CN112310413A - Gas diffusion layer, preparation method and application thereof - Google Patents

Gas diffusion layer, preparation method and application thereof Download PDF

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Publication number
CN112310413A
CN112310413A CN201910672135.5A CN201910672135A CN112310413A CN 112310413 A CN112310413 A CN 112310413A CN 201910672135 A CN201910672135 A CN 201910672135A CN 112310413 A CN112310413 A CN 112310413A
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carbon
diffusion layer
layer
composite
fibers
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CN112310413B (en
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周小春
卫俊
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Priority to PCT/CN2020/103425 priority patent/WO2021013167A1/en
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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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • 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
    • 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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0234—Carbonaceous material
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0241—Composites
    • H01M8/0245—Composites in the form of layered or coated products
    • 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 a gas diffusion layer, a preparation method and application thereof. The gas diffusion layer comprises a supporting layer, and a composite carbon material diffusion layer and a microporous layer which are sequentially arranged on the surface of the supporting layer; the support layer is made of porous materials, and the composite carbon material diffusion layer comprises carbon nanotubes and carbon fibers. The support layer has higher mechanical strength, and can be used as a frame base of a diffusion layer as well as a current collection layer; the carbon nanotube and the carbon fiber are mixed, the carbon fiber is used as a substrate frame, the carbon nanotube is used as a filler of the frame, the requirement of high air permeability of the gas diffusion layer is met, and the carbon nanotube has high mechanical strength; the microporous layer can fill pores with different sizes of the diffusion layer, and can slow down the unevenness of the diffusion layer, further realize the redistribution of water and reaction gas in a flow field and a catalysis layer, increase the conductivity and prolong the service life of the battery.

Description

Gas diffusion layer, preparation method and application thereof
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to a gas diffusion layer, and a preparation method and application thereof.
Background
The fuel cell is one of clean energy-producing devices, has high energy conversion rate, and the product is water, so the fuel cell can be used as a clean energy source. The fuel cell is widely applied to the fields of aerospace, automobiles and the electronic industry. Fuel cells can be divided into: proton exchange membrane fuel cells (polymer electrolyte membrane fuel cells), methanol fuel cells, solid oxide fuel cells, phosphoric acid fuel cells, alkaline fuel cells, and the like. The overall structural design of most fuel cells is similar, except for the fuel and electrolyte.
The fuel cell is characterized in that hydrogen and oxygen react to generate water and then are converted into electric energy, so that a large amount of water is generated in the reaction process to greatly compound the cell, so that the catalyst layer is flooded with water to block the whole cell channel, and the gas cannot be transmitted. Thus, there is a good passage for the gas to pass, and it is important to manage the water produced by the reaction.
The Gas diffusion Layer (GDL for short) plays an extremely important role in fuel cells, and plays important roles in supporting a catalytic Layer, collecting current, conducting Gas, and discharging water, which is a reaction product, in fuel cells. The thickness of the diffusion layer has important influence on the whole fuel cell, and the mass transfer and gas transmission of the whole fuel cell are greatly influenced due to the fact that the diffusion layer is too thick; the diffusion layer is too thin, the carrying capacity for the catalytic layer is reduced, and the current collecting capacity is reduced, which may affect the discharge of the battery. A good diffusion layer should have good mass transfer capability, good electrical conductivity, good catalyst carrying capability.
Meanwhile, the good mass transfer capacity requires that the whole diffusion layer needs higher porosity and cannot be too thick, and gas diffusion layers such as carbon paper and carbon cloth which take carbon fiber felt as a substrate layer have higher air permeability and electrical conductivity but have great limitation on mechanical strength.
CN102856567A discloses an integrated renewable fuel cell diffusion layer and a preparation method thereof, wherein a non-conductive organic synthetic fiber cloth is used as a support body of the diffusion layer, a conductive corrosion-resistant metal/metal oxide network is constructed on the non-conductive organic synthetic fiber cloth, the conductive corrosion-resistant metal/metal oxide network is filled in pores of organic fibers, and a certain hydrophobic agent and a certain bonding agent are combined, so that the diffusion layer achieves proper hydrophilic and hydrophobic properties and a proper pore structure is constructed, and mass transfer balance of URFC under different working modes is ensured. The fuel cell diffusion layer solves the corrosion problem of the URFC supporting body in the prior art, but has poor mass transfer capacity.
CN107012739B discloses an ultrathin carbon fiber paper modified by a conductive polymer film and a preparation method thereof, wherein the conductive polymer film is deposited inside the high-flux unmodified ultrathin carbon fiber paper by an electrochemical deposition method to prepare the conductive polymer film modified ultrathin carbon fiber paper. In the prepared conductive polymer film modified ultrathin carbon fiber paper, the conductive polymer film is coated on carbon fibers and matrix carbon-carbon fiber nodes to form a film network with uniform thickness in the carbon paper. The mass transfer capacity and the air permeability of the ultrathin carbon fiber paper are poor.
Therefore, there is a need in the art for a novel gas diffusion layer for a fuel cell, which has good mass transfer capability, good gas permeability, good electrical conductivity and good mechanical strength, and good catalyst carrying capability, and is simple in preparation process and industrially producible.
Disclosure of Invention
In view of the fact that the commercial carbon paper is thick in thickness and long in gas transfer path, mass transfer resistance is increased, and the diffusion layer structure becomes very fragile and low in mechanical strength after adhesives such as PTFE (polytetrafluoroethylene), phenolic resin and the like are added into the conventional carbon paper and are graphitized at high temperature, so that the phenomenon of breakage easily occurs in the use process, and the discharge performance of the battery is influenced. In view of the above limitations, the present invention breaks through the traditional carbon paper preparation method, and makes the diffusion layer soft and highly conductive without graphitization treatment.
