CN113851659B - Fuel cell gas diffusion layer with hydrophilic and hydrophobic structure and preparation method thereof - Google Patents

Fuel cell gas diffusion layer with hydrophilic and hydrophobic structure and preparation method thereof Download PDF

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CN113851659B
CN113851659B CN202111456265.9A CN202111456265A CN113851659B CN 113851659 B CN113851659 B CN 113851659B CN 202111456265 A CN202111456265 A CN 202111456265A CN 113851659 B CN113851659 B CN 113851659B
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gas diffusion
diffusion layer
hydrophilic
fuel cell
treatment liquid
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CN113851659A (en
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李煜璟
王化伟
张梓厚
严致远
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Beijing Institute of Technology BIT
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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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to a fuel cell gas diffusion layer with a hydrophilic and hydrophobic structure and a preparation method thereof, belonging to the technical field of fuel cells. The method comprises the steps of forming the gas diffusion layer of the fuel cell with a hydrophilic and hydrophobic structure by flowing a treatment liquid through a local area of the gas diffusion layer, wherein the area through which the treatment liquid flows is a hydrophilic area, the area through which the treatment liquid does not flow is a hydrophobic area, and adjacent hydrophilic areas are separated through the hydrophobic area. The gas diffusion layer is provided with the hydrophilic area and the hydrophobic area, so that air suction and moisture discharge in the fuel cell can be distinguished, moisture accumulation and moisture discharge are promoted, the power generation process is rapidly and efficiently carried out, and the performance of the fuel cell is improved; in addition, the preparation method is simple to operate, and the gas diffusion layer can be improved to different degrees by regulating and controlling the concentration of the treatment liquid, the flow rate of the treatment liquid and the impregnation area of the treatment liquid, so that the application requirements under different working conditions are met, and the preparation method has a good application prospect.

Description

Fuel cell gas diffusion layer with hydrophilic and hydrophobic structure and preparation method thereof
Technical Field
The invention relates to a fuel cell gas diffusion layer with a hydrophilic and hydrophobic structure and a preparation method thereof, belonging to the technical field of fuel cells.
Background
A fuel cell is a chemical device that directly converts chemical energy of fuel into electrical energy, and is also called an electrochemical generator. The fuel cell has higher energy conversion efficiency and considerable output power density, demonstration operation is carried out on the international market at present to solve the global energy crisis and improve the climate challenge caused by environmental deterioration, and the energy industry consistently considers that the energy conservation and emission reduction can be really realized only by vigorously developing the fuel cell, so that the fuel cell is green, pollution-free, environment-friendly and efficient.
Among the large class of fuel cells, the pem fuel cell is currently the most widely commercialized, and particularly, in recent years, commercial vehicle models have been used for carrying passengers, and the fuel cell can be used for replacing the vehicle models in places where electric power is required, so that the space for application and the future development of the pem fuel cell are far in the future. In recent years, the breakthrough of the technical bottleneck of the fuel cell and the improvement of the cost and the productivity are continuously focused in China. Among them, the membrane electrode, which is the core component of the fuel cell, is the most concerned, and researchers are dedicated to the development of new membrane electrode products, which also enables the fuel cell products to be iterated quickly.
The proton exchange membrane fuel cell mainly comprises a membrane electrode, a bipolar plate, a sealing sheet, an end plate and the like, wherein the membrane electrode comprises a gas diffusion layer, a catalytic layer and an electrolyte membrane. The proton exchange membrane fuel cell is characterized in that oxygen or air is introduced into the cathode side, hydrogen is introduced into the anode, and protons are transmitted to the cathode side to react with the oxygen under the action of a catalyst and a proton membrane to generate pure water and generate corresponding amount of current. Under the future demand of high power density, as the technology is continuously improved, the current generated per unit area is larger and larger, and the corresponding reaction product, namely water, on the cathode side is also larger and larger, so that the method is particularly important for the water management method of the gas diffusion layer. Common approaches to addressing water management in the cathode side of pem fuel cells include designing new cathode flow plates and additional devices to give specific behavior to the cathode side. However, these methods have the problems of high cost, complicated apparatus, difficulty in scale-up, and the like. Therefore, developing a gas diffusion layer with a hydrophilic-hydrophobic structure to achieve cathode-side water-gas separation management is a historical choice for the development of fuel cells, and has milestone significance for the development of the fuel cell industry.
