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CN111129554A - Gradient hydrophobic membrane electrode and preparation method thereof - Google Patents

Gradient hydrophobic membrane electrode and preparation method thereof Download PDF

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Publication number
CN111129554A
CN111129554A CN201911344599.XA CN201911344599A CN111129554A CN 111129554 A CN111129554 A CN 111129554A CN 201911344599 A CN201911344599 A CN 201911344599A CN 111129554 A CN111129554 A CN 111129554A
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hydrophobic
membrane electrode
layer
hydrophobic agent
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李晓锦
刘文奇
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Priority to PCT/CN2020/091495 priority patent/WO2021128719A1/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
    • H01M8/10—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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention belongs to the field of fuel cells, and particularly relates to a gradient hydrophobic membrane electrode and a preparation method thereof. A catalyst layer, a microporous layer and a support layer which are subjected to hydrophobic treatment by a solution containing a hydrophobic agent and have gradually reduced hydrophobicity are sequentially attached to a proton exchange membrane of the membrane electrode. The preparation method is simple, feasible, green and environment-friendly, and the obtained membrane electrode has higher electrochemical output performance than the membrane electrode treated by the conventional fluorine-containing hydrophobic agent, and can effectively improve the discharge capacity of liquid water and the working performance under high current density. The method has the advantages of low equipment requirement, low raw material cost, simple and quick preparation process, mild conditions and suitability for large-scale industrial production.

Description

Gradient hydrophobic membrane electrode and preparation method thereof
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to a gradient hydrophobic membrane electrode and a preparation method thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are power generation devices that controllably convert Fuel and oxidant into electrical energy through electrochemical reaction under chemical energy, have the characteristics of high energy conversion efficiency, environmental friendliness, and the like, and can be applied to the fields of new energy vehicles, distributed power stations, portable electronic devices, and the like. Water is a key factor affecting the performance of proton exchange membrane fuel cells. The water content is favorable for the proton conductivity of the proton exchange membrane, but the water content in the porous electrode is too high, so that liquid water is formed, the transmission of substances is hindered, and the flooding of the electrode is caused. Therefore, the water drainage performance of the cell has an important influence on the power generation performance of the fuel cell, and excellent water management can provide a favorable help for the industrial development of the proton exchange membrane fuel cell.
At present, the drainage performance of the proton exchange membrane fuel cell is mainly optimized from the inside of the cell structure, including the optimization of the pore structures of the catalyst layer and the diffusion layer, the polar plate flow channel structure and the like. Wherein the gradient design can effectively improve the water management capability of the battery. For example, the jenseng steel and the like (jenseng steel, Zhang Yongsheng, Xiaojin Sheng, etc., school news of science and technology university in China, 2007, 35(9): 45-48) use the diffusion layer with gradient distribution to improve the discharge amount of liquid water and reduce the residual amount thereof. Chun et al (J H Chun, D HJo, S G Kim et al. Renew. energy, 2013, 58: 28-33) have improved drainage of liquid water and working performance at high current density by adding pore-forming agents to obtain a graded microporous layer. It should be noted that, in order to maximize the drainage capacity of the fuel cell, the single structural design of each part cannot meet the requirement, and the overall gradient design of the membrane electrode needs to be matched.
Disclosure of Invention
The invention aims to provide a gradient membrane electrode structure for a proton exchange membrane fuel cell and a preparation method thereof, and the method can improve the discharge capacity of liquid water and the working performance of the cell under high current density. The method has the advantages of high safety, simplicity in operation, good performance and the like.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a gradient hydrophobic membrane electrode is characterized in that a proton exchange membrane of the membrane electrode is sequentially attached with a catalyst layer, a microporous layer and a support layer, wherein the catalyst layer, the microporous layer and the support layer are subjected to hydrophobic treatment by a solution containing a hydrophobic agent, and the hydrophobicity of the catalyst layer, the microporous layer and the support layer is sequentially reduced.
The catalyst layer is subjected to hydrophobic treatment by spraying suspension of a catalyst, a proton conductor and a hydrophobic agent on two sides of a proton exchange membrane to form the catalyst layer subjected to hydrophobic treatment; wherein the mass ratio of the catalyst to the proton conductor to the hydrophobing agent is 1: 0.2-0.8: 0-1.