In view of the deficiencies of the prior art, it is an object of the present invention to provide a gas diffusion layer, a method of making the same and uses thereof. The gas diffusion layer has good mass transfer capacity, good air permeability, good electrical conductivity, good mechanical strength and good catalyst carrying capacity, and the preparation process is simple and can be industrially produced.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention aims to provide a gas diffusion layer, which comprises a support layer, and a composite carbon material diffusion layer and a microporous layer which are sequentially arranged on the surface of the support layer;
the support layer is made of porous materials, and the composite carbon material diffusion layer comprises carbon nanotubes and carbon fibers.
The support layer has higher mechanical strength, and can be used for collecting current and also can be used as a diffusion layer frame substrate; according to the invention, the carbon nano tube and the carbon fiber are mixed, the carbon fiber is used as a substrate frame, the carbon nano tube is used as a filler of the frame, the requirement of high air permeability of the gas diffusion layer is met, and the carbon nano tube has high mechanical strength.
When the composite carbon material diffusion layer is loaded, the surface of the composite carbon material diffusion layer has pores with different sizes like the traditional carbon paper and the surface of the composite carbon material diffusion layer is possibly uneven, so that the microporous layer becomes an important part, the pores with different sizes of the diffusion layer can be filled, the uneven phenomenon of the diffusion layer can be relieved, the redistribution of water and reaction gas in a flow field and a catalytic layer is further realized, the conductivity is increased, and the service life of a battery is prolonged.
The support layer, the composite carbon material diffusion layer and the microporous layer act together to obtain the gas diffusion layer with good mass transfer capacity, good air permeability, good electrical conductivity, good mechanical strength and good catalyst carrying capacity.
Preferably, the support layer is a flexible carbon film, preferably any one of a carbon nanotube film, a graphene film, or a carbon fiber felt.
Preferably, the thickness of the support layer is <50 μm, such as 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm or 45 μm, etc.
Preferably, the porosity of the support layer is 50% to 90%, preferably 70% to 85%, such as 52%, 55%, 58%, 60%, 65%, 70%, 72%, 75%, 78%, 80%, 82%, 85%, 88%, or the like.
Preferably, the pore size of the support layer is >5 μm, preferably 15-22 μm, such as 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 30 μm, 32 μm, 33 μm, 35 μm, 36 μm, 38 μm or 40 μm.
Preferably, the holes in the support layer are through holes.
Preferably, the holes in the support layer include any one or a combination of at least two of circular holes, rectangular holes and rhombic holes.
Preferably, the topography of the holes is an equi-regular hole.
Preferably, the morphology of the pores in the support layer further includes a first pore and n second pores distributed in the first pore.
Preferably, the first hole is a non-penetrating hole.
Preferably, the second hole is a through hole.
Preferably, n.gtoreq.1, such as 2, 3, 4, 5, 6, 7 or 8, etc.
Preferably, the thickness of the composite carbon material diffusion layer is 10 to 60 μm, for example, 12 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, or 58 μm.
Preferably, in the composite carbon material diffusion layer, the mass ratio of the carbon nanotubes to the carbon fibers is 3-10: 1-5, for example, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 3:2, 4:2, 5:2, 7:2, 9:2, 3:3, 4:3, 5:3, 7:3, 8:3, 10:3, 3:4, 5:4, 7:4, 9:4, 3:5, 4:5, 6:5, 7:5, 8:5, or 9: 5.
The mass ratio of the carbon nano tubes to the carbon fibers is 3-10: 1-5, and if the content of the carbon nano tubes is too small, the porosity is too large; if the carbon fiber content is too low, the diffusion layer is too dense.
Preferably, the carbon nanotubes include any one of or a combination of at least two of single-walled carbon nanotubes, multi-walled carbon nanotubes, graphitized carbon nanotubes, and carboxylated carbon nanotubes.
Preferably, the carbon fibers include any one of PP carbon fibers, PE short fibers, PVA short fibers, LM polyester short fibers, cellulose short fibers, and pitch-based carbon fibers or a combination of at least two thereof.
Preferably, the porosity of the composite carbon material diffusion layer is 60% to 90%, such as 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, 82%, 85%, 88%, or the like.
Preferably, the microporous layer has a porosity of 50% to 80%, such as 52%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, 72%, 75%, or 78%, and the like.
Preferably, the microporous layer comprises carbon powder.
Preferably, the loading amount of the carbon powder in the microporous layer is 0.2mg/cm2～0.8mg/cm2E.g. 0.3mg/cm2、0.4mg/cm2、0.5mg/cm2、0.6mg/cm2Or 0.7mg/cm2And the like.
The loading amount of the carbon powder in the microporous layer is 0.2mg/cm2～0.8mg/cm2If the carbon powder content is too low, the conductivity is poor, and the catalyst leakage can occur; the carbon powder content is too much, and the gas transmission path is long.
Preferably, the carbon powder includes any one or a combination of at least two of acetylene black, activated carbon and graphite powder.
A second object of the present invention is to provide a method for preparing a gas diffusion layer according to the first object, the method comprising the steps of:
and coating the composite carbon material slurry on the support layer to obtain a composite carbon material diffusion layer, then coating the hydrophobic slurry to obtain a microporous layer, and calcining to obtain the gas diffusion layer.
Preferably, the preparation process of the support layer comprises: and (3) forming a hole on the flexible carbon film, and then removing cations in the flexible carbon film.