Disclosure of Invention
Aiming at the defects of the existing water management method of the gas diffusion layer, the invention provides the gas diffusion layer of the fuel cell with the hydrophilic and hydrophobic structure and the preparation method thereof, wherein the gas diffusion layer has different hydrophilic and hydrophobic areas, so that the air suction and the moisture discharge in the fuel cell can be distinguished, the moisture accumulation and discharge are promoted, the power generation process is rapidly and efficiently carried out, and the performance of the fuel cell is improved. In addition, the hydrophilicity of the gas diffusion layer can be improved by treating the local area of the gas diffusion layer with the oxidizing treatment liquid, and the gas diffusion layer with a hydrophilic and hydrophobic structure is obtained.
The purpose of the invention is realized by the following technical scheme.
A gas diffusion layer of a fuel cell having a hydrophilic-hydrophobic structure, the gas diffusion layer being formed after a treatment liquid flows through a partial region of the gas diffusion layer to be treated, wherein a region through which the treatment liquid flows is a hydrophilic region, a region through which the treatment liquid does not flow is a hydrophobic region, adjacent hydrophilic regions are separated by the hydrophobic region, the sum of the areas of all the hydrophilic regions accounts for 5% to 95% of the total area of the gas diffusion layer, and the treatment liquid is an acidic solution having an oxidizing property.
Further, the sum of the areas of all the hydrophilic regions accounts for 15% -60% of the total area of the gas diffusion layer.
Further, all the hydrophilic regions are equal in size, and all the hydrophilic regions are equally spaced. The shape of the hydrophilic region may be a regular shape such as a circle, a triangle, a quadrangle, a pentagon, a hexagon, or a heptagon, or may be other irregular shapes, and is preferably a regular shape.
Further, the size of the single hydrophilic region is 1 mm2To 100 mm2And the distance between two adjacent hydrophilic areas is 1 mm to 20 mm.
Further, the treatment liquid is an aqueous solution prepared from an oxidizing component A and an acidic component B, wherein the oxidizing component A is hydrogen peroxide, potassium permanganate or potassium dichromate, and the acidic component B is sulfuric acid, nitric acid, chlorine water, sodium hypochlorite, sulfur dioxide, nitrogen dioxide or nitrogen trioxide; correspondingly, the mass percent of the component A in the treatment liquid is 1-50%, preferably the mass percent of the component A in the treatment liquid is 1-30%, the mass percent of the component B in the treatment liquid is 0.1-60%, and preferably the mass percent of the component B in the treatment liquid is 0.5-10%.
Further, the flow rate of the treatment liquid flowing through the unit area gas diffusion layer is 10. mu.L/s to 10 mL/s.
Further, the gas diffusion layer to be treated is a gas diffusion layer which has been publicly reported for fuel cells, such as pure carbon paper, pure carbon cloth, carbon paper coated with a microporous layer, carbon cloth coated with a microporous layer, and the like.
The invention relates to a preparation method of a fuel cell gas diffusion layer with a hydrophilic and hydrophobic structure, which comprises the following steps:
(1) preparing a treatment solution;
manufacturing an upper template and a lower template with hole structures, wherein the holes on the upper template and the holes on the lower template correspond to each other one by one, and the shape, the size and the distribution of the holes are the same as those of the hydrophilic regions on the gas diffusion layer; or manufacturing an upper template, a lower template and an auxiliary template which have hole structures, wherein the holes in the upper template, the lower template and the auxiliary template are in one-to-one correspondence, and the shape, the size and the distribution of the holes are the same as those of the hydrophilic regions in the gas diffusion layer;
(2) placing more than one gas diffusion layer to be treated between an upper template and a lower template, wherein when the gas diffusion layer contains an auxiliary template, the auxiliary template is placed between the upper template and the gas diffusion layer to be treated or/and the auxiliary template is placed between the gas diffusion layer and the gas diffusion layer; and then, vacuumizing the lower template by using vacuumizing equipment, pouring the treatment liquid onto the upper template, allowing the treatment liquid to flow downwards through the gas diffusion layer to be treated and the holes of the lower template from the holes of the upper template under the action of pressure difference, wherein the area, through which the treatment liquid flows, on the gas diffusion layer to be treated is a hydrophilic area, the area, through which the untreated liquid flows, on the gas diffusion layer to be treated is a hydrophobic area, and the gas diffusion layer to be treated becomes the gas diffusion layer of the fuel cell with a hydrophilic-hydrophobic structure.
Further, 1-10 gas diffusion layers to be treated are stored between the upper template and the lower template.
Has the advantages that:
(1) the gas diffusion layer provided by the invention is provided with the hydrophilic area and the hydrophobic area, so that the air suction and the moisture discharge in the fuel cell can be distinguished at a port or the middle part, the moisture accumulation and discharge are promoted, the power generation process is rapidly and efficiently carried out, and the performance of the fuel cell is improved.
