WO2021179201A1 - Gas diffusion layer for proton exchange membrane fuel cell and preparation method therefor - Google Patents

Gas diffusion layer for proton exchange membrane fuel cell and preparation method therefor Download PDF

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WO2021179201A1
WO2021179201A1 PCT/CN2020/078745 CN2020078745W WO2021179201A1 WO 2021179201 A1 WO2021179201 A1 WO 2021179201A1 CN 2020078745 W CN2020078745 W CN 2020078745W WO 2021179201 A1 WO2021179201 A1 WO 2021179201A1
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diffusion layer
gas diffusion
carbon
exchange membrane
proton exchange
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PCT/CN2020/078745
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French (fr)
Chinese (zh)
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程磊
陈必成
李传玲
闫琰
张晶晶
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罗伯特·博世有限公司
程磊
陈必成
李传玲
闫琰
张晶晶
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Application filed by 罗伯特·博世有限公司, 程磊, 陈必成, 李传玲, 闫琰, 张晶晶 filed Critical 罗伯特·博世有限公司
Priority to CN202080091595.XA priority Critical patent/CN114930584A/en
Priority to PCT/CN2020/078745 priority patent/WO2021179201A1/en
Publication of WO2021179201A1 publication Critical patent/WO2021179201A1/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
    • 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
    • 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 of a proton exchange membrane fuel cell, wherein the gas diffusion layer is a porous substrate based on carbon fibers on which graphene and/or carbon nanotubes are grafted.
  • the present invention also relates to a method for preparing the gas diffusion layer and a proton exchange membrane fuel cell including the gas diffusion layer.
  • the Proton Exchange Membrane Fuel Cell uses hydrogen as a fuel to convert chemical energy into electrical energy through an electrochemical method.
  • the emission is water, which achieves zero emissions in the true sense.
  • the proton exchange membrane fuel cell due to the use of solid polymer membranes as the electrolyte, the proton exchange membrane fuel cell also has the advantages of high energy conversion rate, low temperature start-up, and no electrolyte leakage. Therefore, the proton exchange membrane fuel cell is a promising high-efficiency and environmentally friendly power source, especially for electric vehicles (such as automobiles), regional power stations and portable equipment.
  • the gas diffusion layer is located between the catalyst layer and the bipolar plate to support the catalyst layer and provide electron channels, gas channels and drainage channels for electrochemical reactions.
  • the conventional preparation method of the gas diffusion layer is as follows: First, a porous substrate containing carbon fibers, such as carbon paper, is immersed in polytetrafluoroethylene (PTFE), and the carbon paper impregnated with polytetrafluoroethylene is heated to make the polytetrafluoroethylene The ethylene is sintered, thereby hydrophobicizing the porous carbon paper. Then, the carbon black and the polytetrafluoroethylene emulsion are formulated into a slurry, and the slurry is coated on the side of the hydrophobic treated carbon paper by screen printing or spraying, so as to obtain a gas diffusion layer (as shown in the figure) 1 and Figure 2).
  • PTFE polytetrafluoroethylene
  • Figure 1 is a scanning electron microscope (SEM) image of a gas diffusion layer according to the prior art, in which the black linear material is carbon fiber, and the white cotton-like material filled between the linear carbon fibers is a mixture of polytetrafluoroethylene and carbon powder .
  • Fig. 2 is a scanning electron microscope (SEM) image of a cross section of the gas diffusion layer according to Fig. 1, wherein the magnifications of Fig. (2-a) and Fig. (2-b) are 400 times and 500 times, respectively.
  • PTFE itself is not conductive, and the introduction of hydrophobic material PTFE will sacrifice the conductivity of carbon paper. Moreover, during the charge/discharge cycle of the proton exchange membrane fuel cell, the PTFE coating is easily peeled off in a high temperature (about 80°C) and high humidity environment, which will reduce the hydrophobicity of the gas diffusion layer, which will lead to battery performance ( For example, electrochemical performance and discharge stability) deteriorate.
  • the present disclosure provides a gas diffusion layer for a proton exchange membrane fuel cell, wherein the gas diffusion layer is a porous substrate based on carbon fibers on which graphene and/or carbon nanotubes are grafted.
  • the hydrophobicity, conductivity, and gas transport performance of the gas diffusion layer can be enhanced, thereby improving the electrochemical performance and discharge stability of the proton exchange membrane fuel cell.
  • the present invention also provides a proton exchange membrane fuel cell, which includes the gas diffusion layer as described above.
  • the present disclosure also provides a method for preparing a gas diffusion layer of a proton exchange membrane fuel cell, which includes the following steps:
  • the present disclosure also provides a method for preparing a gas diffusion layer of a proton exchange membrane fuel cell, which includes the following steps:
  • porous substrate impregnated with the carbon nanotube solution is taken out and heated, preferably at a temperature not lower than 850°C, thereby obtaining a porous substrate based on carbon fibers grafted with carbon nanotubes.
  • the proton exchange membrane fuel cell according to the present invention can be used in electric vehicles (such as automobiles), regional power stations, and portable equipment.
  • Fig. 1 is a scanning electron microscope (SEM) image of a gas diffusion layer of a proton exchange membrane fuel cell according to the prior art.
  • Figure 2 is a scanning electron microscope (SEM) image showing a cross section of the gas diffusion layer of the proton exchange membrane fuel cell according to Figure 1, where the magnifications of Figure (2-a) and Figure (2-b) are respectively 400 times and 500 times.
  • SEM scanning electron microscope
  • FIG. 3 shows a schematic diagram of a carbon fiber grafted with graphene and/or carbon nanotubes according to the present disclosure.
  • FIG. 4 shows a schematic cross-sectional view of the contact state of the carbon fiber grafted with graphene and/or carbon nanotubes and the surface of the bipolar plate according to the present disclosure.
  • the proton exchange membrane fuel cell includes a proton exchange membrane, a catalyst layer, a gas diffusion layer and a bipolar plate.
  • the gas diffusion layer (GDL) is located between the catalyst layer and the bipolar plate to support the catalyst layer and provide electron channels, gas channels and drainage channels for electrochemical reactions.
  • the bipolar plate includes a cathode plate and an anode plate. Bipolar plates are used to collect and conduct electricity, block and transport fuels (for example, hydrogen and oxygen), and conduct heat.
