon black, and curve B is a curve obtained by adding the gas diffusion layer prepared in example 1 as the anti-reverse electrode gas diffusion layer to the anode of the fuel cell. As can be seen from fig. 1: at 0.2A/cm2The voltage reverse polarization time of the fuel cell of curve a can only be maintained at about 10 minutes, while the voltage reverse polarization time of the fuel cell of curve B can be maintained at about 50 minutes. The data in fig. 1 can show that when the conductive material of the gas diffusion layer is multi-walled carbon nanotubes, the voltage reverse polarization time of the fuel cell can be prolonged and the reverse polarization resistance of the fuel cell can be significantly improved compared to the prior art carbon black material. The conductive material of the gas diffusion layer is multi-walled carbon nanotube and Ti4O7At least one of the powder and the graphene nanosheets, and the duration of the voltage reverse polarization time of the fuel cell is similar to that of the curve B, and is not listed here.
Specifically, fuel cells were assembled using the gas diffusion layers provided in examples 1 to 5 and comparative examples 1 to 2, respectively, and the fuel cells were tested at 0.2A/cm2Voltage reverse polarization time at current density. Test result columnIn table 1.
As can be seen from the data in table 1, the fuel cell obtained by the technical solution of the embodiment of the present invention has significantly better anti-reversal capability than the fuel cells of comparative examples 1-2.
It will be apparent to those skilled in the art that various changes and modifications may be made in the embodiments of the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (11)
1. A gas diffusion layer comprising a substrate and a microporous layer formed on the substrate, the microporous layer comprising an electrically conductive material comprising multi-walled carbon nanotubes, Ti4O7At least one of powder and graphene nano-sheet.
2. The gas diffusion layer of claim 1, wherein when the conductive material comprises the multi-walled carbon nanotubes, the multi-walled carbon nanotubes have a diameter of 10nm to 20nm and a length of 5 μ ι η to 15 μ ι η.
3. The gas diffusion layer of claim 1, wherein when the electrically conductive material comprises the Ti4O7When powdered, the Ti4O7The specific surface area of the powder was 50m2G to 70m2/g。
4. Gas diffusion according to claim 1A layer, characterized in that, when the conductive material comprises the graphene nanoplatelets, the number of layers of the graphene nanoplatelets is greater than or equal to 10, the thickness of the graphene nanoplatelets is 5nm to 10nm, and the specific surface area of the graphene nanoplatelets is 80m2G to 100m2/g。
5. The gas diffusion layer of claim 1, wherein when the conductive material comprises only the multiwalled carbon nanotubes and graphene nanoplatelets, the mass ratio of the multiwalled carbon nanotubes to the graphene nanoplatelets is 2: 1.
6. The gas diffusion layer of claim 1, wherein the electrically conductive material comprises the multiwall carbon nanotubes and the Ti at the same time4O7Powder and the graphene nanoplatelets, the multiwalled carbon nanotube, the Ti4O7The mass ratio of the powder to the graphene nanosheets is 1:1: 1.
7. A method for preparing a gas diffusion layer, for preparing a gas diffusion layer according to any one of claims 1 to 6, comprising:
mixing a conductive material, a polytetrafluoroethylene emulsion, deionized water, isopropanol and a surfactant according to a preset mass ratio, and ultrasonically stirring for a preset time to obtain uniformly dispersed microporous layer slurry;
coating the microporous layer slurry on the surface of a substrate;
performing a heat treatment on the microporous layer slurry coated on the substrate in an inert atmosphere to form a microporous layer;
removing residual isopropanol and surfactant and allowing the polytetrafluoroethylene in the microporous layer to be uniformly distributed;
wherein the conductive material comprises multi-walled carbon nanotubes and Ti4O7At least one of powder and graphene nano-sheet.
8. The method for producing a gas diffusion layer according to claim 7, wherein the predetermined mass ratio is 3:4:7:25:1, and the predetermined time is 1 to 2 hours.
9. The method for preparing a gas diffusion layer according to claim 7, wherein the microporous layer slurry coated on the substrate is heat-treated in an inert atmosphere, comprising:
heat treatment is carried out in an inert atmosphere at 100 ℃ for 30min-60min, 200 ℃ for 1min-30min and 320 ℃ for 1min-10 min.
10. A fuel cell anode comprising a gas diffusion layer according to any of claims 1 to 6.
11. A fuel cell comprising the fuel cell anode of claim 10.
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