(2) The raw materials of the treatment solution are all conventional chemical reagents, the preparation is simple, the hydrophilicity of the gas diffusion layer can be improved through simple immersion treatment, the use is convenient, and the treatment solution is economical and efficient.
(3) According to the invention, by regulating and controlling the concentration of the treatment liquid, the flow rate of the treatment liquid and the impregnation area of the treatment liquid, the improvement effect of the gas diffusion layer in different degrees can be realized, and the application requirements under different working conditions can be met.
Drawings
Fig. 1 is a schematic diagram illustrating a process for preparing a gas diffusion layer according to the present invention.
FIG. 2 is a scanning electron microscope image of the hydrophobic region on the gas diffusion layer described in example 1.
Figure 3 is a scanning electron microscope image of the hydrophilic region on the gas diffusion layer described in example 1.
Fig. 4 is a graph showing the result of the hydrophilic contact angle test of the hydrophobic region on the gas diffusion layer described in example 1.
Fig. 5 is a graph showing the results of a hydrophilic contact angle test of hydrophilic regions on the gas diffusion layer described in example 1.
Fig. 6 is a graph comparing the results of electrochemical performance tests performed under the same conditions on a fuel cell assembled using the gas diffusion layer to be treated of step (1) of example 1 and a cell assembled using the gas diffusion layer obtained of step (2) of example 1.
Detailed Description
The present invention is further illustrated by the following figures and detailed description, wherein the processes are conventional unless otherwise specified, and the starting materials are commercially available from a public source without further specification.
A Membrane Electrode Assembly (MEA) as described in the following examples, having an effective area of 2 cm x 2 cm; the anode and cathode both adopt Johnson Matthey Hispec 4000 catalyst, and the dosage of the anode and cathode catalyst is 0.2 mg/cm2And 0.4 mg/cm2(ii) a Sealing the anode chamber by a silicone gasket, and compressing to 0.7 MEA compression ratio; the cathode collector is made of a copper plate 2 mm thick; for the getter design, the end plate is machined to have an open area with square openings of 20mm x 20mm in size and open areaIs 400 mm2. The polarization curve of the MEA was measured using an Arbin fuel cell test system, and the discharge performance of the MEA was evaluated at 80 ℃ and 100% humidity.
Example 1
(1) Preparing 500 mL of treatment solution by adopting hydrogen peroxide and a sulfuric acid aqueous solution, wherein the mass fraction of the hydrogen peroxide in the treatment is 24%, and the mass fraction of the sulfuric acid in the treatment solution is 0.8%;
manufacturing two aluminum plates with the size of 60 mm multiplied by 60 mm as an upper template and a lower template, wherein each aluminum plate is provided with three holes with the length of 2 mm multiplied by 20mm at intervals of 3.5 mm as a flow channel of treatment liquid, and the holes on the two aluminum plates are in one-to-one correspondence;
(2) a gas diffusion layer to be treated (i.e., SIGRACET 29BC carbon paper containing a microporous filling layer) is placed between an upper template and a lower template, the lower template is vacuumized by using a vacuumizing device, the treatment liquid is poured onto the upper template, the treatment liquid flows downwards through the gas diffusion layer to be treated and the holes of the lower template at a flow rate of 10 μ L/s under the action of differential pressure, the area of the gas diffusion layer to be treated through which the treatment liquid flows is a hydrophilic area, the area of the gas diffusion layer to be treated through which the untreated liquid flows is a hydrophobic area, and the gas diffusion layer to be treated forms a gas diffusion layer of the fuel cell with a hydrophilic-hydrophobic structure, as shown in fig. 1.
The effective area of the gas diffusion layer of the fuel cell with the hydrophilic and hydrophobic structure formed after the gas diffusion layer to be treated is treated by the treatment liquid is 20mm multiplied by 20mm, the sum of the areas of all the hydrophilic areas accounts for 30 percent of the total area of the effective area of the gas diffusion layer of the fuel cell with the hydrophilic and hydrophobic structure, and the size of each single hydrophilic area is about 40 mm2And the distance between two adjacent hydrophilic regions is about 3.5 mm.
Comparing the gas diffusion layers before and after treatment, naked eyes can find that the color of the modified area has certain change, which is mainly the introduction of oxygen-containing groups; from the characterization results of fig. 2 and 3, it can be found that the pore size and the body structure of the gas diffusion layer before and after the treatment were not damaged.