  • the bipolar plate may be made of graphite or metal (for example, stainless steel, titanium alloy, aluminum alloy, or nickel alloy, etc.).
  • the gas diffusion layer of the proton exchange membrane fuel cell is a porous substrate based on carbon fibers on which graphene and/or carbon nanotubes are grafted.
  • graphene or carbon nanotubes are radially distributed on the surface of the carbon fiber.
  • the distribution of graphene or carbon nanotubes on the surface of the carbon fiber may be uniform or uneven.
  • the diameter of the carbon fiber is about 6 ⁇ m to about 7 ⁇ m. In some examples, the length of the carbon fiber is about 1 mm to about 160 mm, preferably about 1 mm to about 100 mm.
  • the size of the carbon fiber can be read from a scanning electron micrograph of a porous substrate based on carbon fiber, for example, by using ImageJ software.
  • the carbon fiber-based porous substrate is selected from carbon fiber paper, carbon fiber woven fabric, carbon fiber non-woven fabric, and any combination thereof.
  • the graphene is in the form of a sheet, and its length is about 1 ⁇ m to about 80 ⁇ m, and the thickness is about 0.35 nm to about 10 nm.
  • the length of the carbon nanotubes is about 1 ⁇ m to about 80 ⁇ m.
  • the thickness of the gas diffusion layer is about 100 ⁇ m to about 300 ⁇ m.
  • FIG. 3-a shows a carbon fiber 200
  • FIG. 3-b shows that graphene and/or carbon nanotubes 300 are grafted onto the carbon fiber 200.
  • the inventor of the present invention found that the larger the width (W) of the concave portion of the bipolar plate surface morphology, that is, the rougher the surface of the bipolar plate, the smaller the contact resistance between the bipolar plate and the gas diffusion layer. .
  • the surface of the bipolar plate that is too rough cannot withstand the electrochemical corrosion of the proton exchange membrane fuel cell.
  • the width (W) of the concave portion of the surface topography of the bipolar plate is less than or equal to the diameter (D) of the carbon fiber, for example, W is less than or equal to about 7 ⁇ m, and preferably W is less than Or equal to about 6 ⁇ m, more preferably W is less than or equal to about 5 ⁇ m.
  • the width (W) of the concave portion of the surface topography of the bipolar plate can be read from the scanning electron microscopic image of the bipolar plate by using ImageJ software.
  • FIGS. 4-a and 4-b the width (W) of the concave portion of the bipolar plate surface 100 is close to or slightly smaller than the diameter (D) of the carbon fiber 200.
  • the width (W) of the concave portion of the bipolar plate surface 100 is much smaller than the diameter (D, not shown in the figure) of the carbon fiber 200, for example, the width (W) of the concave portion of the bipolar plate surface 100 It is about 1/10 of the diameter (D) of the carbon fiber 200.
  • Reference numeral 300 represents graphene sheets and/or carbon nanotubes grafted to carbon fibers
  • reference numeral 200 represents all or part of the cross-section of the carbon fibers
  • reference numeral 100 represents the surface of the bipolar plate
  • reference numeral D represents The diameter of the carbon fiber
  • the reference symbol W indicates the width of the concave portion on the surface of the bipolar plate.
  • the effective contact points between the surface of the bipolar plate and the gas diffusion layer are increased without changing the surface morphology of the bipolar plate and the diameter of the carbon fiber.
  • graphene and carbon nanotubes themselves have high electrical conductivity, so the electrical conductivity is high at these increased contact sites. Therefore, the interface contact resistance between the bipolar plate and the gas diffusion layer is reduced.
  • graphene and carbon nanotubes are inherently hydrophobic. After the graphene and/or carbon nanotubes are grafted, there are suitable gaps between the carbon nanofibers and the surface of the bipolar plate to allow fuel gas and product water to pass through, thereby giving the gas diffusion layer of the present invention excellent hydrophobicity And gas transmission performance.
  • the gas diffusion layer of the present invention does not require hydrophobic treatment on the carbon fiber-based porous substrate, can achieve high hydrophobicity and gas transmission performance at low cost, and avoid battery performance degradation caused by the use of polytetrafluoroethylene.
  • graphene itself has excellent electrochemical corrosion resistance. Therefore, by grafting graphene on the carbon fiber, the carbon fiber can be protected from or less electrochemically corroded during the charge/discharge cycle of the proton exchange membrane fuel cell. Moreover, as described above, graphene is a hydrophobic material, and graphene grafted on carbon fibers can prevent water from contacting the carbon fibers, avoid the liquid-solid interface required for electrochemical corrosion, and thus prevent the occurrence of electrochemical corrosion reactions. Therefore, the carbon fiber grafted with graphene can improve the electrochemical corrosion resistance of the gas diffusion layer and the proton exchange membrane battery.
  • the gas diffusion layer of the present disclosure can improve the conductivity, hydrophobicity, gas transmission performance, high temperature stability and electrochemical corrosion resistance of the gas diffusion layer by grafting graphene and/or carbon nanotubes on the carbon fiber. Performance, thereby improving the battery performance (for example, electrochemical performance and discharge stability) of the proton exchange membrane battery.
  • the gas diffusion layer may additionally contain additives, such as pore formers and hydrophobic agents.
  • additives such as pore formers and hydrophobic agents.
  • the proton exchange membrane fuel cell may be a single proton exchange membrane fuel cell unit, or a proton exchange membrane fuel cell stack obtained by connecting two or more proton exchange membrane fuel cell units in parallel and/or in series.
  • At least one of the cathode gas diffusion layer and the anode gas diffusion layer of the proton exchange membrane fuel cell is the gas diffusion layer according to the present invention, and preferably the cathode gas diffusion layer and the anode gas diffusion layer of the proton exchange membrane fuel cell are both based on The gas diffusion layer of the present invention.
  • the method for preparing a gas diffusion layer of the present disclosure includes the following steps:
  • the method for preparing a gas diffusion layer of a proton exchange membrane fuel cell of the present disclosure includes the following steps:
  • porous substrate impregnated with the carbon nanotube solution is taken out and heated, preferably at a temperature not lower than 850°C, thereby obtaining a porous substrate based on carbon fibers grafted with carbon nanotubes.
  • the method for preparing the gas diffusion layer of the present invention has simple operation, good controllability, and cost saving.
