CN110071298B - Gas diffusion layer for fuel cell and preparation method thereof - Google Patents

Gas diffusion layer for fuel cell and preparation method thereof Download PDF

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Publication number
CN110071298B
CN110071298B CN201910404858.7A CN201910404858A CN110071298B CN 110071298 B CN110071298 B CN 110071298B CN 201910404858 A CN201910404858 A CN 201910404858A CN 110071298 B CN110071298 B CN 110071298B
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gas diffusion
electrostatic
diffusion layer
preparation
electrostatic spinning
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CN110071298A (en
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于书淳
周媛媛
周佩
张芳芳
王莉
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North China University of Water Resources and Electric Power
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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
    • H01M4/8647—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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Fuel Cell (AREA)
  • Nonwoven Fabrics (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention belongs to the technical field of fuel cell materials, and particularly relates to a gas diffusion layer for a fuel cell and a preparation method thereof. The method provided by the invention comprises the following steps:the preparation method comprises the steps of respectively providing electrostatic spinning liquid containing a conductive material and electrostatic spraying liquid containing a water repellent, carrying out electrostatic spinning on a support body by using the electrostatic spinning liquid, carrying out electrostatic spraying on the support body by using the electrostatic spraying liquid to obtain a prefabricated body, and carrying out heat treatment on the prefabricated body to obtain the gas diffusion layer for the fuel cell, wherein the permeability coefficient of the gas diffusion layer prepared by the method is 1.356 × 10‑12m2The permeability coefficient of the gas diffusion layer prepared by the traditional method is higher than 1.290 × 10‑12m2。

Description

Gas diffusion layer for fuel cell and preparation method thereof
Technical Field
The invention belongs to the technical field of fuel cell materials, and particularly relates to a gas diffusion layer for a fuel cell and a preparation method thereof.
Background
In a fuel cell, a Gas Diffusion Layer (GDL) is located between a catalytic layer and a flow field, and functions mainly to support the catalytic layer, collect current, and provide a transport channel for reactant gas and product water. The water discharge performance of the gas diffusion layer affects the diffusion of reaction gas and the discharge of product water, which in turn affects the performance of the fuel cell, and therefore, it is very important to prepare a diffusion layer having a good water discharge performance. A typical gas diffusion layer is generally composed of a support made of a porous conductive media material such as carbon paper or carbon cloth, and a microporous layer generally composed of a conductive material (e.g., carbon black) and hydrophobic Polytetrafluoroethylene (PTFE). The traditional microporous layer is mostly prepared by brush coating or spray coating process, for example, chinese patents 200510047370.1, 200610047931.2, 200710019376.7 and 201310692107.2, etc. disperse conductive material (carbon powder particles) into organic solvent, then add PTFE emulsion to obtain slurry for forming the microporous layer, and then coat the slurry on the surface of the support by means of spray coating or brush coating to form the microporous layer.
Chinese patent 201811049161.4 discloses a method for preparing a gas diffusion layer by spinning a mixture containing a conductive material and a water repellent on a support using an electrospinning process to form a microporous layer. Compared with the traditional brush coating or spray coating method, the formed microporous structure has better order, and the gas transmission performance of the microporous layer is improved to a certain extent, but the research on further improving the gas transmission and liquid water discharge performance of the microporous layer is still needed.
Disclosure of Invention
The invention aims to provide a preparation method of a gas diffusion layer for a fuel cell, which can enable a water increasing material and a conductive material to be more uniformly distributed on a support body, thereby improving the hydrophobic property of a microporous structure and obtaining the gas diffusion layer with better drainage and gas transmission performance.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a preparation method of a gas diffusion layer for a fuel cell, which comprises the following steps:
(1) respectively providing an electrostatic spinning solution containing a conductive material and an electrostatic spraying solution containing a water repellent;
(2) carrying out electrostatic spinning on the support body by using the electrostatic spinning solution, and carrying out electrostatic spraying on the support body by using the electrostatic spraying solution to obtain a prefabricated body;
(3) and carrying out heat treatment on the prefabricated body to obtain the gas diffusion layer for the fuel cell.
