WO2022222220A1 - Gas diffusion layer, preparation method therefor and application thereof, and fuel cell - Google Patents

Gas diffusion layer, preparation method therefor and application thereof, and fuel cell Download PDF

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Publication number
WO2022222220A1
WO2022222220A1 PCT/CN2021/095937 CN2021095937W WO2022222220A1 WO 2022222220 A1 WO2022222220 A1 WO 2022222220A1 CN 2021095937 W CN2021095937 W CN 2021095937W WO 2022222220 A1 WO2022222220 A1 WO 2022222220A1
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Prior art keywords
wettability
gas diffusion
modules
layer
diffusion layer
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PCT/CN2021/095937
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French (fr)
Chinese (zh)
Inventor
姜海波
李春忠
张文会
陈爱平
周鹰杰
陆吉源
毕瓅元
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华东理工大学
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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
    • H01M4/8605—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
    • 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
    • H01M8/0247—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the form
    • 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
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • 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

  • the present invention relates to a gas diffusion layer and its preparation method, application and fuel cell.
  • PEMFC proton exchange membrane fuel cell
  • the requirements for the power density of fuel cells are getting higher and higher, and the gas diffusion layer plays an important role in improving the power density of fuel cells.
  • the water generated in the cathode catalytic layer is removed through the gas diffusion layer, and the oxygen in the flow channel also reaches the cathode through the gas diffusion layer for redox reaction.
  • PEMFC is a nonlinear complex system with multi-physics coupling, many factors affect its water management failure, especially with the increase of PEMFC power, flooding failure is more likely to occur.
  • flooding occurs, with the continuous accumulation of liquid water, it eventually covers the surface of the gas diffusion layer and the catalyst layer, reducing the activity of the catalyst layer, accelerating the corrosion of materials and the loss of catalyst, reducing the active area, and even accumulating liquid water in the gas flow channel. , resulting in poor gas circulation, seriously affecting the operation, performance and remaining life of the PEMFC.
  • Patent CN109742409A discloses a gas diffusion layer, the microporous layer is composed of graphene doped with sulfur atoms and fluorinated ethylene propylene copolymer, which has good electrical conductivity, hydrophobicity and gas dispersion properties, etc. The cost is high, it is not conducive to industrial production, and the performance improvement is small.
  • Patent CN111799475A discloses a special-shaped fuel cell gas diffusion layer, a preparation method, a fuel cell and an assembly method, which improves the gas diffusion performance and charge drainage performance through the uneven structure of the base layer, but the special-shaped structure is difficult to prepare and is not suitable for popularization and application.
  • the technical problem solved by the present invention is to overcome the defects of the prior art that the proton exchange membrane fuel cell is prone to flooding failure under high power, which seriously affects the performance and service life of the fuel cell, and the improved method is complicated in process and high in cost.
  • the liquid water breakthrough pressure of the gas diffusion layer provided by the invention is greatly reduced, so that the water generated by the catalytic layer can be quickly discharged from the gas diffusion layer, the possibility of flooding is reduced, and the peak power density of the fuel cell is improved. Simple, low cost and easy to industrialize.
  • the invention provides a gas diffusion layer, which includes a base layer and a microporous layer, the microporous layer is supported on the base layer;
  • the gas diffusion layer includes a wettability part, the wettability part includes a plurality of wettability modules arranged at intervals, and the arrangement track of the wettability modules corresponds to the flow channel of the fuel cell bipolar plate, And each of the wettability modules is loaded with a wettability reagent, and the wettability reagent penetrates the base layer and the microporous layer, so that the water on the surface of the microporous layer passes through the wettability. site directly into the flow channel.
  • the area percentage of the wettability portion to the flow channel may be 5% to 30%, preferably 10% to 20%.
  • the area percentage of the wettable portion to the flow channel is 6%, 9%, 11%, 13%, 16% or 23%, preferably 13%.
  • Too high or too low a proportion of the area of the wetting part in the flow channel will cause adverse effects. If the proportion of the wetting part is too high, it will occupy the diffusion and transmission area of oxygen and affect the diffusion and transmission performance of oxygen; If the proportion is too low, the purpose of wettability modification will not be achieved, and there will still be the defect of easy flooding.
  • the shape of a single wettability module can be a square or a circle, preferably a square, more preferably a square.
  • the largest dimension of a single wettability module does not exceed the width of the flow channel.
  • the largest dimension of a single wettability module refers to the diameter or the longest diagonal line of a single wettability module, or the like.
  • the side length of the square may be 0.3-0.8 mm, preferably 0.4-0.6 mm, such as 0.5 mm.
  • the wettability modules may be regularly arranged along the flow channel direction.
  • the wettability modules are arranged at equal intervals along the flow channel direction.
  • the equidistant arrangement means that the center-to-center spacing of two adjacent wettability modules along the direction of the flow channel is equal. More preferably, the arrangement track of the wettability modules is a square matrix.
  • the distance between the centers of two adjacent wettability modules in the direction of the flow channel may be 1 ⁇ 4 mm, for example, 2 mm or 3 mm.
  • the number of the wettability modules can be determined by the length of the flow channel, the maximum size of a single wettability module, and the center of two adjacent wettability modules along the flow channel direction The spacing is determined jointly.
  • the penetration depth of the wettability agent on the gas diffusion layer is 150-190 ⁇ m, preferably 170 ⁇ m.
  • the thickness of the microporous layer may be conventional in the field, generally 10-30 ⁇ m.
  • the matrix material of the microporous layer may include a conductive material and a binder.
  • the conductive material may be conventional in the art, preferably conductive carbon black or graphite.
  • the graphite is preferably small in particle size, high in specific surface area, well-developed in structure, less in impurities trapping ⁇ electrons, high in graphitization, and porous.
  • the conductive carbon black is preferably one or more of Super P, acetylene black and Vulcan XC-72, more preferably a mixture of Super P, acetylene black and Vulcan XC-72.
  • the quality of Super P, acetylene black and Vulcan XC-72 is preferably 1:1:1.
  • the above three conductive carbon blacks and their combination are specially selected by the inventor after long-term experimental research.
  • the carbon black particles of Super P are aggregated into chains or grapes, which have better conductivity.
  • the structure of Vulcan XC-72 is stronger, which is more favorable for the formation of the conductive network of the battery.
  • the dispersion of Vulcan XC-72 is better, and the compounding of the three conductive materials can improve the electrochemical performance of the fuel cell.
  • the binder can be conventional in the art, preferably polytetrafluoroethylene.
  • the mass ratio of the conductive material and the binder may be 1:(0.5-3), for example, 1:1 or 1:0.86.
  • the wetting agent is preferably polyethylene glycol and/or sodium dodecylaminopropionate.
  • wetting agents There are many types of wetting agents, and their wetting properties are also different. Wettability is too high or too low are not conducive to the exclusion of liquid water.
  • the wettability module in addition to the base material, the wettability module further includes a film-forming agent.
  • the film-forming agent can be conventional in the art, preferably polyvinyl acetate and/or polyvinyl alcohol.
  • the presence of the film-forming agent enhances the connection of the conductive material to the wetting agent and improves the durability of the wetting site.
  • the loading amount of the microporous layer on the base layer can be conventional in the field, generally 2-5 mg/cm 2 , preferably 3-4 mg/cm 2 , more preferably 3.3 mg/cm 2 . mg/cm 2 .
  • the loading amount refers to the mass of the microporous layer supported on the base layer per unit area.
  • the loading amount of the conductive material on the base layer is 1-4 mg/cm 2 , preferably 1.5-2.5 mg/cm 2 , more preferably 2 mg/cm 2 .
  • the base layer can be conventional in the art, and generally includes a base layer material and a hydrophobic coating, and the hydrophobic coating is supported on the base layer material.
  • the base layer material can be conventional in the field, such as carbon fiber paper, carbon fiber woven cloth, non-woven cloth or carbon black paper, etc., preferably carbon black paper.
  • the hydrophobic coating can be conventional in the art, preferably polytetrafluoroethylene (PTFE).
  • PTFE polytetrafluoroethylene
  • the mass percentage of the hydrophobic coating in the base layer material may be 10%-50%, such as 20%, 30% or 40%.
  • the wettability agent is polyethylene glycol
  • the wettability module is a square with a side length of 0.5 mm
  • the center-to-center distance between two adjacent wettability modules is 1 mm
  • the area percentage of the wettability parts in the flow channel is 23%
  • the arrangement track of the wettability modules along the flow channel direction is a square matrix.
  • the wettability agent is polyethylene glycol
  • the wettability module is a square with a side length of 0.4 mm
  • the center-to-center distance between two adjacent wettability modules is 2 mm
  • the area percentage of the wettability parts in the flow channel is 11%
  • the arrangement track of the wettability modules along the flow channel direction is a square matrix.
  • the wettability agent is sodium dodecylaminopropionate
  • the wettability module is a square with a side length of 0.3 mm
  • two adjacent wettability modules are The center-to-center spacing of the modules is 3 mm
  • the area percentage of the wettability parts in the flow channel is 6%
  • the arrangement track of the wettability modules along the flow channel direction is a square matrix.
  • the wettability agent is sodium dodecylaminopropionate
  • the wettability module is a square with a side length of 0.4 mm
  • two adjacent wettability modules are The center-to-center spacing of the modules is 3 mm
  • the area percentage of the wettability parts in the flow channel is 9%
  • the arrangement track of the wettability modules along the flow channel direction is a square matrix.
  • the wettability agent is sodium dodecylaminopropionate
  • the wettability module is a square with a side length of 0.5 mm
  • two adjacent wettability modules are The distance between the centers of the modules is 3 mm
  • the area percentage of the wettability parts in the flow channel is 13%
  • the arrangement track of the wettability modules along the flow channel direction is a square matrix.
  • the wettability agent is polyethylene glycol
  • the wettability module is a square with a side length of 0.5 mm
  • the center-to-center distance between two adjacent wettability modules is 2 mm
  • the area percentage of the wettability parts in the flow channel is 16%
  • the arrangement track of the wettability modules along the flow channel direction is a square matrix.
  • the present invention also provides a preparation method of the above-mentioned gas diffusion layer, which comprises the following steps:
  • the wetting slurry includes a wetting agent, a film-forming agent and a solvent.
  • the base layer can be prepared by a conventional method in the art, generally obtained by hydrophobic treatment of the base layer material and forming a hydrophobic coating on the surface.
  • the base layer material may be the base layer material as described above.