  • the density of graphene and/or carbon nanotubes grafted on the carbon fiber can be adjusted, thereby fine-tuning the hydrophobicity, contact resistance and gas transmission performance of the gas diffusion layer.
  • stirring or ultrasound can be used, or both stirring and ultrasound can be used, so that graphene or carbon nanotubes are uniformly grafted on the carbon fiber.
  • stirring and sonication can be performed simultaneously or sequentially in any order. According to actual needs, stirring or sonication can be performed once or multiple times.
  • the solvent in the graphene oxide solution or the carbon nanotube solution, as long as the objective of the present invention can be achieved.
  • the solvent may be water, a non-aqueous solvent, or a mixture of water and a non-aqueous solvent.
  • the non-aqueous solvent may be an alcohol, such as a C1-C4 alcohol, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol.
  • the graphene oxide solution is an aqueous solution of graphene oxide.
  • the carbon nanotube solution is an aqueous solution of carbon nanotubes. Using water as the solvent, raw materials are easily available and environmentally friendly.
  • step b) heating can promote the fusion and close contact between the graphene or carbon nanotubes and the carbon fiber matrix, thereby reducing the contact resistance between the graphene or carbon nanotubes and the carbon fiber.
  • the higher the temperature the higher the processing efficiency and the shorter the processing time.
  • the heating temperature is not lower than 850° C., so as to cause the graphene oxide to undergo a reduction reaction.
  • the heating temperature can be about 850°C, about 900°C, or 1000°C. , 1200°C, 1500°C, 2000°C or 3000°C etc.
  • heating and oxidizing are performed in a vacuum or in a reducing gas atmosphere, and the reducing gas is preferably hydrogen or carbon monoxide.

Abstract

Provided is a gas diffusion layer for a proton exchange membrane fuel cell, wherein the gas diffusion layer is a porous substrate based on carbon fibers, with the carbon fibers being grafted with graphene and/or carbon nanotubes. Further provided are a method for preparing the gas diffusion layer and a proton exchange membrane fuel cell comprising the gas diffusion layer.

Description

质子交换膜燃料电池的气体扩散层及其制备方法Gas diffusion layer of proton exchange membrane fuel cell and preparation method thereof 技术领域Technical field
本发明涉及一种质子交换膜燃料电池的气体扩散层，其中，所述气体扩散层是基于碳纤维的多孔基材，所述碳纤维上接枝有石墨烯和/或碳纳米管。本发明还涉及所述气体扩散层的制备方法、以及包含所述气体扩散层的质子交换膜燃料电池。The present invention relates to a gas diffusion layer of a proton exchange membrane fuel cell, wherein the gas diffusion layer is a porous substrate based on carbon fibers on which graphene and/or carbon nanotubes are grafted. The present invention also relates to a method for preparing the gas diffusion layer and a proton exchange membrane fuel cell including the gas diffusion layer.
背景技术Background technique
质子交换膜燃料电池(PEMFC)以氢为燃料，通过电化学方式将化学能转化为电能，排放物是水，实现了真正意义上的零排放。而且，由于采用固体聚合物膜作为电解质，质子交换膜燃料电池还具有能量转换率高、低温启动、无电解质泄露等优点。因此，质子交换膜燃料电池是一种很有前景的高效环保电源，特别是可以用于电动车辆(如汽车)、区域性电站和便携式设备。The Proton Exchange Membrane Fuel Cell (PEMFC) uses hydrogen as a fuel to convert chemical energy into electrical energy through an electrochemical method. The emission is water, which achieves zero emissions in the true sense. Moreover, due to the use of solid polymer membranes as the electrolyte, the proton exchange membrane fuel cell also has the advantages of high energy conversion rate, low temperature start-up, and no electrolyte leakage. Therefore, the proton exchange membrane fuel cell is a promising high-efficiency and environmentally friendly power source, especially for electric vehicles (such as automobiles), regional power stations and portable equipment.
在质子交换膜燃料电池中，气体扩散层(GDL)位于催化剂层与双极板之间，用于支撑催化剂层，并且为电化学反应提供电子通道、气体通道和排水通道。In the proton exchange membrane fuel cell, the gas diffusion layer (GDL) is located between the catalyst layer and the bipolar plate to support the catalyst layer and provide electron channels, gas channels and drainage channels for electrochemical reactions.
气体扩散层的常规制备方法如下：首先，将包含碳纤维的多孔基材，例如碳纸，浸入聚四氟乙烯(PTFE)中，以及将浸有聚四氟乙烯的碳纸加热以使聚四氟乙烯烧结，由此对多孔碳纸进行疏水处理。然后，将炭黑与聚四氟乙烯乳液配制成浆料，通过丝网印刷或喷涂等方式将所述浆料涂布到经疏水处理的碳纸一侧，从而制得气体扩散层(如图1和图2所示)。图1为根据现有技术的气体扩散层的扫描电子显微镜(SEM)图像，其中黑色线状材料为碳纤维，填充于线状碳纤维之间的白色棉絮状物质为聚四氟乙烯和碳粉的混合物。图2为根据图1的气体扩散层的横截面的扫描电子显微镜(SEM)图像，其中图(2-a)和图(2-b)的放大倍数分别为400倍和500倍。The conventional preparation method of the gas diffusion layer is as follows: First, a porous substrate containing carbon fibers, such as carbon paper, is immersed in polytetrafluoroethylene (PTFE), and the carbon paper impregnated with polytetrafluoroethylene is heated to make the polytetrafluoroethylene The ethylene is sintered, thereby hydrophobicizing the porous carbon paper. Then, the carbon black and the polytetrafluoroethylene emulsion are formulated into a slurry, and the slurry is coated on the side of the hydrophobic treated carbon paper by screen printing or spraying, so as to obtain a gas diffusion layer (as shown in the figure) 1 and Figure 2). Figure 1 is a scanning electron microscope (SEM) image of a gas diffusion layer according to the prior art, in which the black linear material is carbon fiber, and the white cotton-like material filled between the linear carbon fibers is a mixture of polytetrafluoroethylene and carbon powder . Fig. 2 is a scanning electron microscope (SEM) image of a cross section of the gas diffusion layer according to Fig. 1, wherein the magnifications of Fig. (2-a) and Fig. (2-b) are 400 times and 500 times, respectively.