Preferably, in the step (1), the conductive material includes a conductive polymer and a conductive inorganic powder;
the conductive polymer comprises polyaniline and/or polypyrrole;
the conductive inorganic powder comprises one or more of acetylene black, carbon nano tubes, semiconductor metal oxide, titanium nitride and silicon carbide.
Preferably, the mass ratio of the conductive polymer to the conductive inorganic powder is 1: (0.2-0.8).
Preferably, in the electrostatic spinning solution, the mass concentration of the conductive material is 5-25%.
Preferably, the mass concentration of the water repellent in the electrostatic spray liquid is 2-25 per mill.
Preferably, the water repellent comprises one or more of polytetrafluoroethylene, polyfluorinated ethylene propylene, polyvinylidene fluoride and organic silicon.
Preferably, the mass ratio of the water repellent to the conductive material is 1 (1-3).
Preferably, the electrostatic spinning in the step (2) has the following process parameters: the external voltage is 8-25 kV, the distance between the needle head and the support body is 5-20 cm, the advancing speed of the electrostatic spinning solution is 0.02-5 mL/h, and the time is 0.5-5 h;
the technological parameters of electrostatic spraying are as follows: the external voltage is 8-25 kV, the distance between the needle head and the support body is 5-20 cm, the propelling speed of the electrostatic spray liquid is 0.2-20 mL/h, and the time is 0.5-5 h.
Preferably, in the step (3), the temperature of the heat treatment is 60-370 ℃, and the heat preservation time is 30-60 min.
The invention also provides the gas diffusion layer for the fuel cell prepared by the preparation method in the technical scheme.
In order to uniformly disperse a conductive material and a hydrophobic agent, the conventional method generally disperses the two components in the same solution, and transfers the two materials to a support by brushing, spraying or electrostatic spinning, which limits the amount of the hydrophobic agent, but may cause the non-uniform dispersion and even agglomeration of the hydrophobic agent once the amount of the hydrophobic agent is increased, thereby reducing the hydrophobic property of the gas diffusion layer-12m2Is higher than the traditionGas diffusion layer prepared by the method (1.290 × 10)-12m2) Permeability coefficient of (a).
Drawings
FIG. 1 is a graph comparing the change curves of the bulk resistance with pressure of gas diffusion layers prepared in example 1 of the present invention and comparative example 1;
fig. 2 is a graph comparing flow rate and pressure curves of gas diffusion layers prepared in example 1 of the present invention and comparative example 1.
Fig. 3 is a contact angle comparison graph of the surface of the microporous layer of the gas diffusion layers prepared in example 1 of the present invention and comparative example 1.
Detailed Description
The invention provides a preparation method of a gas diffusion layer for a fuel cell, which comprises the following steps:
(1) respectively providing an electrostatic spinning solution containing a conductive material and an electrostatic spraying solution containing a water repellent;
(2) carrying out electrostatic spinning on the support body by using the electrostatic spinning solution, and carrying out electrostatic spraying on the support body by using the electrostatic spraying solution to obtain a prefabricated body;
(3) and carrying out heat treatment on the prefabricated body to obtain the gas diffusion layer for the fuel cell.
The present invention provides an electrospinning liquid including a conductive material and an electrostatic spraying liquid including a water repellent, respectively. In the invention, the electrostatic spinning solution comprises a conductive material, and the mass concentration of the conductive material is preferably 5-25%, more preferably 6-23%, and still more preferably 10-20%. In the present invention, the conductive material preferably includes a conductive polymer and a conductive inorganic powder, and the mass ratio of the conductive polymer to the conductive inorganic powder is preferably 1: (0.2 to 0.8), more preferably 1: (0.3 to 0.7), and preferably 1: (0.4-0.6).