  • the hydrophobic treatment can be performed by a conventional method in the field.
  • the base layer material can be dipped into the hydrophobic material, taken out and dried, and repeated for many times, so that the hydrophobic material reaches a certain loading amount to form hydrophobicity. coating.
  • the base layer material needs to be subjected to ultrasonic treatment before the hydrophobic treatment.
  • the ultrasonic treatment can be carried out by a conventional method in the art, preferably in an acetone solution.
  • the time of the ultrasonic treatment may not be less than 10min, preferably 30min.
  • the hydrophobic material can be conventional in the art, preferably a polytetrafluoroethylene emulsion, more preferably a polytetrafluoroethylene emulsion with a solid content of 10%.
  • the mass percentage of the hydrophobic coating on the base layer material can be as described above.
  • the microporous layer may be supported on the base layer by a conventional method in the art, preferably by spraying the microporous layer slurry on the base layer, and then sintering to obtain it.
  • the microporous layer slurry can be prepared by a conventional method in the field, and generally can be obtained by mixing a conductive material, a pore-forming agent, a binder and a solvent.
  • the binder is prepared first into a binder emulsion with a mass concentration of 10%, and then mix the conductive material, the pore-forming agent, the binder emulsion and the solvent; more preferably, ultrasonic dispersion is performed after mixing, and the The time of ultrasonic dispersion is preferably 3h.
  • the conductive material may be the conductive material as described above.
  • the pore-forming agent can be conventional in the art, preferably NH 4 Cl and/or isopropanol, more preferably a mixture of ammonium chloride and isopropanol.
  • the mass ratio of the ammonium chloride and the isopropanol may be 1:(50-200), preferably 1:100.
  • the pore-forming agent is added during the preparation of the microporous layer slurry, sprayed onto the base layer and then sintered.
  • the pore-forming agent decomposes and volatilizes during the sintering process, and the original pore-forming agent becomes the pore structure.
  • the binder can be the binder as described above.
  • the solvent can be conventional in the art, preferably water, more preferably deionized water.
  • the mass ratio of the conductive material, the pore-forming agent, the binder and the solvent may be conventional in the field, preferably (0.005-0.012): (0.5-2): (0.003- 0.008):1, more preferably (0.006-0.011):(0.8-1.2):(0.004-0.007):1, such as 0.009:1:0.006:1 or 0.0075:1:0.005:1 or 0.0105:1:1 0.006:1.
  • the sintering can be carried out by a conventional method in the art, preferably, it can be placed in a muffle furnace and kept at 360° C. for 1 hour.
  • step S2 the size and arrangement of the wettability modules can be as described above.
  • step S2 the application can be performed by a conventional method in the art, preferably one or more of ultrasonic spraying, pressure spraying and airflow atomization.
  • each of the wettability modules corresponds to the hollow of the mask, and the moist Wet slurry is applied to the hollowed-out locations.
  • the material of the mask can be conventional in the art, preferably an amphiphobic material, more preferably polytetrafluoroethylene.
  • the amphiphobic material can avoid errors caused by improper operation of re-spraying the wetting reagent, the adhesion of the reagent and the mask, and the contamination of the non-wetting area.
  • the hollowing out of the mask can be obtained by a conventional method in the art, preferably by a laser lithography machine.
  • step S2 the preparation method of the wettability slurry can be conventional in the field, and generally, the wettability agent, the film-forming agent and the solvent are mixed.
  • the wettability reagent may be the above-mentioned wettability reagent.
  • the film-forming agent may be the above-mentioned film-forming agent.
  • the solvent can be conventional in the art, preferably water.
  • the mass ratio of the wetting agent, the film-forming agent and the solvent may be 1:(0.5-4):(2-8), preferably 1:(1-2) : (3 to 6), more preferably 1:1.6:4.
  • step S2 when the application method is ultrasonic spraying or pressure spraying, the application time may be 1-5s, preferably 3s.
  • the spraying height can be conventional in the field, generally 3-10 cm, preferably 5 cm.
  • the spraying time and spraying height directly affect the penetration depth of the wetting agent.
  • step S2 the drying can be performed by a conventional method in the art, preferably, it can be placed in an oven at 80° C. for 1 hour.
  • the present invention also provides an application of the above gas diffusion layer in a fuel cell.
  • the present invention also provides a fuel cell including the above-mentioned gas diffusion layer.
  • the reagents and raw materials used in the present invention are all commercially available.
  • the positive improvement effect of the present invention is that the liquid water breakthrough pressure of the gas diffusion layer prepared by the present invention is greatly reduced compared with the prior art. Specifically, the breakthrough pressure can be reduced from 13.6 kPa to below 10 kPa. Down to 3.12kPa, the drop can be as high as 77%.
  • the peak power density of the fuel cell provided by the invention can be higher than 600 mW/cm 2 , even as high as 666 mW/cm 2 , which can be increased by 28% compared with the peak power density of the fuel cell in the prior art.
  • Example 1 is a schematic diagram of the arrangement of wettability modules on the gas diffusion layer of Example 1;
  • Fig. 2 is the distribution diagram of the liquid water transport of the gas diffusion layer obtained in Example 1;
  • Fig. 3 is the distribution diagram of the liquid water transport of the gas diffusion layer obtained in Comparative Example 1;
  • a is the polarization curve
  • b is the power density curve
  • the raw materials and reagents used in the present invention are all commercially available. Some routine tests can be performed in accordance with national standard methods.
  • microporous layer Preparation of microporous layer: Weigh 0.01g of ammonium chloride and add 0.02g of deionized water to form an ammonium chloride solution, take 0.03g each of SuperP, AB type carbon black and Vulcan XC-72, 8g deionized water, 10g isopropanol, 0.6 g of 10% wt polytetrafluoroethylene emulsion was mixed, the above-mentioned ammonium chloride solution was added, and ultrasonically dispersed for 3 hours to form a microporous layer slurry.
  • microporous layer slurry was sprayed onto the base layer by means of pressure spraying so that the load of the conductive material was 2 mg/cm 2 , and then placed in a muffle furnace for sintering at 360° C. for 1 hour.
  • Preparation and coating of wettable slurry take 20 g of deionized water, 5 g of polyethylene glycol as a wetting agent, and 8 g of polyvinyl acetate emulsion as a film-forming agent, mix and stir for 30 minutes to obtain a wettable slurry.
  • a number of wettability modules with a size of 0.5mm*0.5mm and a center-to-center spacing of 1mm were planned, and the wettability parts accounted for 23% of the area of the flow channel. Take a polytetrafluoroethylene film with a thickness of 30 ⁇ m as a mask, and use a laser marking machine to hollow out the mask.
  • the hollowing corresponds to the planned wettability module, and it is spread on the surface of the above-mentioned microporous layer and sprayed.
  • the above wetting slurry was 3 s, the penetration depth of the wetting agent on the gas diffusion layer was 170 ⁇ m, and then it was dried in an oven at 80° C. for 1 hour.
  • the mass of the conductive materials Super P, AB type carbon black, and Vulcan XC-72 in S1 were changed to 0.035g; the size of the wettability module in S2 was changed to 0.4mm*0.4mm, the center spacing was changed to 2mm, and the wettability part
  • the area ratio of the flow channel was 11%, and other operations and conditions were the same as those in Example 1.
  • the wettability reagent was changed to sodium dodecyl aminopropionate
  • the film-forming agent was changed to polyvinyl alcohol
  • the size of the wettability module was changed to 0.3mm*0.3mm
  • the center distance was changed to 3mm
  • the wettability part was changed to The area ratio of the flow channel was 6%, and other operations and conditions were the same as those in Example 1.
  • the wettability reagent was changed to 5g sodium dodecyl aminopropionate, the size of the wettability module was changed to 0.4mm*0.4mm, the center distance was changed to 3mm, and the area ratio of the wettability part to the flow channel was 9%, other operations and conditions are the same as in Example 1.
  • the wettability reagent is changed to 5g sodium dodecyl aminopropionate, the size of the wettability module is changed to 0.5mm*0.5mm, the center distance is changed to 3mm, and the area ratio of the wettability part to the flow channel is 13 %, and other operations and conditions were the same as in Example 1.
  • the size of the wettability module in S2 is 0.5mm*0.5mm, the center distance is 2mm, the area ratio of the wettability part to the flow channel is 16%, and other operations and conditions are the same as in Example 1.
  • S1 is exactly the same as Example 1, and S2 is not performed.
  • FIG. 2 is an experimental diagram of the breakthrough pressure of the gas diffusion layer obtained in Example 1
  • FIG. 3 is an experimental diagram of the breakthrough pressure of the gas diffusion layer obtained in Comparative Example 1. It can be seen from the comparison between Fig. 2 and Fig. 3 that after spraying the wetting agent, liquid water is preferentially transported through the wetting part, and oxygen is transported through the non-wetting part; the gas diffusion without the spraying of the wetting agent layer, the breakthrough pressure is large, and the distribution of liquid water transmission is irregular.
  • the gas diffusion layers prepared in each example and comparative example were assembled into a fuel cell, and the American Gore PRIMEA membrane electrode assembly was used as the catalyst coating membrane, wherein the cathode catalyst Pt/C loading was 0.4 mg/cm 2 , and the anode Pt/C The loading was 0.15 mg/cm 2 .
  • Battery performance test conditions temperature 60°C, humidity 100%, back pressure 50kPa, cathode: 275mL/min air, anode: 110mL/min hydrogen, measured the polarization curve and power density curve, the highest point of the power density curve is the fuel The peak power density value of the battery.
  • Example 1 3.12 543
  • Example 2 4.79 583
  • Example 3 6.82 580
  • Example 4 7.32 606
  • Example 5 8.39 666
  • Example 6 5.98 558 Comparative Example 1 13.61 520
  • the breakthrough pressures of the gas diffusion layers and the peak power densities of the fuel cells of the examples and comparative examples are shown in Table 1.
  • the wettability modification is carried out on the microporous layer, and the breakthrough pressure of water on it is greatly reduced compared with that of the unmodified one, which is conducive to the rapid discharge of liquid water generated by the catalyst layer from the gas diffusion layer, and reduces the pressure on the microporous layer.
  • the risk of flooding failure increases the peak power density of the fuel cell.
  • the polarization curves of the fuel cells of each example and the comparative example are shown in Figure 4.