Preferably, the flexible carbon film pore-forming method comprises any one or a combination of at least two of laser drilling, chemical pore-forming and silicon plate pore-pressing.
Preferably, the flexible carbon film is any one of a carbon nanotube film, a graphene film, or a carbon fiber felt.
Preferably, the removing mode of the cations in the flexible carbon film is acid washing.
Preferably, the acid washing is soaking with sulfuric acid.
Preferably, the concentration of the sulfuric acid is 1-5 mol/L, such as 1.5mol/L, 2mol/L, 2.2mol/L, 2.5mol/L, 2.8mol/L, 3mol/L, 3.5mol/L, 4mol/L or 4.5 mol/L.
Preferably, the temperature of the acid washing is 50 to 100 ℃, such as 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ or 95 ℃.
Preferably, the acid washing time is 10-100 min, such as 20min, 30min, 40min, 50min, 60min, 70min, 80min or 90 min.
Preferably, the preparation process of the composite carbon material slurry comprises the following steps: and mixing the carbon fiber dispersion liquid, the carbon nanotube dispersion liquid, the binder and the hydrophobing agent to obtain the composite carbon material slurry.
Because the carbon nanotube and carbon fiber mixed slurry is directly used as the integral frame of the diffusion layer and is loose, a binder needs to be added into the slurry, and the resistance between the composite carbon material layer and the supporting layer can be reduced.
Preferably, the composite carbon material slurry contains 0 to 100 wt% of carbon nanotubes, and does not contain 0 wt% and 100 wt%, preferably 20 to 40%, such as 1 wt%, 5 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, or 90 wt%, and the like.
Preferably, the composite carbon material slurry contains carbon fibers in an amount of 0 to 100 wt% and does not contain 0 wt% and 100 wt%, preferably 15 to 25%, such as 1 wt%, 5 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, or 90 wt%, and the like.
Preferably, the binder is present in an amount of 0 to 50 wt%, and not 0 wt%, preferably 20 wt% to 30 wt%, such as 1 wt%, 5 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, 30 wt%, 32 wt%, 35 wt%, 38 wt%, 40 wt%, or 45 wt%, and the like.
Preferably, the amount of the hydrophobizing agent is 0 to 50 wt% and does not contain 0 wt%, preferably 20 wt% to 30 wt%, such as 1 wt%, 5 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, or 45 wt%, etc.
Preferably, the mixing is by sonication.
Preferably, the binder comprises any one of polytetrafluoroethylene, polyethylene glycol, polyvinyl alcohol and phenolic resin or a combination of at least two thereof.
Preferably, the hydrophobic agent comprises a fluoropolymer, preferably polytetrafluoroethylene.
Preferably, the coating manner of the composite carbon material slurry includes any one or a combination of at least two of suction filtration, blade coating and screen printing.
Preferably, the composite carbon material slurry further comprises a pressurizing, drying and cleaning process after coating.
Preferably, the pressure for pressurizing is 20-60 kg/cm2E.g. 25kg/cm2、30kg/cm2、35kg/cm2、40kg/cm2、45kg/cm2、50kg/cm2Or 55kg/cm2And the like.
The pressing process of the present invention can make the diffusion layer more robust and flat.
Preferably, the pressurizing time is 1-5 min, such as 2min, 3min or 4 min.
Preferably, the pressing is performed in a hot press.
Preferably, the drying temperature is 20 to 100 ℃, such as 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 90 ℃.
Preferably, the cleaning is performed in a mixed solution of 1-5 mol/L sulfuric acid and an organic solvent, such as 1.5mol/L, 2mol/L, 2.2mol/L, 2.5mol/L, 2.8mol/L, 3mol/L, 3.5mol/L, 4mol/L or 4.5 mol/L.
Preferably, the organic solvent comprises ethanol.
Preferably, the temperature of the cleaning is 30 to 80 ℃, for example, 40 ℃, 50 ℃, 60 ℃ or 70 ℃.
Preferably, the cleaning time is 20-100 min, such as 30min, 40min, 50min, 60min, 70min, 80min or 90 min.
Preferably, the preparation process of the carbon fiber dispersion liquid comprises: and (3) carrying out ultrasonic dispersion on the carbon fibers to obtain a carbon fiber dispersion liquid.
Preferably, the carbon fibers are single length carbon fibers or mixed length carbon fibers.
Preferably, the carbon fibers include any one of PP carbon fibers, PE short fibers, PVA short fibers, LM polyester short fibers, cellulose short fibers, and pitch-based carbon fibers or a combination of at least two thereof.
Preferably, the preparation process of the carbon nanotube dispersion liquid comprises: and (3) pickling the carbon nano tube, and then mixing the pickled carbon nano tube with a surfactant and a solvent to obtain the carbon nano tube dispersion liquid.
Preferably, the carbon nanotubes include any one of or a combination of at least two of single-walled carbon nanotubes, multi-walled carbon nanotubes, graphitized carbon nanotubes, and carboxylated carbon nanotubes.
Preferably, the acid washing is soaking with sulfuric acid.
Preferably, the concentration of the sulfuric acid is 1-5 mol/L, such as 1.5mol/L, 2mol/L, 2.2mol/L, 2.5mol/L, 2.8mol/L, 3mol/L, 3.5mol/L, 4mol/L or 4.5 mol/L.
Preferably, the temperature of the acid washing is 50 to 100 ℃, such as 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ or 95 ℃.
Preferably, the acid washing time is 5-15 h, such as 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h or 14 h.
Preferably, the acid washing is followed by a centrifugal washing process with ethanol and pure water.
Preferably, the mass ratio of the carbon nanotubes to the surfactant is 1:3 to 1:15, such as 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, or 1: 14.