In the present invention, the conductive polymer preferably includes polyaniline and/or polypyrrole, more preferably polypyrrole; when the conductive polymer is a mixture of two components, the invention has no special requirement on the mass ratio of the components in the mixture. In the invention, the conductive inorganic powder preferably comprises one or more of acetylene black, carbon black (VulcanXC-72), carbon nano tubes, semiconductor metal oxide, titanium nitride and silicon carbide, and more preferably comprises the carbon nano tubes, the acetylene black or the silicon carbide; the semiconductor metal oxide preferably comprises one or more of doped tin dioxide, indium tin oxide and fluorine-doped tin dioxide; when the conductive inorganic powder is a mixture of the above components, the invention has no special requirements on the mass ratio of the components in the mixture.
In the present invention, the electrospinning solution further comprises a dispersant, and the dispersant is preferably comprised of N, N-dimethylformamide, N-dimethylacetamide, or N-methylpyrrolidone.
The invention has no special requirement on the supply mode of the electrostatic spinning solution, and the electrostatic spinning solution is prepared by mixing the conductive material and the dispersing agent and then uniformly mixing all the components through ultrasonic or stirring.
In the invention, the electrostatic spray liquid comprises a water repellent, and the mass concentration of the water repellent is preferably 5-23 per thousand, more preferably 8-20 per thousand, and further preferably 10-18 per thousand. In the invention, the water repellent preferably comprises one or more of polytetrafluoroethylene, polyfluorinated ethylene propylene, polyvinylidene fluoride and organic silicon, and more preferably is polyvinylidene fluoride, a mixture of polyvinylidene fluoride and organic silicon, or a mixture of polytetrafluoroethylene and organic silicon; the mass ratio of the polytetrafluoroethylene to the organosilicon is preferably 1: (0.5 to 1), more preferably 1: (0.6-0.8); the mass ratio of the polyvinylidene fluoride to the silicone is preferably 1: (0.5 to 1), more preferably 1: (0.6-0.8). In the present invention, the silicone is preferably polydimethylsiloxane or methyltrifluoropropyl silicone oil.
In the present invention, the electrostatic spray liquid further comprises a dispersant, and the dispersant is preferably water. The invention takes water as the dispersant of the water repellent, can reduce the dosage and the harm of organic solvent, and is more environment-friendly.
The invention has no special requirement on the supply mode of the electrostatic spray liquid, and can be realized by adopting the same mode as the electrostatic spinning liquid.
After the electrostatic spinning solution and the electrostatic spraying solution are obtained, the electrostatic spinning solution is used for carrying out electrostatic spinning on the support body, and meanwhile, the electrostatic spraying solution is used for carrying out electrostatic spraying on the support body, so that a prefabricated body is obtained. In the invention, the support is preferably a porous conductive support, and can be carbon paper, carbon cloth, bucky paper or a wire mesh; the material of the wire mesh is known to those skilled in the art. In the present invention, the support is preferably subjected to a hydrophobic treatment, the hydrophobic agent for hydrophobic treatment being in accordance with the above-described embodiment, the hydrophobic treatment being carried out in a manner well known to those skilled in the art.
In the present invention, when the support is subjected to electrospinning or electrostatic spraying, it is preferable to control the parameters within the following ranges:
during electrostatic spinning, the applied voltage is preferably 8-25 kV, more preferably 10-23 kV, and further preferably 12-20 kV; the distance between the needle head and the support body is preferably 5-20 cm, more preferably 6-19 cm, and further preferably 8-15 cm; the advancing speed of the electrostatic spinning solution is preferably 0.02-5 mL/h, more preferably 0.05-4 mL/h, and still more preferably 0.1-2.5 mL/h; the time is preferably 0.5 to 5 hours, more preferably 1 to 4.5 hours, and still more preferably 1.5 to 4 hours.
