WO2021013167A1 - Gas diffusion layer, preparation method therefor, and use thereof - Google Patents

Gas diffusion layer, preparation method therefor, and use thereof Download PDF

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WO2021013167A1
WO2021013167A1 PCT/CN2020/103425 CN2020103425W WO2021013167A1 WO 2021013167 A1 WO2021013167 A1 WO 2021013167A1 CN 2020103425 W CN2020103425 W CN 2020103425W WO 2021013167 A1 WO2021013167 A1 WO 2021013167A1
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optionally
carbon
diffusion layer
layer
composite
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PCT/CN2020/103425
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French (fr)
Chinese (zh)
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周小春
卫俊
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中国科学院苏州纳米技术与纳米仿生研究所
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Publication of WO2021013167A1 publication Critical 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

Definitions

  • This application belongs to the field of fuel cells, for example, it relates to a gas diffusion layer, and its preparation method and application.
  • Fuel cell is one of clean energy production devices. It has a high energy conversion rate and the product is water, so it can be used as a clean energy source. Fuel cells are widely used in aerospace, automotive, and electronics industries. 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, etc. Except for fuel and electrolyte, the overall structural design of most fuel cells is similar.
  • the fuel cell is the reaction of hydrogen and oxygen to produce water and convert it into electricity. Therefore, a large amount of water will be produced during the reaction, which will cause greater recombination of the battery, causing the catalytic layer to be flooded, blocking the entire battery channel, and preventing gas transmission. Therefore, it is important to have a good channel that can transport gas and manage the water produced by the reaction.
  • the gas diffusion layer plays an extremely important role in fuel cells.
  • the gas diffusion layer plays an important role in supporting the catalytic layer, collecting current, conducting gas, and discharging reaction product water in the fuel cell.
  • the thickness of the diffusion layer has an important impact on the entire fuel cell. If the diffusion layer is too thick, the mass transfer and gas transfer of the entire cell will be greatly affected; if the diffusion layer is too thin, the carrying capacity of the catalytic layer will be weakened, and the current collection The capacity will be weakened, which will affect the discharge of the battery.
  • a good diffusion layer should have good mass transfer capacity, good conductivity, and good catalyst carrying capacity.
  • CN102856567A discloses an integrated renewable fuel cell diffusion layer and a preparation method thereof.
  • a non-conductive organic synthetic fiber cloth is used as a support for the diffusion layer, and a conductive corrosion-resistant metal/metal oxide network is constructed on it to fill Into the pores of the organic fibers, a certain hydrophobic agent and binder are combined to make the diffusion layer achieve suitable hydrophilic and hydrophobic properties and construct a suitable pore structure to ensure the mass transfer balance of URFC in different working modes.
  • the fuel cell diffusion layer solves the corrosion problem of the URFC support in the prior art, but its mass transfer ability is poor.
  • CN107012739B discloses an ultra-thin carbon fiber paper modified by a conductive polymer film and a preparation method thereof.
  • the conductive polymer film is deposited inside the high flux unmodified ultra-thin carbon fiber paper by an electrochemical deposition method to prepare a conductive polymer film.
  • Polymer film modified ultra-thin carbon fiber paper In the prepared conductive polymer film modified ultra-thin carbon fiber paper, the conductive polymer film is coated on the carbon fiber and the matrix carbon-carbon fiber node to form a uniform thickness film network inside the carbon paper.
  • the ultra-thin carbon fiber paper has poor mass transfer capacity and air permeability.
  • the purpose of this application is to provide a gas diffusion layer and its preparation method and use.
  • the gas diffusion layer has good mass transfer ability, good gas permeability, good electrical conductivity, good mechanical strength, and good catalyst carrying capacity, and has a simple preparation process and can be industrially produced.
  • One of the objectives of the present application is to provide a gas diffusion layer including a support layer and a composite carbon material diffusion layer and a microporous layer sequentially arranged on the surface of the support layer;
  • the support layer is a porous material
  • the composite carbon material diffusion layer includes carbon nanotubes and carbon fibers.
  • the support layer described in this application has high mechanical strength, and it can not only collect current but also serve as the frame base of the diffusion layer; this application mixes two materials of carbon nanotubes and carbon fibers, and uses carbon fiber as the base frame and carbon nanotubes as the frame
  • the filling material meets the requirement of high gas permeability of the gas diffusion layer and has high mechanical strength.
  • the composite carbon material diffusion layer When the composite carbon material diffusion layer is loaded, its surface will also have pores of different sizes like traditional carbon paper, and the surface may have unevenness, so the microporous layer becomes an important part, which can make the diffusion
  • the filling of pores with different sizes of the layer can also slow down the unevenness of the diffusion layer, thereby realizing the redistribution of water and reaction gas in the flow field and the catalytic layer, and increase the conductivity and improve the battery life.
  • the support layer, the composite carbon material diffusion layer and the microporous layer of the present invention work together to obtain a material with good mass transfer ability, good air permeability, good electrical conductivity and good mechanical strength, and good catalyst carrying capacity Gas diffusion layer.
  • the support layer is a flexible carbon film, which may be any one of a carbon nanotube film, a graphene film, or a carbon fiber felt.
  • the thickness of the support layer is less than 50 ⁇ m, such as 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 25 ⁇ m, 30 ⁇ m, 35 ⁇ m, 40 ⁇ m, or 45 ⁇ m.
  • the porosity of the support layer is 50% to 90%, optionally 70 to 85%, such as 52%, 55%, 58%, 60%, 65%, 70%, 72%, 75% , 78%, 80%, 82%, 85% or 88% etc.
  • the pore size of the support layer is> 5 ⁇ m, and may be 15-22 ⁇ m, such as 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, 15 ⁇ m, 16 ⁇ m, 17 ⁇ m, 18 ⁇ m, 19 ⁇ m, 20 ⁇ m , 21 ⁇ m, 22 ⁇ m, 23 ⁇ m, 24 ⁇ m, 25 ⁇ m, 26 ⁇ m, 27 ⁇ m, 28 ⁇ m, 30 ⁇ m, 32 ⁇ m, 33 ⁇ m, 35 ⁇ m, 36 ⁇ m, 38 ⁇ m or 40 ⁇ m etc.
  • the holes in the supporting layer are penetrating holes.
  • the holes in the supporting layer include any one or a combination of at least two of a round hole, a rectangular hole and a diamond hole.
  • the morphology of the holes is regular holes.
  • the shape of the hole in the support layer further includes a first hole and n second holes distributed in the first hole.
  • the first hole is a non-penetrating hole.
  • the second hole is a through hole.
  • the n ⁇ 1 such as 2, 3, 4, 5, 6, 7, or 8, etc.
  • the composite carbon material diffusion layer has a thickness of 10-60 ⁇ m, such as 12 ⁇ m, 15 ⁇ m, 20 ⁇ m, 25 ⁇ m, 30 ⁇ m, 35 ⁇ m, 40 ⁇ m, 45 ⁇ m, 50 ⁇ m, 55 ⁇ m, or 58 ⁇ m.
  • the mass ratio of carbon nanotubes and carbon fibers is 3-10:1-5, such as 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 etc.
  • the mass ratio of carbon nanotubes and carbon fibers described in this application is 3-10:1-5. Too little carbon nanotube content means too much porosity; too little carbon fiber content means too dense diffusion layer.
  • the carbon nanotubes include any one or a combination of at least two of single-wall carbon nanotubes, multi-wall carbon nanotubes, graphitized carbon nanotubes, and carboxylated carbon nanotubes.
  • the carbon fiber includes any one or a combination of at least two of PP carbon fiber, PE short fiber, PVA short fiber, LM polyester short fiber, cellulose short fiber and pitch-based carbon fiber.
  • 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% % Or 88% etc.
  • the porosity of the microporous layer is 50% to 80%, such as 52%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, 72%, 75% or 78% etc.
  • the microporous layer includes carbon powder.
  • the loading amount of the carbon powder in the microporous layer is 0.2 mg/cm 2 to 0.8 mg/cm 2 , for example, 0.3 mg/cm 2 , 0.4 mg/cm 2 , 0.5 mg/cm 2 , 0.6 mg /cm 2 or 0.7mg/cm 2 etc.
  • the loading amount of carbon powder in the microporous layer described in this application is 0.2mg/cm 2 ⁇ 0.8mg/cm 2 , if the content of carbon powder is too small, conductivity will be poor and catalyst leakage will occur; too much carbon powder content , The gas transmission path is long.
  • the carbon powder includes any one or a combination of at least two of acetylene black, activated carbon and graphite powder.
  • the second objective of this application is to provide a method for preparing the gas diffusion layer as described in the first objective, and the method includes the following steps:
  • the composite carbon material slurry is coated on the support layer to obtain a composite carbon material diffusion layer, and then the hydrophobic slurry is coated to obtain a microporous layer, which is calcined to obtain a gas diffusion layer.
  • the preparation process of the support layer includes: making holes in the flexible carbon film, and then removing cations in the flexible carbon film.
  • the flexible carbon film hole formation method includes any one or a combination of at least two of laser drilling, chemical hole formation and silicon plate pressing.
  • the flexible carbon film is any one of carbon nanotube film, graphene film or carbon fiber felt.
  • the method for removing cations in the flexible carbon film is pickling.
  • the pickling is immersion in sulfuric acid.
  • the concentration of the sulfuric acid is 1 to 5 mol/L, for example, 1.5 mol/L, 2 mol/L, 2.2 mol/L, 2.5 mol/L, 2.8 mol/L, 3 mol/L, 3.5 mol/L, 4mol/L or 4.5mol/L etc.
  • the temperature of the pickling is 50-100°C, such as 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, or 95°C.
  • the pickling time is 10-100 min, for example, 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, or 90 min.
  • the preparation process of the composite carbon material slurry includes: mixing a carbon fiber dispersion liquid, a carbon nanotube dispersion liquid, a binder, and a hydrophobic agent to obtain a composite carbon material slurry.
  • the mixed slurry of carbon nanotubes and carbon fibers directly serves as the overall frame of the diffusion layer, it is relatively loose, so a binder needs to be added to the slurry to reduce the resistance between the composite carbon material layer and the support layer.
  • the content of carbon nanotubes in the composite carbon material slurry is 0-100% by weight, and does not contain 0% and 100% by weight, and may be 20%-40%, such as 1% by weight, 5% by weight, or 8% by weight.
  • % 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt% or 90wt%, etc. .
  • the carbon fiber content in the composite carbon material slurry is 0-100% by weight, and does not contain 0% and 100% by weight, and can be 15%-25%, such as 1% by weight, 5% by weight, 8% by weight, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt% or 90wt%, etc.
  • the content of the binder is 0-50% by weight, and does not contain 0% by weight, and may be 20%-30% by weight, for example, 1% by weight, 5% by weight, 8% by weight, 10% by weight, 15% by weight, and 20% by weight. , 22wt%, 25wt%, 28wt%, 30wt%, 32wt%, 35wt%, 38wt%, 40wt% or 45wt%, etc.
  • the content of the hydrophobic agent is 0-50% by weight, and does not contain 0% by weight, optionally 20% by weight to 30% by weight, such as 1% by weight, 5% by weight, 8% by weight, 10% by weight, 15% by weight, 20% by weight, 25wt%, 30wt%, 35wt%, 40wt% or 45wt%, etc.
  • the mixing method is ultrasound.
  • the binder includes any one or a combination of at least two of polytetrafluoroethylene, polyethylene glycol, polyvinyl alcohol and phenolic resin.
  • the hydrophobic agent includes a fluorine-containing polymer, optionally polytetrafluoroethylene.
  • the coating method of the composite carbon material slurry includes any one or a combination of at least two of suction filtration, knife coating and screen printing.
  • a process of pressurizing, drying and cleaning is also included.
  • the pressurized pressure is 20-60kg/cm 2 , for example 25kg/cm 2 , 30kg/cm 2 , 35kg/cm 2 , 40kg/cm 2 , 45kg/cm 2 , 50kg/cm 2 or 55kg /cm 2 etc.
  • the pressing process described in this application can make the diffusion layer firmer and smoother.
  • the pressurization time is 1 to 5 minutes, for example, 2 minutes, 3 minutes, or 4 minutes.
  • the pressurizing process is performed in a hot press.
  • the drying temperature is 20-100°C, such as 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, or 90°C.
  • the cleaning is cleaning in a mixed solution of 1 to 5 mol/L sulfuric acid and an organic solvent, such as 1.5 mol/L, 2 mol/L, 2.2 mol/L, 2.5 mol/L, 2.8 mol/L, 3 mol/L /L, 3.5mol/L, 4mol/L or 4.5mol/L etc.
  • the organic solvent includes ethanol.
  • the cleaning temperature is 30-80°C, such as 40°C, 50°C, 60°C, or 70°C.
  • the cleaning time is 20-100 minutes, such as 30 minutes, 40 minutes, 50 minutes, 60 minutes, 70 minutes, 80 minutes, or 90 minutes.
  • the preparation process of the carbon fiber dispersion liquid includes: ultrasonically dispersing carbon fibers to obtain a carbon fiber dispersion liquid.
  • the carbon fiber is a single-length carbon fiber or a mixed-length carbon fiber.