然而，聚四氟乙烯本身不导电，引入疏水材料聚四氟乙烯会牺牲碳纸的导电性。而且，在质子交换膜燃料电池进行充/放电循环时，聚四氟乙烯涂层在高温(80℃左右)高湿环境中容易脱落，这会降低气体扩散层的疏水性，进而导致电池性能(例如，电化学性能和放电稳定性)劣化。However, PTFE itself is not conductive, and the introduction of hydrophobic material PTFE will sacrifice the conductivity of carbon paper. Moreover, during the charge/discharge cycle of the proton exchange membrane fuel cell, the PTFE coating is easily peeled off in a high temperature (about 80°C) and high humidity environment, which will reduce the hydrophobicity of the gas diffusion layer, which will lead to battery performance ( For example, electrochemical performance and discharge stability) deteriorate.
因此，仍然需要改进质子交换膜燃料电池的气体扩散层，特别是改善气体扩散层的疏水性、导电性和气体传输性能，进而改善质子交换膜燃料电池的电池性能(例如，电化学性能和放电稳定性)。Therefore, there is still a need to improve the gas diffusion layer of the proton exchange membrane fuel cell, especially to improve the hydrophobicity, conductivity and gas transmission performance of the gas diffusion layer, thereby improving the cell performance of the proton exchange membrane fuel cell (for example, electrochemical performance and discharge performance). stability).
发明内容Summary of the invention
为此，一方面，本公开提供质子交换膜燃料电池的气体扩散层，其中，所述气体扩散层是基于碳纤维的多孔基材，所述碳纤维上接枝有石墨烯和/或碳纳米管。由此，可以增强气体扩散层的疏水性、导电性和气体传输性能，进而改进质子交换膜燃料电池的电化学性能和放电稳定性。To this end, in one aspect, the present disclosure provides a gas diffusion layer for a proton exchange membrane fuel cell, wherein the gas diffusion layer is a porous substrate based on carbon fibers on which graphene and/or carbon nanotubes are grafted. As a result, the hydrophobicity, conductivity, and gas transport performance of the gas diffusion layer can be enhanced, thereby improving the electrochemical performance and discharge stability of the proton exchange membrane fuel cell.
另一方面，本发明还提供质子交换膜燃料电池，其包括如上所述的气体扩散层。On the other hand, the present invention also provides a proton exchange membrane fuel cell, which includes the gas diffusion layer as described above.
另一方面，本公开还提供质子交换膜燃料电池的气体扩散层的制备方法，其包括以下步骤：On the other hand, the present disclosure also provides a method for preparing a gas diffusion layer of a proton exchange membrane fuel cell, which includes the following steps:
a)将基于碳纤维的多孔基材在氧化石墨烯溶液中浸泡约10分钟至约200分钟；以及a) Soak the carbon fiber-based porous substrate in the graphene oxide solution for about 10 minutes to about 200 minutes; and
b)将浸有氧化石墨烯溶液的多孔基材取出，并且在不低于850℃的温度下，将所述氧化石墨烯加热还原，由此得到基于接枝有石墨烯的碳纤维的多孔基材。b) Take out the porous substrate impregnated with the graphene oxide solution, and heat and reduce the graphene oxide at a temperature not lower than 850°C, thereby obtaining a porous substrate based on graphene-grafted carbon fibers .
另一方面，本公开还提供质子交换膜燃料电池的气体扩散层的制备方法，其包括以下步骤：On the other hand, the present disclosure also provides a method for preparing a gas diffusion layer of a proton exchange membrane fuel cell, which includes the following steps:
a)将基于碳纤维的多孔基材在碳纳米管溶液中浸泡约10分钟至约200分钟；以及a) Soak the carbon fiber-based porous substrate in the carbon nanotube solution for about 10 minutes to about 200 minutes; and
b)将浸有碳纳米管溶液的多孔基材取出并加热，优选在不低于850℃的温度下加热，由此得到基于接枝有碳纳米管的碳纤维的多孔 基材。b) The porous substrate impregnated with the carbon nanotube solution is taken out and heated, preferably at a temperature not lower than 850°C, thereby obtaining a porous substrate based on carbon fibers grafted with carbon nanotubes.
根据本发明的质子交换膜燃料电池可用于电动车辆(如汽车)、区域性电站和便携式设备中。The proton exchange membrane fuel cell according to the present invention can be used in electric vehicles (such as automobiles), regional power stations, and portable equipment.
参考以下附图，本发明的各种其它特征、方面和优点会变得更加显而易见。这些附图并非按比例绘制，旨在示意性地解释说明各种结构及位置关系，并且不应理解为限制性的。在附图中，在不同的视图中，相同的附图标记通常指代相同的部分。Various other features, aspects and advantages of the present invention will become more apparent with reference to the following drawings. These drawings are not drawn to scale, and are intended to schematically explain various structures and positional relationships, and should not be construed as restrictive. In the drawings, the same reference numerals generally refer to the same parts in different views.
附图说明Description of the drawings
图1是根据现有技术的质子交换膜燃料电池的气体扩散层的扫描电子显微镜(SEM)图像。Fig. 1 is a scanning electron microscope (SEM) image of a gas diffusion layer of a proton exchange membrane fuel cell according to the prior art.
图2是扫描电子显微镜(SEM)图像，示出了根据图1的质子交换膜燃料电池的气体扩散层的横截面，其中图(2-a)和图(2-b)的放大倍数分别为400倍和500倍。Figure 2 is a scanning electron microscope (SEM) image showing a cross section of the gas diffusion layer of the proton exchange membrane fuel cell according to Figure 1, where the magnifications of Figure (2-a) and Figure (2-b) are respectively 400 times and 500 times.
图3示出了根据本公开的接枝有石墨烯和/或碳纳米管的碳纤维的示意图。FIG. 3 shows a schematic diagram of a carbon fiber grafted with graphene and/or carbon nanotubes according to the present disclosure.
图4示出了根据本公开的接枝有石墨烯和/或碳纳米管的碳纤维与双极板表面的接触情形的示意性截面图。4 shows a schematic cross-sectional view of the contact state of the carbon fiber grafted with graphene and/or carbon nanotubes and the surface of the bipolar plate according to the present disclosure.
具体实施方式Detailed ways
除非另外定义，本文使用的所有技术和科学术语均为与本发明所属领域技术人员通常理解的含义。若存在不一致的地方，则以本申请提供的定义为准。Unless otherwise defined, all technical and scientific terms used herein have the meanings commonly understood by those skilled in the art to which the present invention belongs. If there is any inconsistency, the definition provided in this application shall prevail.
