CN114976050A - Gas diffusion layer for fuel cell and preparation process thereof - Google Patents
Gas diffusion layer for fuel cell and preparation process thereof Download PDFInfo
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- CN114976050A CN114976050A CN202210523587.9A CN202210523587A CN114976050A CN 114976050 A CN114976050 A CN 114976050A CN 202210523587 A CN202210523587 A CN 202210523587A CN 114976050 A CN114976050 A CN 114976050A
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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
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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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
- H01M4/88—Processes of manufacture
- H01M4/8817—Treatment of supports before application of the catalytic active composition
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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
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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
- H01M8/0241—Composites
- H01M8/0245—Composites in the form of layered or coated products
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- 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 discloses a gas diffusion layer for a fuel cell, which belongs to the technical field of fuel cells. The preparation process comprises the following steps: coating conductive carbon slurry on carbon paper or carbon cloth to form a conductive carbon layer and carrying out heating treatment, coating hydrophobic agent slurry on the conductive carbon layer to form a hydrophobic agent layer and carrying out heating treatment; then coating conductive carbon slurry on the water repellent agent layer to form a conductive carbon layer and carrying out heating treatment, wherein the conductive carbon slurry forms a snake-shaped coating path II which is staggered with the snake-shaped slurry path I under the action of a spray head group II of coating equipment; and repeating the steps to form the microporous layer of the gas diffusion layer with a plurality of conductive carbon layers and a plurality of water repellent agent layers. The invention can balance air permeability and conductivity while realizing the laminated construction of the conductive carbon layer and the hydrophobic agent layer, enhance the mechanical property of the gas diffusion layer and improve the overall battery performance of the gas diffusion layer.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a gas diffusion layer for a fuel cell and a preparation process thereof.
Background
The proton exchange membrane fuel cell is a high-efficiency and environment-friendly power generation device, and the core component of the proton exchange membrane fuel cell is membrane electrode triad which is usually prepared by a gas diffusion layer, a catalyst layer and a proton exchange membrane through a hot pressing process.
The gas diffusion is composed of conductive porous materials, plays multiple roles of supporting a catalyst layer, collecting current, conducting gas, discharging water and the like, realizes redistribution of reaction gas and product water between a flow field and the catalyst layer, is one of key components influencing the performance of an electrode, and an ideal gas diffusion layer can meet 3 conditions: good drainage, good air permeability and good electrical conductivity. The microporous layer is a carbon powder layer which is usually manufactured on the surface of the substrate layer in order to improve the pore structure of the substrate layer, the thickness of the microporous layer is about 10-100 microns, the microporous layer is generally manufactured on the surface of the substrate layer through processes of silk screen printing, blade coating, sputtering and the like after the substrate layer is subjected to leveling treatment, the microporous layer mainly has the effects of reducing the contact resistance between the catalyst layer and the substrate layer, redistributing gas and water, preventing the electrode catalyst layer from being flooded with water and simultaneously preventing the catalyst layer from leaking to the substrate layer in the manufacturing process.
Chinese patent (CN113241448) discloses a gradient microporous layer and a preparation method thereof, which describes gas diffusion layers prepared by using different conductive carbon slurries (including different carbon black and concentration) and performance characteristics thereof, and can reduce the 'flooding probability' of GDL due to the gradient microporous structure. Chinese patent (CN111900417A) discloses a preparation method of a gas diffusion layer with high carbon content, and particularly, a carbon fiber paper substrate is respectively immersed into three kinds of conductive ink, and then the steps of curing, heat treatment and the like are carried out, so that the prepared GDL has high mechanical strength, high porosity and stable chemical performance.
Disclosure of Invention
The invention aims to provide a gas diffusion layer for a fuel cell and a preparation process thereof aiming at the existing problems.
The invention is realized by the following technical scheme:
a gas diffusion layer for a fuel cell, comprising a microporous layer having hydrophobic and hydrophilic properties, characterized in that: the microporous layer is composed of a plurality of conductive carbon layers and a plurality of water repellent layers, wherein the water repellent layers are arranged between the two conductive carbon layers.
Furthermore, the thickness of the microporous layer is 10-120 mu m.