  • the carbon fiber includes any one or a combination of at least two of PP carbon fiber, PE short fiber, PVA short fiber, LM polyester short fiber, cellulose short fiber and pitch-based carbon fiber.
  • the preparation process of the carbon nanotube dispersion liquid includes: pickling the carbon nanotubes, and then mixing with a surfactant and a solvent to obtain a carbon nanotube dispersion liquid.
  • the carbon nanotubes include any one or a combination of at least two of single-wall carbon nanotubes, multi-wall carbon nanotubes, graphitized carbon nanotubes, and carboxylated carbon nanotubes.
  • the pickling is immersion in sulfuric acid.
  • the concentration of the sulfuric acid is 1 to 5 mol/L, for example, 1.5 mol/L, 2 mol/L, 2.2 mol/L, 2.5 mol/L, 2.8 mol/L, 3 mol/L, 3.5 mol/L, 4mol/L or 4.5mol/L etc.
  • the temperature of the pickling is 50-100°C, such as 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, or 95°C.
  • the pickling time is 5-15h, such as 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h or 14h.
  • a centrifugal washing process with ethanol and pure water is also included.
  • 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 etc.
  • the surfactant includes any one or a combination of at least two of sodium dodecylbenzene sulfonate, polyvinylpyrrolidone, and sodium lauryl sulfate.
  • the solvent is any one or a combination of at least two of pure water, ethanol, acetone and isopropanol.
  • the mixing method is ultrasound.
  • the ultrasonic instrument is an ultrasonic instrument and/or a cell disruptor.
  • the mixing time is 1-15h, such as 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h or 14h.
  • the ultrasonic instrument is an ultrasonic instrument
  • the mixing time is 5 to 15 hours, such as 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, or 14 hours.
  • the ultrasonic instrument is a cell disruptor, and the mixing time is 1 to 4 hours, such as 1 hour, 2 hours, 3 hours, or 4 hours.
  • the preparation process of the hydrophobic slurry includes: mixing the carbon powder slurry with a hydrophobic agent to obtain the hydrophobic slurry.
  • the content of the carbon powder slurry toner is 0.4 ⁇ 0.5mg / cm 2, for example, 0.41mg / cm 2, 0.42mg / cm 2, 0.43mg / cm 2, 0.44mg / cm 2, 0.45 mg / cm 2, 0.46mg / cm 2, 0.47mg / cm 2, 0.48mg / cm 2 or 0.49mg / cm 2 and the like.
  • the carbon powder includes any one or a combination of at least two of acetylene black, activated carbon and graphite powder.
  • the coating method of the hydrophobic slurry includes any one or a combination of at least two of blade coating, spray coating, screen printing and drip coating, and screen printing can be selected.
  • the calcination temperature is 100-600°C, such as 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, 450°C, 500°C, or 550°C.
  • the calcination time is 10-100 min, for example, 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, or 90 min.
  • the method for preparing the gas diffusion layer described in this application includes the following steps:
  • the content of carbon nanotubes in the composite carbon material slurry is 20 wt% to 40 wt%,
  • the content of carbon fiber is 15% to 25% by weight, the content of binder is 20% to 30% by weight, and the content of hydrophobic agent is 20% to 30% by weight;
  • step (1) Coating the composite carbon material slurry on the surface of the support layer obtained in step (1), pressurizing in a hot press at 20-60 kg/cm 2 for 1 to 5 minutes, and drying at 20 to 100°C, Wash in a mixed solution of 1 to 5 mol/L sulfuric acid and ethanol at 30 to 80°C for 20 to 100 minutes to obtain a composite carbon material diffusion layer;
  • the carbon powder slurry is mixed with a hydrophobic agent to obtain a hydrophobic slurry, and then the hydrophobic slurry is coated on the surface of the composite carbon material diffusion layer in step (2) to obtain micropores Floor;
  • step (3) The product obtained in step (3) is calcined at 100-600°C for 10-100 minutes to obtain a gas diffusion layer.
  • the third objective of the present application is to provide a fuel cell including the gas diffusion layer described in one of the objectives.
  • the support layer described in this application has high mechanical strength, which can not only collect current but also serve as the base of the diffusion layer frame; this application mixes two materials of carbon nanotubes and carbon fibers, and uses carbon fiber as the base frame. As the filler of the frame, the tube meets the requirement of high air permeability of the gas diffusion layer and has high mechanical strength.
  • the composite carbon material diffusion layer When the composite carbon material diffusion layer is loaded, its surface will also have pores of different sizes like traditional carbon paper, and the surface may have unevenness, so the microporous layer becomes an important part.
  • the pores of different sizes in the diffusion layer can be filled, and the unevenness of the diffusion layer can be reduced, thereby realizing the redistribution of water and reaction gas in the flow field and the catalytic layer, increasing the conductivity and improving the battery life.
  • the support layer, the composite carbon material diffusion layer and the microporous layer described in the present invention work together to obtain a good mass transfer capacity, good gas permeability, good conductivity, good mechanical strength, and good catalyst Gas diffusion layer with bearing capacity.
  • FIG. 1 is a schematic diagram of the supporting layer structure obtained in specific embodiment 1 of the present application.
  • FIG. 2 is a schematic diagram of the structure of the support layer obtained in specific embodiment 2 of the present application.
  • Example 3 is a schematic diagram of the structure of the gas diffusion layer obtained in Example 1 of the present application.
  • a method for preparing a gas diffusion layer includes the following steps:
  • Preparation of the support layer laser perforate a carbon nanotube film with a thickness of 20 ⁇ m, and then use 3mol/L sulfuric acid to soak at 80°C for 60 minutes to remove the cations in the carbon nanotube film to obtain a support layer structure
  • the schematic diagram is shown in Fig. 1, and it can be seen from the figure that the holes in the support layer are circular holes with a diameter of 35 ⁇ m and are arranged regularly, and the porosity of the support layer is 80%;
  • step (1) Scrape the composite carbon material slurry on the surface of the support layer obtained in step (1), press in a hot press at a pressure of 40kg/cm 2 for 3 minutes, dry at 80°C, and dry at 3mol/L sulfuric acid and Wash in a mixed solution of ethanol for 60 minutes at 60°C to obtain a composite carbon material diffusion layer with an average thickness of 50 ⁇ m;
  • Step (3) Preparation of the microporous layer: mixing carbon powder with polytetrafluoroethylene to obtain a hydrophobic slurry, and then scraping the hydrophobic slurry on the surface of the composite carbon material diffusion layer in step (2) to obtain carbon powder
  • step (3) The product obtained in step (3) is calcined at 500° C. for 60 minutes to obtain a gas diffusion layer.
  • the structure diagram of the gas diffusion layer is shown in FIG. 3, in which 1 is a support layer, 2 is a composite carbon material diffusion layer, and 3 is a microporous layer.
  • step (1) the carbon nanotube film is laser-drilled, and the structure of the obtained support layer is shown in Figure 2. It can be seen from the figure that the holes in the support layer are 100 ⁇ m in diameter. The first round hole and two second round holes with a diameter of 40 ⁇ m distributed in the first round hole, wherein the first round hole is an impermeable hole, and the second round hole is a permeable hole. The porosity of the support layer was 82%.
  • Example 1 The difference from Example 1 is that the diameter of the circular holes in the supporting layer in step (1) is 30 ⁇ m, and the porosity of the supporting layer is 75%.
  • Example 1 The difference from Example 1 is that the mass ratio of carbon nanotubes and carbon fibers in the composite carbon material diffusion layer in step (d) is 1:6.
  • Example 1 The difference from Example 1 is that the mass ratio of carbon nanotubes and carbon fibers in the composite carbon material diffusion layer in step (d) is 12:1.
  • Example 1 The difference from Example 1 is that the loading of acetylene black in step (3) is 0.1 mg/cm 2 of the microporous layer.
  • Example 1 The difference from Example 1 is that the acetylene black in step (3) has a microporous layer with a loading amount of 1 mg/cm 2 .
  • a method for preparing a gas diffusion layer includes the following steps:
  • a graphene film with a thickness of 25 ⁇ m is made with calcium carbonate, a chemical substance, and then immersed in 1mol/L sulfuric acid at 100°C for 100 minutes to remove the cations in the graphene film to obtain the support layer
  • the holes in the support layer are square holes with a side length of 45 ⁇ m and are regularly arranged, and the porosity of the support layer is 78%;
  • step (1) The composite carbon material slurry is suction filtered and coated on the surface of the support layer obtained in step (1), pressurized in a hot press at a pressure of 20kg/cm 2 for 5 minutes, dried at 50°C, and dried at 1mol/L Wash in a mixed solution of sulfuric acid and ethanol at 30°C for 100 minutes to obtain a composite carbon material diffusion layer with an average thickness of 60 ⁇ m and a mass ratio of multi-walled carbon nanotubes and pitch-based carbon fibers of 3:2;
  • microporous layer Preparation of the microporous layer: mixing activated carbon and polytetrafluoroethylene to obtain a hydrophobic slurry, and then coating the hydrophobic slurry on the surface of the composite carbon material diffusion layer in step (2) by a drop coating method, A microporous layer with an activated carbon loading of 0.2mg/cm 2 and an average thickness of 10 ⁇ m is obtained;
  • step (3) The product obtained in step (3) is calcined at 100° C. for 100 minutes to obtain a gas diffusion layer.
  • a method for preparing a gas diffusion layer includes the following steps:
  • a carbon fiber felt with a thickness of 30 ⁇ m is immersed in 5mol/L sulfuric acid at 50°C for 80 minutes to remove cations in the carbon fiber felt to obtain a support layer;
  • step (1) Scrape the composite carbon material slurry on the surface of the support layer obtained in step (1), press in a hot press at a pressure of 60kg/cm 2 for 1 min, dry at 100°C, and dry in 5mol/L sulfuric acid and Wash in a mixed solution of ethanol at 80°C for 20 minutes to obtain a diffusion layer with an average thickness of 50 microns and a composite carbon material diffusion layer with a mass ratio of carbon nanotubes and LM polyester short fibers of 7:3;
  • Step (3) Preparation of the microporous layer: mixing graphite powder with polytetrafluoroethylene to obtain a hydrophobic slurry, and then drip coating the hydrophobic slurry on the surface of the composite carbon material diffusion layer in step (2) to obtain A microporous layer with a graphite powder loading capacity of 0.8 mg/cm 2 and an average thickness of 15 ⁇ m;
  • step (3) The product obtained in step (3) is calcined at 600° C. for 10 minutes to obtain a gas diffusion layer.
  • step (2) Toray carbon paper is used as the diffusion layer, that is, the composite carbon material diffusion layer is replaced.
  • Example 1 The difference from Example 1 is that the composite carbon material slurry in step (c) does not add carbon nanotube dispersion liquid, that is, there is no carbon nanotube in the composite carbon material diffusion layer.
  • Example 1 The difference from Example 1 is that the composite carbon material slurry in step (c) does not add carbon fiber dispersion, that is, there is no PP carbon fiber in the composite carbon material diffusion layer.
  • step (3) is not performed, that is, there is no microporous layer in the obtained gas diffusion layer.
  • Assemble the fuel cell with the prepared gas diffusion layer coat the microporous layer on the prepared diffusion layer, dry at 350°C, and then coat platinum-carbon catalyst, bake at 105°C for 2 hours, and then the proton exchange membrane (DuPont) Place it between the yin and yang poles and press at 130°C for two minutes to get MEA for packaging.
  • Test method seal the hydrogen side, insert two thin tubes into the symmetrical sides of the battery, pass hydrogen at the lower end, discharge hydrogen at the upper end, and expose the oxygen side to the air.
  • Use electrochemistry at room temperature and pressure Workstation for battery test
  • Electrochemical performance test use linear voltammetry to test under current density of 0.1A/cm 2 , 0.2A/cm 2 , 0.3A/cm 2 , 0.4A/cm 2 and 0.5A/cm 2
  • the power density unit is mW/cm 2 , expressed as W in Table 1
  • voltage unit is V, expressed as V in Table 1).
  • Example 4 the performance of the fuel cell assembly of the gas diffusion layer obtained in Example 4 and Example 5 is poorer than that in Example 1, because the content of carbon nanotubes in Example 4 is too small and the porosity is too large.
  • Example 5 if the carbon fiber content is too small, the obtained diffusion layer is too dense and has poor air permeability. The porosity of the gas diffusion layer is too large or too small to have a greater impact on its electrochemical performance. Therefore, Examples 4 and 5 are compared to the implementation The gas diffusion layer obtained in Example 1 has poor electrochemical performance.
  • Example 6 and Example 7 are relatively The gas diffusion layer obtained in Example 1 has poor electrochemical performance.
  • Comparative Example 1 uses Toray carbon paper as the diffusion layer to assemble a fuel cell, and its electrochemical performance is poorer than that of the gas diffusion layer obtained in Example 1.
  • Comparative Examples 2-4 Nanotubes, no PP carbon fiber or no microporous layer, the resulting gas diffusion layer has poor electrochemical performance, indicating that the support layer, composite carbon material diffusion layer and microporous layer in the present application work together and cannot lack any One layer, and the carbon nanotubes and carbon fibers in the composite carbon material diffusion layer must exist at the same time, so that the obtained gas diffusion layer can not only meet the requirements of high gas permeability, but also have good electrochemical performance.