The support layer is subjected to hydrophobic treatment by immersing the support material into a solution containing a hydrophobic agent; wherein the solution containing the hydrophobic agent is formed by mixing the hydrophobic agent and an organic solvent, and the mass concentration fraction of the hydrophobic agent in the mixed solution is 3-30%.
The hydrophobic treatment of the microporous layer is to dissolve a hydrophobic agent and a carbon nano material in an organic solvent to form a suspension, and blade-coat or spray-coat the suspension on one side of the supporting layer opposite to the proton exchange membrane to form the hydrophobic microporous layer.
The hydrophobic agent is an organosiloxane.
A method for preparing a gradient hydrophobic membrane electrode,
1) the hydrophobic treatment is to spray a suspension of a catalyst, a proton conductor and a hydrophobic agent on two sides of a proton exchange membrane to form a catalytic layer for hydrophobic treatment; wherein the mass ratio of the catalyst to the proton conductor to the hydrophobing agent is 1: 0.2-0.8: 0 to 1;
2) the support layer is subjected to hydrophobic treatment by immersing the support material into a solution containing a hydrophobic agent; wherein the solution containing the hydrophobic agent is formed by mixing the hydrophobic agent and an organic solvent, and the mass concentration fraction of the hydrophobic agent in the mixed solution is 3-30%;
3) the hydrophobic treatment of the microporous layer is to dissolve a hydrophobic agent and a carbon nano material in an organic solvent to form a suspension, and the suspension is blade-coated or sprayed on one side of the supporting layer opposite to the proton exchange membrane to form a hydrophobic microporous layer; the final concentration of the hydrophobic agent in the suspension is 1 wt% -30 wt%, and the final concentration of the carbon nano material is 1 wt% -40 wt%. Preferably 1 to 5 weight percent and 2 to 10 weight percent respectively;
4) and (3) hot-pressing the treated proton exchange membrane with the hydrophobic catalytic layer and the hydrophobic support layer with the hydrophobic microporous layer to form the membrane electrode.
The hydrophobicity of each layer after the hydrophobic treatment is that the contact angle of the catalyst layer is as follows: 140 ℃ and 160 DEG; microporous layer contact angle: 130-150 degree; contact angle of support layer: 120-140 deg.
The carbon nano material is one or more of carbon black, acetylene black and carbon nano tubes; preferably carbon black;
the organic solvent is one or more of tetrahydrofuran, chloroform, dichloromethane, toluene, dimethyl ether and carbon tetrachloride; preferably tetrahydrofuran;
the organic siloxane is one or more of polydimethylsiloxane, polymethylsiloxane and α omega-dihydroxy polysiloxane, preferably polydimethylsiloxane
The carbon material and the hydrophobic agent loading amount on the surface of the microporous layer prepared by blade coating or spraying are 0.5-5.0mg/cm2. Preferably 0.5-2.0mg/cm2。
Compared with the prior art, the invention has the following characteristics:
the invention carries out hydrophobic treatment on different layers of the electrode, and the hydrophobic properties of the membrane electrode catalyst layer, the microporous layer and the diffusion layer after treatment are in a gradient decreasing trend. Compared with the membrane electrode treated by the conventional fluorine-containing hydrophobic agent, the membrane electrode has higher electrochemical output performance, and can effectively improve the discharge capacity of liquid water and the working performance under high current density; by adopting a gradient hydrophobic membrane electrode structure, the liquid water discharge capacity of the membrane electrode can be optimized, and the electrical output performance under high current density is improved; the preparation method is simple, rapid, mild in condition, feasible, green and environment-friendly, and is suitable for large-scale industrial production; the method has the advantages of low equipment requirement, low raw material cost and simple preparation process
Drawings
FIG. 1 is a schematic diagram of the present invention and the contact angles obtained by testing the structure of each part in example 1.
FIG. 2 is a photo-photograph of a membrane electrode of example 1 according to an embodiment of the present invention.
FIG. 3 is a polarization diagram of a membrane electrode of example 1 provided by an embodiment of the present invention.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation. The present invention will be described in detail below by way of examples.