The hydrophilic contact angle test is performed on the hydrophilic region and the hydrophobic region of the gas diffusion layer prepared in this example, and it can be seen from the test results of fig. 4 and 5 that the contact angle of the hydrophilic region is reduced by 77.5 degrees compared with the contact angle of the hydrophobic region, which indicates that the hydrophilicity of the gas diffusion layer can be significantly improved by the treatment of the treatment solution.
And respectively adopting the SIGGRACET 29BC carbon paper before and after treatment as a gas diffusion layer, and correspondingly assembling the MEA before and after treatment. The discharge performance of the two MEA's before and after the treatment was evaluated at 80 ℃ and 100% humidity, and it can be seen from the test results of FIG. 6 that the peak power density of the MEA before the treatment was 58.5mW/cm2The peak power density of the treated MEA was 67.7mW/cm2And after the gas diffusion layer is treated by the treatment liquid, the power density of the battery is effectively improved by 15.7%.
Example 2
(1) Preparing 800 mL of treatment liquid by adopting hydrogen peroxide and a sulfuric acid aqueous solution, wherein the mass fraction of the hydrogen peroxide in the treatment is 24%, and the mass fraction of the sulfuric acid in the treatment liquid is 4%;
manufacturing two aluminum plates with the size of 100 mm multiplied by 100 mm as an upper template and a lower template, uniformly distributing 20 circular holes with the diameter of 2 mm as flow channels of treatment liquid by taking the geometric center of the aluminum plates as a symmetric center, and enabling the holes on the two aluminum plates to correspond one to one;
(2) two gas diffusion layers to be treated (DONGLICON PAPER TGP-H-090) are arranged between an upper template and a lower template, then the lower template is vacuumized by utilizing a vacuumizing device, treatment liquid is poured on the upper template, the treatment liquid flows downwards through the gas diffusion layers to be treated and the holes of the lower template from the holes of the upper template at the flow rate of 800 mu L/s under the action of differential pressure, the areas, through which the treatment liquid flows, on the gas diffusion layers to be treated are hydrophilic areas, the areas, through which the treatment liquid does not flow, on the gas diffusion layers to be treated are hydrophobic areas, and the two gas diffusion layers to be treated form the gas diffusion layers of the fuel cell with hydrophilic and hydrophobic structures.
The effective area of each gas diffusion layer of the fuel cell with the hydrophilic and hydrophobic structure formed after each gas diffusion layer to be treated is treated by the treatment liquid is 20mm20mm, the sum of the areas of all hydrophilic regions accounts for 15.7 percent of the total area of the effective area of the gas diffusion layer of the fuel cell with the hydrophilic-hydrophobic structure, and the size of each hydrophilic region is about 3.14 mm2And the distance between two adjacent hydrophilic areas is about 2 mm.
And respectively carrying out hydrophilic contact angle tests on the hydrophilic area and the hydrophobic area of the treated gas diffusion layer, and measuring that the contact angle of the hydrophilic area is 28.2 degrees and the contact angle of the hydrophobic area is 111.1 degrees, wherein the contact angle of the hydrophilic area is reduced by 82.9 degrees compared with the contact angle of the hydrophobic area, which shows that the hydrophilicity of the gas diffusion layer can be obviously improved by treatment of the treatment liquid.
The DORRY carbon paper TGP-H-090 before and after treatment is respectively adopted as a gas diffusion layer, and the MEA before the treatment and the MEA after the treatment are correspondingly assembled. The discharge performance of the two MEA's before and after the treatment was evaluated at 80 ℃ and 100% humidity, and it was found from the test results that the peak power density of the MEA before the treatment was 58.0 mW/cm2The peak power density of the treated MEA was 67.6 mW/cm2And after the gas diffusion layer is treated by the treatment liquid, the power density of the battery is effectively improved by 16.6%.
Example 3
(1) Preparing 800 mL of treatment solution by adopting hydrogen peroxide and a nitric acid aqueous solution, wherein the mass fraction of hydrogen peroxide in the treatment is 3%, and the mass fraction of nitric acid in the treatment solution is 5%;
manufacturing two aluminum plates with the size of 60 mm multiplied by 60 mm as an upper template and a lower template, wherein each aluminum plate is provided with three holes with the length of 3 mm multiplied by 20mm with the interval of 3.5 mm as a flow channel of treatment liquid, and the holes on the two aluminum plates are in one-to-one correspondence;
(2) a gas diffusion layer to be treated (DONGLICON PAPER TGP-H-060) is arranged between an upper template and a lower template, then the lower template is vacuumized by utilizing a vacuumizing device, treatment liquid is poured on the upper template, the treatment liquid flows downwards through the gas diffusion layer to be treated and the holes of the lower template from the holes of the upper template at the flow rate of 10 mu L/s under the action of differential pressure, the area of the gas diffusion layer to be treated, through which the treatment liquid flows, is a hydrophilic area, the area of the gas diffusion layer to be treated, through which the treatment liquid does not flow, is a hydrophobic area, and the gas diffusion layer to be treated forms the gas diffusion layer of the fuel cell with a hydrophilic and hydrophobic structure.