During electrostatic spraying, the applied voltage is preferably 8-25 kV, more preferably 10-23 kV, and further preferably 12-20 kV; the distance between the needle head and the support body is preferably 5-20 cm, more preferably 6-19 cm, and further preferably 8-15 cm; the propelling speed of the electrostatic spray liquid is preferably 0.2-20 mL/h, more preferably 0.4-15 mL/h, and still more preferably 0.5-10 mL/h; the time is preferably 0.5 to 5 hours, more preferably 1 to 4.5 hours, and still more preferably 1.5 to 4 hours.
The invention preferably realizes the control of the dosage of the conductive material and the water repellent by adjusting the concentration and the advancing speed of the electrostatic spinning solution and the electrostatic spraying solution. In the present invention, the ratio of the water repellent to the conductive material is preferably 1: (1-3), more preferably 1 (1.5-2.5).
In the present invention, the electrospinning and the electrostatic spraying are simultaneously performed to uniformly mix the conductive material with the water repellent and attach the same to the support, thereby forming a microporous structure having excellent conductivity and hydrophobicity.
The invention uses electrostatic spinning and electrostatic spraying together, which can make the conductive material and hydrophobic agent uniformly dispersed on the surface of the support, and the obtained microstructure is regular and ordered, shortens the length of gas and water channels, and improves the permeability and drainage performance.
After obtaining the preform, the invention carries out heat treatment on the preform to obtain the gas diffusion layer for the fuel cell. In the invention, the heat treatment is preferably carried out under the protection of nitrogen, the temperature of the heat treatment is preferably 60-370 ℃, and is specifically determined by the composition of the used water repellent, so that the water repellent can be melted without decomposition; the heat preservation time is preferably 30-60 min, more preferably 35-55 min, and still more preferably 40-50 min. The invention enhances the binding force between the conductive material and the water repellent which are attached on the support body through heat treatment, thereby obtaining a stable microporous layer structure.
The invention also provides a gas diffusion layer for the fuel cell, which is prepared by the preparation method of the technical scheme, and comprises a support body and a microporous layer, wherein the thickness of the microporous layer is 1-6 mu m, the porosity is 50-80%, and the permeability coefficient is (1.0 × 10)-12～1.5×10-12)m2。
In order to further illustrate the present invention, a gas diffusion layer for a fuel cell and a method for manufacturing the same according to the present invention will be described in detail with reference to the accompanying drawings and examples, which should not be construed as limiting the scope of the present invention.
Example 1
Respectively adding carbon nano tubes, N, N-dimethylformamide and polypyrrole into a volumetric flask, and uniformly stirring to obtain a solution with the total mass fraction of 10% for electrostatic spinning, wherein the mass of the carbon nano tubes is 5%; and (3) applying polyvinylidene fluoride solution with the mass fraction of 5 per mill to electrostatic spraying. Controlling the voltage of electrostatic spinning and electrostatic spraying to be 10kV, the advancing speed of a spinning solution to be 0.02mL/h and the advancing speed of a spraying solution to be 0.4mL/h, covering hydrophobic treated Toray carbon paper on a negative receiving plate to collect spinning fibers, wherein the distance between a needle point and the receiving plate is 10cm, and obtaining a microporous layer with the thickness of 3 mu m by controlling the receiving time; and finally, placing the carbon paper and the microporous layer together in a nitrogen-filled oven to be sintered for 30min at 250 ℃ to obtain the gas diffusion layer (containing the carbon paper and the microporous layer) with the micro-ordered structure.
Example 2
Respectively adding acetylene black, N, N-dimethylformamide and polyaniline into a volumetric flask, and uniformly stirring to obtain a solution with the total mass fraction of 10% for electrostatic spinning, wherein the mass of the acetylene black is 7%; and (3) applying a dilute solution of polyvinylidene fluoride and polydimethylsiloxane (in a mass ratio of 1: 0.8) with the mass fraction of 6 per thousand to electrostatic spraying. Controlling the voltage of electrostatic spinning and electrostatic spraying to be 15kV, the advancing speed of a spinning solution to be 0.2mL/h and the advancing speed of a spraying solution to be 2mL/h, covering hydrophobic treated Toray carbon paper on a negative receiving plate, collecting spinning fibers, wherein the distance between a needle point and the receiving plate is 15cm, and obtaining a microporous layer with the thickness of 3 mu m by controlling the receiving time; and finally, placing the carbon paper and the microporous layer together in a nitrogen-filled oven to be sintered for 30min at 300 ℃ to obtain the gas diffusion layer (containing the carbon paper and the microporous layer) with the micro-ordered structure.