Preferably, the surfactant comprises any one of sodium dodecylbenzene sulfonate, polyvinylpyrrolidone and sodium dodecyl sulfate or a combination of at least two of them.
Preferably, the solvent is any one of pure water, ethanol, acetone and isopropanol or a combination of at least two of the above.
Preferably, the mixing is by sonication.
Preferably, the ultrasonic instrument is an ultrasonic instrument and/or a cell disruptor.
Preferably, the mixing time is 1-15 h, such as 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h or 14 h.
Preferably, the ultrasonic instrument is an ultrasonic instrument, and the mixing time is 5-15 h, such as 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h or 14 h.
Preferably, the ultrasonic device is a cell disruptor, and the mixing time is 1-4 h, such as 1h, 2h, 3h or 4 h.
Preferably, the preparation process of the hydrophobic slurry comprises the following steps: and mixing the carbon powder slurry with a hydrophobic agent to obtain hydrophobic slurry.
Preferably, the content of the carbon powder in the carbon powder slurry is 0.4-0.5 mg/cm2For example 0.41mg/cm2、0.42mg/cm2、0.43mg/cm2、0.44mg/cm2、0.45mg/cm2、0.46mg/cm2、0.47mg/cm2、0.48mg/cm2Or 0.49mg/cm2And the like.
Preferably, the carbon powder includes any one or a combination of at least two of acetylene black, activated carbon and graphite powder.
Preferably, the hydrophobic paste is applied by any one or a combination of at least two of knife coating, spray coating, screen printing and drop coating, preferably screen printing.
Preferably, the temperature of the calcination is 100 to 600 ℃, for example, 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, or 550 ℃.
Preferably, the calcination time is 10-100 min, such as 20min, 30min, 40min, 50min, 60min, 70min, 80min or 90 min.
As a preferred technical solution, the method for preparing a gas diffusion layer according to the present invention comprises the steps of:
(1) preparation of a support layer: forming a hole on the flexible carbon film, and then soaking the flexible carbon film for 10-100 min at 50-100 ℃ by adopting 1-5 mol/L sulfuric acid to remove cations in the flexible carbon film;
(2) preparing a composite carbon material diffusion layer:
(a) ultrasonically dispersing carbon fibers to obtain a carbon fiber dispersion liquid;
(b) soaking a carbon nano tube in 1-5 mol/L sulfuric acid at 50-100 ℃ for 5-15 h, centrifugally cleaning with ethanol and pure water, and ultrasonically mixing the carbon nano tube with a surfactant and a solvent for 1-15 h, wherein the mass ratio of the carbon nano tube to the surfactant is 1: 3-1: 15, so as to obtain a carbon nano tube dispersion liquid;
(c) ultrasonically mixing a carbon fiber dispersion liquid, a carbon nanotube dispersion liquid, a binder and a hydrophobing agent to obtain composite carbon material slurry, wherein the content of the carbon nanotubes in the composite carbon material slurry is 20-40 wt%, the content of the carbon fibers is 15-25 wt%, the content of the binder is 20-30 wt%, and the content of the hydrophobing agent is 20-30 wt%;
(d) coating the composite carbon material slurry on the surface of the support layer obtained in the step (1), and placing the support layer in a hot press for 20-60 kg/cm2Pressurizing for 1-5 min under pressure, drying at 20-100 ℃, and cleaning for 20-100 min in a mixed solution of 1-5 mol/L sulfuric acid and ethanol at 30-80 ℃ to obtain a composite carbon material diffusion layer;
(3) preparation of microporous layer: mixing the carbon powder slurry with a hydrophobic agent to obtain hydrophobic slurry, and then coating the hydrophobic slurry on the surface of the composite carbon material diffusion layer in the step (2) to obtain a microporous layer;
(4) and (4) calcining the product obtained in the step (3) at 100-600 ℃ for 10-100 min to obtain the gas diffusion layer.
It is a further object of the present invention to provide a fuel cell including the gas diffusion layer according to one of the objects.
Compared with the prior art, the invention has the following beneficial effects:
(1) the support layer has higher mechanical strength, and can be used for collecting current and also can be used as a diffusion layer frame substrate; according to the invention, the carbon nano tube and the carbon fiber are mixed, the carbon fiber is used as a substrate frame, the carbon nano tube is used as a filler of the frame, the requirement of high air permeability of the gas diffusion layer is met, and the carbon nano tube has high mechanical strength.
(2) When the composite carbon material diffusion layer is loaded, the surface of the composite carbon material diffusion layer has pores with different sizes like the traditional carbon paper and the surface of the composite carbon material diffusion layer is possibly uneven, so that the microporous layer becomes an important part, the pores with different sizes of the diffusion layer can be filled, the uneven phenomenon of the diffusion layer can be relieved, the redistribution of water and reaction gas in a flow field and a catalytic layer is further realized, the conductivity is increased, and the service life of a battery is prolonged.
(3) The support layer, the composite carbon material diffusion layer and the microporous layer act together to obtain the gas diffusion layer with good mass transfer capacity, good air permeability, good electrical conductivity, good mechanical strength and good catalyst carrying capacity.