The effective area of the gas diffusion layer of the fuel cell with the hydrophilic and hydrophobic structure formed after the gas diffusion layer to be treated is treated by the treatment liquid is 20mm multiplied by 20mm, the sum of the areas of all the hydrophilic areas accounts for 45 percent of the total area of the effective area of the gas diffusion layer of the fuel cell with the hydrophilic and hydrophobic structure, and the size of each single hydrophilic area is about 60 mm2And the distance between two adjacent hydrophilic regions is about 3.5 mm.
Hydrophilic contact angle tests are respectively carried out on the hydrophilic area and the hydrophobic area of the gas diffusion layer prepared in the embodiment, and the contact angle of the hydrophilic area is 30.2 degrees and the contact angle of the hydrophobic area is 112.1 degrees, so that the contact angle of the hydrophilic area is reduced by 81.9 degrees compared with the contact angle of the hydrophobic area, which shows that the hydrophilicity of the gas diffusion layer can be obviously improved after the treatment of the treatment liquid.
And adopting the DORRETC paper TGP-H-060 before and after treatment as a gas diffusion layer respectively, and correspondingly assembling the MEA before treatment and the MEA after treatment. The discharge performance of the two MEA's before and after the treatment was evaluated at 80 ℃ and 100% humidity, and it was found from the test results that the peak power density of the MEA before the treatment was 57.2 mW/cm2The peak power density of the treated MEA was 64.24 mW/cm2And after the gas diffusion layer is treated by the treatment liquid, the power density of the battery is effectively improved by 12.3%.
Example 4
(1) Preparing 500 mL of treatment solution by adopting a potassium permanganate aqueous solution and a sulfuric acid aqueous solution, wherein the mass fraction of potassium permanganate in the treatment is 4%, and the mass fraction of sulfuric acid in the treatment solution is 0.8%;
manufacturing two rectangular aluminum plates which are 50mm multiplied by 50mm and are provided with 1 long hole which is 2 mm multiplied by 20mm as an upper template and a lower template;
(2) placing three gas diffusion layers (codgbo carbon cloth) to be treated between an upper template and a lower template, vacuumizing the lower template by using vacuumizing equipment, pouring treatment liquid on the upper template, allowing the treatment liquid to flow downwards through the gas diffusion layers to be treated and holes of the lower template from the holes of the upper template at a flow rate of 80 mu L/s under the action of differential pressure, wherein the regions, through which the treatment liquid flows, on the gas diffusion layers to be treated are hydrophilic regions, and the regions, through which the untreated liquid flows, on the gas diffusion layers to be treated are hydrophobic regions, so that a first hydrophilic region is formed on the gas diffusion layers; then transversely offsetting the template by 3.5 mm, and carrying out hydrophilic treatment again according to the treatment step of the first hydrophilic region to correspondingly form a second hydrophilic region on the gas diffusion layer; and then, continuously shifting the template for 3.5 mm transversely, performing hydrophilic treatment again according to the treatment step of the first hydrophilic region, and accordingly forming a third hydrophilic region on the gas diffusion layer, wherein three hydrophilic regions (each hydrophilic region is 2 mm multiplied by 20mm in size) which are distributed at equal intervals (the distance is 3.5 mm) are formed on the gas diffusion layer, namely three gas diffusion layers to be treated form the gas diffusion layer of the fuel cell with a hydrophilic-hydrophobic structure.
The effective area of the gas diffusion layer of the fuel cell with the hydrophilic and hydrophobic structure formed after each gas diffusion layer to be treated is treated by the treatment liquid is 20mm multiplied by 20mm, the sum of the areas of all hydrophilic areas accounts for 30 percent of the total area of the effective area of the gas diffusion layer of the fuel cell with the hydrophilic and hydrophobic structure, and the size of each single hydrophilic area is about 40 mm2And the distance between two adjacent hydrophilic regions is about 3.5 mm.
And respectively carrying out hydrophilic contact angle tests on the hydrophilic area and the hydrophobic area of the treated gas diffusion layer, and measuring that the contact angle of the hydrophilic area is 28.4 degrees and the contact angle of the hydrophobic area is 111.2 degrees, wherein the contact angle of the hydrophilic area is reduced by 82.8 degrees compared with the contact angle of the hydrophobic area, which shows that the hydrophilicity of the gas diffusion layer can be obviously improved by treatment of the treatment liquid.