除非另外指出，本文所列出的数值范围旨在包括范围的端点，和该范围之内的所有数值和所有子范围。Unless otherwise indicated, the numerical ranges listed herein are intended to include the endpoints of the range, and all values and all subranges within the range.
本文的材料、含量、方法、设备、附图和实例均是示例性的，除非特别说明，不应理解为限制性的。The materials, contents, methods, equipment, drawings, and examples herein are all exemplary, and should not be construed as restrictive unless otherwise specified.
本文所用术语“包含”、“包括”和“具有”均表示可以将不影响最终效果的其他组分或其他步骤包括在内。这些术语涵盖“由……组成”和“基本上由……组成”的含义。根据本发明的产品和方法可以 包含或包括本公开中描述的必要技术特征，以及额外的和/或任选存在的组分、成分、步骤或本文描述的其他限制性特征；或者可以由本公开中描述的必要技术特征，以及额外的和/或任选存在的组分、成分、步骤或本文描述的其他限制性特征组成；或者基本上由本公开中描述的必要技术特征，以及额外的和/或任选存在的组分、成分、步骤或本文描述的其他限制性特征组成。The terms "comprising", "including" and "having" as used herein all mean that other components or other steps that do not affect the final effect can be included. These terms cover the meanings of "consisting of" and "essentially consisting of". The products and methods according to the present invention may contain or include the necessary technical features described in the present disclosure, as well as additional and/or optional components, ingredients, steps or other restrictive features described herein; or may be determined by the present disclosure The essential technical features described, as well as additional and/or optional components, ingredients, steps or other restrictive features described herein; or basically consist of the essential technical features described in the present disclosure, and additional and/or Optional components, ingredients, steps, or other restrictive features described herein.
除非另有明确说明，本公开中所用的所有材料和试剂均商购可得。Unless expressly stated otherwise, all materials and reagents used in this disclosure are commercially available.
除非另外指出或者明显矛盾，本文进行的操作都可以在室温和常压下进行。Unless otherwise indicated or obviously contradictory, the operations performed in this article can be performed at room temperature and normal pressure.
除非另外指出或者明显矛盾，可以任何合适的次序进行本公开中的方法步骤。Unless otherwise indicated or obviously contradictory, the method steps in the present disclosure may be performed in any suitable order.
以下将详细描述本公开的实例。Hereinafter, examples of the present disclosure will be described in detail.
质子交换膜燃料电池Proton exchange membrane fuel cell
质子交换膜燃料电池包括质子交换膜、催化剂层、气体扩散层和双极板。气体扩散层(GDL)位于催化剂层与双极板之间，用于支撑催化剂层，并且为电化学反应提供电子通道、气体通道和排水通道。双极板包括阴极板和阳极板。双极板用于收集和传导电流，阻隔和传送燃料(例如，氢气和氧气)，以及导热等。在一些实例中，双极板可以由石墨或金属(例如不锈钢、钛合金、铝合金或镍合金等)制成。The proton exchange membrane fuel cell includes a proton exchange membrane, a catalyst layer, a gas diffusion layer and a bipolar plate. The gas diffusion layer (GDL) is located between the catalyst layer and the bipolar plate to support the catalyst layer and provide electron channels, gas channels and drainage channels for electrochemical reactions. The bipolar plate includes a cathode plate and an anode plate. Bipolar plates are used to collect and conduct electricity, block and transport fuels (for example, hydrogen and oxygen), and conduct heat. In some examples, the bipolar plate may be made of graphite or metal (for example, stainless steel, titanium alloy, aluminum alloy, or nickel alloy, etc.).
根据本公开，质子交换膜燃料电池的气体扩散层是基于碳纤维的多孔基材，所述碳纤维上接枝有石墨烯和/或碳纳米管。According to the present disclosure, the gas diffusion layer of the proton exchange membrane fuel cell is a porous substrate based on carbon fibers on which graphene and/or carbon nanotubes are grafted.
在一些实例中，石墨烯或碳纳米管呈辐射状分布在碳纤维的表面。取决于制备工艺，石墨烯或碳纳米管在碳纤维表面的分布可以是均匀的，也可以是不均匀的。In some examples, graphene or carbon nanotubes are radially distributed on the surface of the carbon fiber. Depending on the preparation process, the distribution of graphene or carbon nanotubes on the surface of the carbon fiber may be uniform or uneven.
在一些实例中，所述碳纤维的直径是约6μm至约7μm。在一些实例中，所述碳纤维的长度是约1mm至约160mm，优选约1mm至约100mm。碳纤维的尺寸例如可以通过采用ImageJ软件从基于碳纤维的多孔基材的扫描电子显微图像中读取。In some examples, the diameter of the carbon fiber is about 6 μm to about 7 μm. In some examples, the length of the carbon fiber is about 1 mm to about 160 mm, preferably about 1 mm to about 100 mm. The size of the carbon fiber can be read from a scanning electron micrograph of a porous substrate based on carbon fiber, for example, by using ImageJ software.
在一些实例中，基于碳纤维的多孔基材选自碳纤维纸、碳纤维编织布、碳纤维无纺布以及它们的任意组合。In some examples, the carbon fiber-based porous substrate is selected from carbon fiber paper, carbon fiber woven fabric, carbon fiber non-woven fabric, and any combination thereof.
在一些实例中，石墨烯为片材形式，并且其长度为约1μm至约80μm，厚度为约0.35nm至约10nm。In some examples, the graphene is in the form of a sheet, and its length is about 1 μm to about 80 μm, and the thickness is about 0.35 nm to about 10 nm.
在一些实例中，碳纳米管的长度为约1μm至约80μm。In some examples, the length of the carbon nanotubes is about 1 μm to about 80 μm.
在一些实例中，气体扩散层的厚度为约100μm至约300μm。In some examples, the thickness of the gas diffusion layer is about 100 μm to about 300 μm.
如图3所示，图3-a表示碳纤维200，图3-b表示在碳纤维200上接枝有石墨烯和/或碳纳米管300。As shown in FIG. 3, FIG. 3-a shows a carbon fiber 200, and FIG. 3-b shows that graphene and/or carbon nanotubes 300 are grafted onto the carbon fiber 200.