Drawings
FIG. 1 is a schematic view of a supporting layer structure obtained in embodiment 1 of the present invention;
FIG. 2 is a schematic view of a supporting layer structure obtained in example 2 of the present invention;
fig. 3 is a schematic structural view of a gas diffusion layer obtained in embodiment 1 of the present invention.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A preparation method of a gas diffusion layer comprises the following steps:
(1) preparation of a support layer: laser drilling is carried out on a carbon nanotube film with the thickness of 20 microns, then 3mol/L sulfuric acid is adopted to soak the carbon nanotube film for 60min at 80 ℃, cations in the carbon nanotube film are removed, the structural schematic diagram of the obtained supporting layer is shown in figure 1, holes in the supporting layer are circular holes with the diameter of 35 microns and in regular arrangement, and the porosity of the supporting layer is 80%;
(2) preparing a composite carbon material diffusion layer:
(a) ultrasonically dispersing PP carbon fibers in pure water to obtain a carbon fiber dispersion liquid;
(b) soaking a single-walled carbon nanotube in 3mol/L sulfuric acid at 80 ℃ for 8h, centrifugally cleaning with ethanol and pure water, and ultrasonically mixing the single-walled carbon nanotube with sodium dodecyl benzene sulfonate and pure water in a cell disruptor for 3h, wherein the mass ratio of the single-walled carbon nanotube to the sodium dodecyl benzene sulfonate is 1:10, so as to obtain a carbon nanotube dispersion liquid;
(c) ultrasonically mixing carbon fiber dispersion liquid, carbon nanotube dispersion liquid, polytetrafluoroethylene and polyvinyl alcohol to obtain composite carbon material slurry, wherein the content of single-wall carbon nanotubes in the composite carbon material slurry is 30 wt%, the content of PP carbon fibers is 20 wt%, the content of polytetrafluoroethylene is 25 wt%, and the content of polyvinyl alcohol is 25 wt%;
(d) blade-coating the composite carbon material slurry on the surface of the support layer obtained in the step (1), and placing the support layer in a hot press for 40kg/cm2Pressurizing for 3min under pressure, drying at 80 ℃, and cleaning for 60min at 60 ℃ in a mixed solution of 3mol/L sulfuric acid and ethanol to obtain a composite carbon material diffusion layer with the average thickness of 50 mu m;
(3) preparation of microporous layer: mixing carbon powder and polytetrafluoroethylene to obtain hydrophobic slurry, and then coating the hydrophobic slurry on the surface of the diffusion layer of the composite carbon material in the step (2) in a scraping manner to obtain the carbon powder loading amount of 0.5mg/cm2A microporous layer having an average thickness of 5 μm;
(4) and (4) calcining the product obtained in the step (3) at 500 ℃ for 60min to obtain the gas diffusion layer. The structure schematic diagram of the gas diffusion layer is shown in fig. 3, wherein 1 is a support layer, 2 is a composite carbon material diffusion layer, and 3 is a microporous layer.
Example 2
The difference from example 1 is that, in step (1), the carbon nanotube film is subjected to laser drilling, and the structural schematic diagram of the obtained support layer is shown in fig. 2, and it can be seen from the diagram that the holes in the support layer are first round holes with a diameter of 100 μm and two second round holes with a diameter of 40 μm distributed in the first round holes, where the first round holes are non-permeable holes and the second round holes are permeable holes. The porosity of the support layer was 82%.
Example 3
The difference from example 1 is that the diameter of the circular holes in the support layer in step (1) is 30 μm, and the porosity of the support layer is 75%.
Example 4
The difference from the example 1 is that the mass ratio of the carbon nanotubes to the carbon fibers in the composite carbon material diffusion layer in the step (d) is 1: 6.
Example 5
The difference from the example 1 is that the mass ratio of the carbon nanotubes to the carbon fibers in the composite carbon material diffusion layer in the step (d) is 12: 1.
Example 6
The difference from the example 1 is that the acetylene black loading amount in the step (3) is 0.1mg/cm2A microporous layer of (a).
Example 7
The difference from the example 1 is that the acetylene black loading amount in the step (3) is 1mg/cm2A microporous layer of (a).
Example 8
A preparation method of a gas diffusion layer comprises the following steps:
(1) preparation of a support layer: carrying out pore forming on a graphene film with the thickness of 25 mu m by using a chemical substance calcium carbonate, then soaking for 100min at 100 ℃ by using 1mol/L sulfuric acid to remove cations in the graphene film, thus obtaining a supporting layer, wherein holes in the supporting layer are square holes with the side length of 45 mu m and are regularly arranged, and the porosity of the supporting layer is 78%;
(2) preparing a composite carbon material diffusion layer:
(a) ultrasonically dispersing PE short fibers and asphalt-based carbon fibers in ethanol to obtain a carbon fiber dispersion liquid;
(b) soaking a multi-walled carbon nanotube in 1mol/L sulfuric acid at 100 ℃ for 8h, centrifugally cleaning with ethanol and pure water, and ultrasonically mixing the multi-walled carbon nanotube with polyvinylpyrrolidone and ethanol in an ultrasonic instrument for 10h, wherein the mass ratio of the multi-walled carbon nanotube to the polyvinylpyrrolidone is 1:3, so as to obtain a carbon nanotube dispersion liquid;
(c) ultrasonically mixing carbon fiber dispersion liquid, carbon nanotube dispersion liquid, polyethylene glycol and polytetrafluoroethylene to obtain composite carbon material slurry, wherein the composite carbon material slurry contains 32 wt% of multi-wall carbon nanotubes, 22 wt% of asphalt-based carbon fibers, 26 wt% of polyethylene glycol and 20 wt% of a hydrophobizing agent;
(d) performing suction filtration on the surface of the support layer obtained in the step (1) to coat the composite carbon material slurry, and placing the support layer in a hot press for 20kg/cm2Pressurizing for 5min under pressure, drying at 50 ℃, and cleaning in a mixed solution of 1mol/L sulfuric acid and ethanol at 30 ℃ for 100min to obtain a composite carbon material diffusion layer with the average thickness of 60 mu m and the mass ratio of the multi-wall carbon nano tube to the asphalt-based carbon fiber of 3: 2;
(3) preparation of microporous layer: mixing activated carbon and polytetrafluoroethylene to obtain hydrophobic slurry, and coating the hydrophobic slurry on the surface of the diffusion layer of the composite carbon material in the step (2) by using a drop coating method to obtain the activated carbon with the loading amount of 0.2mg/cm2A microporous layer having an average thickness of 10 μm;
(4) and (4) calcining the product obtained in the step (3) at 100 ℃ for 100min to obtain the gas diffusion layer.