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Abstract

Disclosed are a gas diffusion layer, a preparation method therefor, and a use thereof. The gas diffusion layer comprises a support layer, and a composite carbon material diffusion layer and a microporous layer sequentially disposed on a surface of the support layer. The support layer is made of a porous material, and the composite carbon material diffusion layer comprises carbon nanotubes and carbon fibers.

Description

一种气体扩散层、及其制备方法和用途Gas diffusion layer, and preparation method and application thereof 技术领域Technical field
本申请属于燃料电池领域，例如涉及一种气体扩散层、及其制备方法和用途。This application belongs to the field of fuel cells, for example, it relates to a gas diffusion layer, and its preparation method and application.
背景技术Background technique
燃料电池就是清洁产能装置之一，它的能量转化率高，产物为水，因此可以作为一种清洁能源使用。燃料电池广泛的应用于航空航天，汽车领域，电子工业中。燃料电池可分为：质子交换膜燃料电池(聚合物电解质膜燃料电池)、甲醇燃料电池、固体氧化物燃料电池、磷酸燃料电池、碱燃料电池等。除了燃料和电解质外，大多数燃料电池的总体结构设计类似。Fuel cell is one of clean energy production devices. It has a high energy conversion rate and the product is water, so it can be used as a clean energy source. Fuel cells are widely used in aerospace, automotive, and electronics industries. 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, etc. Except for fuel and electrolyte, the overall structural design of most fuel cells is similar.
燃料电池是氢与氧反应产生水而转化为电能，因此反应过程中会产生大量的水对电池造成较大的复合，使催化层被水淹，堵塞整个电池通道，使气体无法传输。因此有一个良好的通道，能够传送气体，管理反应所产生的水就很重要。The fuel cell is the reaction of hydrogen and oxygen to produce water and convert it into electricity. Therefore, a large amount of water will be produced during the reaction, which will cause greater recombination of the battery, causing the catalytic layer to be flooded, blocking the entire battery channel, and preventing gas transmission. Therefore, it is important to have a good channel that can transport gas and manage the water produced by the reaction.
气体扩散层(Gas Duffusion Layer简称GDL)，在燃料电池中有极为重要的作用，气体扩散层在燃料电池中起到支撑催化层、收集电流、传导气体和排出反应产物水的重要作用。扩散层的厚度对整个燃料电池有着重要的影响，扩散层太厚，整个电池的传质和气体传输会受到较大的影响；扩散层太薄，对催化层的承载能力减弱，并且收集电流的能力会减弱，对电池的放电会造成影响。一个好的扩散层应具有良好的传质能力、良好的导电性、良好的催化剂承载能力。The gas diffusion layer (Gas Duffusion Layer for short GDL) plays an extremely important role in fuel cells. The gas diffusion layer plays an important role in supporting the catalytic layer, collecting current, conducting gas, and discharging reaction product water in the fuel cell. The thickness of the diffusion layer has an important impact on the entire fuel cell. If the diffusion layer is too thick, the mass transfer and gas transfer of the entire cell will be greatly affected; if the diffusion layer is too thin, the carrying capacity of the catalytic layer will be weakened, and the current collection The capacity will be weakened, which will affect the discharge of the battery. A good diffusion layer should have good mass transfer capacity, good conductivity, and good catalyst carrying capacity.
同时，良好的传质能力就要求整个扩散层需要较高的孔隙度，厚度也不能 过厚，碳纸、碳布等以碳纤维毡布作为基底层的气体扩散层拥有较高的透气性、导电性但是机械强度却有很大的局限性。At the same time, good mass transfer capability requires that the entire diffusion layer needs high porosity and the thickness cannot be too thick. Gas diffusion layers such as carbon paper and carbon cloth with carbon fiber felt as the base layer have high air permeability and conductivity. But the mechanical strength has great limitations.
CN102856567A公开了一种一体式可再生燃料电池扩散层及其制备方法，采用不导电的有机合成纤维布作为扩散层的支撑体，通过在其上构造导电的耐腐蚀金属/金属氧化物网络，填充到有机纤维的孔隙中，结合一定的疏水剂、粘结剂，使扩散层达到适宜的亲疏水性能以及构造合适的孔结构，以保证URFC在不同工作模式下的传质平衡。所述燃料电池扩散层解决了现有技术中URFC支撑体的腐蚀问题，但是其传质能力较差。CN102856567A discloses an integrated renewable fuel cell diffusion layer and a preparation method thereof. A non-conductive organic synthetic fiber cloth is used as a support for the diffusion layer, and a conductive corrosion-resistant metal/metal oxide network is constructed on it to fill Into the pores of the organic fibers, a certain hydrophobic agent and binder are combined to make the diffusion layer achieve suitable hydrophilic and hydrophobic properties and construct a suitable pore structure to ensure the mass transfer balance of URFC in different working modes. The fuel cell diffusion layer solves the corrosion problem of the URFC support in the prior art, but its mass transfer ability is poor.
CN107012739B公开了一种导电高分子薄膜改性的超薄炭纤维纸及其制备方法，采用电化学沉积的方法在高通量无改性超薄炭纤维纸内部沉积导电高分子薄膜，制得导电高分子薄膜改性超薄炭纤维纸。在所制的导电高分子薄膜改性超薄炭纤维纸中，导电高分子薄膜包覆在炭纤维、基体炭-炭纤维节点上，在炭纸内部形成厚度均匀的薄膜网络。所述超薄炭纤维纸的传质能力和气透率较差。CN107012739B discloses an ultra-thin carbon fiber paper modified by a conductive polymer film and a preparation method thereof. The conductive polymer film is deposited inside the high flux unmodified ultra-thin carbon fiber paper by an electrochemical deposition method to prepare a conductive polymer film. Polymer film modified ultra-thin carbon fiber paper. In the prepared conductive polymer film modified ultra-thin carbon fiber paper, the conductive polymer film is coated on the carbon fiber and the matrix carbon-carbon fiber node to form a uniform thickness film network inside the carbon paper. The ultra-thin carbon fiber paper has poor mass transfer capacity and air permeability.
因此，本领域亟需一种新型燃料电池用气体扩散层，所述气体扩散层具有良好的传质能力、良好的透气性、良好的导电性和良好的机械强度、以及良好的催化剂承载能力，并且制备过程简单，可工业化生产。Therefore, there is an urgent need in the art for a new type of gas diffusion layer for fuel cells, which has good mass transfer ability, good gas permeability, good electrical conductivity, good mechanical strength, and good catalyst carrying capacity. And the preparation process is simple, and it can be industrialized.
发明内容Summary of the invention
鉴于目前商业化的碳纸厚度较厚，气体传递路径长，增加了传质阻力，并且传统碳纸加入胶黏剂如PTFE、酚醛树脂等经过高温石墨化后扩散层结构会变得很脆，机械强度较低，在使用的过程中容易发生断裂的现象，影响电池放电性能。鉴于以上的局限性，本申请突破传统的碳纸制备方法不经过石墨化处理 手段，使扩散层变得柔软且具有高导电性。In view of the thicker thickness of the current commercial carbon paper, the long gas transmission path, which increases the mass transfer resistance, and the traditional carbon paper is added with adhesives such as PTFE, phenolic resin, etc. after high temperature graphitization, the diffusion layer structure will become very brittle. The mechanical strength is low, and the phenomenon of breakage easily occurs during use, which affects the discharge performance of the battery. In view of the above limitations, this application breaks through the traditional carbon paper preparation method without graphitization treatment, so that the diffusion layer becomes soft and has high conductivity.
本申请的目的在于提供一种气体扩散层、及其制备方法和用途。所述气体扩散层具有良好的传质能力、良好的透气性、良好的导电性和良好的机械强度、以及良好的催化剂承载能力，并且制备过程简单，可工业化生产。The purpose of this application is to provide a gas diffusion layer and its preparation method and use. The gas diffusion layer has good mass transfer ability, good gas permeability, good electrical conductivity, good mechanical strength, and good catalyst carrying capacity, and has a simple preparation process and can be industrially produced.
为达此目的，本申请采用以下技术方案：To achieve this goal, this application adopts the following technical solutions:
本申请的目的之一在于提供一种气体扩散层，所述气体扩散层包括支撑层和依次设置于所述支撑层表面的复合碳材料扩散层和微孔层；One of the objectives of the present application is to provide a gas diffusion layer including a support layer and a composite carbon material diffusion layer and a microporous layer sequentially arranged on the surface of the support layer;
所述支撑层为多孔材料，所述复合碳材料扩散层包括碳纳米管和碳纤维。The support layer is a porous material, and the composite carbon material diffusion layer includes carbon nanotubes and carbon fibers.
本申请所述支撑层具有较高的机械强度，其既可集流又可作为扩散层框架基底；本申请将碳纳米管和碳纤维两种材料混合，以碳纤维作为基底框架，碳纳米管作为框架的填充物，满足了气体扩散层高透气性的要求，并且拥有较高的机械强度。The support layer described in this application has high mechanical strength, and it can not only collect current but also serve as the frame base of the diffusion layer; this application mixes two materials of carbon nanotubes and carbon fibers, and uses carbon fiber as the base frame and carbon nanotubes as the frame The filling material meets the requirement of high gas permeability of the gas diffusion layer and has high mechanical strength.
在负载复合碳材料扩散层时，它的表面也会像传统碳纸那样有大小不一的孔隙并且表面可能存在凹凸不平的现象，所以微孔层就成了一个重要的部分，它可以使扩散层大小不一的孔隙填补，还可以减缓扩散层的不平整现象，进而实现水和反应气体在流场和催化层的再分配，并且增加了电导率，提高了电池寿命。When the composite carbon material diffusion layer is loaded, its surface will also have pores of different sizes like traditional carbon paper, and the surface may have unevenness, so the microporous layer becomes an important part, which can make the diffusion The filling of pores with different sizes of the layer can also slow down the unevenness of the diffusion layer, thereby realizing the redistribution of water and reaction gas in the flow field and the catalytic layer, and increase the conductivity and improve the battery life.
本发所述支撑层、复合碳材料扩散层和微孔层共同作用，可以得到具有良好的传质能力、良好的透气性、良好的导电性和良好的机械强度、以及良好的催化剂承载能力的气体扩散层。The support layer, the composite carbon material diffusion layer and the microporous layer of the present invention work together to obtain a material with good mass transfer ability, good air permeability, good electrical conductivity and good mechanical strength, and good catalyst carrying capacity Gas diffusion layer.
可选地，所述支撑层为柔性碳膜，可选为碳纳米管膜、石墨烯膜或碳纤维毡中的任意一种。Optionally, the support layer is a flexible carbon film, which may be any one of a carbon nanotube film, a graphene film, or a carbon fiber felt.
可选地，所述支撑层的厚度<50μm，例如10μm、15μm、20μm、25μm、30μm、35μm、40μm或45μm等。Optionally, the thickness of the support layer is less than 50 μm, such as 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, or 45 μm.
可选地，所述支撑层的孔隙率为50％～90％，可选为70～85％，例如52％、55％、58％、60％、65％、70％、72％、75％、78％、80％、82％、85％或88％等。Optionally, the porosity of the support layer is 50% to 90%, optionally 70 to 85%, such as 52%, 55%, 58%, 60%, 65%, 70%, 72%, 75% , 78%, 80%, 82%, 85% or 88% etc.
可选地，所述支撑层的孔径>5μm，可选为15～22μm，例如6μm、7μm、8μm、9μm、10μm、11μm、12μm、13μm、14μm、15μm、16μm、17μm、18μm、19μm、20μm、21μm、22μm、23μm、24μm、25μm、26μm、27μm、28μm、30μm、32μm、33μm、35μm、36μm、38μm或40μm等。Optionally, the pore size of the support layer is> 5 μm, and may be 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 , 21μm, 22μm, 23μm, 24μm, 25μm, 26μm, 27μm, 28μm, 30μm, 32μm, 33μm, 35μm, 36μm, 38μm or 40μm etc.
可选地，所述支撑层中的孔为贯穿性的孔。Optionally, the holes in the supporting layer are penetrating holes.
可选地，所述支撑层中的孔包括圆孔、矩形孔和菱形孔中的任意一种或至少两种的组合。Optionally, the holes in the supporting layer include any one or a combination of at least two of a round hole, a rectangular hole and a diamond hole.
可选地，所述孔的形貌为等规则的孔。Optionally, the morphology of the holes is regular holes.
可选地，所述支撑层中孔的形貌还包括第一孔与分布于所述第一孔内的n个第二孔。Optionally, the shape of the hole in the support layer further includes a first hole and n second holes distributed in the first hole.
可选地，所述第一孔为非贯穿性的孔。Optionally, the first hole is a non-penetrating hole.
可选地，所述第二孔为贯穿性的孔。Optionally, the second hole is a through hole.
可选地，所述n≥1，例如2、3、4、5、6、7或8等。Optionally, the n≧1, such as 2, 3, 4, 5, 6, 7, or 8, etc.
可选地，所述复合碳材料扩散层的厚度为10～60μm，例如12μm、15μm、20μm、25μm、30μm、35μm、40μm、45μm、50μm、55μm或58μm等。Optionally, the composite carbon material diffusion layer has a thickness of 10-60 μm, such as 12 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, or 58 μm.