  • the diffusion performance of the gas diffusion layer of each example is better than that of the gas diffusion layer of the comparative example, and the risk of flooding failure of the fuel cell is Compared with the comparative example, the peak power density is significantly higher than that of the comparative example, especially the peak power density of the fuel cell of Example 5 is as high as 666 mW/cm 2 , which is 28% higher than that of the comparative example 1.

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Abstract

Disclosed in the present invention are a gas diffusion layer, a preparation method therefor and an application thereof, and a fuel cell. The gas diffusion layer comprises a base layer and a microporous layer, and the microporous layer is supported on the base layer; the gas diffusion layer comprises a wetting portion; the wetting portion comprises a plurality of wetting modules arranged at intervals; the arrangement track of the wetting modules corresponds to the flow channel of a fuel cell bipolar plate, and each wetting module is loaded with a wetting reagent; and the wetting reagent permeates the base layer and the microporous layer, so that water on the surface of the microporous layer directly enters the flow channel by means of the wetting portion. The liquid water breakthrough pressure of the gas diffusion layer provided by the present invention is greatly reduced, so that water generated by a catalytic layer can be rapidly discharged from the gas diffusion layer, the possibility of submersion in water is reduced, and the peak power density of the fuel cell is improved; and moreover, the preparation method is simple, low in cost, and easy to industrialize.

Description

气体扩散层及其制备方法、应用和燃料电池Gas diffusion layer and its preparation method, application and fuel cell
本申请要求申请日为2021/4/21的中国专利申请2021104296029的优先权。本申请引用上述中国专利申请的全文。This application claims the priority of Chinese patent application 2021104296029 with the filing date of 2021/4/21. This application cites the full text of the above Chinese patent application.
技术领域technical field
本发明涉及一种气体扩散层及其制备方法、应用和燃料电池。The present invention relates to a gas diffusion layer and its preparation method, application and fuel cell.
背景技术Background technique
质子交换膜燃料电池(PEMFC)作为一种能量转化装置，具有能量转化效率高、清洁污染少、比能量高等优点，在氢能经济发展过程中扮演着不可替代的作用。随着经济社会发展，对燃料电池的功率密度要求越来越高，气体扩散层在提高燃料电池功率密度方面起着重要作用。燃料电池在运行过程中阴极催化层中产生的水，通过气体扩散层进行排除，流道中的氧气也通过气体扩散层到达阴极进行氧化还原反应。燃料电池在运行过程中由于温度处于60-100℃，水汽凝结在气体扩散层表面，影响液态水和氧气的传输，导致质量传输损失，降低功率密度，因此提高气体扩散层的质量传输至关重要。As an energy conversion device, proton exchange membrane fuel cell (PEMFC) has the advantages of high energy conversion efficiency, less clean pollution, high specific energy, and plays an irreplaceable role in the development of hydrogen energy economy. With the development of economy and society, the requirements for the power density of fuel cells are getting higher and higher, and the gas diffusion layer plays an important role in improving the power density of fuel cells. During the operation of the fuel cell, the water generated in the cathode catalytic layer is removed through the gas diffusion layer, and the oxygen in the flow channel also reaches the cathode through the gas diffusion layer for redox reaction. Due to the temperature of 60-100 ℃ during the operation of the fuel cell, water vapor condenses on the surface of the gas diffusion layer, which affects the transmission of liquid water and oxygen, resulting in loss of mass transmission and reduced power density. Therefore, it is very important to improve the mass transport of the gas diffusion layer. .
PEMFC是一种多物理场耦合的非线性复杂***，许多因素影响着其水管理故障，尤其随着PEMFC功率增大，水淹故障更易发生。水淹发生时，随着液态水的不断堆积，最终覆盖气体扩散层和催化剂层表面，降低催化层活性、加快材料的腐蚀和催化剂的流失、减少活性面积，甚至出现液态水在气体流道内集聚，导致气体流通不畅，严重影响PEMFC的运行、性能和剩余寿命。PEMFC is a nonlinear complex system with multi-physics coupling, many factors affect its water management failure, especially with the increase of PEMFC power, flooding failure is more likely to occur. When flooding occurs, with the continuous accumulation of liquid water, it eventually covers the surface of the gas diffusion layer and the catalyst layer, reducing the activity of the catalyst layer, accelerating the corrosion of materials and the loss of catalyst, reducing the active area, and even accumulating liquid water in the gas flow channel. , resulting in poor gas circulation, seriously affecting the operation, performance and remaining life of the PEMFC.
目前，气体扩散层的改进主要集中在微孔层材料和基底层的结构设计上，针对气体扩散层的结构设计已经做了很多工作。专利CN109742409A公开了一种气体扩散层，其微孔层由硫原子掺杂的石墨烯和氟化乙烯丙烯共聚物组成，具有良好的导电性能、疏水性能和气体分散性能等，但其工艺复杂、成 本高、不利于工业化生产，并且对性能的提升较小。专利CN111799475A公开了一种异型燃料电池气体扩散层、制备方法、燃料电池及装配方法，其通过基底层的凹凸异形结构提高气体扩散性能电荷排水性能，但该异形结构制备困难，不适合推广应用。At present, the improvement of the gas diffusion layer mainly focuses on the structural design of the microporous layer material and the base layer, and a lot of work has been done on the structural design of the gas diffusion layer. Patent CN109742409A discloses a gas diffusion layer, the microporous layer is composed of graphene doped with sulfur atoms and fluorinated ethylene propylene copolymer, which has good electrical conductivity, hydrophobicity and gas dispersion properties, etc. The cost is high, it is not conducive to industrial production, and the performance improvement is small. Patent CN111799475A discloses a special-shaped fuel cell gas diffusion layer, a preparation method, a fuel cell and an assembly method, which improves the gas diffusion performance and charge drainage performance through the uneven structure of the base layer, but the special-shaped structure is difficult to prepare and is not suitable for popularization and application.
发明内容SUMMARY OF THE INVENTION
本发明解决的技术问题在于克服了现有技术中质子交换膜燃料电池在高功率下容易发生水淹故障而严重影响燃料电池性能和使用寿命，改进的方法工艺复杂、成本高的缺陷，提供了一种气体扩散层及其制备方法、应用和燃料电池。本发明提供的气体扩散层的液态水突破压力大幅降低，使催化层产生的水能快速从气体扩散层排出，降低了水淹发生的可能性，提高了燃料电池的峰功率密度，并且制备方法简单、成本低、易工业化。The technical problem solved by the present invention is to overcome the defects of the prior art that the proton exchange membrane fuel cell is prone to flooding failure under high power, which seriously affects the performance and service life of the fuel cell, and the improved method is complicated in process and high in cost. A gas diffusion layer and its preparation method, application and fuel cell. The liquid water breakthrough pressure of the gas diffusion layer provided by the invention is greatly reduced, so that the water generated by the catalytic layer can be quickly discharged from the gas diffusion layer, the possibility of flooding is reduced, and the peak power density of the fuel cell is improved. Simple, low cost and easy to industrialize.
为了实现上述目的，本发明采用下述技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
本发明提供了一种气体扩散层，其包括基底层和微孔层，所述微孔层负载在所述基底层上；The invention provides a gas diffusion layer, which includes a base layer and a microporous layer, the microporous layer is supported on the base layer;
所述气体扩散层包括润湿性部位，所述润湿性部位包括间隔设置的多个润湿性模块，所述润湿性模块的排布轨迹与燃料电池双极板的流道相对应，且各所述润湿性模块上均负载有润湿性试剂，所述润湿性试剂渗透所述基底层和所述微孔层，使所述微孔层表面的水通过所述润湿性部位直接进入所述流道。The gas diffusion layer includes a wettability part, the wettability part includes a plurality of wettability modules arranged at intervals, and the arrangement track of the wettability modules corresponds to the flow channel of the fuel cell bipolar plate, And each of the wettability modules is loaded with a wettability reagent, and the wettability reagent penetrates the base layer and the microporous layer, so that the water on the surface of the microporous layer passes through the wettability. site directly into the flow channel.
本发明中，所述润湿性部位的面积占所述流道的面积百分比可为5％-30％，较佳地为10％～20％。In the present invention, the area percentage of the wettability portion to the flow channel may be 5% to 30%, preferably 10% to 20%.
本发明中，所述润湿性部位的面积占所述流道的面积百分比为6％、9％、11％、13％、16％或23％，较佳地为13％。In the present invention, the area percentage of the wettable portion to the flow channel is 6%, 9%, 11%, 13%, 16% or 23%, preferably 13%.
润湿性部位占流道的面积比例太高或太低均会造成不良影响，润湿性部位所占比例过高，会挤占氧气的扩散传输区域，影响氧气的扩散传输性能； 润湿性部位所占比例过低，则达不到润湿性改性的目的，依然会存在易水淹的缺陷。Too high or too low a proportion of the area of the wetting part in the flow channel will cause adverse effects. If the proportion of the wetting part is too high, it will occupy the diffusion and transmission area of oxygen and affect the diffusion and transmission performance of oxygen; If the proportion is too low, the purpose of wettability modification will not be achieved, and there will still be the defect of easy flooding.
本发明中，单个所述润湿性模块的形状可为方形或圆形，较佳地为方形，更佳地为正方形。In the present invention, the shape of a single wettability module can be a square or a circle, preferably a square, more preferably a square.
其中，单个所述润湿性模块的最大尺寸不超过所述流道的宽度。单个所述润湿性模块的最大尺寸是指单个所述润湿性模块的直径或最长对角线等。Wherein, the largest dimension of a single wettability module does not exceed the width of the flow channel. The largest dimension of a single wettability module refers to the diameter or the longest diagonal line of a single wettability module, or the like.
当所述润湿性模块的形状为正方形时，所述正方形的边长可为0.3～0.8mm，较佳地为0.4～0.6mm，例如0.5mm。When the shape of the wettability module is a square, the side length of the square may be 0.3-0.8 mm, preferably 0.4-0.6 mm, such as 0.5 mm.
本发明中，所述润湿性模块可沿所述流道方向规则排布，较佳地，所述润湿性模块沿所述流道方向等间距排布。所述等间距排布是指沿所述流道的方向相邻两个所述润湿性模块的中心间距相等。更佳地，所述润湿性模块的排布轨迹为方阵。In the present invention, the wettability modules may be regularly arranged along the flow channel direction. Preferably, the wettability modules are arranged at equal intervals along the flow channel direction. The equidistant arrangement means that the center-to-center spacing of two adjacent wettability modules along the direction of the flow channel is equal. More preferably, the arrangement track of the wettability modules is a square matrix.