本发明的发明人经过深入研究，发现双极板表面形貌的凹部宽度(W)越大，即，双极板的表面越粗糙，双极板与气体扩散层的之间的接触电阻越小。然而，太粗糙的双极板表面无法耐受质子交换膜燃料电池的电化学腐蚀。因此，在一些实例中，为了平衡接触电阻和耐腐蚀性，双极板的表面形貌的凹部宽度(W)小于或等于碳纤维的直径(D)，例如W小于或等于约7μm，优选W小于或等于约6μm，更优选W小于或等于约5μm。例如，可以通过采用ImageJ软件从双极板的扫描电子显微图像中读取双极板的表面形貌的凹部宽度(W)。After in-depth research, the inventor of the present invention found that the larger the width (W) of the concave portion of the bipolar plate surface morphology, that is, the rougher the surface of the bipolar plate, the smaller the contact resistance between the bipolar plate and the gas diffusion layer. . However, the surface of the bipolar plate that is too rough cannot withstand the electrochemical corrosion of the proton exchange membrane fuel cell. Therefore, in some examples, in order to balance contact resistance and corrosion resistance, the width (W) of the concave portion of the surface topography of the bipolar plate is less than or equal to the diameter (D) of the carbon fiber, for example, W is less than or equal to about 7 μm, and preferably W is less than Or equal to about 6 μm, more preferably W is less than or equal to about 5 μm. For example, the width (W) of the concave portion of the surface topography of the bipolar plate can be read from the scanning electron microscopic image of the bipolar plate by using ImageJ software.
图4示出了根据本公开的接枝有石墨烯和/或碳纳米管的碳纤维与双极板表面的接触情形的示意性截面图。在图4-a和4-b中，双极板表面100的凹部宽度(W)接近或略小于碳纤维200的直径(D)。在图4-c和4-d中，双极板表面100的凹部宽度(W)远小于碳纤维200的直径(D，图中未示出)，例如双极板表面100的凹部宽度(W)为碳纤维200的直径(D)的约1/10。附图标记300表示接枝至碳纤维的石墨烯片层和/或碳纳米管，附图标记200表示碳纤维的全部或部分横截面，附图标记100表示双极板的表面，附图标记D表示碳纤维的直径，附图标记W表示双极板表面的凹部宽度。4 shows a schematic cross-sectional view of the contact state of the carbon fiber grafted with graphene and/or carbon nanotubes and the surface of the bipolar plate according to the present disclosure. In FIGS. 4-a and 4-b, the width (W) of the concave portion of the bipolar plate surface 100 is close to or slightly smaller than the diameter (D) of the carbon fiber 200. In FIGS. 4-c and 4-d, the width (W) of the concave portion of the bipolar plate surface 100 is much smaller than the diameter (D, not shown in the figure) of the carbon fiber 200, for example, the width (W) of the concave portion of the bipolar plate surface 100 It is about 1/10 of the diameter (D) of the carbon fiber 200. Reference numeral 300 represents graphene sheets and/or carbon nanotubes grafted to carbon fibers, reference numeral 200 represents all or part of the cross-section of the carbon fibers, reference numeral 100 represents the surface of the bipolar plate, and reference numeral D represents The diameter of the carbon fiber, and the reference symbol W indicates the width of the concave portion on the surface of the bipolar plate.
通过在碳纤维上接枝石墨烯和/或碳纳米管，在不改变双极板表面形貌和碳纤维直径的情况下，双极板表面与气体扩散层的有效接触位点增多。而且，石墨烯和碳纳米管本身具有高导电性，因此，在这些增加的接触位点处，导电性很高。因此，双极板与气体扩散层的界面接触电阻降低。By grafting graphene and/or carbon nanotubes on the carbon fiber, the effective contact points between the surface of the bipolar plate and the gas diffusion layer are increased without changing the surface morphology of the bipolar plate and the diameter of the carbon fiber. Moreover, graphene and carbon nanotubes themselves have high electrical conductivity, so the electrical conductivity is high at these increased contact sites. Therefore, the interface contact resistance between the bipolar plate and the gas diffusion layer is reduced.
而且，石墨烯和碳纳米管本身具有疏水性。在接枝了石墨烯和/或碳纳米管之后，碳纳米纤维与双极板表面之间具有合适的空隙，允许燃料气体和产物水通过，由此赋予本发明的气体扩散层优异的疏水性和气体传输性能。本发明的气体扩散层不需要对基于碳纤维的多孔基材进行疏水处理，可以低成本实现高的疏水性和气体传输性能，并且避免由于采用聚四氟乙烯导致的电池性能劣化。Moreover, graphene and carbon nanotubes are inherently hydrophobic. After the graphene and/or carbon nanotubes are grafted, there are suitable gaps between the carbon nanofibers and the surface of the bipolar plate to allow fuel gas and product water to pass through, thereby giving the gas diffusion layer of the present invention excellent hydrophobicity And gas transmission performance. The gas diffusion layer of the present invention does not require hydrophobic treatment on the carbon fiber-based porous substrate, can achieve high hydrophobicity and gas transmission performance at low cost, and avoid battery performance degradation caused by the use of polytetrafluoroethylene.
而且，在质子交换膜电池工作时的高温(80℃左右)高湿环境中，石墨烯和碳纳米管具有稳定性，不会像聚四氟乙烯涂层一样发生脱落，从而改善了气体扩散层和质子交换膜电池的高温稳定性。Moreover, in the high temperature (about 80°C) and high humidity environment when the proton exchange membrane battery is working, graphene and carbon nanotubes are stable and will not fall off like a PTFE coating, thereby improving the gas diffusion layer And the high temperature stability of the proton exchange membrane battery.
另外，石墨烯本身具有优异的电化学耐腐蚀性，因此，通过在碳纤维上接枝石墨烯，可以保护碳纤维在质子交换膜燃料电池的充/放电循环中免受或少受电化学腐蚀。而且，如上所述，石墨烯是疏水材料，接枝在碳纤维上的石墨烯可以阻止水与碳纤维接触，避免发生电化学腐蚀所需要的液-固界面，从而阻止电化学腐蚀反应的发生。因此，接枝有石墨烯的碳纤维可以改善气体扩散层和质子交换膜电池的耐电化学腐蚀性。In addition, graphene itself has excellent electrochemical corrosion resistance. Therefore, by grafting graphene on the carbon fiber, the carbon fiber can be protected from or less electrochemically corroded during the charge/discharge cycle of the proton exchange membrane fuel cell. Moreover, as described above, graphene is a hydrophobic material, and graphene grafted on carbon fibers can prevent water from contacting the carbon fibers, avoid the liquid-solid interface required for electrochemical corrosion, and thus prevent the occurrence of electrochemical corrosion reactions. Therefore, the carbon fiber grafted with graphene can improve the electrochemical corrosion resistance of the gas diffusion layer and the proton exchange membrane battery.