可选地，所述复合碳材料扩散层中，碳纳米管和碳纤维质量比为3～10:1～5，例如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或9:5 等。Optionally, in the composite carbon material diffusion layer, the mass ratio of carbon nanotubes and carbon fibers is 3-10:1-5, such as 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 etc.
本申请所述碳纳米管和碳纤维质量比为3～10:1～5，碳纳米管含量过少，则孔隙度过大；碳纤维含量过少，则扩散层太过致密。The mass ratio of carbon nanotubes and carbon fibers described in this application is 3-10:1-5. Too little carbon nanotube content means too much porosity; too little carbon fiber content means too dense diffusion layer.
可选地，所述碳纳米管包括单壁碳纳米管、多壁碳纳米管、石墨化碳纳米管和羧基化碳纳米管中的任意一种或至少两种的组合。Optionally, the carbon nanotubes include any one or a combination of at least two of single-wall carbon nanotubes, multi-wall carbon nanotubes, graphitized carbon nanotubes, and carboxylated carbon nanotubes.
可选地，所述碳纤维包括PP碳纤维、PE短纤维、PVA短纤维、LM聚酯短纤维、纤维素短纤维和沥青基碳纤维中的任意一种或至少两种的组合。Optionally, the carbon fiber includes any one or a combination of at least two of PP carbon fiber, PE short fiber, PVA short fiber, LM polyester short fiber, cellulose short fiber and pitch-based carbon fiber.
可选地，所述复合碳材料扩散层的孔隙率为60％～90％，例如62％、65％、68％、70％、72％、75％、78％、80％、82％、85％或88％等。Optionally, 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% % Or 88% etc.
可选地，所述微孔层的孔隙率为50％～80％，例如52％、55％、58％、60％、62％、65％、68％、70％、72％、75％或78％等。Optionally, the porosity of the microporous layer is 50% to 80%, such as 52%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, 72%, 75% or 78% etc.
可选地，所述微孔层包括碳粉。Optionally, the microporous layer includes carbon powder.
可选地，所述微孔层中碳粉的担载量为0.2mg/cm 2～0.8mg/cm 2，例如0.3mg/cm 2、0.4mg/cm 2、0.5mg/cm 2、0.6mg/cm 2或0.7mg/cm 2等。 Optionally, the loading amount of the carbon powder in the microporous layer is 0.2 mg/cm 2 to 0.8 mg/cm 2 , for example, 0.3 mg/cm 2 , 0.4 mg/cm 2 , 0.5 mg/cm 2 , 0.6 mg /cm 2 or 0.7mg/cm 2 etc.
本申请所述微孔层中碳粉的担载量为0.2mg/cm 2～0.8mg/cm 2，碳粉含量过少，则导电性较差，会发生催化剂渗漏；碳粉含量过多，气体传输路径长。 The loading amount of carbon powder in the microporous layer described in this application is 0.2mg/cm 2 ～0.8mg/cm 2 , if the content of carbon powder is too small, conductivity will be poor and catalyst leakage will occur; too much carbon powder content , The gas transmission path is long.
可选地，所述碳粉包括乙炔黑、活性炭和石墨粉中的任意一种或至少两种的组合。Optionally, the carbon powder includes any one or a combination of at least two of acetylene black, activated carbon and graphite powder.
本申请的目的之二在于提供一种如目的之一所述气体扩散层的制备方法，所述方法包括如下步骤：The second objective of this application is to provide a method for preparing the gas diffusion layer as described in the first objective, and the method includes the following steps:
在支撑层上涂覆复合碳材料浆料，得到复合碳材料扩散层，然后再涂覆疏水浆料，得到微孔层，煅烧得到气体扩散层。The composite carbon material slurry is coated on the support layer to obtain a composite carbon material diffusion layer, and then the hydrophobic slurry is coated to obtain a microporous layer, which is calcined to obtain a gas diffusion layer.
可选地，所述支撑层的制备过程包括：将柔性碳膜造孔，然后除去柔性碳膜中的阳离子。Optionally, the preparation process of the support layer includes: making holes in the flexible carbon film, and then removing cations in the flexible carbon film.
可选地，所述柔性碳膜造孔的方式包括激光打孔、化学造孔和硅板压孔中的任意一种或至少两种的组合。Optionally, the flexible carbon film hole formation method includes any one or a combination of at least two of laser drilling, chemical hole formation and silicon plate pressing.
可选地，所述柔性碳膜为碳纳米管膜、石墨烯膜或碳纤维毡中的任意一种。Optionally, the flexible carbon film is any one of carbon nanotube film, graphene film or carbon fiber felt.
可选地，所述柔性碳膜中阳离子的除去方式为酸洗。Optionally, the method for removing cations in the flexible carbon film is pickling.
可选地，所述酸洗为采用硫酸浸泡。Optionally, the pickling is immersion in sulfuric acid.
可选地，所述硫酸的浓度为1～5mol/L，例如1.5mol/L、2mol/L、2.2mol/L、2.5mol/L、2.8mol/L、3mol/L、3.5mol/L、4mol/L或4.5mol/L等。Optionally, the concentration of the sulfuric acid is 1 to 5 mol/L, for example, 1.5 mol/L, 2 mol/L, 2.2 mol/L, 2.5 mol/L, 2.8 mol/L, 3 mol/L, 3.5 mol/L, 4mol/L or 4.5mol/L etc.
可选地，所述酸洗的温度为50～100℃，例如55℃、60℃、65℃、70℃、75℃、80℃、85℃、90℃或95℃等。Optionally, the temperature of the pickling is 50-100°C, such as 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, or 95°C.
可选地，所述酸洗的时间为10～100min，例如20min、30min、40min、50min、60min、70min、80min或90min等。Optionally, the pickling time is 10-100 min, for example, 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, or 90 min.
可选地，所述复合碳材料浆料的制备过程包括：将碳纤维分散液、碳纳米管分散液、粘结剂和疏水剂混合，得到复合碳材料浆料。Optionally, the preparation process of the composite carbon material slurry includes: mixing a carbon fiber dispersion liquid, a carbon nanotube dispersion liquid, a binder, and a hydrophobic agent to obtain a composite carbon material slurry.
由于碳纳米管、碳纤维混合浆料直接作为扩散层整体框架较为松散，需在浆料中加入粘结剂，可以降低复合碳材料层和支撑层之间的电阻。Since the mixed slurry of carbon nanotubes and carbon fibers directly serves as the overall frame of the diffusion layer, it is relatively loose, so a binder needs to be added to the slurry to reduce the resistance between the composite carbon material layer and the support layer.
可选地，所述复合碳材料浆料中，碳纳米管的含量为0～100wt％，且不含0wt％和100wt％，可选为20％～40％，例如1wt％、5wt％、8wt％、10wt％、15wt％、20wt％、25wt％、30wt％、35wt％、40wt％、45wt％、50wt％、55wt％、60wt％、65wt％、70wt％、75wt％、80wt％或90wt％等。Optionally, the content of carbon nanotubes in the composite carbon material slurry is 0-100% by weight, and does not contain 0% and 100% by weight, and may be 20%-40%, such as 1% by weight, 5% by weight, or 8% by weight. %, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt% or 90wt%, etc. .
可选地，所述复合碳材料浆料中，碳纤维的含量为0～100wt％，且不含0wt％ 和100wt％，可选为15％～25％，例如1wt％、5wt％、8wt％、10wt％、15wt％、20wt％、25wt％、30wt％、35wt％、40wt％、45wt％、50wt％、55wt％、60wt％、65wt％、70wt％、75wt％、80wt％或90wt％等。Optionally, the carbon fiber content in the composite carbon material slurry is 0-100% by weight, and does not contain 0% and 100% by weight, and can be 15%-25%, such as 1% by weight, 5% by weight, 8% by weight, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt% or 90wt%, etc.
可选地，所述粘结剂的含量为0～50wt％，且不含0wt％，可选为20wt％～30wt％，例如1wt％、5wt％、8wt％、10wt％、15wt％、20wt％、22wt％、25wt％、28wt％、30wt％、32wt％、35wt％、38wt％、40wt％或45wt％等。Optionally, the content of the binder is 0-50% by weight, and does not contain 0% by weight, and may be 20%-30% by weight, for example, 1% by weight, 5% by weight, 8% by weight, 10% by weight, 15% by weight, and 20% by weight. , 22wt%, 25wt%, 28wt%, 30wt%, 32wt%, 35wt%, 38wt%, 40wt% or 45wt%, etc.
可选地，所述疏水剂的含量为0～50wt％，且不含0wt％，可选为20wt％～30wt％，例如1wt％、5wt％、8wt％、10wt％、15wt％、20wt％、25wt％、30wt％、35wt％、40wt％或45wt％等。Optionally, the content of the hydrophobic agent is 0-50% by weight, and does not contain 0% by weight, optionally 20% by weight to 30% by weight, such as 1% by weight, 5% by weight, 8% by weight, 10% by weight, 15% by weight, 20% by weight, 25wt%, 30wt%, 35wt%, 40wt% or 45wt%, etc.
可选地，所述混合的方式为超声。Optionally, the mixing method is ultrasound.
可选地，所述粘结剂包括聚四氟乙烯、聚乙二醇、聚乙烯醇和酚醛树脂中的任意一种或至少两种的组合。Optionally, the binder includes any one or a combination of at least two of polytetrafluoroethylene, polyethylene glycol, polyvinyl alcohol and phenolic resin.
可选地，所述疏水剂包括含氟聚物，可选为聚四氟乙烯。Optionally, the hydrophobic agent includes a fluorine-containing polymer, optionally polytetrafluoroethylene.
可选地，所述复合碳材料浆料的涂覆方式包括抽滤、刮涂和丝网印刷中的任意一种或至少两种的组合。Optionally, the coating method of the composite carbon material slurry includes any one or a combination of at least two of suction filtration, knife coating and screen printing.
可选地，所述复合碳材料浆料涂覆之后还包括加压、烘干和清洗的过程。Optionally, after the composite carbon material slurry is coated, a process of pressurizing, drying and cleaning is also included.
可选地，所述加压的压力为20～60kg/cm 2，例如25kg/cm 2、30kg/cm 2、35kg/cm 2、40kg/cm 2、45kg/cm 2、50kg/cm 2或55kg/cm 2等。 Optionally, the pressurized pressure is 20-60kg/cm 2 , for example 25kg/cm 2 , 30kg/cm 2 , 35kg/cm 2 , 40kg/cm 2 , 45kg/cm 2 , 50kg/cm 2 or 55kg /cm 2 etc.
本申请所述加压过程可以使扩散层更加牢固并且平整。The pressing process described in this application can make the diffusion layer firmer and smoother.
可选地，所述加压的时间为1～5min，例如2min、3min或4min等。Optionally, the pressurization time is 1 to 5 minutes, for example, 2 minutes, 3 minutes, or 4 minutes.
可选地，所述加压的过程在热压机中进行。Optionally, the pressurizing process is performed in a hot press.
可选地，所述烘干的温度为20～100℃，例如30℃、40℃、50℃、60℃、70℃、 80℃或90℃等。Optionally, the drying temperature is 20-100°C, such as 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, or 90°C.
可选地，所述清洗为在1～5mol/L硫酸和有机溶剂的混合溶液中清洗，例如1.5mol/L、2mol/L、2.2mol/L、2.5mol/L、2.8mol/L、3mol/L、3.5mol/L、4mol/L或4.5mol/L等。Optionally, the cleaning is cleaning in a mixed solution of 1 to 5 mol/L sulfuric acid and an organic solvent, such as 1.5 mol/L, 2 mol/L, 2.2 mol/L, 2.5 mol/L, 2.8 mol/L, 3 mol/L /L, 3.5mol/L, 4mol/L or 4.5mol/L etc.
可选地，所述有机溶剂包括乙醇。Optionally, the organic solvent includes ethanol.
可选地，所述清洗的温度为30～80℃，例如40℃、50℃、60℃或70℃等。Optionally, the cleaning temperature is 30-80°C, such as 40°C, 50°C, 60°C, or 70°C.
可选地，所述清洗的时间为20～100min，例如30min、40min、50min、60min、70min、80min或90min等。Optionally, the cleaning time is 20-100 minutes, such as 30 minutes, 40 minutes, 50 minutes, 60 minutes, 70 minutes, 80 minutes, or 90 minutes.
可选地，所述碳纤维分散液的制备过程包括：将碳纤维超声分散，得到碳纤维分散液。Optionally, the preparation process of the carbon fiber dispersion liquid includes: ultrasonically dispersing carbon fibers to obtain a carbon fiber dispersion liquid.
可选地，所述碳纤维为单一长度的碳纤维或混合长度的碳纤维。Optionally, the carbon fiber is a single-length carbon fiber or a mixed-length carbon fiber.
可选地，所述碳纤维包括PP碳纤维、PE短纤维、PVA短纤维、LM聚酯短纤维、纤维素短纤维和沥青基碳纤维中的任意一种或至少两种的组合。Optionally, the carbon fiber includes any one or a combination of at least two of PP carbon fiber, PE short fiber, PVA short fiber, LM polyester short fiber, cellulose short fiber and pitch-based carbon fiber.