And respectively adopting the CODEBC before and after treatment as gas diffusion layers, and correspondingly assembling the MEA before treatment and the MEA after treatment. The discharge performance of the two MEA's before and after the treatment was evaluated at 80 ℃ and 100% humidity, and it was found from the test results that the peak power density of the MEA before the treatment was 58.1 mW/cm2The peak power density of the treated MEA was 66.4 mW/cm2After the gas diffusion layer is treated by the treatment liquid, the battery power is effectively improved by 14.3 percentDensity.
Example 5
(1) Preparing 500 mL of treatment solution by adopting a potassium permanganate aqueous solution and a sulfuric acid aqueous solution, wherein the mass fraction of potassium permanganate in the treatment is 4%, and the mass fraction of sulfuric acid in the treatment solution is 1%;
manufacturing three templates with the size of 60 mm multiplied by 60 mm, wherein three templates are PVC plastic plates, two templates are aluminum plates, the two aluminum plates are respectively used as an upper template and a lower template, and one PVC plastic plate is used as an auxiliary template; three holes with the length of 2 mm multiplied by 20mm and the interval of 3 mm are arranged on each template and used as a flow channel of the treatment fluid, and the holes on the three templates are in one-to-one correspondence;
(2) the method comprises the steps of placing three gas diffusion layers to be treated (namely SIGGRACET 29BC carbon paper containing a microporous filling layer) between an upper template and a lower template, placing an auxiliary template between the upper template and the gas diffusion layers to be treated, vacuumizing the lower template by using vacuumizing equipment, pouring treatment liquid on the upper template, allowing the treatment liquid to flow downwards through the gas diffusion layers to be treated and holes of the lower template at a flow rate of 200 mu L/s under the action of differential pressure, wherein the regions, through which the treatment liquid flows, on the gas diffusion layers to be treated are hydrophilic regions, the regions, through which the untreated liquid flows, on the gas diffusion layers to be treated are hydrophobic regions, and the three gas diffusion layers to be treated form the gas diffusion layers of the fuel cell with hydrophilic-hydrophobic structures.
The effective area of the gas diffusion layer of the fuel cell with the hydrophilic and hydrophobic structure formed after each gas diffusion layer to be treated is treated by the treatment liquid is 20mm multiplied by 20mm, the sum of the areas of all hydrophilic areas accounts for 30 percent of the total area of the effective area of the gas diffusion layer of the fuel cell with the hydrophilic and hydrophobic structure, and the size of each single hydrophilic area is about 40 mm2And the distance between two adjacent hydrophilic areas is about 3 mm.
And respectively carrying out hydrophilic contact angle tests on the hydrophilic area and the hydrophobic area of the treated gas diffusion layer, and measuring that the contact angle of the hydrophilic area is 30.2 degrees and the contact angle of the hydrophobic area is 112.1 degrees, wherein the contact angle of the hydrophilic area is 81.9 degrees lower than that of the hydrophobic area, which shows that the hydrophilicity of the gas diffusion layer can be obviously improved by treatment of the treatment liquid.
And respectively adopting the SIGGRACET 29BC carbon paper before and after treatment as a gas diffusion layer, and correspondingly assembling the MEA before and after treatment. The discharge performance of the two MEA's before and after the treatment was evaluated at 80 ℃ and 100% humidity, and it was found from the test results that the peak power density of the MEA before the treatment was 58.5mW/cm2The peak power density of the treated MEA was 64.8 mW/cm2And after the gas diffusion layer is treated by the treatment liquid, the power density of the battery is effectively improved by 10.8%.
Example 6
(1) Preparing 500 mL of treatment solution by adopting hydrogen peroxide and a sulfuric acid aqueous solution, wherein the mass fraction of the hydrogen peroxide in the treatment is 10%, and the mass fraction of the sulfuric acid in the treatment solution is 1%;
manufacturing two PVC plastic plates with the size of 60 mm multiplied by 60 mm as an upper template and a lower template, wherein each PVC plastic plate is provided with three holes with the length of 3 mm multiplied by 20mm with the interval of 3 mm as a flow channel of treatment liquid, and the holes on the two plastic plates are in one-to-one correspondence;
(2) five gas diffusion layers to be treated (namely SIGGRACET 29BC carbon paper containing a micropore filling layer) are placed between an upper template and a lower template, then the lower template is vacuumized by utilizing vacuumizing equipment, then the treating fluid is poured on the upper template, the treating fluid flows downwards through the gas diffusion layers to be treated and the holes of the lower template at the flow rate of 300 mu L/s under the action of differential pressure, the regions, through which the treating fluid flows, on the gas diffusion layers to be treated are hydrophilic regions, the regions, through which the untreated fluid flows, on the gas diffusion layers to be treated are hydrophobic regions, and then the five gas diffusion layers to be treated all form the gas diffusion layers of the fuel cell with a hydrophilic-hydrophobic structure.