Furthermore, the number of the electric carbon layer and the hydrophobic agent layer is respectively N +1 and N, and the value range of N is 1-4.
A preparation process of a gas diffusion layer for a fuel cell comprises the following steps:
(1) hydrophobic treatment:
soaking carbon paper or carbon cloth into a water repellent agent solution, and then putting the carbon paper or carbon cloth into an oven for high-temperature treatment;
(2) preparing a first conductive carbon layer:
coating conductive carbon slurry on the carbon paper or carbon cloth treated in the step (1) to form a conductive carbon layer and heating the conductive carbon layer, wherein the conductive carbon slurry forms a snake-shaped coating path I along the width range of the carbon paper or the carbon cloth under the action of a spray head group I of coating equipment;
(3) coating a first hydrophobizing agent layer:
coating the conductive carbon layer obtained by the treatment in the step (2) with a hydrophobizing agent slurry along the coating path in the step (1) to form a hydrophobizing agent layer and carrying out heating treatment;
(4) applying a second conductive carbon layer:
coating conductive carbon slurry on the water repellent agent layer obtained by the treatment in the step (3) to form a conductive carbon layer and carrying out heating treatment, wherein the conductive carbon slurry forms a snake-shaped coating path II which is staggered with the snake-shaped slurry path I under the action of a spray head group II of coating equipment;
(5) repeating the steps (2) and (4):
repeating the steps (2) and (4) to form a microporous layer of the gas diffusion layer with a plurality of conductive carbon layers and a plurality of water repellent agent layers;
(6) and (3) heat treatment:
and (3) putting the product obtained through the treatment in the steps (1) to (5) into an oven for heat treatment to form the gas diffusion layer with a plurality of conductive carbon layers and a plurality of water repellent agent layers.
Further, the step of hydrophobic treatment is completed by dipping a hydrophobic agent, the concentration of the solution of the hydrophobic agent is 2-15%, and the dipping time is 5-40 min.
Further, the coating method is one of a wire bar coating method, a doctor blade coating method, an ultrasonic spraying method, an electrostatic spraying method, a screen printing method and a slit coating method.
Furthermore, the first spray head group is vertical to the conveying direction of the carbon paper or the carbon cloth; and the second spray head group is parallel to the conveying direction of the carbon paper or the carbon cloth.
Further, the conductive carbon slurry is: mixing one or more of carbon black, graphite, carbon nano tubes, graphene and pearl carbon with a hydrophobing agent, wherein the hydrophobing agent solution accounts for 0.01-20% of the total volume fraction.
Further, the water repellent layer is prepared by coating a water repellent slurry.
Further, the hydrophobic agent is one or more of polytetrafluoroethylene emulsion, vinylidene fluoride emulsion and fluorinated ethylene propylene.
Furthermore, the thickness of each layer of the conductive carbon layer is 5-20 μm; the thickness of each layer of the hydrophobing agent layer is 0.5-5 mu m.
Further, the heat treatment conditions are as follows: the heat treatment temperature is 300-450 ℃, and the heat treatment time is 60-120 min.
Compared with the prior art, the invention has the following advantages:
in view of this, the present invention aims to provide a gas diffusion layer with a multi-layer microporous layer structure and a preparation method thereof, wherein the multi-layer microporous structure has a plurality of sets of repeated structural units of conductive carbon layer-hydrophobing agent layer-conductive carbon layer, and the gas diffusion layer can balance air permeability and conductivity, enhance mechanical properties of the gas diffusion layer, and improve overall battery performance of the gas diffusion layer while achieving stacking of the conductive carbon layer and the hydrophobing agent layer.
1. The microporous layer structure of the gas diffusion layer adopts a sandwich structure of a conductive carbon layer, a hydrophobic agent layer and a conductive carbon layer, and the hydrophobic agent and the conductive carbon are distributed more hierarchically, so that the overall hydrophobic performance and the conductivity of the gas diffusion layer are greatly improved;
2. compared with the traditional printing or coating process, the coated microporous layer is more uniform and loose, and the gas diffusion layer has stronger gas permeability;
3. the conductive carbon layer and the water repellent agent layer are prepared in a snake-shaped staggered mode, so that the consistency of the overall distribution of the microporous layer is guaranteed;
4. the microporous layer is prepared by adopting a coating mode, so that the direct contact between the spray head and the base material is avoided, the yield in the production process of the diffusion layer is improved, and the continuous production of the diffusion layer can be realized.