In the following examples, the reagents used are as follows: polydimethylsiloxane (SYLGARD184) was purchased from Dow Corning, carbon paper from Toray-H-60, Dongli, Japan, 60% Pt/C catalyst from Johnson Matthey, carbon black (VXC-72R) from Cabot, acetylene black from New York dynamics, Inc., proton exchange membranes and Nafion solution from Kemu, USA, and other reagents from Chemicals, Inc., national drug group.
The contact angle was measured by a contact angle measuring instrument CA 100A.
The membrane electrode polarization curve test was measured by a laboratory self-contained test platform.
The hydrophobicity of the membrane electrode treated by the method is from high to low through the treatment of organic siloxane from the catalyst layer to the microporous layer and then to the supporting layer. Specifically, the hydrophobic performance of the membrane electrode is integrally designed in a gradient manner by using organic siloxane, and the hydrophobic performance of a catalyst layer, a microporous layer and a diffusion layer of the membrane electrode after treatment is in a gradient reduction trend. The preparation method is simple, feasible, green and environment-friendly, and the obtained membrane electrode has higher electrochemical output performance than the membrane electrode treated by the conventional fluorine-containing hydrophobic agent, and can effectively improve the discharge capacity of liquid water and the working performance under high current density. The method has the advantages of low equipment requirement, low raw material cost, simple and quick preparation process, mild conditions and suitability for large-scale industrial production.
Example 1
Treatment of the catalytic layer (preparation of Catalyst Coated Membrane (CCM)): 0.1488g of Pt/C catalyst, 0.992g of 5% Nafion solution and 0.015g of polydimethylsiloxane are weighed and sequentially added into 8ml of isopropanol, and stirred and ultrasonically vibrated for about 1-2 hours; then spraying it on both sides of proton exchange membrane, vacuum drying in oven at 80 deg.C for 0.5h, weighing to make its catalyst loading amount be 0.5mg/cm2。
And (3) processing the support layer: completely immersing the carbon paper into a tetrahydrofuran solution containing 5 wt% of polydimethylsiloxane for 10min for hydrophobic treatment, taking out, and drying at room temperature;
preparing a microporous layer: dissolving 3g of polydimethylsiloxane and 3g of carbon black in tetrahydrofuran (the mass fraction of the polydimethylsiloxane is 3 wt%), mechanically stirring, ultrasonically treating to form uniform suspension, and blade-coating one side of the hydrophobic carbon paper with the suspension until the loading amount of the carbon black is 0.5mg/cm2Naturally drying, placing in a drying oven, and sintering at 160 deg.C for 10 min.
Membrane electrode assembly and hot pressing: and hot-pressing the CCM proton exchange membrane and the prepared support layer with the microporous layer at 140 ℃ and 0.1MPa for 1min to prepare the membrane electrode.
Example 2
In the CCM preparation, 0.015g of polydimethylsiloxane was changed to 0.15g of polydimethylsiloxane, as in example 1.
Example 3
In the treatment of the support layer, a 5 wt% polydimethylsiloxane solution was changed to a 30 wt% polydimethylsiloxane solution, as in example 1.
Example 4
The microporous layer was prepared by changing 3g of polydimethylsiloxane to 30g of polydimethylsiloxane, as in example 1.
Example 5
The polydimethylsiloxane in example 1 was changed to polymethylsiloxane, and the rest was the same as in example 1.
Example 6
The carbon black of example 1 was changed to acetylene black, and the rest was the same as example 1.
Example 7
The procedure of example 1 was otherwise the same as that of example 1 except that tetrahydrofuran in example 1 was changed to chloroform.
Example 8
In the preparation of the microporous layer, carbon black is loaded at 0.5mg/cm2Modified to 5mg/cm2Otherwise, the same procedure as in example 1 was repeated.
And (3) performance testing:
(1) hydrophobicity test:
the assembled electrode of example 1 above was subjected to an optical test (see fig. 2), and the treated layers were subjected to a hydrophobicity test to measure the contact angle of each layer.
As can be seen from fig. 1, after the hydrophobic treatment, the hydrophobicity of the catalytic layer, the microporous layer, and the support layer decreases in sequence.
It can be seen from FIG. 2 that the membrane electrode has a flat surface after hydrophobic treatment and hot-pressing assembly.