The effective area of the gas diffusion layer of the fuel cell with the hydrophilic and hydrophobic structure formed after each gas diffusion layer to be treated is treated by the treatment liquid is 20mm multiplied by 20mm, the sum of the areas of all hydrophilic areas accounts for 45 percent of the total area of the effective area of the gas diffusion layer of the fuel cell with the hydrophilic and hydrophobic structure, and the size of each single hydrophilic area is about 60 mm2And the distance between two adjacent hydrophilic areas is about 3 mm.
Hydrophilic contact angle tests are respectively carried out on the hydrophilic area and the hydrophobic area of the gas diffusion layer prepared in the embodiment, and the contact angle of the hydrophilic area is 32.1 degrees and the contact angle of the hydrophobic area is 114.1 degrees, so that the contact angle of the hydrophilic area is reduced by 82.0 degrees compared with the contact angle of the hydrophobic area, which shows that the hydrophilicity of the gas diffusion layer can be obviously improved after the treatment of the treatment liquid.
And respectively adopting the SIGGRACET 29BC carbon paper before and after treatment as a gas diffusion layer, and correspondingly assembling the MEA before and after treatment. The discharge performance of the two MEA's before and after the treatment was evaluated at 80 ℃ and 100% humidity, and it was found from the test results that the peak power density of the MEA before the treatment was 58.5mW/cm2The peak power density of the treated MEA was 66.4 mW/cm2And after the gas diffusion layer is treated by the treatment liquid, the power density of the battery is effectively improved by 13.5%.
Example 7
(1) Preparing 500 mL of treatment solution by adopting hydrogen peroxide and a sulfuric acid aqueous solution, wherein the mass fraction of the hydrogen peroxide in the treatment is 22%, and the mass fraction of the sulfuric acid in the treatment solution is 1.5%;
manufacturing five templates with the size of 60 mm multiplied by 60 mm, wherein three templates are PVC plastic plates, two templates are aluminum plates, the two aluminum plates are respectively used as an upper template and a lower template, and the three PVC plastic plates are used as auxiliary templates; three holes with the length of 2 mm multiplied by 20mm and the interval of 3.5 mm are arranged on the five templates and are used as flow channels of the treatment liquid, and the holes on the five templates are in one-to-one correspondence;
(2) four gas diffusion layers to be treated (a SIGGRACET 29BC carbon paper C containing microporous flat-packed layers) and three auxiliary templates are alternately arranged between the upper template and the lower template, so that the holes of each layer of auxiliary template correspond to the holes of the upper template and the lower template one by one, then, the lower template is vacuumized by utilizing vacuuming equipment to ensure that the auxiliary template, the gas diffusion layer, the upper template and the lower template are completely attached, then the treatment liquid is poured on the upper template, under the action of pressure difference, the gas diffusion layer to be treated and the holes of the lower template flow downwards through the holes of the upper template at the flow rate of 1000 mu L/s, the area of the gas diffusion layer to be treated, through which the treatment liquid flows, is a hydrophilic area, the area of the gas diffusion layer to be treated, through which the untreated liquid flows, is a hydrophobic area, four gas diffusion layers to be treated each form a fuel cell gas diffusion layer having an hydrophilic-hydrophobic structure.
The effective area of the gas diffusion layer of the fuel cell with the hydrophilic and hydrophobic structure formed after each gas diffusion layer to be treated is treated by the treatment liquid is 20mm multiplied by 20mm, the sum of the areas of all hydrophilic areas on each gas diffusion layer accounts for 30 percent of the total area of the effective area of the gas diffusion layer of the fuel cell with the hydrophilic and hydrophobic structure, and the size of each single hydrophilic area is about 40 mm2And the distance between two adjacent hydrophilic regions is about 3.5 mm.
Hydrophilic contact angle tests are respectively carried out on the hydrophilic areas and the hydrophobic areas of the plurality of gas diffusion layers prepared in the embodiment, and the average contact angle of the hydrophilic areas is 30.1 degrees and the average contact angle of the hydrophobic areas is 112.7 degrees, so that the contact angle of the hydrophilic areas is reduced by 82.6 degrees compared with the contact angle of the hydrophobic areas, which indicates that the hydrophilicity of the gas diffusion layers can be obviously improved after the treatment of the treatment liquid.