可选地，所述碳纳米管分散液的制备过程包括：将碳纳米管酸洗，然后与表面活性剂和溶剂混合，得到碳纳米管分散液。Optionally, the preparation process of the carbon nanotube dispersion liquid includes: pickling the carbon nanotubes, and then mixing with a surfactant and a solvent to obtain a carbon nanotube dispersion liquid.
可选地，所述碳纳米管包括单壁碳纳米管、多壁碳纳米管、石墨化碳纳米管和羧基化碳纳米管中的任意一种或至少两种的组合。Optionally, the carbon nanotubes include any one or a combination of at least two of single-wall carbon nanotubes, multi-wall carbon nanotubes, graphitized carbon nanotubes, and carboxylated carbon nanotubes.
可选地，所述酸洗为采用硫酸浸泡。Optionally, the pickling is immersion in sulfuric acid.
可选地，所述硫酸的浓度为1～5mol/L，例如1.5mol/L、2mol/L、2.2mol/L、2.5mol/L、2.8mol/L、3mol/L、3.5mol/L、4mol/L或4.5mol/L等。Optionally, the concentration of the sulfuric acid is 1 to 5 mol/L, for example, 1.5 mol/L, 2 mol/L, 2.2 mol/L, 2.5 mol/L, 2.8 mol/L, 3 mol/L, 3.5 mol/L, 4mol/L or 4.5mol/L etc.
可选地，所述酸洗的温度为50～100℃，例如55℃、60℃、65℃、70℃、75℃、80℃、85℃、90℃或95℃等。Optionally, the temperature of the pickling is 50-100°C, such as 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, or 95°C.
可选地，所述酸洗的时间为5～15h，例如6h、7h、8h、9h、10h、11h、12h、13h或14h等。Optionally, the pickling time is 5-15h, such as 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h or 14h.
可选地，所述酸洗之后还包括用乙醇和纯水离心清洗的过程。Optionally, after the acid washing, a centrifugal washing process with ethanol and pure water is also included.
可选地，所述碳纳米管与表面活性剂的质量比为1:3～1:15，例如1:4、1:5、1:6、1:7、1:8、1:9、1:10、1:11、1:12、1:13或1:14等。Optionally, 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 etc.
可选地，所述表面活性剂包括十二烷基苯磺酸钠、聚乙烯吡咯烷酮和十二烷基硫酸钠中的任意一种或至少两种的组合。Optionally, the surfactant includes any one or a combination of at least two of sodium dodecylbenzene sulfonate, polyvinylpyrrolidone, and sodium lauryl sulfate.
可选地，所述溶剂为纯水、乙醇、丙酮和异丙醇中的任意一种或至少两种的组合。Optionally, the solvent is any one or a combination of at least two of pure water, ethanol, acetone and isopropanol.
可选地，所述混合的方式为超声。Optionally, the mixing method is ultrasound.
可选地，所述超声的仪器为超声仪和/或细胞破碎仪。Optionally, the ultrasonic instrument is an ultrasonic instrument and/or a cell disruptor.
可选地，所述混合的时间为1～15h，例如2h、3h、4h、5h、6h、7h、8h、9h、10h、11h、12h、13h或14h等。Optionally, the mixing time is 1-15h, such as 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h or 14h.
可选地，所述超声的仪器为超声仪，所述混合的时间为5～15h，例如6h、7h、8h、9h、10h、11h、12h、13h或14h等。Optionally, the ultrasonic instrument is an ultrasonic instrument, and the mixing time is 5 to 15 hours, such as 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, or 14 hours.
可选地，所述超声的仪器为细胞破碎仪，所述混合的时间为1～4h，例如1h、2h、3h或4h等。Optionally, the ultrasonic instrument is a cell disruptor, and the mixing time is 1 to 4 hours, such as 1 hour, 2 hours, 3 hours, or 4 hours.
可选地，所述疏水浆料的制备过程包括：将碳粉浆料与疏水剂混合，得到疏水浆料。Optionally, the preparation process of the hydrophobic slurry includes: mixing the carbon powder slurry with a hydrophobic agent to obtain the hydrophobic slurry.
可选地，所述碳粉浆料中碳粉的含量为0.4～0.5mg/cm 2，例如0.41mg/cm 2、0.42mg/cm 2、0.43mg/cm 2、0.44mg/cm 2、0.45mg/cm 2、0.46mg/cm 2、0.47mg/cm 2、0.48mg/cm 2或0.49mg/cm 2等。 Alternatively, the content of the carbon powder slurry toner is 0.4 ~ 0.5mg / cm 2, for example, 0.41mg / cm 2, 0.42mg / cm 2, 0.43mg / cm 2, 0.44mg / cm 2, 0.45 mg / cm 2, 0.46mg / cm 2, 0.47mg / cm 2, 0.48mg / cm 2 or 0.49mg / cm 2 and the like.
可选地，所述碳粉包括乙炔黑、活性炭和石墨粉中的任意一种或至少两种的组合。Optionally, the carbon powder includes any one or a combination of at least two of acetylene black, activated carbon and graphite powder.
可选地，所述疏水浆料的涂覆方式包括刮涂、喷涂、丝网印刷和滴涂中的任意一种或至少两种的组合，可选为丝网印刷。Optionally, the coating method of the hydrophobic slurry includes any one or a combination of at least two of blade coating, spray coating, screen printing and drip coating, and screen printing can be selected.
可选地，所述煅烧的温度为100～600℃，例如150℃、200℃、250℃、300℃、350℃、400℃、450℃、500℃或550℃等。Optionally, the calcination temperature is 100-600°C, such as 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, 450°C, 500°C, or 550°C.
可选地，所述煅烧的时间为10～100min，例如20min、30min、40min、50min、60min、70min、80min或90min等。Optionally, the calcination time is 10-100 min, for example, 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, or 90 min.
作为可选技术方案，本申请所述气体扩散层的制备方法包括如下步骤：As an optional technical solution, the method for preparing the gas diffusion layer described in this application includes the following steps:
(1)支撑层的制备：将柔性碳膜造孔，然后采用1～5mol/L的硫酸，在50～100℃浸泡10～100min，除去柔性碳膜中的阳离子；(1) Preparation of the support layer: Make holes in the flexible carbon film, then use 1 to 5 mol/L sulfuric acid to soak at 50 to 100°C for 10 to 100 minutes to remove cations in the flexible carbon film;
(2)复合碳材料扩散层的制备：(2) Preparation of composite carbon material diffusion layer:
(a)将碳纤维超声分散，得到碳纤维分散液；(a) Disperse the carbon fibers ultrasonically to obtain a carbon fiber dispersion;
(b)将碳纳米管在1～5mol/L的硫酸中，50～100℃浸泡5～15h，用乙醇和纯水离心清洗，然后与表面活性剂和溶剂超声混合1～15h，所述碳纳米管与表面活性剂的质量比为1:3～1:15，得到碳纳米管分散液；(b) Soak the carbon nanotubes in 1～5mol/L sulfuric acid at 50～100℃ for 5～15h, clean them by centrifugation with ethanol and pure water, and then mix them with surfactant and solvent ultrasonically for 1～15h. The mass ratio of the nanotubes to the surfactant is 1:3 to 1:15 to obtain a carbon nanotube dispersion;
(c)将碳纤维分散液、碳纳米管分散液、粘结剂和疏水剂超声混合，得到复合碳材料浆料，所述复合碳材料浆料中碳纳米管的含量为20wt％～40wt％，碳纤维的含量为15wt％～25wt％，粘结剂的含量为20wt％～30wt％，疏水剂的含量为20wt％～30wt％；(c) ultrasonically mixing the carbon fiber dispersion, the carbon nanotube dispersion, the binder, and the hydrophobic agent to obtain a composite carbon material slurry. The content of carbon nanotubes in the composite carbon material slurry is 20 wt% to 40 wt%, The content of carbon fiber is 15% to 25% by weight, the content of binder is 20% to 30% by weight, and the content of hydrophobic agent is 20% to 30% by weight;
(d)将所述复合碳材料浆料涂覆于步骤(1)得到的支撑层表面，在热压机中20～60kg/cm 2压力下加压1～5min，20～100℃烘干，在1～5mol/L硫酸和乙醇 的混合溶液中30～80℃清洗20～100min，得到复合碳材料扩散层； (d) Coating the composite carbon material slurry on the surface of the support layer obtained in step (1), pressurizing in a hot press at 20-60 kg/cm 2 for 1 to 5 minutes, and drying at 20 to 100°C, Wash in a mixed solution of 1 to 5 mol/L sulfuric acid and ethanol at 30 to 80°C for 20 to 100 minutes to obtain a composite carbon material diffusion layer;
(3)微孔层的制备：将碳粉浆料与疏水剂混合，得到疏水浆料，然后将所述疏水浆料涂覆于步骤(2)所述复合碳材料扩散层表面，得到微孔层；(3) Preparation of the microporous layer: the carbon powder slurry is mixed with a hydrophobic agent to obtain a hydrophobic slurry, and then the hydrophobic slurry is coated on the surface of the composite carbon material diffusion layer in step (2) to obtain micropores Floor;
(4)将步骤(3)得到的产品在100～600℃煅烧10～100min，得到气体扩散层。(4) The product obtained in step (3) is calcined at 100-600°C for 10-100 minutes to obtain a gas diffusion layer.
本申请的目的之三在于提供一种燃料电池，所述燃料电池包括目的之一所述的气体扩散层。The third objective of the present application is to provide a fuel cell including the gas diffusion layer described in one of the objectives.
与现有技术相比，本申请具有如下有益效果：Compared with the prior art, this application has the following beneficial effects:
(1)本申请所述支撑层具有较高的机械强度，其既可集流又可作为扩散层框架基底；本申请将碳纳米管和碳纤维两种材料混合，以碳纤维作为基底框架，碳纳米管作为框架的填充物，满足了气体扩散层高透气性的要求，并且拥有较高的机械强度。(1) The support layer described in this application has high mechanical strength, which can not only collect current but also serve as the base of the diffusion layer frame; this application mixes two materials of carbon nanotubes and carbon fibers, and uses carbon fiber as the base frame. As the filler of the frame, the tube meets the requirement of high air permeability of the gas diffusion layer and has high mechanical strength.
(2)在负载复合碳材料扩散层时，它的表面也会像传统碳纸那样有大小不一的孔隙并且表面可能存在凹凸不平的现象，所以微孔层就成了一个重要的部分，它可以使扩散层大小不一的孔隙填补，还可以减缓扩散层的不平整现象，进而实现水和反应气体在流场和催化层的再分配，并且增加了电导率，提高了电池寿命。(2) When the composite carbon material diffusion layer is loaded, its surface will also have pores of different sizes like traditional carbon paper, and the surface may have unevenness, so the microporous layer becomes an important part. The pores of different sizes in the diffusion layer can be filled, and the unevenness of the diffusion layer can be reduced, thereby realizing the redistribution of water and reaction gas in the flow field and the catalytic layer, increasing the conductivity and improving the battery life.
(3)本发所述支撑层、复合碳材料扩散层和微孔层共同作用，可以得到具有良好的传质能力、良好的透气性、良好的导电性和良好的机械强度、以及良好的催化剂承载能力的气体扩散层。(3) The support layer, the composite carbon material diffusion layer and the microporous layer described in the present invention work together to obtain a good mass transfer capacity, good gas permeability, good conductivity, good mechanical strength, and good catalyst Gas diffusion layer with bearing capacity.
附图说明Description of the drawings
图1是本申请具体实施例1得到的支撑层结构示意图；FIG. 1 is a schematic diagram of the supporting layer structure obtained in specific embodiment 1 of the present application;
图2是本申请具体实施例2得到的支撑层结构示意图；2 is a schematic diagram of the structure of the support layer obtained in specific embodiment 2 of the present application;
图3是本申请具体实施例1得到的气体扩散层的结构示意图。3 is a schematic diagram of the structure of the gas diffusion layer obtained in Example 1 of the present application.
具体实施方式Detailed ways
为便于理解本申请，本申请列举实施例如下。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。To facilitate the understanding of this application, the following examples are listed in this application. It should be understood by those skilled in the art that the described embodiments are only to help understand the application and should not be regarded as specific limitations to the application.