本发明中，沿所述流道的方向相邻两个所述润湿性模块的中心间距可为1～4mm，例如2mm或3mm。In the present invention, the distance between the centers of two adjacent wettability modules in the direction of the flow channel may be 1˜4 mm, for example, 2 mm or 3 mm.
本发明中，所述润湿性模块的个数可由所述流道的长度、单个所述润湿性模块的最大尺寸以及沿所述流道方向相邻两个所述润湿性模块的中心间距共同决定。In the present invention, the number of the wettability modules can be determined by the length of the flow channel, the maximum size of a single wettability module, and the center of two adjacent wettability modules along the flow channel direction The spacing is determined jointly.
本发明中，所述润湿性试剂在所述气体扩散层上的渗透深度为150～190μm，较佳地为170μm。In the present invention, the penetration depth of the wettability agent on the gas diffusion layer is 150-190 μm, preferably 170 μm.
本发明中，所述微孔层的厚度可为本领域常规，一般地为10～30μm。In the present invention, the thickness of the microporous layer may be conventional in the field, generally 10-30 μm.
本发明中，所述微孔层的基体材料可包括导电材料和粘结剂。In the present invention, the matrix material of the microporous layer may include a conductive material and a binder.
其中，所述导电材料可为本领域常规，优选为导电炭黑或石墨。所述石墨较佳地为粒径小、比表面积高、结构发达、俘获∏电子的杂质少、石墨化程度高、具有多孔性。所述导电炭黑较佳地为Super P、乙炔黑和Vulcan XC-72中的一种或多种，更佳地为Super P、乙炔黑和Vulcan XC-72的混合物。其中，所述Super P、乙炔黑和Vulcan XC-72的混合物中，Super P、乙炔黑 和Vulcan XC-72的质量比较佳地为1∶1∶1。Wherein, the conductive material may be conventional in the art, preferably conductive carbon black or graphite. The graphite is preferably small in particle size, high in specific surface area, well-developed in structure, less in impurities trapping ∏ electrons, high in graphitization, and porous. The conductive carbon black is preferably one or more of Super P, acetylene black and Vulcan XC-72, more preferably a mixture of Super P, acetylene black and Vulcan XC-72. Wherein, in the mixture of Super P, acetylene black and Vulcan XC-72, the quality of Super P, acetylene black and Vulcan XC-72 is preferably 1:1:1.
以上三种导电炭黑及其配比联用是发明人经过长期的实验研究，特别筛选而来，Super P的炭黑粒子间聚成链状或葡萄状，具有更好的导电性，乙炔黑的结构性更强，对电池的导电网络形成更有利，Vulcan XC-72的分散性更好，三种导电材料的复配能提高燃料电池的电化学性能。The above three conductive carbon blacks and their combination are specially selected by the inventor after long-term experimental research. The carbon black particles of Super P are aggregated into chains or grapes, which have better conductivity. The structure of Vulcan XC-72 is stronger, which is more favorable for the formation of the conductive network of the battery. The dispersion of Vulcan XC-72 is better, and the compounding of the three conductive materials can improve the electrochemical performance of the fuel cell.
其中，所述粘结剂可为本领域常规，较佳地为聚四氟乙烯。Wherein, the binder can be conventional in the art, preferably polytetrafluoroethylene.
其中，所述导电材料和所述粘结剂的质量比可为1∶(0.5～3)，例如1∶1或1∶0.86。Wherein, the mass ratio of the conductive material and the binder may be 1:(0.5-3), for example, 1:1 or 1:0.86.
本发明中，所述润湿性试剂较佳地为聚乙二醇和/或十二烷基氨基丙酸钠盐。润湿性试剂的种类有很多种，其润湿性能也不尽相同。润湿性太高或太低均不利于液态水的排除。In the present invention, the wetting agent is preferably polyethylene glycol and/or sodium dodecylaminopropionate. There are many types of wetting agents, and their wetting properties are also different. Wettability is too high or too low are not conducive to the exclusion of liquid water.
本发明中，所述润湿性模块除了所述基体材料外，还包括成膜剂。In the present invention, in addition to the base material, the wettability module further includes a film-forming agent.
其中，所述成膜剂可为本领域常规，较佳地为聚醋酸乙烯和/或聚乙烯醇。Wherein, the film-forming agent can be conventional in the art, preferably polyvinyl acetate and/or polyvinyl alcohol.
成膜剂的存在可增强导电材料与润湿性试剂的连接，提高润湿性部位的耐久性。The presence of the film-forming agent enhances the connection of the conductive material to the wetting agent and improves the durability of the wetting site.
本发明中，所述微孔层在所述基底层上的负载量可为本领域常规，一般地为2～5mg/cm 2，较佳地为3～4mg/cm 2，更佳地为3.3mg/cm 2。所述负载量指的是单位面积的所述基底层上负载的所述微孔层的质量。 In the present invention, the loading amount of the microporous layer on the base layer can be conventional in the field, generally 2-5 mg/cm 2 , preferably 3-4 mg/cm 2 , more preferably 3.3 mg/cm 2 . mg/cm 2 . The loading amount refers to the mass of the microporous layer supported on the base layer per unit area.
本发明中，所述导电材料在所述基底层上的负载量为1～4mg/cm 2，较佳地为1.5～2.5mg/cm 2，更佳地为2mg/cm 2。 In the present invention, the loading amount of the conductive material on the base layer is 1-4 mg/cm 2 , preferably 1.5-2.5 mg/cm 2 , more preferably 2 mg/cm 2 .
本发明中，所述基底层可为本领域常规，一般地包括基底层材料和疏水性涂层，所述疏水性涂层负载在所述基底层材料上。In the present invention, the base layer can be conventional in the art, and generally includes a base layer material and a hydrophobic coating, and the hydrophobic coating is supported on the base layer material.
其中，所述基底层材料可为本领域常规，例如碳纤维纸、碳纤维编织布、非织造布或炭黑纸等，较佳地为炭黑纸。Wherein, the base layer material can be conventional in the field, such as carbon fiber paper, carbon fiber woven cloth, non-woven cloth or carbon black paper, etc., preferably carbon black paper.
其中，所述疏水性涂层可为本领域常规，较佳地为聚四氟乙烯(PTFE)。Wherein, the hydrophobic coating can be conventional in the art, preferably polytetrafluoroethylene (PTFE).
其中，所述疏水性涂层占所述基底层材料的质量百分比可为10％-50％， 例如20％、30％或40％。Wherein, the mass percentage of the hydrophobic coating in the base layer material may be 10%-50%, such as 20%, 30% or 40%.
本发明某些优选实施方案中，所述润湿性试剂为聚乙二醇，所述润湿性模块为边长为0.5mm的正方形，相邻两个所述润湿性模块的中心间距为1mm，所述润湿性部位占所述流道的面积百分比为23％，所述润湿性模块沿流道方向的排布轨迹为方阵。In some preferred embodiments of the present invention, the wettability agent is polyethylene glycol, the wettability module is a square with a side length of 0.5 mm, and the center-to-center distance between two adjacent wettability modules is 1 mm, the area percentage of the wettability parts in the flow channel is 23%, and the arrangement track of the wettability modules along the flow channel direction is a square matrix.
本发明某些优选实施方案中，所述润湿性试剂为聚乙二醇，所述润湿性模块为边长为0.4mm的正方形，相邻两个所述润湿性模块的中心间距为2mm，所述润湿性部位占所述流道的面积百分比为11％，所述润湿性模块沿流道方向的排布轨迹为方阵。In some preferred embodiments of the present invention, the wettability agent is polyethylene glycol, the wettability module is a square with a side length of 0.4 mm, and the center-to-center distance between two adjacent wettability modules is 2 mm, the area percentage of the wettability parts in the flow channel is 11%, and the arrangement track of the wettability modules along the flow channel direction is a square matrix.
本发明某些优选实施方案中，所述润湿性试剂为十二烷基氨基丙酸钠盐，所述润湿性模块为边长为0.3mm的正方形，相邻两个所述润湿性模块的中心间距为3mm，所述润湿性部位占所述流道的面积百分比为6％，所述润湿性模块沿流道方向的排布轨迹为方阵。In certain preferred embodiments of the present invention, the wettability agent is sodium dodecylaminopropionate, the wettability module is a square with a side length of 0.3 mm, and two adjacent wettability modules are The center-to-center spacing of the modules is 3 mm, the area percentage of the wettability parts in the flow channel is 6%, and the arrangement track of the wettability modules along the flow channel direction is a square matrix.
本发明某些优选实施方案中，所述润湿性试剂为十二烷基氨基丙酸钠盐，所述润湿性模块为边长为0.4mm的正方形，相邻两个所述润湿性模块的中心间距为3mm，所述润湿性部位占所述流道的面积百分比为9％，所述润湿性模块沿流道方向的排布轨迹为方阵。In some preferred embodiments of the present invention, the wettability agent is sodium dodecylaminopropionate, the wettability module is a square with a side length of 0.4 mm, and two adjacent wettability modules are The center-to-center spacing of the modules is 3 mm, the area percentage of the wettability parts in the flow channel is 9%, and the arrangement track of the wettability modules along the flow channel direction is a square matrix.
本发明某些优选实施方案中，所述润湿性试剂为十二烷基氨基丙酸钠盐，所述润湿性模块为边长为0.5mm的正方形，相邻两个所述润湿性模块的中心间距为3mm，所述润湿性部位占所述流道的面积百分比为13％，所述润湿性模块沿流道方向的排布轨迹为方阵。本发明某些优选实施方案中，所述润湿性试剂为聚乙二醇，所述润湿性模块为边长为0.5mm的正方形，相邻两个所述润湿性模块的中心间距为2mm，所述润湿性部位占所述流道的面积百分比为16％，所述润湿性模块沿流道方向的排布轨迹为方阵。In some preferred embodiments of the present invention, the wettability agent is sodium dodecylaminopropionate, the wettability module is a square with a side length of 0.5 mm, and two adjacent wettability modules are The distance between the centers of the modules is 3 mm, the area percentage of the wettability parts in the flow channel is 13%, and the arrangement track of the wettability modules along the flow channel direction is a square matrix. In some preferred embodiments of the present invention, the wettability agent is polyethylene glycol, the wettability module is a square with a side length of 0.5 mm, and the center-to-center distance between two adjacent wettability modules is 2 mm, the area percentage of the wettability parts in the flow channel is 16%, and the arrangement track of the wettability modules along the flow channel direction is a square matrix.