Example 9
A preparation method of a gas diffusion layer comprises the following steps:
(1) preparation of a support layer: soaking a carbon fiber felt with the thickness of 30 mu m in 5mol/L sulfuric acid at 50 ℃ for 80min, and removing cations in the carbon fiber felt to obtain a supporting layer;
(2) preparing a composite carbon material diffusion layer:
(a) ultrasonically dispersing LM polyester staple fibers in pure water to obtain a carbon fiber dispersion liquid;
(b) soaking a graphitized carbon nanotube in 5mol/L sulfuric acid at 50 ℃ for 15h, centrifugally cleaning with ethanol and pure water, and ultrasonically mixing with sodium dodecyl sulfate and pure water in a cell disruption instrument for 2h, wherein the mass ratio of the graphitized carbon nanotube to the sodium dodecyl sulfate is 1:15, so as to obtain a carbon nanotube dispersion liquid;
(c) ultrasonically mixing carbon fiber dispersion liquid, carbon nanotube dispersion liquid, phenolic resin and polytetrafluoroethylene to obtain composite carbon material slurry, wherein the content of graphitized carbon nanotubes in the composite carbon material slurry is 40 wt%, the content of LM polyester staple fibers is 15 wt%, the content of phenolic resin is 20 wt%, and the content of a hydrophobizing agent is 25 wt%;
(d) blade-coating the composite carbon material slurry on the surface of the support layer obtained in the step (1), and placing the support layer in a hot press for 60kg/cm2Pressurizing for 1min under pressure, drying at 100 ℃, and cleaning in a mixed solution of 5mol/L sulfuric acid and ethanol at 80 ℃ for 20min to obtain a diffusion layer with the average thickness of 50 microns and a composite carbon material diffusion layer with the mass ratio of the carbon nano tubes to the LM polyester staple fibers being 7: 3;
(3) preparation of microporous layer: mixing graphite powder and polytetrafluoroethylene to obtain hydrophobic slurry, and then drop-coating the hydrophobic slurry on the surface of the diffusion layer of the composite carbon material obtained in the step (2) to obtain graphite powder with the loading amount of 0.8mg/cm2A microporous layer having an average thickness of 15 μm;
(4) and (4) calcining the product obtained in the step (3) at 600 ℃ for 10min to obtain the gas diffusion layer.
Comparative example 1
The difference from example 1 is that step (2) uses Dongli carbon paper as the diffusion layer, i.e., in place of the composite carbon material diffusion layer.
Comparative example 2
The difference from example 1 is that no carbon nanotube dispersion liquid is added to the composite carbon material slurry in step (c), i.e., no carbon nanotubes are present in the composite carbon material diffusion layer.
Comparative example 3
The difference from example 1 is that no carbon fiber dispersion is added to the composite carbon material slurry in step (c), i.e., no PP carbon fibers are present in the composite carbon material diffusion layer.
Comparative example 4
The difference from example 1 is that step (3) is not performed, that is, a microporous layer is not present in the resulting gas diffusion layer.
And (3) performance testing:
assembling a fuel cell with the prepared gas diffusion layer: coating a microporous layer on the prepared diffusion layer, drying at 350 ℃, then coating a platinum-carbon catalyst, drying at 105 ℃ for 2 hours, then placing a proton exchange membrane (DuPont) between a cathode and an anode, and carrying out hot pressing at 130 ℃ for two minutes to obtain MEA (membrane electrode assembly) for packaging. The obtained fuel cell was subjected to the following performance tests (test method: the hydrogen side was sealed, two thin tubes were inserted into the two symmetrical sides of the cell, hydrogen was introduced into the lower end, hydrogen was discharged from the upper end, the oxygen side was exposed to the air, and the cell was tested at normal temperature and pressure using an electrochemical workstation):
(1) and (3) electrochemical performance testing: respectively measuring at a current density of 0.1A/cm by linear voltammetry2、0.2A/cm2、0.3A/cm2、0.4A/cm2And 0.5A/cm2Power Density under conditions (in mW/cm)2Denoted by W in table 1) and voltage (in units of V, denoted by V in table 1).
TABLE 1
Figure BDA0002142069850000171
As can be seen from table 1, the assembly of the gas diffusion layers obtained in example 4 and example 5 with respect to example 1 is poor in performance of the fuel cell, because the content of carbon nanotubes is too low in example 4, the porosity is too large, the content of carbon fibers is too low in example 5, the obtained diffusion layers are too dense and have poor gas permeability, and the electrochemical performance of the gas diffusion layers is greatly affected by too large or too small of the porosity of the gas diffusion layers, so that the electrochemical performance of the gas diffusion layers obtained in example 4 and example 5 with respect to example 1 is poor.
As can be seen from table 1, the gas diffusion layers obtained in examples 6 and 7 relative to example 1 are assembled into a fuel cell with poor performance, because the acetylene black loading in example 6 is too small, the conductivity is poor, and the catalyst leakage occurs, and the acetylene black loading in example 7 is too large, the gas transmission path is long, and the performance is adversely affected by too large or too small of the acetylene black loading, so the electrochemical performance of the gas diffusion layers obtained in examples 6 and 7 relative to example 1 is poor.