实施例1Example 1
一种气体扩散层的制备方法包括如下步骤：A method for preparing a gas diffusion layer includes the following steps:
(1)支撑层的制备：将厚度为20μm的碳纳米管膜进行激光打孔，然后采用3mol/L的硫酸，在80℃浸泡60min，除去碳纳米管膜中的阳离子，得到的支撑层结构示意图如图1所示，由图中可以看出所述支撑层中的孔为直径35μm且呈规则排列的圆孔，所述支撑层的孔隙率为80％；(1) Preparation of the support layer: laser perforate a carbon nanotube film with a thickness of 20μm, and then use 3mol/L sulfuric acid to soak at 80°C for 60 minutes to remove the cations in the carbon nanotube film to obtain a support layer structure The schematic diagram is shown in Fig. 1, and it can be seen from the figure that the holes in the support layer are circular holes with a diameter of 35 μm and are arranged regularly, and the porosity of the support layer is 80%;
(2)复合碳材料扩散层的制备：(2) Preparation of composite carbon material diffusion layer:
(a)将PP碳纤维在纯水中超声分散，得到碳纤维分散液；(a) Ultrasonic dispersion of PP carbon fiber in pure water to obtain a carbon fiber dispersion;
(b)将单壁碳纳米管在3mol/L的硫酸中，80℃浸泡8h，用乙醇和纯水离心清洗，然后与十二烷基苯磺酸钠和纯水在细胞破碎仪中超声混合3h，所述单壁碳纳米管与十二烷基苯磺酸钠的质量比为1:10，得到碳纳米管分散液；(b) Soak the single-walled carbon nanotubes in 3mol/L sulfuric acid at 80°C for 8 hours, clean them by centrifugation with ethanol and pure water, and then mix them with sodium dodecylbenzene sulfonate and pure water ultrasonically in a cell disruptor 3h, the mass ratio of the single-walled carbon nanotubes to the sodium dodecylbenzene sulfonate is 1:10 to obtain a carbon nanotube dispersion;
(c)将碳纤维分散液、碳纳米管分散液、聚四氟乙烯和聚乙烯醇超声混合，得到复合碳材料浆料，所述复合碳材料浆料中单壁碳纳米管的含量为30wt％，PP碳纤维的含量为20wt％，聚四氟乙烯的含量为25wt％，聚乙烯醇的含量为25wt％；(c) Ultrasonic mixing of carbon fiber dispersion, carbon nanotube dispersion, polytetrafluoroethylene and polyvinyl alcohol to obtain composite carbon material slurry, the content of single-walled carbon nanotubes in the composite carbon material slurry is 30wt% , PP carbon fiber content is 20wt%, polytetrafluoroethylene content is 25wt%, polyvinyl alcohol content is 25wt%;
(d)将所述复合碳材料浆料刮涂于步骤(1)得到的支撑层表面，在热压机中40kg/cm 2压力下加压3min，80℃烘干，在3mol/L硫酸和乙醇的混合溶液 中60℃清洗60min，得到平均厚度为50μm的复合碳材料扩散层； (d) Scrape the composite carbon material slurry on the surface of the support layer obtained in step (1), press in a hot press at a pressure of 40kg/cm 2 for 3 minutes, dry at 80°C, and dry at 3mol/L sulfuric acid and Wash in a mixed solution of ethanol for 60 minutes at 60°C to obtain a composite carbon material diffusion layer with an average thickness of 50 μm;
(3)微孔层的制备：将碳粉与聚四氟乙烯混合，得到疏水浆料，然后将所述疏水浆料刮涂于步骤(2)所述复合碳材料扩散层表面，得到碳粉担载量为0.5mg/cm 2，平均厚度为5μm的微孔层； (3) Preparation of the microporous layer: mixing carbon powder with polytetrafluoroethylene to obtain a hydrophobic slurry, and then scraping the hydrophobic slurry on the surface of the composite carbon material diffusion layer in step (2) to obtain carbon powder A microporous layer with a loading capacity of 0.5 mg/cm 2 and an average thickness of 5 μm;
(4)将步骤(3)得到的产品在500℃煅烧60min，得到气体扩散层。所述气体扩散层的结构示意图如图3所示，图中1为支撑层，2为复合碳材料扩散层，3为微孔层。(4) The product obtained in step (3) is calcined at 500° C. for 60 minutes to obtain a gas diffusion layer. The structure diagram of the gas diffusion layer is shown in FIG. 3, in which 1 is a support layer, 2 is a composite carbon material diffusion layer, and 3 is a microporous layer.
实施例2Example 2
与实施例1的区别在于，步骤(1)将碳纳米管膜进行激光打孔，得到的支撑层结构示意图如图2所示，由图中可以看出所述支撑层中的孔为直径100μm的第一圆孔与分布于所述第一圆孔内的两个直径40μm的第二圆孔，其中第一圆孔为非透过性孔，第二圆孔为透过性孔。所述支撑层的孔隙率为82％。The difference from Example 1 is that in step (1), the carbon nanotube film is laser-drilled, and the structure of the obtained support layer is shown in Figure 2. It can be seen from the figure that the holes in the support layer are 100 μm in diameter. The first round hole and two second round holes with a diameter of 40 μm distributed in the first round hole, wherein the first round hole is an impermeable hole, and the second round hole is a permeable hole. The porosity of the support layer was 82%.
实施例3Example 3
与实施例1的区别在于，步骤(1)所述支撑层中圆孔的直径为30μm，所述支撑层的孔隙率为75％。The difference from Example 1 is that the diameter of the circular holes in the supporting layer in step (1) is 30 μm, and the porosity of the supporting layer is 75%.
实施例4Example 4
与实施例1的区别在于，步骤(d)所述复合碳材料扩散层中碳纳米管和碳纤维质量比为1:6。The difference from Example 1 is that the mass ratio of carbon nanotubes and carbon fibers in the composite carbon material diffusion layer in step (d) is 1:6.
实施例5Example 5
与实施例1的区别在于，步骤(d)所述复合碳材料扩散层中碳纳米管和碳纤维质量比为12:1。The difference from Example 1 is that the mass ratio of carbon nanotubes and carbon fibers in the composite carbon material diffusion layer in step (d) is 12:1.
实施例6Example 6
与实施例1的区别在于，步骤(3)所述乙炔黑担载量为0.1mg/cm 2的微孔层。 The difference from Example 1 is that the loading of acetylene black in step (3) is 0.1 mg/cm 2 of the microporous layer.
实施例7Example 7
与实施例1的区别在于，步骤(3)所述乙炔黑担载量为1mg/cm 2的微孔层。 The difference from Example 1 is that the acetylene black in step (3) has a microporous layer with a loading amount of 1 mg/cm 2 .
实施例8Example 8
一种气体扩散层的制备方法包括如下步骤：A method for preparing a gas diffusion layer includes the following steps:
(1)支撑层的制备：将厚度为25μm的石墨烯膜用化学物质碳酸钙造孔，然后采用1mol/L的硫酸，在100℃浸泡100min，除去石墨烯膜中的阳离子，得到的支撑层，所述支撑层中的孔为边长45μm且呈规则排列的正方形孔，所述支撑层的孔隙率为78％；(1) Preparation of the support layer: a graphene film with a thickness of 25μm is made with calcium carbonate, a chemical substance, and then immersed in 1mol/L sulfuric acid at 100°C for 100 minutes to remove the cations in the graphene film to obtain the support layer The holes in the support layer are square holes with a side length of 45 μm and are regularly arranged, and the porosity of the support layer is 78%;
(2)复合碳材料扩散层的制备：(2) Preparation of composite carbon material diffusion layer:
(a)将PE短纤维和沥青基碳纤维在乙醇中超声分散，得到碳纤维分散液；(a) Disperse PE short fiber and pitch-based carbon fiber ultrasonically in ethanol to obtain a carbon fiber dispersion;
(b)将多壁碳纳米管在1mol/L的硫酸中，100℃浸泡8h，用乙醇和纯水离心清洗，然后与聚乙烯吡咯烷酮和乙醇在超声仪中超声混合10h，所述多壁碳纳米管与聚乙烯吡咯烷酮的质量比为1:3，得到碳纳米管分散液；(b) The multi-walled carbon nanotubes were soaked in 1mol/L sulfuric acid at 100°C for 8 hours, cleaned by centrifugation with ethanol and pure water, and then mixed with polyvinylpyrrolidone and ethanol in an ultrasonic instrument for 10 hours. The mass ratio of nanotubes to polyvinylpyrrolidone is 1:3 to obtain a carbon nanotube dispersion;
(c)将碳纤维分散液、碳纳米管分散液、聚乙二醇和聚四氟乙烯超声混合，得到复合碳材料浆料，所述复合碳材料浆料中多壁碳纳米管的含量为32wt％，沥青基碳纤维的含量为22wt％，聚乙二醇的含量为26wt％，疏水剂的含量为20wt％；(c) Ultrasonic mixing of carbon fiber dispersion, carbon nanotube dispersion, polyethylene glycol and polytetrafluoroethylene to obtain composite carbon material slurry, the content of multi-walled carbon nanotubes in the composite carbon material slurry is 32wt% , The content of pitch-based carbon fiber is 22wt%, the content of polyethylene glycol is 26wt%, and the content of hydrophobic agent is 20wt%;
(d)将所述复合碳材料浆料抽滤涂覆于步骤(1)得到的支撑层表面，在热压机中20kg/cm 2压力下加压5min，50℃烘干，在1mol/L硫酸和乙醇的混合溶液中30℃清洗100min，得到平均厚度为60μm，多壁碳纳米管和沥青基碳纤 维质量比为3:2的复合碳材料扩散层； (d) The composite carbon material slurry is suction filtered and coated on the surface of the support layer obtained in step (1), pressurized in a hot press at a pressure of 20kg/cm 2 for 5 minutes, dried at 50°C, and dried at 1mol/L Wash in a mixed solution of sulfuric acid and ethanol at 30°C for 100 minutes to obtain a composite carbon material diffusion layer with an average thickness of 60 μm and a mass ratio of multi-walled carbon nanotubes and pitch-based carbon fibers of 3:2;
(3)微孔层的制备：将活性炭与聚四氟乙烯混合，得到疏水浆料，然后将所述疏水浆料用滴涂方法涂覆于步骤(2)所述复合碳材料扩散层表面，得到活性炭担载量为0.2mg/cm 2，平均厚度为10μm的微孔层； (3) Preparation of the microporous layer: mixing activated carbon and polytetrafluoroethylene to obtain a hydrophobic slurry, and then coating the hydrophobic slurry on the surface of the composite carbon material diffusion layer in step (2) by a drop coating method, A microporous layer with an activated carbon loading of 0.2mg/cm 2 and an average thickness of 10 μm is obtained;
(4)将步骤(3)得到的产品在100℃煅烧100min，得到气体扩散层。(4) The product obtained in step (3) is calcined at 100° C. for 100 minutes to obtain a gas diffusion layer.
实施例9Example 9
一种气体扩散层的制备方法包括如下步骤：A method for preparing a gas diffusion layer includes the following steps:
(1)支撑层的制备：将厚度为30μm的碳纤维毡采用5mol/L的硫酸，在50℃浸泡80min，除去碳纤维毡中的阳离子，得到支撑层；(1) Preparation of the support layer: a carbon fiber felt with a thickness of 30 μm is immersed in 5mol/L sulfuric acid at 50°C for 80 minutes to remove cations in the carbon fiber felt to obtain a support layer;
(2)复合碳材料扩散层的制备：(2) Preparation of composite carbon material diffusion layer:
(a)将LM聚酯短纤维在纯水中超声分散，得到碳纤维分散液；(a) Disperse LM polyester staple fiber ultrasonically in pure water to obtain a carbon fiber dispersion;
(b)将石墨化碳纳米管在5mol/L的硫酸中，50℃浸泡15h，用乙醇和纯水离心清洗，然后与十二烷基硫酸钠和纯水在细胞破碎仪中超声混合2h，所述石墨化碳纳米管与十二烷基硫酸钠的质量比为1:15，得到碳纳米管分散液；(b) Soak the graphitized carbon nanotubes in 5mol/L sulfuric acid at 50°C for 15h, centrifuge and clean with ethanol and pure water, and then mix with sodium lauryl sulfate and pure water in a cell disruptor ultrasonically for 2h The mass ratio of the graphitized carbon nanotubes to the sodium lauryl sulfate is 1:15 to obtain a carbon nanotube dispersion;
(c)将碳纤维分散液、碳纳米管分散液、酚醛树脂和聚四氟乙烯超声混合，得到复合碳材料浆料，所述复合碳材料浆料中石墨化碳纳米管的含量为40wt％，LM聚酯短纤维的含量为15wt％，酚醛树脂的含量为20wt％，疏水剂的含量为25wt％；(c) ultrasonically mixing carbon fiber dispersion, carbon nanotube dispersion, phenolic resin and polytetrafluoroethylene to obtain a composite carbon material slurry, wherein the content of graphitized carbon nanotubes in the composite carbon material slurry is 40wt%, The content of LM polyester staple fiber is 15wt%, the content of phenolic resin is 20wt%, and the content of hydrophobic agent is 25wt%;
(d)将所述复合碳材料浆料刮涂于步骤(1)得到的支撑层表面，在热压机中60kg/cm 2压力下加压1min，100℃烘干，在5mol/L硫酸和乙醇的混合溶液中80℃清洗20min，得到平均厚度为50微米的扩散层，碳纳米管和LM聚酯短纤维质量比为7:3的复合碳材料扩散层； (d) Scrape the composite carbon material slurry on the surface of the support layer obtained in step (1), press in a hot press at a pressure of 60kg/cm 2 for 1 min, dry at 100°C, and dry in 5mol/L sulfuric acid and Wash in a mixed solution of ethanol at 80°C for 20 minutes to obtain a diffusion layer with an average thickness of 50 microns and a composite carbon material diffusion layer with a mass ratio of carbon nanotubes and LM polyester short fibers of 7:3;
(3)微孔层的制备：将石墨粉与聚四氟乙烯混合，得到疏水浆料，然后将所述疏水浆料滴涂涂覆于步骤(2)所述复合碳材料扩散层表面，得到石墨粉担载量为0.8mg/cm 2，平均厚度为15μm的微孔层； (3) Preparation of the microporous layer: mixing graphite powder with polytetrafluoroethylene to obtain a hydrophobic slurry, and then drip coating the hydrophobic slurry on the surface of the composite carbon material diffusion layer in step (2) to obtain A microporous layer with a graphite powder loading capacity of 0.8 mg/cm 2 and an average thickness of 15 μm;
(4)将步骤(3)得到的产品在600℃煅烧10min，得到气体扩散层。(4) The product obtained in step (3) is calcined at 600° C. for 10 minutes to obtain a gas diffusion layer.