(2) Polarization curve test conditions: the test uses hydrogen as fuel gas, oxygen as oxidant, the pressure is 0.1MPa, the working temperature is set to 60 ℃, the cell is activated for 2 hours under constant current, after the cell reaches stable test environment and performance, the corresponding current and voltage values are recorded by adjusting the external circuit resistance, and the cell polarization curve is obtained according to the current and voltage values (see figure 3).
The cell to be tested was the electrode obtained from example 1, while a conventional membrane electrode not treated with polydimethylsiloxane was used as a comparison.
As can be seen from FIG. 3, the membrane electrode prepared by the embodiment has overall better performance than the conventional membrane electrode, and is more obvious in a high current density area, which shows that the membrane electrode prepared by the method has better mass transfer capability. (conclusions are given in connection with the effect data according to the effects embodied on the figure)
Meanwhile, the membrane electrodes obtained by the above embodiments 2 to 8 are tested to have the structure and corresponding characteristics of the above embodiment 1.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (8)

1.一种梯度疏水膜电极，其特征在于，膜电极的质子交换膜上依次附有经含疏水剂的溶液疏水处理的疏水性依次递减的催化层、微孔层以及支撑层。1. A gradient hydrophobic membrane electrode, characterized in that, the proton exchange membrane of the membrane electrode is sequentially attached with a catalytic layer, a microporous layer and a support layer whose hydrophobicity is successively reduced by hydrophobic treatment of a solution containing a hydrophobic agent. 2.按权利要求1所述的梯度疏水膜电极，其特征在于，所述催化层疏水处理为通过催化剂、质子导体及疏水剂的悬浊液喷涂于质子交换膜两侧，形成疏水处理的催化层；其中，催化剂、质子导体及疏水剂的质量比为1:0.2-0.8：0-1。2. The gradient hydrophobic membrane electrode according to claim 1, wherein the hydrophobic treatment of the catalytic layer is to spray the suspension of the catalyst, the proton conductor and the hydrophobic agent on both sides of the proton exchange membrane to form a hydrophobic treatment catalysis layer; wherein, the mass ratio of catalyst, proton conductor and hydrophobic agent is 1:0.2-0.8:0-1. 3.按权利要求1所述的梯度疏水膜电极，其特征在于，所述支撑层疏水处理为将支撑材料浸入含疏水剂的溶液中进行疏水处理；其中，含疏水剂的溶液为疏水剂与有机溶剂混合，混合溶液中疏水剂的质量浓度分数为3％-30％。3. The gradient hydrophobic membrane electrode according to claim 1, wherein the hydrophobic treatment of the support layer is performed by immersing the support material in a solution containing a hydrophobic agent; wherein, the solution containing a hydrophobic agent is a hydrophobic agent and a hydrophobic agent. Organic solvents are mixed, and the mass concentration fraction of the hydrophobic agent in the mixed solution is 3%-30%. 4.按权利要求1所述的梯度疏水膜电极，其特征在于，所述微孔层疏水处理为将疏水剂和碳纳米材料溶于有机溶剂形成悬浊液，并将其刮涂或喷涂于与质子交换膜相对的支撑层的其中一侧，形成疏水性微孔层。4. The gradient hydrophobic membrane electrode according to claim 1, wherein the hydrophobic treatment of the microporous layer is to dissolve the hydrophobic agent and the carbon nanomaterial in an organic solvent to form a suspension, and scrape or spray it on the One side of the support layer opposite to the proton exchange membrane forms a hydrophobic microporous layer. 5.按权利要求1-4任意一项所述的梯度疏水膜电极，其特征在于，所述疏水剂为有机硅氧烷。5 . The gradient hydrophobic membrane electrode according to claim 1 , wherein the hydrophobic agent is an organosiloxane. 6 . 6.