由此可见，本公开的气体扩散层通过在碳纤维上接枝有石墨烯和/或碳纳米管，可以改善气体扩散层的导电性、疏水性、气体传输性能、高温稳定性和耐电化学腐蚀性，进而改善质子交换膜电池的电池性能(例如，电化学性能和放电稳定性)。It can be seen that the gas diffusion layer of the present disclosure can improve the conductivity, hydrophobicity, gas transmission performance, high temperature stability and electrochemical corrosion resistance of the gas diffusion layer by grafting graphene and/or carbon nanotubes on the carbon fiber. Performance, thereby improving the battery performance (for example, electrochemical performance and discharge stability) of the proton exchange membrane battery.
在一些实例中，气体扩散层中可以额外含有添加剂，例如成孔剂和疏水剂。对添加剂的具体种类和含量没有特别限制，只要不影响本发明目的的实现即可。In some examples, the gas diffusion layer may additionally contain additives, such as pore formers and hydrophobic agents. There are no particular restrictions on the specific types and content of additives, as long as they do not affect the realization of the purpose of the present invention.
根据本公开，质子交换膜燃料电池可以是单个的质子交换膜燃料电池单元，也可以是两个以上质子交换膜燃料电池单元通过并联和/或串联得到的质子交换膜燃料电池堆。According to the present disclosure, the proton exchange membrane fuel cell may be a single proton exchange membrane fuel cell unit, or a proton exchange membrane fuel cell stack obtained by connecting two or more proton exchange membrane fuel cell units in parallel and/or in series.
优选地，质子交换膜燃料电池的阴极气体扩散层和阳极气体扩散层中的至少一个为根据本发明的气体扩散层，优选质子交换膜燃料电池的阴极气体扩散层和阳极气体扩散层均为根据本发明的气体扩散层。Preferably, at least one of the cathode gas diffusion layer and the anode gas diffusion layer of the proton exchange membrane fuel cell is the gas diffusion layer according to the present invention, and preferably the cathode gas diffusion layer and the anode gas diffusion layer of the proton exchange membrane fuel cell are both based on The gas diffusion layer of the present invention.
气体扩散层的制备方法Preparation method of gas diffusion layer
本公开的制备气体扩散层的方法包括以下步骤：The method for preparing a gas diffusion layer of the present disclosure includes the following steps:
a)将基于碳纤维的多孔基材在氧化石墨烯溶液中浸泡约10分钟至约200分钟；以及a) Soak the carbon fiber-based porous substrate in the graphene oxide solution for about 10 minutes to about 200 minutes; and
b)将浸有氧化石墨烯溶液的多孔基材取出，并且在不低于850℃的温度下，将所述氧化石墨烯加热还原，由此得到基于接枝有石墨烯的碳纤维的多孔基材。b) Take out the porous substrate impregnated with the graphene oxide solution, and heat and reduce the graphene oxide at a temperature not lower than 850°C, thereby obtaining a porous substrate based on graphene-grafted carbon fibers .
替代地，本公开的制备质子交换膜燃料电池的气体扩散层的方法包括以下步骤：Alternatively, the method for preparing a gas diffusion layer of a proton exchange membrane fuel cell of the present disclosure includes the following steps:
a)将基于碳纤维的多孔基材在碳纳米管溶液浸泡约10分钟至约200分钟；以及a) Soak the carbon fiber-based porous substrate in the carbon nanotube solution for about 10 minutes to about 200 minutes; and
b)将浸有碳纳米管溶液的多孔基材取出并加热，优选在不低于850℃的温度下加热，由此得到基于接枝有碳纳米管的碳纤维的多孔基材。b) The porous substrate impregnated with the carbon nanotube solution is taken out and heated, preferably at a temperature not lower than 850°C, thereby obtaining a porous substrate based on carbon fibers grafted with carbon nanotubes.
本发明的制备气体扩散层的方法操作简单，可控性好，并且成本节约。通过改变工艺条件和工艺参数，可以调节碳纤维上接枝的石墨烯和/或碳纳米管的密度，从而微调气体扩散层的疏水性、接触电阻和气体传输性能。The method for preparing the gas diffusion layer of the present invention has simple operation, good controllability, and cost saving. By changing the process conditions and process parameters, the density of graphene and/or carbon nanotubes grafted on the carbon fiber can be adjusted, thereby fine-tuning the hydrophobicity, contact resistance and gas transmission performance of the gas diffusion layer.
在步骤a)中，可以采用搅拌或超声、或者既进行搅拌又进行超声，从而使石墨烯或者碳纳米管在碳纤维上均匀接枝。在既进行搅拌又进行超声的情况下，可以任意次序同时或先后进行搅拌和超声。根据实际需要，搅拌或超声可以进行1次，也可以进行多次。In step a), stirring or ultrasound can be used, or both stirring and ultrasound can be used, so that graphene or carbon nanotubes are uniformly grafted on the carbon fiber. In the case of both stirring and sonication, stirring and sonication can be performed simultaneously or sequentially in any order. According to actual needs, stirring or sonication can be performed once or multiple times.
在步骤a)中，对所述氧化石墨烯溶液或碳纳米管溶液中的溶剂没有具体限制，只要能实现本发明的目的即可。例如，溶剂可以是水、非水溶剂、或者水与非水溶剂的混合物。非水溶剂可以是醇，例如C1-C4醇，例如，甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、叔丁醇。在一些实例中，氧化石墨烯溶液是氧化石墨烯的水溶液。在一些实例中，碳纳米管溶液是碳纳米管的水溶液。采用水作为溶剂，原料易得，环境友好。In step a), there is no specific limitation on the solvent in the graphene oxide solution or the carbon nanotube solution, as long as the objective of the present invention can be achieved. For example, the solvent may be water, a non-aqueous solvent, or a mixture of water and a non-aqueous solvent. The non-aqueous solvent may be an alcohol, such as a C1-C4 alcohol, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol. In some examples, the graphene oxide solution is an aqueous solution of graphene oxide. In some examples, the carbon nanotube solution is an aqueous solution of carbon nanotubes. Using water as the solvent, raw materials are easily available and environmentally friendly.