Drawings
FIG. 1 is a schematic view of the structure of a gas diffusion layer of a multi-layer microporous layer according to the present application;
FIG. 2 is an exemplary process for preparing a gas diffusion layer of a multi-layer microporous layer according to the present application;
figure 3 is a flow chart illustrating the steps performed in the present application for a multi-layer microporous gas diffusion layer.
In the figure: 1. a conductive carbon layer; 1a, a first conductive carbon layer; 1b, a second conductive carbon layer; 1c, a third conductive carbon layer; 2. a water repellent layer; 2a, a first hydrophobizing agent layer; 2b, a second hydrophobizing agent layer; 3. longitudinally coating a conductive carbon layer; 4. longitudinally coating a hydrophobic agent layer; 5. transversely coating a conductive carbon layer; 6. a layer of hydrophobizing agent is applied laterally.
Detailed Description
For further explanation of the invention, reference should be made to the following description taken in conjunction with the accompanying drawings.
Example 1
A microporous layer of a gas diffusion layer for a fuel cell is formed by overlapping a plurality of conductive carbon layers 1 and a plurality of water repellent layers 2 as shown in FIG. 1.
A process for preparing a gas diffusion layer for a fuel cell, as shown in fig. 3, comprises the steps of:
(1) and (3) hydrophobic treatment of carbon paper:
cutting a 190-micrometer carbon paper, preparing a water repellent agent PTFE solution with the concentration of 5% for standby application at 300 x 200, ultrasonically stirring uniformly, immersing the carbon paper in the PTFE solution for 1min, taking out, drying at 100 ℃ for 10min, putting the heat-treated carbon paper into a high-temperature furnace, performing high-temperature treatment for 60min at 350 ℃, and taking out after the lapse of time to obtain a hydrophobic carbon paper sample;
(2) preparing a microporous layer:
coating a first conductive agent layer and a first hydrophobic agent layer:
mixing acetylene black carbon powder, deionized water, an ethanol solution and a PTFE solution with the volume fraction of 0.01%, uniformly stirring until slurry is viscous, putting a treated carbon paper sample on a first coating group table board, setting the temperature of a platform to be 80 ℃, uniformly coating the conductive carbon slurry on the surface of the carbon paper by adopting a longitudinal coating mode to form a first conductive carbon layer (1a), setting the coating thickness to be 20 mu m, immediately longitudinally coating the PTFE solution with the concentration of 0.01% on the surface of the first conductive carbon layer (1a) after coating to form a first hydrophobing agent layer (2a), and putting the coated sample into a tunnel oven for heat treatment for 5 min;
coating a second conductive agent layer and a second hydrophobic agent layer: uniformly coating the conductive carbon slurry on the surface of the sample treated by the coating group I by adopting a transverse coating mode on a coating group II platform to form a second conductive carbon layer (1b), wherein the coating thickness is set to be 20 mu m, and a PTFE solution with the concentration of 0.01 percent is randomly transversely coated on the surface of the second conductive carbon layer (1b) after the coating is finished to form a second hydrophobizing agent layer (2b), and the coated sample enters a tunnel oven for heat treatment;
the coating operation was repeated:
repeating the coating step for 2 times, putting the sample into a high-temperature furnace for high-temperature treatment at 380 ℃ for 80min, and taking out after the high-temperature treatment is finished to obtain the gas diffusion layer with the microporous layer having the structure of the multi-layer conductive carbon layer and the multi-layer hydrophobic agent layer;
to further illustrate the technical effects of the embodiments of the present invention, different numbers of gas diffusion layers of fuel cells implemented using the present invention were tested, and the results of the test are shown in table 1 below.