一种权利要求1所述梯度疏水膜电极的制备方法，其特征在于，6. a preparation method of the described gradient hydrophobic membrane electrode of claim 1, is characterized in that, 1)疏水处理为通过催化剂、质子导体及疏水剂的悬浊液喷涂于质子交换膜两侧，形成疏水处理的催化层；其中，催化剂、质子导体及疏水剂的质量比为1:0.2-0.8：0-1；1) Hydrophobic treatment is to spray the suspension of catalyst, proton conductor and hydrophobic agent on both sides of the proton exchange membrane to form a hydrophobic treated catalytic layer; wherein, the mass ratio of catalyst, proton conductor and hydrophobic agent is 1:0.2-0.8 : 0-1; 2)所述支撑层疏水处理为将支撑材料浸入含疏水剂的溶液中进行疏水处理；其中，含疏水剂的溶液为疏水剂与有机溶剂混合，混合溶液中疏水剂的质量浓度分数为3％-30％；2) The hydrophobic treatment of the support layer is performed by immersing the support material in a solution containing a hydrophobic agent; wherein, the solution containing a hydrophobic agent is a mixture of a hydrophobic agent and an organic solvent, and the mass concentration fraction of the hydrophobic agent in the mixed solution is 3% -30%; 3)所述微孔层疏水处理为将疏水剂和碳纳米材料溶于有机溶剂形成悬浊液，并将其刮涂或喷涂于与质子交换膜相对的支撑层的其中一侧，形成疏水性微孔层；所述悬浊液中疏水剂终浓度为1wt％-30wt％、碳纳米材料终浓度为1wt％-40wt％。3) The hydrophobic treatment of the microporous layer is to dissolve the hydrophobic agent and the carbon nanomaterial in an organic solvent to form a suspension, and scrape or spray it on one side of the support layer opposite to the proton exchange membrane to form a hydrophobicity The microporous layer; the final concentration of the hydrophobic agent in the suspension is 1wt%-30wt%, and the final concentration of the carbon nanomaterial is 1wt%-40wt%. 4)将上述处理后的带有疏水催化层的质子交换膜与带有疏水性微孔层的经疏水处理的支撑层热压制成膜电极。4) Hot pressing the proton exchange membrane with the hydrophobic catalytic layer and the hydrophobic-treated support layer with the hydrophobic microporous layer after the above treatment to form a membrane electrode. 7.按权利要求6所述梯度疏水膜电极的制备方法，其特征在于，7. according to the preparation method of the described gradient hydrophobic membrane electrode of claim 6, it is characterized in that, 所述碳纳米材料为炭黑、乙炔黑、碳纳米管中的一种或几种；The carbon nanomaterial is one or more of carbon black, acetylene black, and carbon nanotubes; 所述有机溶剂为四氢呋喃、氯仿、二氯甲烷、甲苯、二甲醚、四氯化碳中的一种或几种；The organic solvent is one or more of tetrahydrofuran, chloroform, dichloromethane, toluene, dimethyl ether, and carbon tetrachloride; 所述有机硅氧烷为聚二甲基硅氧烷、聚甲基硅氧烷、α,ω-二羟基聚硅氧烷中的一种或几种。The organosiloxane is one or more of polydimethylsiloxane, polymethylsiloxane, and α,ω-dihydroxypolysiloxane. 8.按权利要求6所述梯度疏水膜电极的制备方法，其特征在于，所述刮涂或喷涂制备微孔层表面的碳材料和疏水剂载量为0.5-5.0mg/cm2。8 . The preparation method of the gradient hydrophobic membrane electrode according to claim 6 , wherein the carbon material and the hydrophobic agent on the surface of the microporous layer prepared by the scraping or spraying are 0.5-5.0 mg/cm 2 .
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Cited By (5)

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CN111725523A (en) * 2020-06-04 2020-09-29 浙江高成绿能科技有限公司 Thin-layer hydrophobic fuel cell membrane electrode and preparation method thereof
CN111900428A (en) * 2020-06-22 2020-11-06 浙江高成绿能科技有限公司 Fuel cell stack with high water drainage capacity and preparation method thereof
WO2021128719A1 (en) * 2019-12-24 2021-07-01 中国科学院青岛生物能源与过程研究所 Gradient hydrophobic membrane electrode and preparation method therefor
CN114976050A (en) * 2022-05-13 2022-08-30 上海碳际实业集团有限公司 Gas diffusion layer for fuel cell and preparation process thereof
CN117276576A (en) * 2023-10-20 2023-12-22 苏州大学 A microporous layer of a proton exchange membrane fuel cell and its preparation method and application

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