在步骤b)中，加热可以促进石墨烯或碳纳米管与碳纤维基体的融合和紧密接触，从而降低石墨烯或碳纳米管与碳纤维的接触电阻。一般来说，温度越高，处理效率越高，处理时间越短。In step b), heating can promote the fusion and close contact between the graphene or carbon nanotubes and the carbon fiber matrix, thereby reducing the contact resistance between the graphene or carbon nanotubes and the carbon fiber. Generally speaking, the higher the temperature, the higher the processing efficiency and the shorter the processing time.
在碳纤维上接枝石墨烯的情况下，在制备气体扩散层的方法的步骤b)中，加热温度为不低于850℃，以便使氧化石墨烯发生还原反应。对于加热温度的上限没有具体限制，本领域技术人员可以根据实际需要，例如，在还原反应的速度、转化率和成本之间进行权衡，例如加热温度可以是约850℃、约900℃、1000℃、1200℃、1500℃、2000℃或3000℃等。在步骤b)中，在真空中或在还原气体气氛中进行加热氧化，所述还原气体优选为氢气或一氧化碳。In the case of grafting graphene on the carbon fiber, in step b) of the method for preparing the gas diffusion layer, the heating temperature is not lower than 850° C., so as to cause the graphene oxide to undergo a reduction reaction. There is no specific limitation on the upper limit of the heating temperature. Those skilled in the art can weigh the reduction reaction speed, conversion rate and cost according to actual needs. For example, the heating temperature can be about 850°C, about 900°C, or 1000°C. , 1200℃, 1500℃, 2000℃ or 3000℃ etc. In step b), heating and oxidizing are performed in a vacuum or in a reducing gas atmosphere, and the reducing gas is preferably hydrogen or carbon monoxide.

Claims (10)

  1. 质子交换膜燃料电池的气体扩散层，其中，所述气体扩散层是基于碳纤维的多孔基材，所述碳纤维上接枝有石墨烯和/或碳纳米管。The gas diffusion layer of a proton exchange membrane fuel cell, wherein the gas diffusion layer is a porous substrate based on carbon fibers, and the carbon fibers are grafted with graphene and/or carbon nanotubes.
  2. 如权利要求1所述的气体扩散层，其中，所述石墨烯或碳纳米管呈辐射状分布在所述碳纤维的表面。3. The gas diffusion layer according to claim 1, wherein the graphene or carbon nanotubes are radially distributed on the surface of the carbon fiber.
  3. 如权利要求1或2所述的气体扩散层，其中，所述碳纤维的直径是约6μm至约7μm；长度是约1mm至约160mm，优选约1mm至约100mm。The gas diffusion layer according to claim 1 or 2, wherein the diameter of the carbon fiber is about 6 μm to about 7 μm; the length is about 1 mm to about 160 mm, preferably about 1 mm to about 100 mm.
  4. 如前述权利要求中任一项所述的气体扩散层，其中，所述石墨烯为片材形式，并且其长度为约1μm至约80μm，厚度为约0.35nm至约10nm。The gas diffusion layer according to any one of the preceding claims, wherein the graphene is in the form of a sheet, and has a length of about 1 μm to about 80 μm and a thickness of about 0.35 nm to about 10 nm.
  5. 如前述权利要求中任一项所述的气体扩散层，其中，所述碳纳米管的长度为约1μm至约80μm。The gas diffusion layer according to any one of the preceding claims, wherein the length of the carbon nanotubes is about 1 μm to about 80 μm.
  6. 如前述权利要求中任一项所述的气体扩散层，其中，所述基于碳纤维的多孔基材选自碳纤维纸、碳纤维编织布、碳纤维无纺布以及它们的任意组合。The gas diffusion layer according to any one of the preceding claims, wherein the carbon fiber-based porous substrate is selected from the group consisting of carbon fiber paper, carbon fiber woven fabric, carbon fiber non-woven fabric, and any combination thereof.
  7. 质子交换膜燃料电池，其包括如权利要求1-6中任一项所述的气体扩散层。A proton exchange membrane fuel cell, which includes the gas diffusion layer according to any one of claims 1-6.
  8. 质子交换膜燃料电池的气体扩散层的制备方法，其包括以下步骤：The preparation method of the gas diffusion layer of the proton exchange membrane fuel cell includes the following steps:
    a)将基于碳纤维的多孔基材在氧化石墨烯溶液中浸泡约10分钟至约200分钟；以及a) Soak the carbon fiber-based porous substrate in the graphene oxide solution for about 10 minutes to about 200 minutes; and
    b)将浸有氧化石墨烯溶液的多孔基材取出，并且在不低于850℃的温度下，将所述氧化石墨烯加热还原，由此得到基于接枝有石墨烯的碳纤维的多孔基材。b) Take out the porous substrate impregnated with the graphene oxide solution, and heat and reduce the graphene oxide at a temperature not lower than 850°C, thereby obtaining a porous substrate based on graphene-grafted carbon fibers .
  9. 如权利要求8所述的方法，其中，在步骤b)中，在真空中或在还原气体气氛中进行加热还原，所述还原气体优选为氢气或一氧化碳。The method according to claim 8, wherein in step b), heating and reduction are performed in a vacuum or in a reducing gas atmosphere, and the reducing gas is preferably hydrogen or carbon monoxide.
  10. 质子交换膜燃料电池的气体扩散层的制备方法，其包括以下步骤：The preparation method of the gas diffusion layer of the proton exchange membrane fuel cell includes the following steps:
    a)将基于碳纤维的多孔基材在碳纳米管溶液中浸泡约10分钟至约200分钟；以及a) Soak the carbon fiber-based porous substrate in the carbon nanotube solution for about 10 minutes to about 200 minutes; and
    b)将浸有碳纳米管溶液的多孔基材取出并加热，优选在不低于850℃的温度下加热，由此得到基于接枝有碳纳米管的碳纤维的多孔基材。b) The porous substrate impregnated with the carbon nanotube solution is taken out and heated, preferably at a temperature not lower than 850°C, thereby obtaining a porous substrate based on carbon fibers grafted with carbon nanotubes.
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