Table 1 technical parameters of gas diffusion layers prepared with different numbers of layers implemented
As can be seen from table 1 above, the multi-layer microporous structure of the present invention has a plurality of sets of repeating structural units of conductive carbon layer-hydrophobizing agent layer-conductive carbon layer, and can balance air permeability and electrical conductivity, enhance mechanical properties of the gas diffusion layer, and improve overall battery performance of the gas diffusion layer while achieving stacking of the conductive carbon layer and the hydrophobizing agent layer.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (10)
1. A gas diffusion layer for a fuel cell, comprising a microporous layer having hydrophobic properties and hydrophilic properties, characterized in that: the microporous layer is composed of a plurality of conductive carbon layers and a plurality of water repellent layers, wherein the water repellent layers are arranged between the two conductive carbon layers.
2. The gas diffusion layer for a fuel cell according to claim 1, wherein the thickness of the microporous layer is 10 to 120 μm.
3. The gas diffusion layer for a fuel cell according to claim 1, wherein the number of the electric carbon layer and the hydrophobizing agent layer is N +1 and N, respectively, and N is in a range of 1 to 4.
4. A process for producing a gas diffusion layer for a fuel cell according to any one of claims 1 to 3, comprising the steps of:
(1) hydrophobic treatment:
soaking carbon paper or carbon cloth into a water repellent agent solution, and then putting the carbon paper or carbon cloth into an oven for high-temperature treatment;
(2) preparing a first conductive carbon layer:
coating conductive carbon slurry on the carbon paper or the carbon cloth treated in the step (1) to form a conductive carbon layer and carrying out heating treatment, wherein the conductive carbon slurry forms a snake-shaped coating path I along the width range of the carbon paper or the carbon cloth under the action of a spray head group I of coating equipment;
(3) coating a first hydrophobizing agent layer:
coating the conductive carbon layer treated in the step (2) with a water repellent slurry along the coating path in the step (1) to form a water repellent layer and performing heating treatment;
(4) applying a second conductive carbon layer:
coating conductive carbon slurry on the water repellent agent layer obtained by the treatment in the step (3) to form a conductive carbon layer and carrying out heating treatment, wherein the conductive carbon slurry forms a snake-shaped coating path II which is staggered with the snake-shaped slurry path I under the action of a spray head group II of coating equipment;
(5) repeating the steps (2) and (4):
repeating the steps (2) and (4) to form a microporous layer of the gas diffusion layer with a plurality of conductive carbon layers and a plurality of hydrophobic agent layers;
(6) and (3) heat treatment:
and (3) putting the product obtained through the treatment in the steps (1) to (5) into an oven for heat treatment to form the gas diffusion layer with a plurality of conductive carbon layers and a plurality of water repellent agent layers.
5. The process for preparing a gas diffusion layer for a fuel cell according to claim 4, wherein the step of hydrophobic treatment is performed by impregnating a hydrophobic agent, the concentration of the solution of the hydrophobic agent is 2 to 15%, and the impregnating time is 5 to 40 min; the hydrophobic agent layer is prepared by coating hydrophobic agent slurry, and the hydrophobic agent is one or more of polytetrafluoroethylene emulsion, vinylidene fluoride emulsion and fluorinated ethylene propylene.
6. The process for producing a gas diffusion layer for a fuel cell according to claim 4, wherein the coating method is one of a wire bar coating method, a doctor blade coating method, an ultrasonic spraying method, an electrostatic spraying method, a screen printing method, and a slit coating method.
7. The process for preparing a gas diffusion layer for a fuel cell according to claim 4, wherein the first nozzle group is perpendicular to a transport direction of the carbon paper or the carbon cloth; and the second spray head group is parallel to the conveying direction of the carbon paper or the carbon cloth.
8. The process for preparing a gas diffusion layer for a fuel cell according to claim 4, wherein the conductive carbon slurry is: mixing one or more of carbon black, graphite, carbon nano tubes, graphene and pearl carbon with a hydrophobing agent, wherein the hydrophobing agent solution accounts for 0.01-20% of the total volume fraction.
9. The process for preparing a gas diffusion layer for a fuel cell according to claim 4, wherein the thickness of each layer of the conductive carbon layer is 5 to 20 μm; the thickness of each layer of the water repellent agent layer is 0.5-5 mu m.
10. The process for producing a gas diffusion layer for a fuel cell according to claim 4, wherein the heat treatment conditions are: the heat treatment temperature is 300-450 ℃, and the heat treatment time is 60-120 min.
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