本发明还提供一种上述气体扩散层的制备方法，其包括如下步骤：The present invention also provides a preparation method of the above-mentioned gas diffusion layer, which comprises the following steps:
S1、在基底层上负载微孔层；S1. Load the microporous layer on the base layer;
S2、在所述微孔层上沿与电极板的流道相对应的轨迹间隔施加润湿性浆料，烘干，得到多个润湿性模块，形成润湿性部位；S2, applying wettability slurry on the microporous layer at intervals along the track corresponding to the flow channel of the electrode plate, and drying to obtain a plurality of wettability modules to form wettability parts;
步骤S2中，所述润湿性浆料包括润湿性试剂、成膜剂和溶剂。In step S2, the wetting slurry includes a wetting agent, a film-forming agent and a solvent.
步骤S1中，所述基底层可采用本领域常规方法制备，一般地可由基底层材料经过疏水处理、在表面形成疏水性涂层得到。In step S1, the base layer can be prepared by a conventional method in the art, generally obtained by hydrophobic treatment of the base layer material and forming a hydrophobic coating on the surface.
其中，所述基底层材料可为如上所述的基底层材料。Wherein, the base layer material may be the base layer material as described above.
其中，所述疏水处理可采用本领域常规方法进行，一般地可将所述基底层材料浸渍到疏水材料中，取出烘干，反复多次，使所述疏水材料达到一定的负载量形成疏水性涂层。Wherein, the hydrophobic treatment can be performed by a conventional method in the field. Generally, the base layer material can be dipped into the hydrophobic material, taken out and dried, and repeated for many times, so that the hydrophobic material reaches a certain loading amount to form hydrophobicity. coating.
较佳地，所述基底层材料在进行疏水处理前还需进行超声处理。Preferably, the base layer material needs to be subjected to ultrasonic treatment before the hydrophobic treatment.
其中，所述超声处理可采用本领域常规方法进行，较佳地可在丙酮溶液中进行。Wherein, the ultrasonic treatment can be carried out by a conventional method in the art, preferably in an acetone solution.
其中，所述超声处理的时间可不低于10min，较佳地为30min。Wherein, the time of the ultrasonic treatment may not be less than 10min, preferably 30min.
其中，所述疏水材料可为本领域常规，较佳地为聚四氟乙烯乳液，更佳地为固含量为10％的聚四氟乙烯乳液。Wherein, the hydrophobic material can be conventional in the art, preferably a polytetrafluoroethylene emulsion, more preferably a polytetrafluoroethylene emulsion with a solid content of 10%.
其中，所述疏水性涂层占所述基底层材料上的质量百分比可如上所述。Wherein, the mass percentage of the hydrophobic coating on the base layer material can be as described above.
步骤S1中，所述微孔层可采用本领域常规方法负载到所述基底层上，较佳地为将微孔层浆料喷涂到所述基底层上，然后进行烧结，即得。In step S1, the microporous layer may be supported on the base layer by a conventional method in the art, preferably by spraying the microporous layer slurry on the base layer, and then sintering to obtain it.
其中，所述微孔层浆料可采用本领域常规方法制备得到，一般地可将导电材料、造孔剂、粘结剂和溶剂混合即得，较佳地，先将所述粘结剂配成质量浓度为10％的粘结剂乳液，再将所述导电材料、所述造孔剂、所述粘结剂乳液和所述溶剂混合；更佳地，混合后再进行超声分散，所述超声分散的时间较佳地为3h。Wherein, the microporous layer slurry can be prepared by a conventional method in the field, and generally can be obtained by mixing a conductive material, a pore-forming agent, a binder and a solvent. Preferably, the binder is prepared first into a binder emulsion with a mass concentration of 10%, and then mix the conductive material, the pore-forming agent, the binder emulsion and the solvent; more preferably, ultrasonic dispersion is performed after mixing, and the The time of ultrasonic dispersion is preferably 3h.
其中，所述导电材料可为如上所述的导电材料。Wherein, the conductive material may be the conductive material as described above.
其中，所述造孔剂可为本领域常规，较佳地为NH 4Cl和/或异丙醇，更佳地为氯化铵和异丙醇的混合物。其中，所述混合物中，所述氯化铵和所述 异丙醇的质量比可为1∶(50～200)，较佳地为1∶100。 Wherein, the pore-forming agent can be conventional in the art, preferably NH 4 Cl and/or isopropanol, more preferably a mixture of ammonium chloride and isopropanol. Wherein, in the mixture, the mass ratio of the ammonium chloride and the isopropanol may be 1:(50-200), preferably 1:100.
造孔剂在制备微孔层浆料时添加，喷涂到基底层后进行烧结，造孔剂在烧结过程中分解、挥发，原造孔剂的位置处即成为孔结构。The pore-forming agent is added during the preparation of the microporous layer slurry, sprayed onto the base layer and then sintered. The pore-forming agent decomposes and volatilizes during the sintering process, and the original pore-forming agent becomes the pore structure.
其中，粘结剂可为如上所述的粘结剂。Wherein, the binder can be the binder as described above.
其中，所述溶剂可为本领域常规，较佳地为水，更佳地为去离子水。Wherein, the solvent can be conventional in the art, preferably water, more preferably deionized water.
其中，所述导电材料、所述造孔剂、所述粘结剂和所述溶剂的质量比可为本领域常规，较佳地为(0.005～0.012)∶(0.5～2)∶(0.003～0.008)∶1，更佳地为(0.006～0.011)∶(0.8～1.2)∶(0.004～0.007)∶1，例如0.009∶1∶0.006∶1或0.0075∶1∶0.005∶1或0.0105∶1∶0.006∶1。Wherein, the mass ratio of the conductive material, the pore-forming agent, the binder and the solvent may be conventional in the field, preferably (0.005-0.012): (0.5-2): (0.003- 0.008):1, more preferably (0.006-0.011):(0.8-1.2):(0.004-0.007):1, such as 0.009:1:0.006:1 or 0.0075:1:0.005:1 or 0.0105:1:1 0.006:1.
其中，所述烧结可采用本领域常规方法进行，较佳地，可放于马弗炉中，360℃保温1h。Wherein, the sintering can be carried out by a conventional method in the art, preferably, it can be placed in a muffle furnace and kept at 360° C. for 1 hour.
步骤S2中，所述润湿性模块的大小和排布方式可如上所述。In step S2, the size and arrangement of the wettability modules can be as described above.
步骤S2中，所述施加可采用本领域常规方法进行，较佳地为超声喷涂、压力喷涂和气流雾化中的一种或多种。In step S2, the application can be performed by a conventional method in the art, preferably one or more of ultrasonic spraying, pressure spraying and airflow atomization.
其中，在所述施加之前，较佳地还需在所述微孔层表面铺设一张镂空的掩膜，各所述润湿性模块均与所述掩膜的镂空相对应，将所述润湿性浆料涂覆到所述镂空的位置处。Wherein, before the application, preferably a hollow mask needs to be laid on the surface of the microporous layer, each of the wettability modules corresponds to the hollow of the mask, and the moist Wet slurry is applied to the hollowed-out locations.
其中，所述掩膜的材料可为本领域常规，较佳地为双疏性材料，更佳地为聚四氟乙烯。Wherein, the material of the mask can be conventional in the art, preferably an amphiphobic material, more preferably polytetrafluoroethylene.
双疏性材料可以避免再喷涂润湿性试剂时因操作不当，试剂与掩膜粘连，污染非润湿性区域，造成误差。The amphiphobic material can avoid errors caused by improper operation of re-spraying the wetting reagent, the adhesion of the reagent and the mask, and the contamination of the non-wetting area.
其中，所述掩膜的镂空可采用本领域常规方法制得，较佳地为通过激光光刻机制得。Wherein, the hollowing out of the mask can be obtained by a conventional method in the art, preferably by a laser lithography machine.
步骤S2中，所述润湿性浆料的制备方法可为本领域常规，一般地，将所述润湿性试剂、所述成膜剂和所述溶剂混合即得。In step S2, the preparation method of the wettability slurry can be conventional in the field, and generally, the wettability agent, the film-forming agent and the solvent are mixed.
步骤S2中，所述润湿性试剂可为如上所述的润湿性试剂。In step S2, the wettability reagent may be the above-mentioned wettability reagent.
步骤S2中，所述成膜剂可为如上所述的成膜剂。In step S2, the film-forming agent may be the above-mentioned film-forming agent.
步骤S2中，所述溶剂可为本领域常规，较佳地为水。In step S2, the solvent can be conventional in the art, preferably water.
步骤S2中，所述润湿性试剂、所述成膜剂和所述溶剂的质量比可为1∶(0.5～4)∶(2～8)，较佳地为1∶(1～2)∶(3～6)，更佳地为1∶1.6∶4。In step S2, the mass ratio of the wetting agent, the film-forming agent and the solvent may be 1:(0.5-4):(2-8), preferably 1:(1-2) : (3 to 6), more preferably 1:1.6:4.
步骤S2中，所述施加的方式为超声喷涂或压力喷涂时，所述施加的时间可为1～5s，较佳地为3s。In step S2, when the application method is ultrasonic spraying or pressure spraying, the application time may be 1-5s, preferably 3s.
步骤S2中，所述施加的方式为超声喷涂或压力喷涂时，喷涂高度可为本领域常规，一般地为3-10cm，较佳的5cm。In step S2, when the application method is ultrasonic spraying or pressure spraying, the spraying height can be conventional in the field, generally 3-10 cm, preferably 5 cm.
施加方式为喷涂时，喷涂的时间和喷涂的高度直接影响润湿性试剂的渗透深度。When the application method is spraying, the spraying time and spraying height directly affect the penetration depth of the wetting agent.
步骤S2中，所述烘干可采用本领域常规方法进行，较佳地，可置于80℃的烘箱中1h。In step S2, the drying can be performed by a conventional method in the art, preferably, it can be placed in an oven at 80° C. for 1 hour.
本发明还提供一种上述气体扩散层在燃料电池中的应用。The present invention also provides an application of the above gas diffusion layer in a fuel cell.
本发明还提供一种包括上述气体扩散层的燃料电池。The present invention also provides a fuel cell including the above-mentioned gas diffusion layer.
在符合本领域常识的基础上，上述各优选条件，可任意组合，即得本发明各较佳实例。On the basis of conforming to common knowledge in the art, the above preferred conditions can be combined arbitrarily to obtain preferred examples of the present invention.