对比例1Comparative example 1
与实施例1的区别在于，步骤(2)用东丽碳纸作为扩散层，即替换复合碳材料扩散层。The difference from Embodiment 1 is that in step (2), Toray carbon paper is used as the diffusion layer, that is, the composite carbon material diffusion layer is replaced.
对比例2Comparative example 2
与实施例1的区别在于，步骤(c)所述复合碳材料浆料中不添加碳纳米管分散液，即复合碳材料扩散层中不存在碳纳米管。The difference from Example 1 is that the composite carbon material slurry in step (c) does not add carbon nanotube dispersion liquid, that is, there is no carbon nanotube in the composite carbon material diffusion layer.
对比例3Comparative example 3
与实施例1的区别在于，步骤(c)所述复合碳材料浆料中不添加碳纤维分散液，即复合碳材料扩散层中不存在PP碳纤维。The difference from Example 1 is that the composite carbon material slurry in step (c) does not add carbon fiber dispersion, that is, there is no PP carbon fiber in the composite carbon material diffusion layer.
对比例4Comparative example 4
与实施例1的区别在于，不进行步骤(3)，即得到的气体扩散层中不存在微孔层。The difference from Example 1 is that step (3) is not performed, that is, there is no microporous layer in the obtained gas diffusion layer.
性能测试：Performance Testing:
以制备得到的气体扩散层组装成燃料电池：在制备的扩散层上涂覆微孔层，350℃烘干，然后涂覆铂碳催化剂，105℃烘2小时，然后将质子交换膜(杜邦)放置在阴阳两极间，130℃热压两分钟，得到MEA进行封装。将得到的燃料电池进行如下性能测试(测试方法：将氢气侧密封，用两根细管***电池对称两侧，下端通氢气，上端排出氢气，氧气侧暴露空气中，常温常压下用电化学工 作站进行电池测试)：Assemble the fuel cell with the prepared gas diffusion layer: coat the microporous layer on the prepared diffusion layer, dry at 350°C, and then coat platinum-carbon catalyst, bake at 105°C for 2 hours, and then the proton exchange membrane (DuPont) Place it between the yin and yang poles and press at 130°C for two minutes to get MEA for packaging. Perform the following performance test of the obtained fuel cell (test method: seal the hydrogen side, insert two thin tubes into the symmetrical sides of the battery, pass hydrogen at the lower end, discharge hydrogen at the upper end, and expose the oxygen side to the air. Use electrochemistry at room temperature and pressure) Workstation for battery test):
(1)电化学性能测试：用线性伏安法，分别测试在电流密度为0.1A/cm 2、0.2A/cm 2、0.3A/cm 2、0.4A/cm 2和0.5A/cm 2条件下的功率密度(单位为mW/cm 2，在表1中以W表示)和电压(单位为V，在表1中以V表示)。 (1) Electrochemical performance test: use linear voltammetry to test under current density of 0.1A/cm 2 , 0.2A/cm 2 , 0.3A/cm 2 , 0.4A/cm 2 and 0.5A/cm 2 The power density (unit is mW/cm 2 , expressed as W in Table 1) and voltage (unit is V, expressed as V in Table 1).
表1Table 1
Figure PCTCN2020103425-appb-000001
Figure PCTCN2020103425-appb-000001
通过表1可以看出，实施例4和实施例5相对于实施例1得到的气体扩散层组装成燃料电池性能较差，因为实施例4中碳纳米管含量过少，孔隙度过大， 实施例5中碳纤维含量过少，得到的扩散层太过致密，透气性差，气体扩散层的孔隙度过大或过小对于其电化学性能影响较大，因此实施例4和实施例5相对于实施例1得到的气体扩散层电化学性能较差。It can be seen from Table 1 that the performance of the fuel cell assembly of the gas diffusion layer obtained in Example 4 and Example 5 is poorer than that in Example 1, because the content of carbon nanotubes in Example 4 is too small and the porosity is too large. In Example 5, if the carbon fiber content is too small, the obtained diffusion layer is too dense and has poor air permeability. The porosity of the gas diffusion layer is too large or too small to have a greater impact on its electrochemical performance. Therefore, Examples 4 and 5 are compared to the implementation The gas diffusion layer obtained in Example 1 has poor electrochemical performance.
通过表1可以看出，实施例6和实施例7相对于实施例1得到的气体扩散层组装成燃料电池性能较差，因为实施例6中乙炔黑担载量过小，导电性较差，会发生催化剂渗漏，实施例7中乙炔黑担载量过大，气体传输路径长，乙炔黑担载量过大或过小皆会对性能造成不利影响，因此实施例6和实施例7相对于实施例1得到的气体扩散层电化学性能较差。It can be seen from Table 1 that compared with the gas diffusion layer obtained in Example 1, the performance of the fuel cell assembled in Example 6 and Example 7 is poor, because the acetylene black loading in Example 6 is too small and the conductivity is poor. Catalyst leakage will occur. In Example 7, the acetylene black loading is too large, the gas transmission path is long, and the acetylene black loading is too large or too small, which will adversely affect the performance. Therefore, Example 6 and Example 7 are relatively The gas diffusion layer obtained in Example 1 has poor electrochemical performance.
通过表1可以看出，对比例1采用东丽碳纸作为扩散层组装成燃料电池，其电化学性能相对于实施例1得到的气体扩散层性能较差，对比例2-4中不存在碳纳米管、不存在PP碳纤维或不存在微孔层，得到的气体扩散层电化学性能皆较差，说明本申请中支撑层、复合碳材料扩散层和微孔层是共同作用的，不能缺少任意一层，且复合碳材料扩散层中碳纳米管和碳纤维必须同时存在，得到的气体扩散层才能在满足了高透气性的要求的同时，还具有良好的电化学性能。It can be seen from Table 1 that Comparative Example 1 uses Toray carbon paper as the diffusion layer to assemble a fuel cell, and its electrochemical performance is poorer than that of the gas diffusion layer obtained in Example 1. There is no carbon in Comparative Examples 2-4 Nanotubes, no PP carbon fiber or no microporous layer, the resulting gas diffusion layer has poor electrochemical performance, indicating that the support layer, composite carbon material diffusion layer and microporous layer in the present application work together and cannot lack any One layer, and the carbon nanotubes and carbon fibers in the composite carbon material diffusion layer must exist at the same time, so that the obtained gas diffusion layer can not only meet the requirements of high gas permeability, but also have good electrochemical performance.
表1中“/”代表测不到相应的数据，放电量达不到。"/" in Table 1 means that the corresponding data cannot be measured and the discharge capacity cannot be reached.
申请人声明，本申请通过上述实施例来说明本申请的详细工艺设备和工艺流程，但本申请并不局限于上述详细工艺设备和工艺流程，即不意味着本申请必须依赖上述详细工艺设备和工艺流程才能实施。The applicant declares that this application uses the above embodiments to illustrate the detailed process equipment and process flow of this application, but this application is not limited to the above detailed process equipment and process flow, which does not mean that the application must rely on the above detailed process equipment and process flow. The process can be implemented.

Claims (12)

  1. 一种气体扩散层，其包括支撑层和依次设置于所述支撑层表面的复合碳材料扩散层和微孔层；A gas diffusion layer, which comprises a support layer and a composite carbon material diffusion layer and a microporous layer sequentially arranged on the surface of the support layer;
    其中，所述支撑层为多孔材料，所述复合碳材料扩散层包括碳纳米管和碳纤维。Wherein, the support layer is a porous material, and the composite carbon material diffusion layer includes carbon nanotubes and carbon fibers.
  2. 如权利要求1所述的气体扩散层，其中，所述复合碳材料扩散层中，碳纳米管和碳纤维质量比为10～3:1～5。8. The gas diffusion layer according to claim 1, wherein the mass ratio of carbon nanotubes and carbon fibers in the composite carbon material diffusion layer is 10-3:1-5.
  3. 如权利要求1或2所述的气体扩散层，其中，所述支撑层的孔隙率为50％～90％。The gas diffusion layer according to claim 1 or 2, wherein the porosity of the support layer is 50% to 90%.
  4. 如权利要求1-3中任一项所述的气体扩散层，其中，所述支撑层的孔隙率为70～85％；The gas diffusion layer according to any one of claims 1 to 3, wherein the porosity of the supporting layer is 70-85%;
    可选地，所述支撑层为柔性碳膜，可选为碳纳米管膜、石墨烯膜或碳纤维毡中的任意一种；Optionally, the support layer is a flexible carbon film, which may be any one of a carbon nanotube film, a graphene film, or a carbon fiber felt;
    可选地，所述支撑层的厚度<50μm；Optionally, the thickness of the support layer is <50 μm;
    可选地，所述支撑层的孔径>5μm，可选为15～22μm；Optionally, the pore size of the support layer is >5 μm, and may be 15-22 μm;
    可选地，所述支撑层中的孔为贯穿性的孔；Optionally, the holes in the supporting layer are penetrating holes;
    可选地，所述支撑层中孔的形貌包括圆孔、矩形孔和菱形孔中的任意一种或至少两种的组合；Optionally, the shape of the hole in the support layer includes any one or a combination of at least two of a round hole, a rectangular hole and a diamond hole;
    可选地，所述孔的形貌为等规则的孔；Optionally, the morphology of the holes is a regular hole;
    可选地，所述支撑层中孔的形貌还包括第一孔与分布于所述第一孔内的n个第二孔；Optionally, the shape of the holes in the support layer further includes a first hole and n second holes distributed in the first hole;
    可选地，所述第一孔为非贯穿性的孔；Optionally, the first hole is a non-penetrating hole;
    可选地，所述第二孔为贯穿性的孔；Optionally, the second hole is a through hole;
    可选地，所述n≥1。Optionally, the n≧1.
  5. 如权利要求1-4中任一项所述的气体扩散层，其中，所述复合碳材料扩散层的厚度为10～60μm；The gas diffusion layer according to any one of claims 1 to 4, wherein the thickness of the composite carbon material diffusion layer is 10-60 μm;
    可选地，所述碳纳米管包括单壁碳纳米管、多壁碳纳米管、石墨化碳纳米管和羧基化碳纳米管中的任意一种或至少两种的组合；Optionally, the carbon nanotubes include any one or a combination of at least two of single-wall carbon nanotubes, multi-wall carbon nanotubes, graphitized carbon nanotubes, and carboxylated carbon nanotubes;
    可选地，所述碳纤维包括PP碳纤维、PE短纤维、PVA短纤维、LM聚酯短纤维、纤维素短纤维和沥青基碳纤维中的任意一种或至少两种的组合；Optionally, the carbon fiber includes any one or a combination of at least two of PP carbon fiber, PE short fiber, PVA short fiber, LM polyester short fiber, cellulose short fiber and pitch-based carbon fiber;
    可选地，所述复合碳材料扩散层的孔隙率为60％～90％；Optionally, the porosity of the composite carbon material diffusion layer is 60% to 90%;
    可选地，所述微孔层的孔隙率为50％～80％；Optionally, the porosity of the microporous layer is 50% to 80%;
    可选地，所述微孔层包括碳粉；Optionally, the microporous layer includes carbon powder;
    可选地，所述微孔层中碳粉的担载量为0.2mg/cm 2～0.8mg/cm 2； Optionally, the loading amount of carbon powder in the microporous layer is 0.2 mg/cm 2 to 0.8 mg/cm 2 ;
    可选地，所述碳粉包括乙炔黑、活性炭和石墨粉中的任意一种或至少两种的组合。Optionally, the carbon powder includes any one or a combination of at least two of acetylene black, activated carbon and graphite powder.
  6. 一种如权利要求1-5之一所述气体扩散层的制备方法，其包括如下步骤：A method for preparing the gas diffusion layer according to any one of claims 1 to 5, which comprises the following steps:
    在支撑层上涂覆复合碳材料浆料，得到复合碳材料扩散层，然后再涂覆疏水浆料，得到微孔层，煅烧得到气体扩散层。The composite carbon material slurry is coated on the support layer to obtain a composite carbon material diffusion layer, and then the hydrophobic slurry is coated to obtain a microporous layer, which is calcined to obtain a gas diffusion layer.