Example 3
Respectively adding carbon nano tubes, N, N-dimethylformamide, polypyrrole and polyaniline into a volumetric flask according to a mass ratio of 1: 1, uniformly stirring to obtain a solution with the total mass fraction of 15% for electrostatic spinning, wherein the mass of the carbon nano tube is 5%; polyvinylidene fluoride with the mass fraction of 20 per mill and organic silicon (the mass ratio is 1: 0.5) dilute solution are used for electrostatic spraying. Controlling the voltage of electrostatic spinning and electrostatic spraying to be 12kV, the advancing speed of a spinning solution to be 0.1mL/h and the advancing speed of a spraying solution to be 5mL/h, covering hydrophobic treated Toray carbon paper on a negative receiving plate, collecting spinning fibers, wherein the distance between a needle point and the receiving plate is 10cm, and obtaining microporous layers with different thicknesses by controlling the receiving time; and finally, placing the carbon paper and the microporous layer together in a nitrogen-filled oven to be sintered for 45min at 330 ℃ to obtain the gas diffusion layer (containing the carbon paper and the microporous layer) with the micro-ordered structure.
Gas diffusion layers were prepared in the same manner except for the amounts of the components shown in table 1.
Comparative example 1
A gas diffusion layer was prepared in the same amount as in example 1, except that a water repellent was mixed in the electrospinning solution, and the other operational parameters were the same as in example 1.
Performance testing and results
The bulk resistance (longitudinal resistance) of the gas diffusion layers obtained in examples 1 to 3 and comparative example 1 was measured by a universal tester. Placing a sample to be detected between the two gold-plated blocks, connecting the two gold-plated blocks with a constant current source, adjusting the current intensity to 5A, applying a constant current according to the proportion of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 and 16 kg-cm-2Applying force at a force application speed of 3 N.s-1. When the test pressure is shown to each force point, the voltage value is recorded.
The test results of example 1 and comparative example 1 were plotted as a bulk resistance-pressure relationship curve, as shown in fig. 1. Fig. 1 shows the results of the test on the gas diffusion layers obtained in example 1 and comparative example 1, and it can be seen from fig. 1 that the gas diffusion layer prepared by the method of the present invention has a lower bulk resistance than the gas diffusion layer prepared by the conventional method under the same thickness and amount, which indicates that the method of the present invention can improve the electrical conductivity of the gas diffusion layer. The test results of other examples are shown in Table 1.
Measurement of N with Aperture Analyzer2The relationship between the flow rate and the pressure difference of different gas diffusion layers is shown in fig. 2, wherein the test results of example 1 and comparative example 1 are shown in fig. 2. it can be seen from fig. 2 that the gas flow rate of the gas diffusion layer obtained in example 1 is higher than that of comparative example 1 under the same pressure condition, and the permeation coefficient is calculated according to the gas flow rate, and the result shows that the permeation coefficient of the gas diffusion layer prepared according to the present invention is 1.356 × 10-12m2Slightly higher than the permeability coefficient of the gas diffusion layer prepared by the conventional method (1.290 × 10)-12m2). The test results of other examples are shown in Table 1.
Table 1 results of performance test of gas diffusion layers obtained in examples and comparative examples
Performance of Example 1 Example 2 Example 3 Comparative example 1
Bulk resistance (m omega cm)2) 43 44 45 48
Coefficient of permeability (m)2) 1.356×10-12 1.349×10-12 1.325×10-12 1.290×10-12
Remarking: the test results in Table 1 are those obtained by testing under a pressure of 1.0 MPa.