And respectively adopting the SIGGRACET 29BC carbon paper before and after treatment as a gas diffusion layer, and correspondingly assembling the MEA before and after treatment. The discharge performance of the two MEA's before and after the treatment was evaluated at 80 ℃ and 100% humidity, and it was found from the test results that the peak power density of the MEA before the treatment was 58.5mW/cm2The peak power density of the treated MEA was 65.7 mW/cm2And after the gas diffusion layer is treated by the treatment liquid, the power density of the battery is effectively improved by 12.3%.
In summary, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. A preparation method of a fuel cell gas diffusion layer with a hydrophilic and hydrophobic structure is characterized by comprising the following steps: the steps of the method are as follows,
(1) preparing a treatment solution;
manufacturing an upper template and a lower template with hole structures, wherein the holes in the upper template correspond to the holes in the lower template one by one, and the shape, size and distribution of the holes are the same as those of the hydrophilic regions in the gas diffusion layer; or manufacturing an upper template, a lower template and an auxiliary template which have hole structures, wherein the holes in the upper template, the lower template and the auxiliary template are in one-to-one correspondence, and the shape, the size and the distribution of the holes are the same as those of the hydrophilic regions in the gas diffusion layer;
(2) placing more than one gas diffusion layer to be treated between an upper template and a lower template, wherein when the gas diffusion layer contains an auxiliary template, the auxiliary template is placed between the upper template and the gas diffusion layer to be treated or/and the auxiliary template is placed between the gas diffusion layer and the gas diffusion layer; then, vacuumizing the lower template by using vacuumizing equipment, pouring the treatment liquid on the upper template, and enabling the treatment liquid to flow downwards through the gas diffusion layer to be treated and the holes of the lower template from the holes of the upper template under the action of pressure difference, so that the gas diffusion layer to be treated becomes the gas diffusion layer of the fuel cell with a hydrophilic and hydrophobic structure;
wherein the region through which the treatment liquid flows is a hydrophilic region, the region through which the treatment liquid does not flow is a hydrophobic region, adjacent hydrophilic regions are separated by the hydrophobic region, the sum of the areas of all the hydrophilic regions accounts for 5% to 95% of the total area of the gas diffusion layer, and the treatment liquid is an acidic solution having oxidizing properties.
2. The method for producing a gas diffusion layer for a fuel cell having a hydrophilic-hydrophobic structure according to claim 1, wherein: the sum of the areas of all hydrophilic regions accounts for 15-60% of the total area of the gas diffusion layer.
3. The method for producing a gas diffusion layer for a fuel cell having a hydrophilic-hydrophobic structure according to claim 1, wherein: all hydrophilic areas are equal in size and are equally spaced.
4. The method for producing a fuel cell gas diffusion layer having an lyophilic and hydrophobic structure according to any one of claims 1 to 3, characterized in that: the size of the single hydrophilic region is 1 mm2~100 mm2And the distance between two adjacent hydrophilic regions is 1 mm-20 mm.
5. The method for producing a gas diffusion layer for a fuel cell having a hydrophilic-hydrophobic structure according to claim 1, wherein: the treatment liquid is an aqueous solution prepared from an oxidizing component A and an acidic component B, wherein the oxidizing component A is hydrogen peroxide, potassium permanganate or potassium dichromate, and the acidic component B is sulfuric acid, nitric acid, chlorine water, sodium hypochlorite, sulfur dioxide, nitrogen dioxide or nitrogen trioxide.
6. The method for producing a gas diffusion layer for a fuel cell having a hydrophilic-hydrophobic structure according to claim 5, wherein: the mass percent of the oxidizing component A in the treatment fluid is 1-50%, and the mass percent of the acidic component B in the treatment fluid is 0.1-60%.
7. The method for producing a gas diffusion layer for a fuel cell having a hydrophilic-hydrophobic structure according to claim 5, wherein: the mass percent of the oxidizing component A in the treatment fluid is 1-30%, and the mass percent of the acidic component B in the treatment fluid is 0.5-10%.
8. The method for producing a gas diffusion layer for a fuel cell having a hydrophilic-hydrophobic structure according to claim 1, wherein: the flow rate of the treatment liquid flowing through the unit area gas diffusion layer is 10. mu.L/s to 10 mL/s.
9. The method for producing a gas diffusion layer for a fuel cell having a hydrophilic-hydrophobic structure according to claim 1, wherein: and 1-10 gas diffusion layers to be treated are stored between the upper template and the lower template, and the gas diffusion layers to be treated are pure carbon paper, pure carbon cloth, carbon paper coated with microporous layers or carbon cloth coated with microporous layers.
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