本发明所用试剂和原料均市售可得。The reagents and raw materials used in the present invention are all commercially available.
本发明的积极进步效果在于：本发明制得的气体扩散层的液态水突破压较现有技术的大幅降低，具体地，突破压可由13.6kPa降至10kPa以下，在一较佳实施例中可降至3.12kPa，降幅可高达77％。本发明提供的燃料电池的峰功率密度可高于600mW/cm 2，甚至高达666mW/cm 2，较现有技术的燃料电池的峰功率密度可提升28％。 The positive improvement effect of the present invention is that the liquid water breakthrough pressure of the gas diffusion layer prepared by the present invention is greatly reduced compared with the prior art. Specifically, the breakthrough pressure can be reduced from 13.6 kPa to below 10 kPa. Down to 3.12kPa, the drop can be as high as 77%. The peak power density of the fuel cell provided by the invention can be higher than 600 mW/cm 2 , even as high as 666 mW/cm 2 , which can be increased by 28% compared with the peak power density of the fuel cell in the prior art.
附图说明Description of drawings
图1为实施例1的气体扩散层上润湿性模块排布示意图；1 is a schematic diagram of the arrangement of wettability modules on the gas diffusion layer of Example 1;
图2为实施例1所得气体扩散层的液态水传输的分布图；Fig. 2 is the distribution diagram of the liquid water transport of the gas diffusion layer obtained in Example 1;
图3为对比例1所得气体扩散层的液态水传输的分布图；Fig. 3 is the distribution diagram of the liquid water transport of the gas diffusion layer obtained in Comparative Example 1;
图4为各实施例和对比例的气体扩散层组装成的燃料电池的极化曲线和功率密度曲线图，其中a为极化曲线；b为功率密度曲线。4 is a graph of polarization curves and power density curves of fuel cells assembled with gas diffusion layers of various embodiments and comparative examples, wherein a is the polarization curve; b is the power density curve.
附图标记reference number
1-润湿性模块(掩膜的镂空区域)；2-流道对应的轨迹。1- Wetability module (the hollow area of the mask); 2- The track corresponding to the runner.
具体实施方式Detailed ways
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在所述的实施例范围之中。下列实施例中未注明具体条件的实验方法，按照常规方法和条件，或按照商品说明书选择。The present invention is further described below by way of examples, but the present invention is not limited to the scope of the described examples. The experimental methods that do not specify specific conditions in the following examples are selected according to conventional methods and conditions, or according to the product description.
本发明所用原料、试剂均市售可得。部分常规测试按照国家标准方法即可。The raw materials and reagents used in the present invention are all commercially available. Some routine tests can be performed in accordance with national standard methods.
实施例1Example 1
S1：基底层制备：将碳纸放置于丙酮溶液中超声30min，取出放入60℃烘箱中烘干，置于质量分数为10％的PTFE乳液中浸泡，然后放至烘箱中烘干，反复几次，直至PTFE在碳纸上的负载量达到30％。S1: Preparation of base layer: put carbon paper in acetone solution and ultrasonic for 30min, take it out and put it in a 60°C oven to dry, soak it in PTFE emulsion with a mass fraction of 10%, and then put it in the oven to dry, repeat several times times until the loading of PTFE on carbon paper reaches 30%.
微孔层制备：称取氯化铵0.01g加入0.02g去离子水形成氯化铵溶液，取SuperP、AB型碳黑和Vulcan XC-72各0.03g，8g去离子水，异丙醇10g，10％wt的聚四氟乙烯乳液0.6g进行混合，加入上述的氯化铵溶液，超声分散3h，形成微孔层浆料。将微孔层浆料采用压力喷涂的方法喷涂至基底层使导电材料的负载量为2mg/cm 2，然后放于马弗炉中360℃烧结1h。 Preparation of microporous layer: Weigh 0.01g of ammonium chloride and add 0.02g of deionized water to form an ammonium chloride solution, take 0.03g each of SuperP, AB type carbon black and Vulcan XC-72, 8g deionized water, 10g isopropanol, 0.6 g of 10% wt polytetrafluoroethylene emulsion was mixed, the above-mentioned ammonium chloride solution was added, and ultrasonically dispersed for 3 hours to form a microporous layer slurry. The microporous layer slurry was sprayed onto the base layer by means of pressure spraying so that the load of the conductive material was 2 mg/cm 2 , and then placed in a muffle furnace for sintering at 360° C. for 1 hour.
S2：润湿性浆料制备及涂覆：取去离子水20g、润湿性试剂聚乙二醇5g、成膜剂聚醋酸乙烯乳液8g，混合，搅拌30min，得润湿性浆料。在微孔层上与流道相对应的轨迹上，规划出大小为0.5mm*0.5mm、中心间距为1mm的多个润湿性模块，润湿性部位占流道的面积比例为23％。取一张厚度为30μm的聚四氟乙烯薄膜作为掩膜，用激光刻度机对掩膜进行镂空，镂空与规划好 的润湿性模块完全对应，将其铺于上述微孔层的表面，喷涂上述润湿性浆料3s，润湿性试剂在气体扩散层上的渗透深度为170μm，然后置于80℃烘箱中烘干1h。S2: Preparation and coating of wettable slurry: take 20 g of deionized water, 5 g of polyethylene glycol as a wetting agent, and 8 g of polyvinyl acetate emulsion as a film-forming agent, mix and stir for 30 minutes to obtain a wettable slurry. On the trajectory corresponding to the flow channel on the microporous layer, a number of wettability modules with a size of 0.5mm*0.5mm and a center-to-center spacing of 1mm were planned, and the wettability parts accounted for 23% of the area of the flow channel. Take a polytetrafluoroethylene film with a thickness of 30 μm as a mask, and use a laser marking machine to hollow out the mask. The hollowing corresponds to the planned wettability module, and it is spread on the surface of the above-mentioned microporous layer and sprayed. The above wetting slurry was 3 s, the penetration depth of the wetting agent on the gas diffusion layer was 170 μm, and then it was dried in an oven at 80° C. for 1 hour.
实施例2Example 2
S1中导电材料Super P、AB型碳黑、Vulcan XC-72的质量均改为0.035g；S2中润湿性模块的大小改为0.4mm*0.4mm，中心间距改为2mm，润湿性部位占流道的面积比例为11％，其他操作与条件均与实施例1相同。The mass of the conductive materials Super P, AB type carbon black, and Vulcan XC-72 in S1 were changed to 0.035g; the size of the wettability module in S2 was changed to 0.4mm*0.4mm, the center spacing was changed to 2mm, and the wettability part The area ratio of the flow channel was 11%, and other operations and conditions were the same as those in Example 1.
实施例3Example 3
S2中润湿性试剂改为十二烷基氨基丙酸钠盐，成膜剂改为聚乙烯醇，润湿性模块大小改为0.3mm*0.3mm，中心间距改为3mm，润湿性部位占流道的面积比例为6％，其他操作与条件均与实施例1相同。In S2, the wettability reagent was changed to sodium dodecyl aminopropionate, the film-forming agent was changed to polyvinyl alcohol, the size of the wettability module was changed to 0.3mm*0.3mm, the center distance was changed to 3mm, and the wettability part was changed to The area ratio of the flow channel was 6%, and other operations and conditions were the same as those in Example 1.
实施例4Example 4
S2中润湿性试剂改为十二烷基氨基丙酸钠盐5g，润湿性模块的大小改为0.4mm*0.4mm，中心间距改为3mm，润湿性部位占流道的面积比例为9％，其他操作与条件均与实施例1相同。In S2, the wettability reagent was changed to 5g sodium dodecyl aminopropionate, the size of the wettability module was changed to 0.4mm*0.4mm, the center distance was changed to 3mm, and the area ratio of the wettability part to the flow channel was 9%, other operations and conditions are the same as in Example 1.
实施例5Example 5
S2中润湿性试剂改为十二烷基氨基丙酸钠盐5g，润湿性模块大小改为0.5mm*0.5mm，中心间距改为3mm，润湿性部位占流道的面积比例为13％，其他操作与条件均与实施例1相同。In S2, the wettability reagent is changed to 5g sodium dodecyl aminopropionate, the size of the wettability module is changed to 0.5mm*0.5mm, the center distance is changed to 3mm, and the area ratio of the wettability part to the flow channel is 13 %, and other operations and conditions were the same as in Example 1.
实施例6Example 6
S1中Super P、AB型碳黑、Vulcan XC-72各为0.025g，聚四氟乙烯乳液为0.5g，成膜剂改为聚乙烯醇8g；In S1, Super P, AB type carbon black, Vulcan XC-72 are each 0.025g, PTFE emulsion is 0.5g, and the film-forming agent is changed to polyvinyl alcohol 8g;
S2中润湿性模块的大小为0.5mm*0.5mm，中心间距为2mm，润湿性部位占流道的面积比例为16％，其他操作与条件均与实施例1相同。The size of the wettability module in S2 is 0.5mm*0.5mm, the center distance is 2mm, the area ratio of the wettability part to the flow channel is 16%, and other operations and conditions are the same as in Example 1.
对比例1Comparative Example 1
S1与实施例1完全相同，不进行S2。S1 is exactly the same as Example 1, and S2 is not performed.
实施例1～6的润湿性模块的排布轨迹如图1所示。The arrangement tracks of the wettability modules of Examples 1 to 6 are shown in FIG. 1 .
效果实施例Effect Example
1.突破压测试1. Breakthrough pressure test
将各实施例和对比例所制备的气体扩散层装于突破压测试装置，测其突破压，当碳纸表面有液滴出现时，记录此时的测控仪显示屏的读数即为气体扩散层的突破压。图2为实施例1所得气体扩散层突破压实验图，图3为对比例1所得气体扩散层的突破压实验图。由图2和图3的对比可以看出，在喷涂润湿性试剂后，液态水优先通过润湿性部位进行传输，氧气通过非润湿性部位进行传输；未喷涂润湿性试剂的气体扩散层，突破压较大，液态水传输分布没有规律。The gas diffusion layer prepared by each embodiment and the comparative example is installed in the breakthrough pressure test device, and its breakthrough pressure is measured. When droplets appear on the surface of the carbon paper, record the reading on the display screen of the measurement and control instrument at this time, which is the gas diffusion layer. breakthrough pressure. FIG. 2 is an experimental diagram of the breakthrough pressure of the gas diffusion layer obtained in Example 1, and FIG. 3 is an experimental diagram of the breakthrough pressure of the gas diffusion layer obtained in Comparative Example 1. It can be seen from the comparison between Fig. 2 and Fig. 3 that after spraying the wetting agent, liquid water is preferentially transported through the wetting part, and oxygen is transported through the non-wetting part; the gas diffusion without the spraying of the wetting agent layer, the breakthrough pressure is large, and the distribution of liquid water transmission is irregular.