As can be seen from table 1, in comparative example 1, the fuel cell assembled by using the Dongli carbon paper as the diffusion layer has poorer electrochemical performance than the gas diffusion layer obtained in example 1, and in comparative examples 2 to 4, no carbon nanotube, no PP carbon fiber or no microporous layer exists, so that the obtained gas diffusion layers have poorer electrochemical performance.
In Table 1, "/" indicates that the corresponding data could not be detected and the discharge amount could not be reached.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. The gas diffusion layer is characterized by comprising a support layer, and a composite carbon material diffusion layer and a microporous layer which are sequentially arranged on the surface of the support layer;
the support layer is made of porous materials, and the composite carbon material diffusion layer comprises carbon nanotubes and carbon fibers.
2. The gas diffusion layer according to claim 1, wherein the support layer is a flexible carbon film, preferably any one of a carbon nanotube film, a graphene film, or a carbon fiber felt;
preferably, the thickness of the support layer is <50 μm;
preferably, the porosity of the support layer is 50% -90%, and preferably 70% -85%;
preferably, the aperture of the support layer is larger than 5 μm, preferably 15-22 μm;
preferably, the holes in the support layer are through holes;
preferably, the morphology of the holes in the support layer comprises any one or a combination of at least two of circular holes, rectangular holes and rhombic holes;
preferably, the morphology of the holes is equiregular holes;
preferably, the morphology of the pores in the support layer further includes a first pore and n second pores distributed in the first pore;
preferably, the first hole is a non-penetrating hole;
preferably, the second hole is a through hole;
preferably, n.gtoreq.1.
3. The gas diffusion layer according to claim 1 or 2, wherein the composite carbon material diffusion layer has a thickness of 10 to 60 μm;
preferably, in the composite carbon material diffusion layer, the mass ratio of the carbon nanotubes to the carbon fibers is 10-3: 1-5;
preferably, the carbon nanotubes comprise any one or a combination of at least two of single-walled carbon nanotubes, multi-walled carbon nanotubes, graphitized carbon nanotubes and carboxylated carbon nanotubes;
preferably, the carbon fibers include any one or a combination of at least two of PP carbon fibers, PE short fibers, PVA short fibers, LM polyester short fibers, cellulose short fibers, and pitch-based carbon fibers;
preferably, the porosity of the composite carbon material diffusion layer is 60-90%;
preferably, the microporous layer has a porosity of 50% to 80%;
preferably, the microporous layer comprises carbon powder;
preferably, the loading amount of the carbon powder in the microporous layer is 0.2mg/cm2～0.8mg/cm2；
Preferably, the carbon powder includes any one or a combination of at least two of acetylene black, activated carbon and graphite powder.
4. A method of preparing a gas diffusion layer according to any of claims 1 to 3, comprising the steps of:
and coating the composite carbon material slurry on the support layer to obtain a composite carbon material diffusion layer, then coating the hydrophobic slurry to obtain a microporous layer, and calcining to obtain the gas diffusion layer.
5. The method of claim 4, wherein the step of preparing the support layer comprises: forming a hole on the flexible carbon film, and then removing cations in the flexible carbon film;
preferably, the flexible carbon film pore-forming method comprises any one or a combination of at least two of laser drilling, chemical pore-forming and silicon plate pore-pressing;
preferably, the flexible carbon film is any one of a carbon nanotube film, a graphene film or a carbon fiber felt;
preferably, the removing mode of the cations in the flexible carbon film is acid washing;
preferably, the acid washing is soaking by using sulfuric acid;
preferably, the concentration of the sulfuric acid is 1-5 mol/L;
preferably, the pickling temperature is 50-100 ℃;
preferably, the pickling time is 10-100 min.
6. The production method according to claim 4 or 5, wherein the production process of the composite carbon material slurry comprises: mixing the carbon fiber dispersion liquid, the carbon nanotube dispersion liquid, the binder and the hydrophobing agent to obtain composite carbon material slurry;
preferably, the content of the carbon nanotubes in the composite carbon material slurry is 0-100 wt%, and the carbon nanotubes do not contain 0 wt% and 100 wt%, preferably 20 wt% -40 wt%;
preferably, in the composite carbon material slurry, the content of the carbon fiber is 0-100 wt%, and is not 0 wt% or 100 wt%, preferably 15 wt% to 25 wt%;
preferably, the content of the binder is 0-50 wt%, and does not contain 0 wt%, preferably 20-30 wt%;
preferably, the content of the hydrophobic agent is 0-50 wt%, and 0 wt% is not contained, preferably 20-30 wt%;
preferably, the manner of mixing is sonication;
preferably, the binder comprises any one or a combination of at least two of polytetrafluoroethylene, polyethylene glycol, polyvinyl alcohol and phenolic resin;
preferably, the hydrophobic agent comprises a fluoropolymer, preferably polytetrafluoroethylene;
preferably, the coating mode of the composite carbon material slurry comprises any one or a combination of at least two of suction filtration, blade coating and screen printing;
preferably, the composite carbon material slurry further comprises the processes of pressurizing, drying and cleaning after being coated;
preferably, the pressure for pressurizing is 20-60 kg/cm2；
Preferably, the pressurizing time is 1-5 min;
preferably, the process of pressurizing is carried out in a hot press;
preferably, the drying temperature is 20-100 ℃;
preferably, the cleaning is performed in a mixed solution of 1-5 mol/L sulfuric acid and an organic solvent;
preferably, the organic solvent comprises ethanol;
preferably, the cleaning temperature is 30-80 ℃;
preferably, the cleaning time is 20-100 min.