According to the test results in table 1, compared with comparative example 1, the gas diffusion layer prepared by the invention has lower bulk resistance and high permeability coefficient, which indicates that the gas diffusion layer has more suitable gas and water guide pore passages, and further shows more excellent mass transfer performance, which is beneficial to improving the electrochemical performance of the fuel cell.
The surface contact angle of the microporous layer was measured by the fixed Drop method (Sessiledrop method) using a Drop image analysis system Drop Shape Analyzer 100 to characterize the hydrophobic properties of the microporous layer structure. In order to reflect the hydrophobic property of the surface of the microporous layer more truly, a plurality of different positions on the surface of each sample are selected for measurement. The test results of example 1 and comparative example 1 are shown in fig. 3, the surface contact angle of the microporous layer prepared in example 1 of the present invention fluctuates up and down at 156.9 ° with a small fluctuation range, compared with the microporous layer prepared by the conventional method with a large fluctuation range of the surface contact angle, which is mainly caused by the different dispersion properties of PTFE in different microporous layers, the microporous layer prepared by the present invention has a small change range of the surface contact angle, which indicates that the distribution of PTFE in the microporous layer prepared by the present invention is more uniform, and the microporous layer prepared by the present invention can play a positive role in water and gas mass transfer.
From the above embodiments, the method provided by the present invention can improve the uniform dispersion degree of the water repellent and the conductive material in the gas diffusion layer, and improve the gas permeability of the gas diffusion layer. The electrostatic spraying process adopted by the invention has low requirements on the dispersibility and the demand of the solvent, and even a small amount of water is used as the dispersing agent, the water repellent can be uniformly dispersed on the support body, so that the using amount of the organic solvent is reduced, and the electrostatic spraying process is more environment-friendly.
The preparation method provided by the invention has high reliability and is easy to expand production.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.

Claims (8)

1. A preparation method of a gas diffusion layer for a fuel cell comprises the following steps:
(1) respectively providing an electrostatic spinning solution containing a conductive material and an electrostatic spraying solution containing a water repellent;
(2) carrying out electrostatic spinning on the support body by using the electrostatic spinning solution, and carrying out electrostatic spraying on the support body by using the electrostatic spraying solution to obtain a prefabricated body;
(3) carrying out heat treatment on the prefabricated body to obtain a gas diffusion layer for a fuel cell;
in the step (3), the temperature of the heat treatment is 60-370 ℃, and the heat preservation time is 30-60 min.
2. The method according to claim 1, wherein in the step (1), the conductive material comprises a conductive polymer and a conductive inorganic powder;
the conductive polymer comprises polyaniline and/or polypyrrole;
the conductive inorganic powder comprises one or more of carbon black, carbon nano tubes, semiconductor metal oxide, titanium nitride and silicon carbide.
3. The method according to claim 2, wherein the mass ratio of the conductive polymer to the conductive inorganic powder is 1: (0.2-0.8).
4. The method according to claim 1, wherein the mass concentration of the conductive material in the electrospinning solution is 5 to 25%.
5. The preparation method of claim 1, wherein the mass concentration of the water repellent in the electrostatic spray liquid is 2 to 25 ‰.
6. The preparation method of claim 1 or 5, wherein the water repellent comprises one or more of polytetrafluoroethylene, fluorinated ethylene propylene, polyvinylidene fluoride and organic silicon.
7. The preparation method of claim 1 or 5, wherein the mass ratio of the water repellent to the conductive material is 1 (1-3).
8. The preparation method of claim 1, wherein the electrostatic spinning in the step (2) has the following process parameters:
the external voltage is 8-25 kV, the distance between the needle head and the support body is 5-20 cm, the advancing speed of the electrostatic spinning solution is 0.02-5 mL/h, and the time is 0.5-5 h;
the technological parameters of electrostatic spraying are as follows: the external voltage is 8-25 kV, the distance between the needle head and the support body is 5-20 cm, the propelling speed of the electrostatic spray liquid is 0.2-20 mL/h, and the time is 0.5-5 h.
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