2.燃料电池的极化曲线和功率密度曲线测试2. Polarization curve and power density curve test of fuel cell
将各实施例和对比例所制备的气体扩散层组装成燃料电池，采用美国Gore PRIMEA膜电极组件作为催化剂涂层膜，其中阴极催化剂Pt/C载量为0.4mg/cm 2，阳极Pt/C载量为0.15mg/cm 2。电池性能测试条件：温度60℃，湿度100％，背压50kPa，阴极：275mL/min空气，阳极：110mL/min氢气，测得极化曲线和功率密度曲线，功率密度曲线的最高点即为燃料电池的峰功率密度值。 The gas diffusion layers prepared in each example and comparative example were assembled into a fuel cell, and the American Gore PRIMEA membrane electrode assembly was used as the catalyst coating membrane, wherein the cathode catalyst Pt/C loading was 0.4 mg/cm 2 , and the anode Pt/C The loading was 0.15 mg/cm 2 . Battery performance test conditions: temperature 60°C, humidity 100%, back pressure 50kPa, cathode: 275mL/min air, anode: 110mL/min hydrogen, measured the polarization curve and power density curve, the highest point of the power density curve is the fuel The peak power density value of the battery.
表1实施例和对比例的效果表征Table 1 Effect Characterization of Examples and Comparative Examples
项目project 突破压/kPaBreakthrough pressure/kPa 峰功率密度/(mW/cm 2) Peak power density/(mW/cm 2 )
实施例1Example 1 3.123.12 543543
实施例2Example 2 4.794.79 583583
实施例3Example 3 6.826.82 580580
实施例4Example 4 7.327.32 606606
实施例5Example 5 8.398.39 666666
实施例6Example 6 5.985.98 558558
对比例1Comparative Example 1 13.6113.61 520520
各实施例和对比例的气体扩散层的突破压以及燃料电池的峰功率密度如表1所示。各实施例通过在微孔层上进行润湿性改性，水在其上的突破压均较未改性的有大幅降低，有利于催化剂层产生的液态水从气体扩散层快速排出，降低了水淹故障的风险，提高了燃料电池的峰功率密度。各实施例和对比例燃料电池的极化曲线如图4所示，由图4可以看出，各实施例气体扩散层的扩散性能均优于对比例气体扩散层，燃料电池水淹故障的风险较对比例明显降低，峰功率密度较对比例大幅提高，尤其是实施例5的燃料电池的峰功率密度高达666mW/cm 2，较对比例1提高28％。 The breakthrough pressures of the gas diffusion layers and the peak power densities of the fuel cells of the examples and comparative examples are shown in Table 1. In each example, the wettability modification is carried out on the microporous layer, and the breakthrough pressure of water on it is greatly reduced compared with that of the unmodified one, which is conducive to the rapid discharge of liquid water generated by the catalyst layer from the gas diffusion layer, and reduces the pressure on the microporous layer. The risk of flooding failure increases the peak power density of the fuel cell. The polarization curves of the fuel cells of each example and the comparative example are shown in Figure 4. It can be seen from Figure 4 that the diffusion performance of the gas diffusion layer of each example is better than that of the gas diffusion layer of the comparative example, and the risk of flooding failure of the fuel cell is Compared with the comparative example, the peak power density is significantly higher than that of the comparative example, especially the peak power density of the fuel cell of Example 5 is as high as 666 mW/cm 2 , which is 28% higher than that of the comparative example 1.
虽然以上描述了本发明的具体实施方式，但是本领域的技术人员应当理解，这些仅是举例说明，在不背离本发明的原理和实质的前提下，可以对这些实施方式做出多种变更或修改。因此，本发明的保护范围由所附权利要求书限定。Although the specific embodiments of the present invention have been described above, those skilled in the art should understand that these are only examples, and various changes may be made to these embodiments without departing from the principle and essence of the present invention. Revise. Accordingly, the scope of protection of the present invention is defined by the appended claims.

Claims (10)

  1. 一种气体扩散层，其包括基底层和微孔层，所述微孔层负载在所述基底层上；A gas diffusion layer comprising a base layer and a microporous layer, the microporous layer being supported on the base layer;
    所述气体扩散层包括润湿性部位，所述润湿性部位包括间隔设置的多个润湿性模块，所述润湿性模块的排布轨迹与燃料电池双极板的流道相对应，且各所述润湿性模块上均负载有润湿性试剂，所述润湿性试剂渗透所述基底层和所述微孔层，使所述微孔层表面的水通过所述润湿性部位直接进入所述流道。The gas diffusion layer includes a wettability part, the wettability part includes a plurality of wettability modules arranged at intervals, and the arrangement track of the wettability modules corresponds to the flow channel of the fuel cell bipolar plate, And each of the wettability modules is loaded with a wettability reagent, and the wettability reagent penetrates the base layer and the microporous layer, so that the water on the surface of the microporous layer passes through the wettability. site directly into the flow channel.
  2. 如权利要求1所述的气体扩散层，其特征在于，所述润湿性部位的面积占所述流道的面积百分比为5％-30％，较佳地为10％～20％；The gas diffusion layer according to claim 1, characterized in that, the area percentage of the wettability portion to the area of the flow channel is 5%-30%, preferably 10%-20%;
    其中，较佳地，所述润湿性部位的面积占所述流道的面积百分比为6％、9％、11％、13％、16％或23％；Wherein, preferably, the area of the wettable part accounts for 6%, 9%, 11%, 13%, 16% or 23% of the area of the flow channel;
    和/或，单个所述润湿性模块的最大尺寸不超过所述流道的宽度；And/or, the largest dimension of a single wettability module does not exceed the width of the flow channel;
    和/或，单个所述润湿性模块的形状为方形或圆形，较佳地为正方形；其中，所述正方形的边长优选为0.3～0.8mm，更优选为0.4～0.6mm，例如0.5mm；And/or, the shape of a single wettability module is a square or a circle, preferably a square; wherein, the side length of the square is preferably 0.3-0.8 mm, more preferably 0.4-0.6 mm, such as 0.5 mm mm;
    和/或，所述润湿性模块沿所述流道方向规则排布；较佳地，所述润湿性模块沿所述流道方向等间距排布；更佳地，所述润湿性模块的排布轨迹为方阵；And/or, the wettability modules are regularly arranged along the flow channel direction; preferably, the wettability modules are arranged at equal intervals along the flow channel direction; more preferably, the wettability modules The arrangement track of the module is a square matrix;
    和/或，沿所述流道的方向相邻两个所述润湿性模块的中心间距为1～4mm，例如2mm或3mm；And/or, the center-to-center distance between two adjacent wettability modules in the direction of the flow channel is 1-4 mm, for example, 2 mm or 3 mm;
    和/或，所述润湿性模块规则排布，较佳地，所述润湿性模块的排布轨迹为方阵；And/or, the wettability modules are regularly arranged, preferably, the arrangement track of the wettability modules is a square matrix;
    和/或，所述润湿性试剂在所述气体扩散层上的渗透深度为150～190μm，例如170μm。And/or, the penetration depth of the wetting agent on the gas diffusion layer is 150-190 μm, for example, 170 μm.
  3. 如权利要求1或2所述的气体扩散层，其特征在于，所述润湿性试 剂为聚乙二醇和/或十二烷基氨基丙酸钠盐；The gas diffusion layer according to claim 1 or 2, wherein the wettability agent is polyethylene glycol and/or sodium dodecylaminopropionate;
    和/或，所述润湿性模块还负载有成膜剂，所述成膜剂较佳地为聚醋酸乙烯和/或聚乙烯醇；And/or, the wettability module is also loaded with a film-forming agent, and the film-forming agent is preferably polyvinyl acetate and/or polyvinyl alcohol;
    和/或，所述微孔层的基体材料包括导电材料和粘结剂；And/or, the matrix material of the microporous layer includes a conductive material and a binder;
    其中，所述导电材料优选为导电炭黑或石墨，更优选为SuperP、乙炔黑和Vulcan XC-72中的一种或多种，进一步优选为Super P、乙炔黑和Vulcan XC-72的混合物，更进一步优选为Super P、乙炔黑和Vulcan XC-72的质量比为1∶1∶1的混合物；Wherein, the conductive material is preferably conductive carbon black or graphite, more preferably one or more of SuperP, acetylene black and Vulcan XC-72, further preferably a mixture of Super P, acetylene black and Vulcan XC-72, More preferably, the mass ratio of Super P, acetylene black and Vulcan XC-72 is a mixture of 1:1:1;
    其中，所述粘结剂较佳地为聚四氟乙烯；Wherein, the binder is preferably polytetrafluoroethylene;
    其中，所述导电材料和所述粘结剂的质量比较佳地为1∶(0.5～3)，例如1∶1或1∶0.86；Wherein, the mass of the conductive material and the binder is preferably 1:(0.5-3), for example, 1:1 or 1:0.86;
    其中，所述导电材料在所述基底层上的负载量优选为1～4mg/cm2，更优选为1.5～2.5mg/cm 2，进一步优选为2mg/cm 2； Wherein, the loading amount of the conductive material on the base layer is preferably 1-4 mg/cm 2 , more preferably 1.5-2.5 mg/cm 2 , and even more preferably 2 mg/cm 2 ;
    和/或，所述基底层包括基底层材料和疏水性涂层，所述疏水性涂层负载在所述基底层材料上；其中，所述基底层材料较佳地为碳纸；所述疏水性涂层较佳地为聚四氟乙烯；所述疏水性涂层占所述基底层材料的质量百分比较佳地为10％-50％，例如20％、30％或40％。And/or, the base layer includes a base layer material and a hydrophobic coating, and the hydrophobic coating is supported on the base layer material; wherein, the base layer material is preferably carbon paper; the hydrophobic coating is The hydrophobic coating is preferably polytetrafluoroethylene; the mass percentage of the hydrophobic coating in the base layer material is preferably 10%-50%, such as 20%, 30% or 40%.