7. The method according to claim 6, wherein the carbon fiber dispersion is prepared by a process comprising: ultrasonically dispersing carbon fibers to obtain a carbon fiber dispersion liquid;
preferably, the carbon fibers are single length carbon fibers or mixed length carbon fibers;
preferably, the carbon fibers include any one or a combination of at least two of PP carbon fibers, PE short fibers, PVA short fibers, LM polyester short fibers, cellulose short fibers, and pitch-based carbon fibers;
preferably, the preparation process of the carbon nanotube dispersion liquid comprises: pickling the carbon nano tube, and then mixing the carbon nano tube with a surfactant and a solvent to obtain a carbon nano tube dispersion liquid;
preferably, the carbon nanotubes comprise any one or a combination of at least two of single-walled carbon nanotubes, multi-walled carbon nanotubes, graphitized carbon nanotubes and carboxylated carbon nanotubes;
preferably, the acid washing is soaking by using sulfuric acid;
preferably, the concentration of the sulfuric acid is 1-5 mol/L;
preferably, the pickling temperature is 50-100 ℃;
preferably, the pickling time is 5-15 h;
preferably, the acid washing process further comprises a centrifugal washing process by using ethanol and pure water;
preferably, the mass ratio of the carbon nano tube to the surfactant is 1: 3-1: 15;
preferably, the surfactant comprises any one or a combination of at least two of sodium dodecylbenzene sulfonate, polyvinylpyrrolidone and sodium dodecyl sulfate;
preferably, the solvent is any one of pure water, ethanol, acetone and isopropanol or a combination of at least two of pure water, ethanol, acetone and isopropanol;
preferably, the manner of mixing is sonication;
preferably, the ultrasonic instrument is an ultrasonic instrument and/or a cell disruptor;
preferably, the mixing time is 1-15 h;
preferably, the ultrasonic instrument is an ultrasonic instrument, and the mixing time is 5-15 h;
preferably, the ultrasonic instrument is a cell disruptor, and the mixing time is 1-4 h.
8. The method according to any one of claims 4 to 7, wherein the hydrophobic slurry is prepared by a process comprising: mixing the carbon powder slurry with a hydrophobic agent to obtain hydrophobic slurry;
preferably, the content of the carbon powder in the carbon powder slurry is 0.4-0.5 mg/cm2；
Preferably, the carbon powder comprises any one or a combination of at least two of acetylene black, activated carbon and graphite powder;
preferably, the hydrophobic paste is coated by any one or a combination of at least two of blade coating, spray coating, screen printing and drop coating, preferably screen printing;
preferably, the calcining temperature is 100-600 ℃;
preferably, the calcining time is 10-100 min.
9. The method according to any one of claims 4 to 8, wherein the method comprises the steps of:
(1) preparation of a support layer: forming a hole on the flexible carbon film, and then soaking the flexible carbon film for 10-100 min at 50-100 ℃ by adopting 1-5 mol/L sulfuric acid to remove cations in the flexible carbon film;
(2) preparing a composite carbon material diffusion layer:
(a) ultrasonically dispersing carbon fibers to obtain a carbon fiber dispersion liquid;
(b) soaking a carbon nano tube in 1-5 mol/L sulfuric acid at 50-100 ℃ for 5-15 h, centrifugally cleaning with ethanol and pure water, and ultrasonically mixing the carbon nano tube with a surfactant and a solvent for 1-15 h, wherein the mass ratio of the carbon nano tube to the surfactant is 1: 3-1: 15, so as to obtain a carbon nano tube dispersion liquid;
(c) ultrasonically mixing a carbon fiber dispersion liquid, a carbon nanotube dispersion liquid, a binder and a hydrophobing agent to obtain composite carbon material slurry, wherein the content of the carbon nanotubes in the composite carbon material slurry is 20-40 wt%, the content of the carbon fibers is 15-25 wt%, the content of the binder is 20-30 wt%, and the content of the hydrophobing agent is 20-30 wt%;
(d) coating the composite carbon material slurry on the surface of the support layer obtained in the step (1), and placing the support layer in a hot press for 20-60 kg/cm2Pressurizing for 1-5 min under pressure, drying at 20-100 ℃, and cleaning for 20-100 min in a mixed solution of 1-5 mol/L sulfuric acid and ethanol at 30-80 ℃ to obtain a composite carbon material diffusion layer;
(3) preparation of microporous layer: mixing the carbon powder slurry with a hydrophobic agent to obtain hydrophobic slurry, and then coating the hydrophobic slurry on the surface of the composite carbon material diffusion layer in the step (2) to obtain a microporous layer;
(4) and (4) calcining the product obtained in the step (3) at 100-600 ℃ for 10-100 min to obtain the gas diffusion layer.
10. A fuel cell comprising a gas diffusion layer according to any one of claims 1 to 3.
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CN114347510A (en) * 2022-01-10 2022-04-15 浙江联洋新材料股份有限公司 Preparation process and application of polyurethane resin composite polyurethane foam material
CN115000446A (en) * 2022-07-22 2022-09-02 上海电气集团股份有限公司 Gas diffusion layer, preparation method thereof, membrane electrode, cell and application
CN115133048A (en) * 2022-08-09 2022-09-30 一汽解放汽车有限公司 Gas diffusion layer and preparation method and application thereof
CN115133048B (en) * 2022-08-09 2024-04-09 一汽解放汽车有限公司 Gas diffusion layer and preparation method and application thereof

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