  7. 如权利要求6所述的制备方法，其中，所述支撑层的制备过程包括：将柔性碳膜造孔，然后除去柔性碳膜中的阳离子；8. The preparation method of claim 6, wherein the preparation process of the support layer comprises: making holes in the flexible carbon film, and then removing cations in the flexible carbon film;
    可选地，所述柔性碳膜造孔的方式包括激光打孔、化学造孔和硅板压孔中的任意一种或至少两种的组合；Optionally, the method for making holes in the flexible carbon film includes any one or a combination of at least two of laser drilling, chemical hole making and silicon plate pressing;
    可选地，所述柔性碳膜为碳纳米管膜、石墨烯膜或碳纤维毡中的任意一种；Optionally, the flexible carbon film is any one of a carbon nanotube film, a graphene film or a carbon fiber felt;
    可选地，所述柔性碳膜中阳离子的除去方式为酸洗；Optionally, the method for removing cations in the flexible carbon film is pickling;
    可选地，所述酸洗为采用硫酸浸泡；Optionally, the pickling is immersion in sulfuric acid;
    可选地，所述硫酸的浓度为1～5mol/L；Optionally, the concentration of the sulfuric acid is 1 to 5 mol/L;
    可选地，所述酸洗的温度为50～100℃；Optionally, the temperature of the pickling is 50-100°C;
    可选地，所述酸洗的时间为10～100min。Optionally, the pickling time is 10-100 min.
  8. 如权利要求6或7所述的制备方法，其中，所述复合碳材料浆料的制备过程包括：将碳纤维分散液、碳纳米管分散液、粘结剂和疏水剂混合，得到复合碳材料浆料；The preparation method according to claim 6 or 7, wherein the preparation process of the composite carbon material slurry comprises: mixing a carbon fiber dispersion, a carbon nanotube dispersion, a binder, and a hydrophobic agent to obtain a composite carbon material slurry material;
    可选地，所述复合碳材料浆料中，碳纳米管的含量为0～100wt％，且不含0wt％和100wt％，可选为20wt％～40wt％；Optionally, the content of carbon nanotubes in the composite carbon material slurry is 0-100 wt%, and does not contain 0 wt% and 100 wt%, and may be 20 wt%-40 wt%;
    可选地，所述复合碳材料浆料中，碳纤维的含量为0～100wt％，且不含0wt％和100wt％，可选为15wt％～25wt％；Optionally, the content of carbon fiber in the composite carbon material slurry is 0-100% by weight, and does not contain 0% and 100% by weight, and may be 15%-25% by weight;
    可选地，所述粘结剂的含量为0～50wt％，且不含0wt％，可选为20wt％～30wt％；Optionally, the content of the binder is 0-50% by weight, and does not contain 0% by weight, and can be 20-30% by weight;
    可选地，所述疏水剂的含量为0～50wt％，且不含0wt％，可选为20wt％～30wt％；Optionally, the content of the hydrophobic agent is 0-50% by weight, and does not contain 0% by weight, and can be 20%-30% by weight;
    可选地，所述混合的方式为超声；Optionally, the mixing method is ultrasound;
    可选地，所述粘结剂包括聚四氟乙烯、聚乙二醇、聚乙烯醇和酚醛树脂中的任意一种或至少两种的组合；Optionally, the binder includes any one or a combination of at least two of polytetrafluoroethylene, polyethylene glycol, polyvinyl alcohol and phenolic resin;
    可选地，所述疏水剂包括含氟聚物，可选为聚四氟乙烯；Optionally, the hydrophobic agent includes a fluorine-containing polymer, optionally polytetrafluoroethylene;
    可选地，所述复合碳材料浆料的涂覆方式包括抽滤、刮涂和丝网印刷中的任意一种或至少两种的组合；Optionally, the coating method of the composite carbon material slurry includes any one or a combination of at least two of suction filtration, knife coating and screen printing;
    可选地，所述复合碳材料浆料涂覆之后还包括加压、烘干和清洗的过程；Optionally, after the composite carbon material slurry is coated, a process of pressurizing, drying and cleaning is further included;
    可选地，所述加压的压力为20～60kg/cm 2； Optionally, the pressurized pressure is 20-60 kg/cm 2 ;
    可选地，所述加压的时间为1～5min；Optionally, the pressurization time is 1 to 5 minutes;
    可选地，所述加压的过程在热压机中进行；Optionally, the pressurizing process is performed in a hot press;
    可选地，所述烘干的温度为20～100℃；Optionally, the drying temperature is 20-100°C;
    可选地，所述清洗为在1～5mol/L硫酸和有机溶剂的混合溶液中清洗；Optionally, the cleaning is cleaning in a mixed solution of 1 to 5 mol/L sulfuric acid and an organic solvent;
    可选地，所述有机溶剂包括乙醇；Optionally, the organic solvent includes ethanol;
    可选地，所述清洗的温度为30～80℃；Optionally, the cleaning temperature is 30-80°C;
    可选地，所述清洗的时间为20～100min。Optionally, the cleaning time is 20-100 minutes.
  9. 如权利要求8所述的制备方法，其中，所述碳纤维分散液的制备过程包括：将碳纤维超声分散，得到碳纤维分散液；8. The preparation method according to claim 8, wherein the preparation process of the carbon fiber dispersion liquid comprises: ultrasonically dispersing carbon fibers to obtain a carbon fiber dispersion liquid;
    可选地，所述碳纤维为单一长度的碳纤维或混合长度的碳纤维；Optionally, the carbon fiber is a single-length carbon fiber or a mixed-length carbon fiber;
    可选地，所述碳纤维包括PP碳纤维、PE短纤维、PVA短纤维、LM聚酯短纤维、纤维素短纤维和沥青基碳纤维中的任意一种或至少两种的组合；Optionally, the carbon fiber includes any one or a combination of at least two of PP carbon fiber, PE short fiber, PVA short fiber, LM polyester short fiber, cellulose short fiber and pitch-based carbon fiber;
    可选地，所述碳纳米管分散液的制备过程包括：将碳纳米管酸洗，然后与表面活性剂和溶剂混合，得到碳纳米管分散液；Optionally, the preparation process of the carbon nanotube dispersion liquid includes: pickling the carbon nanotubes, and then mixing with a surfactant and a solvent to obtain a carbon nanotube dispersion liquid;
    可选地，所述碳纳米管包括单壁碳纳米管、多壁碳纳米管、石墨化碳纳米管和羧基化碳纳米管中的任意一种或至少两种的组合；Optionally, the carbon nanotubes include any one or a combination of at least two of single-wall carbon nanotubes, multi-wall carbon nanotubes, graphitized carbon nanotubes, and carboxylated carbon nanotubes;
    可选地，所述酸洗为采用硫酸浸泡；Optionally, the pickling is immersion in sulfuric acid;
    可选地，所述硫酸的浓度为1～5mol/L；Optionally, the concentration of the sulfuric acid is 1 to 5 mol/L;
    可选地，所述酸洗的温度为50～100℃；Optionally, the temperature of the pickling is 50-100°C;
    可选地，所述酸洗的时间为5～15h；Optionally, the pickling time is 5-15h;
    可选地，所述酸洗之后还包括用乙醇和纯水离心清洗的过程；Optionally, after the acid washing, a centrifugal washing process with ethanol and pure water is included;
    可选地，所述碳纳米管与表面活性剂的质量比为1:3～1:15；Optionally, the mass ratio of the carbon nanotubes to the surfactant is 1:3 to 1:15;
    可选地，所述表面活性剂包括十二烷基苯磺酸钠、聚乙烯吡咯烷酮和十二烷基硫酸钠中的任意一种或至少两种的组合；Optionally, the surfactant includes any one or a combination of at least two of sodium dodecylbenzene sulfonate, polyvinylpyrrolidone and sodium lauryl sulfate;
    可选地，所述溶剂为纯水、乙醇、丙酮和异丙醇中的任意一种或至少两种的组合；Optionally, the solvent is any one or a combination of at least two of pure water, ethanol, acetone and isopropanol;
    可选地，所述混合的方式为超声；Optionally, the mixing method is ultrasound;
    可选地，所述超声的仪器为超声仪和/或细胞破碎仪；Optionally, the ultrasonic instrument is an ultrasonic instrument and/or a cell disruptor;
    可选地，所述混合的时间为1～15h；Optionally, the mixing time is 1-15h;
    可选地，所述超声的仪器为超声仪，所述混合的时间为5～15h；Optionally, the ultrasonic instrument is an ultrasonic instrument, and the mixing time is 5 to 15 hours;
    可选地，所述超声的仪器为细胞破碎仪，所述混合的时间为1～4h。Optionally, the ultrasonic instrument is a cell disruptor, and the mixing time is 1 to 4 hours.
  10. 如权利要求6-9之一所述的制备方法，其中，所述疏水浆料的制备过程包括：将碳粉浆料与疏水剂混合，得到疏水浆料；9. The preparation method according to any one of claims 6-9, wherein the preparation process of the hydrophobic slurry comprises: mixing the carbon powder slurry with a hydrophobic agent to obtain the hydrophobic slurry;
    可选地，所述碳粉浆料中碳粉的含量为0.4～0.5mg/cm 2； Optionally, the content of carbon powder in the carbon powder slurry is 0.4-0.5 mg/cm 2 ;
    可选地，所述碳粉包括乙炔黑、活性炭和石墨粉中的任意一种或至少两种的组合；Optionally, the carbon powder includes any one or a combination of at least two of acetylene black, activated carbon and graphite powder;
    可选地，所述疏水浆料的涂覆方式包括刮涂、喷涂、丝网印刷和滴涂中的任意一种或至少两种的组合，可选为丝网印刷；Optionally, the coating method of the hydrophobic slurry includes any one or a combination of at least two of blade coating, spray coating, screen printing and drip coating, and may be screen printing;
    可选地，所述煅烧的温度为100～600℃；Optionally, the calcination temperature is 100-600°C;
    可选地，所述煅烧的时间为10～100min。Optionally, the calcination time is 10-100 min.
  11. 如权利要求6-10之一所述的制备方法，其中，所述制备方法包括如下步骤：The preparation method according to any one of claims 6-10, wherein the preparation method comprises the following steps:
    (1)支撑层的制备：将柔性碳膜造孔，然后采用1～5mol/L的硫酸，在 50～100℃浸泡10～100min，除去柔性碳膜中的阳离子；(1) Preparation of the support layer: Make holes in the flexible carbon film, and then use 1-5 mol/L sulfuric acid to soak at 50-100°C for 10-100 minutes to remove cations in the flexible carbon film;
    (2)复合碳材料扩散层的制备：(2) Preparation of composite carbon material diffusion layer:
    (a)将碳纤维超声分散，得到碳纤维分散液；(a) Disperse the carbon fibers ultrasonically to obtain a carbon fiber dispersion;
    (b)将碳纳米管在1～5mol/L的硫酸中，50～100℃浸泡5～15h，用乙醇和纯水离心清洗，然后与表面活性剂和溶剂超声混合1～15h，所述碳纳米管与表面活性剂的质量比为1:3～1:15，得到碳纳米管分散液；(b) Soak the carbon nanotubes in 1～5mol/L sulfuric acid at 50～100℃ for 5～15h, clean them by centrifugation with ethanol and pure water, and then mix them with surfactant and solvent ultrasonically for 1～15h. The mass ratio of the nanotubes to the surfactant is 1:3 to 1:15 to obtain a carbon nanotube dispersion;
    (c)将碳纤维分散液、碳纳米管分散液、粘结剂和疏水剂超声混合，得到复合碳材料浆料，所述复合碳材料浆料中碳纳米管的含量为20wt％～40wt％，碳纤维的含量为15wt％～25wt％，粘结剂的含量为20wt％～30wt％，疏水剂的含量为20wt％～30wt％；(c) ultrasonically mixing the carbon fiber dispersion, the carbon nanotube dispersion, the binder, and the hydrophobic agent to obtain a composite carbon material slurry. The content of carbon nanotubes in the composite carbon material slurry is 20 wt% to 40 wt%, The content of carbon fiber is 15% to 25% by weight, the content of binder is 20% to 30% by weight, and the content of hydrophobic agent is 20% to 30% by weight;
    (d)将所述复合碳材料浆料涂覆于步骤(1)得到的支撑层表面，在热压机中20～60kg/cm 2压力下加压1～5min，20～100℃烘干，在1～5mol/L硫酸和乙醇的混合溶液中30～80℃清洗20～100min，得到复合碳材料扩散层； (d) Coating the composite carbon material slurry on the surface of the support layer obtained in step (1), pressurizing in a hot press at 20-60 kg/cm 2 for 1 to 5 minutes, and drying at 20 to 100°C, Wash in a mixed solution of 1 to 5 mol/L sulfuric acid and ethanol at 30 to 80°C for 20 to 100 minutes to obtain a composite carbon material diffusion layer;
    (3)微孔层的制备：将碳粉浆料与疏水剂混合，得到疏水浆料，然后将所述疏水浆料涂覆于步骤(2)所述复合碳材料扩散层表面，得到微孔层；(3) Preparation of the microporous layer: the carbon powder slurry is mixed with a hydrophobic agent to obtain a hydrophobic slurry, and then the hydrophobic slurry is coated on the surface of the composite carbon material diffusion layer in step (2) to obtain micropores Floor;
    (4)将步骤(3)得到的产品在100～600℃煅烧10～100min，得到气体扩散层。(4) The product obtained in step (3) is calcined at 100-600°C for 10-100 minutes to obtain a gas diffusion layer.
  12. 一种燃料电池，其中，所述燃料电池包括权利要求1-5之一所述的气体扩散层。A fuel cell, wherein the fuel cell includes the gas diffusion layer according to any one of claims 1-5.
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