  4. 如权利要求1～3中至少一项所述的气体扩散层，其特征在于，所述润湿性试剂为十二烷基氨基丙酸钠盐，所述润湿性部位的面积占所述流道的面积百分比为13％，所述润湿性模块为边长为0.5mm的正方形，相邻两个所述润湿性模块的中心间距为3mm，所述润湿性模块沿流道方向的排布轨迹为方阵。The gas diffusion layer according to at least one of claims 1 to 3, wherein the wettability agent is sodium salt of dodecyl aminopropionate, and the area of the wettability portion occupies the area of the flow The area percentage of the channel is 13%, the wettability module is a square with a side length of 0.5mm, the center distance of two adjacent wettability modules is 3mm, and the wettability modules are in the direction of the flow channel. The arrangement track is a square matrix.
  5. 一种如权利要求1～4中至少一项所述的气体扩散层的制备方法，其包括如下步骤：A method for preparing a gas diffusion layer as claimed in at least one of claims 1 to 4, comprising the steps of:
    S1、在基底层上负载微孔层；S1. Load the microporous layer on the base layer;
    S2、在所述微孔层上沿与电极板的流道相对应的轨迹间隔施加润湿性浆 料，烘干，得到多个润湿性模块，形成润湿性部位；S2, apply wettability slurry on the microporous layer along the track interval corresponding to the flow channel of the electrode plate, dry, obtain a plurality of wettability modules, and form wettability parts;
    步骤S2中，所述润湿性浆料包括润湿性试剂、成膜剂和溶剂。In step S2, the wetting slurry includes a wetting agent, a film-forming agent and a solvent.
  6. 如权利要求5所述的气体扩散层的制备方法，其特征在于，所述基底层由基底层材料经过疏水处理、在表面形成疏水性涂层得到；The method for preparing a gas diffusion layer according to claim 5, wherein the base layer is obtained by subjecting the base layer material to hydrophobic treatment and forming a hydrophobic coating on the surface;
    其中，所述疏水处理较佳地为将所述基底层材料浸渍到疏水材料中，取取出烘干，反复多次，使所述疏水材料在所述基底层材料表面形成疏水性涂层；Wherein, the hydrophobic treatment is preferably performed by dipping the base layer material into the hydrophobic material, taking it out and drying it, and repeating it multiple times, so that the hydrophobic material forms a hydrophobic coating on the surface of the base layer material;
    较佳地，所述疏水材料为聚四氟乙烯乳液，更佳地为固含量为10％的聚四氟乙烯乳液；Preferably, the hydrophobic material is a polytetrafluoroethylene emulsion, more preferably a polytetrafluoroethylene emulsion with a solid content of 10%;
    和/或，所述微孔层可通过将微孔层浆料喷涂到所述基底层上，然后进行烧结制得；所述微孔层浆料包括导电材料材料、造孔剂、粘结剂和溶剂；And/or, the microporous layer can be prepared by spraying the microporous layer slurry on the base layer and then sintering; the microporous layer slurry includes conductive material, pore-forming agent, and binder and solvent;
    其中，所述微孔层浆料较佳地为将所述导电材料、所述造孔剂、所述粘结剂和溶剂混合得到；更佳地，先将所述粘结剂配成质量浓度为10％的粘结剂乳液，再将所述导电材料、所述造孔剂、所述粘结剂乳液和所述溶剂混合，再进行超声分散3h；Wherein, the microporous layer slurry is preferably obtained by mixing the conductive material, the pore-forming agent, the binder and the solvent; more preferably, the binder is first prepared to a mass concentration is 10% binder emulsion, then the conductive material, the pore-forming agent, the binder emulsion and the solvent are mixed, and then ultrasonically dispersed for 3 hours;
    其中，所述造孔剂较佳地为NH4C1和/或异丙醇，更佳地为氯化铵和乙二醇的质量比为1∶100的混合物；Wherein, the pore-forming agent is preferably NH4Cl and/or isopropanol, more preferably a mixture of ammonium chloride and ethylene glycol in a mass ratio of 1:100;
    其中，所述溶剂较佳地为水；Wherein, the solvent is preferably water;
    其中，所述导电材料、所述造孔剂、所述粘结剂和所述溶剂的质量比优选为(0.005～0.012)∶(0.5～2)∶(0.003～0.008)∶1，更优选为(0.006～0.011)∶(0.8～1.2)∶(0.004～0.007)∶1，例如0.009∶1∶0.006∶1或0.0075∶1∶0.005∶1或0.0105∶1∶0.006∶1。Wherein, the mass ratio of the conductive material, the pore-forming agent, the binder and the solvent is preferably (0.005-0.012):(0.5-2):(0.003-0.008):1, more preferably (0.006-0.011):(0.8-1.2):(0.004-0.007):1, for example 0.009:1:0.006:1 or 0.0075:1:0.005:1 or 0.0105:1:0.006:1.
  7. 如权利要求5或6所述的气体扩散层的制备方法，其特征在于，The method for preparing a gas diffusion layer according to claim 5 or 6, wherein:
    步骤S2中，所述润湿性模块的大小和排布方式如权利要求2所述；In step S2, the size and arrangement of the wettability modules are as described in claim 2;
    和/或，步骤S2中，所述施加为超声喷涂、压力喷涂和气流雾化中的一种或多种；And/or, in step S2, described applying is one or more in ultrasonic spraying, pressure spraying and airflow atomization;
    其中，较佳地，在所述施加之前还需在所述微孔层表面铺设一张镂空的掩膜，各所述润湿性模块均与所述掩膜的镂空相对应，将所述润湿性浆料涂覆到所述镂空的位置处；Preferably, a hollow mask needs to be laid on the surface of the microporous layer before the application, and each wettability module corresponds to the hollow of the mask. The wet slurry is applied to the hollowed-out position;
    其中，所述掩膜的材料较佳地为双疏性材料，更佳地为聚四氟乙烯；Wherein, the material of the mask is preferably an amphiphobic material, more preferably polytetrafluoroethylene;
    其中，所述掩膜的镂空较佳地为通过激光光刻机制得。Wherein, the hollow of the mask is preferably obtained by a laser lithography machine.
  8. 如权利要求5～7中至少一项所述的气体扩散层的制备方法，其特征在于，The method for preparing a gas diffusion layer according to at least one of claims 5 to 7, wherein:
    步骤S2中，每个所述润湿性模块施加所述润湿性浆料的时间均相同；和/或，所述施加的方式为超声喷涂或压力喷涂时，所述施加的时间为1～5s，较佳地为3s；In step S2, the time for applying the wettability slurry to each wettability module is the same; and/or, when the application method is ultrasonic spraying or pressure spraying, the application time is 1 to 5s, preferably 3s;
    和/或，步骤S2中，所述润湿性浆料的制备方法为将所述润湿性试剂、所述成膜剂和所述溶剂混合制得；And/or, in step S2, the preparation method of the wettability slurry is prepared by mixing the wettability reagent, the film-forming agent and the solvent;
    和/或，步骤S2中，所述溶剂为水；And/or, in step S2, described solvent is water;
    其中，所述润湿性试剂、所述成膜剂和所述溶剂的质量比优选为1∶(0.5～4)∶(2～8)，进一步优选为1∶(1～2)∶(3～6)，更进一步优选为1∶1.6∶4。Wherein, the mass ratio of the wetting agent, the film-forming agent and the solvent is preferably 1:(0.5-4):(2-8), more preferably 1:(1-2):(3 ~6), more preferably 1:1.6:4.
  9. 一种如权利要求1～4中至少一项所述的气体扩散层在燃料电池中的应用。1. Use of a gas diffusion layer according to at least one of claims 1 to 4 in a fuel cell.
  10. 一种包括如权利要求1～4中至少一项所述的气体扩散层的燃料电池。A fuel cell comprising a gas diffusion layer as claimed in at least one of claims 1 to 4.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009272163A (en) * 2008-05-08 2009-11-19 Nissan Motor Co Ltd Fuel cell
JP2010061966A (en) * 2008-09-03 2010-03-18 Mitsubishi Electric Corp Polymer electrolyte fuel cell
CN101800320A (en) * 2010-03-30 2010-08-11 上海恒劲动力科技有限公司 Breathable layer of fuel cell
CN110614742A (en) * 2019-09-23 2019-12-27 天津大学 Microporous layer with surface hydrophilic and hydrophobic characteristics alternately distributed, mold and preparation method thereof
CN111029605A (en) * 2019-11-20 2020-04-17 华东理工大学 Gas diffusion layer for fuel cell and preparation method and application thereof
CN111129507A (en) * 2019-12-13 2020-05-08 同济大学 Gas diffusion layer for fuel cell and preparation method and application thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI334237B (en) * 2007-01-05 2010-12-01 Ind Tech Res Inst Gas diffusion layer, manufacturing apparatus and manufacturing method thereof
US20080206615A1 (en) * 2007-02-22 2008-08-28 Paul Nicotera Gas diffusion layer with controlled diffusivity over active area
CN102437343A (en) * 2011-11-17 2012-05-02 华南理工大学 Membrane electrode containing hydrophilic high polymer in anode catalytic layer and preparation method thereof
CN111540921A (en) * 2020-04-21 2020-08-14 南京格致高新环保技术有限公司 Fuel cell gas diffusion layer integrated with flow field and preparation method thereof
CN111509253A (en) * 2020-04-23 2020-08-07 天津大学 High-efficiency porous transport layer of proton exchange membrane fuel cell
CN111584887A (en) * 2020-05-27 2020-08-25 无锡威孚高科技集团股份有限公司 Preparation method of gas diffusion layer for proton exchange membrane fuel cell
CN111867275B (en) * 2020-07-31 2021-08-24 国网河南省电力公司西峡县供电公司 Browning method for improving interlayer binding force of printed circuit board

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009272163A (en) * 2008-05-08 2009-11-19 Nissan Motor Co Ltd Fuel cell
JP2010061966A (en) * 2008-09-03 2010-03-18 Mitsubishi Electric Corp Polymer electrolyte fuel cell
CN101800320A (en) * 2010-03-30 2010-08-11 上海恒劲动力科技有限公司 Breathable layer of fuel cell
CN110614742A (en) * 2019-09-23 2019-12-27 天津大学 Microporous layer with surface hydrophilic and hydrophobic characteristics alternately distributed, mold and preparation method thereof
CN111029605A (en) * 2019-11-20 2020-04-17 华东理工大学 Gas diffusion layer for fuel cell and preparation method and application thereof
CN111129507A (en) * 2019-12-13 2020-05-08 同济大学 Gas diffusion layer for fuel cell and preparation method and application thereof

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