CN113270593A - Membrane electrode for proton exchange membrane fuel cell and preparation method thereof - Google Patents
Membrane electrode for proton exchange membrane fuel cell and preparation method thereof Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- H—ELECTRICITY
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- H01M4/00—Electrodes
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- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/8636—Inert electrodes with catalytic activity, e.g. for fuel cells with a gradient in another property than porosity
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Abstract
The invention relates to a membrane electrode for a proton exchange membrane fuel cell and a preparation method thereof. The preparation method comprises the following steps: step A: spinning the catalyst slurry onto a microporous layer on the surface of the hydrophobic carbon paper by adopting a variable voltage electrostatic spinning process to obtain a gas diffusion and catalysis layer integrated electrode; and B: and assembling the gas diffusion catalyst layer integrated electrode, the proton exchange membrane and the gas diffusion catalyst layer integrated electrode according to the assembling sequence, and preparing the membrane electrode for the proton exchange membrane fuel cell by a hot pressing or cold pressing process after assembling. The invention directly spins the catalyst layer on the gas diffusion layer by means of the electrostatic spinning technology, is beneficial to reducing the thickness of the catalyst layer and the loading capacity of the catalyst, improves the dispersibility of the catalyst, obtains a fibrous structure with good uniformity and rich and moderate pore structure by spinning, is beneficial to improving the water transmission and air mass transfer in a high-current density area of the fuel cell, and improves the performance of the cell.
Description
Technical Field
The invention relates to the technical field of proton exchange membrane fuel cells, in particular to a preparation method of a membrane electrode for a proton exchange membrane fuel cell.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are an energy device that directly converts hydrogen energy into electrical energy, and the energy conversion efficiency is as high as 60% -70%. The hydrogen fuel cell has the outstanding characteristics of low working temperature (about 80 ℃), high energy density, environmental friendliness and the like, and is expected to be applied to the fields of automobiles, aerospace and the like in large scale in the future.
The membrane electrode is used as the core component of the proton exchange membrane fuel cell and consists of a cathode, a proton exchange membrane and an anode, and the quality of the membrane electrode directly determines the performance of the fuel cell. Currently, whether commercialized or in the laboratory stage of research, the main catalyst in membrane electrodes is still Pt-based, which is expensive, and the utilization rate of the catalyst is directly related to the cost of fuel cells. Therefore, the preparation mode of the catalyst layer in the membrane electrode is particularly critical, and the improvement of the preparation mode of the catalyst layer of the membrane electrode is one of important means for improving the cost performance of the fuel cell.
In the prior art, the catalyst layer is usually placed on the surface of a carbon paper coated with a microporous layer or a water management layer, hot-pressed, then a proton exchange membrane is placed between two identical gas diffusion layer electrodes, the membrane is in contact with the catalyst layer, and hot-pressed to obtain the catalyst layer, or the catalyst layer, the proton exchange membrane, the catalyst layer and the carbon paper are arranged in sequence, and then hot-pressed to obtain the catalyst layer, but the prior art has the following defects: when the porous proton exchange membrane is directly soaked in the catalyst slurry and then dried and hot-pressed, the carbon-supported catalyst is only in macroscopic contact with Nafion, and the Nafion is difficult to completely wrap Pt microscopically through hot pressing.
Based on the above, a new membrane electrode preparation method is desired, which can directly spin a catalyst layer onto a microporous layer by an electrostatic spinning technology to form a gas diffusion catalyst layer integrated electrode, and which can be applied to a plurality of catalyst layers of different thicknesses, and the obtained catalyst layer has an extremely high catalyst utilization rate, and the porous structure of the catalyst layer is easily adjusted, and the preparation method can greatly improve the performance of the fuel cell. In addition, the spraying voltage of the last time during spraying is 1.5-2.5 times of the rated spraying voltage, so that the contact resistance between the proton membrane and the gas diffusion electrode can be reduced.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a membrane electrode for a proton exchange membrane fuel cell and a preparation method thereof. According to the invention, the catalyst layer is spun on the gas diffusion layer by an electrostatic spinning technology, so that the thickness of the catalyst layer and the loading capacity of the catalyst are reduced, the dispersibility of the catalyst is improved, the uniformity of the final hierarchical structure obtained by spinning is good, the pore structure is rich and moderate, the water transmission and the air mass transfer in a high-current density area of the fuel cell are improved, and the cell performance is improved.
In order to achieve the above object, the present invention provides a method for preparing a membrane electrode for a proton exchange membrane fuel cell, the method comprising the steps of:
step A: spinning catalyst slurry onto a microporous layer on the surface of hydrophobic carbon paper by adopting a variable voltage electrostatic spinning process to obtain a gas diffusion and catalysis layer integrated electrode, wherein the gas diffusion and catalysis layer integrated electrode has a hierarchical structure with different pore sizes by controlling the change of voltage;
and B: and assembling the gas diffusion catalyst layer integrated electrode, the proton exchange membrane and the gas diffusion catalyst layer integrated electrode according to the assembling sequence, and preparing the membrane electrode for the proton exchange membrane fuel cell by a hot pressing or cold pressing process after assembling.
In the technical scheme of the invention, the layered structure of the gas diffusion and catalysis layer integrated electrode is a gas diffusion and catalysis layer, and the gas diffusion and catalysis layer integrated electrode comprises a carbon paper layer, a microporous layer and a catalysis layer. Specifically, hydrophobic carbon paper is used as a base layer (i.e., a carbon paper layer), and then carbon powder and polytetrafluoroethylene emulsion are coated on the surface of the carbon paper layer, so that a microporous layer (MPL) is formed on the surface of the carbon paper layer, and a catalyst slurry is spun on the microporous layer by an electrostatic spinning technology to form a final catalytic layer.
In the above technical solution, the pore diameter of the catalytic layer gradually increases in layers toward the microporous layer.
Preferably, the step a specifically includes the steps of:
step A1: immersing the carbon paper in the polytetrafluoroethylene emulsion, taking out and drying, immersing in the polytetrafluoroethylene emulsion again, taking out and drying for a plurality of times until the mass percentage of polytetrafluoroethylene (PTFE for short) in the carbon paper is 5-6%, thus obtaining the hydrophobic carbon paper;
step A2: mixing carbon powder and polytetrafluoroethylene emulsion, uniformly coating the mixture on the surface of hydrophobic carbon paper, and drying to obtain hydrophobic carbon paper with a microporous layer on the surface;
step A3: dispersing a catalyst, an ionic resin solution and a high-molecular adhesive in a dispersing agent according to the mass ratio of 1:0.3: 0.1-1: 0.7:0.3, and stirring to obtain catalyst slurry, wherein the addition amount of the dispersing agent is 5-15 mL/g of the mass of the catalyst;
and A4, spraying the prepared catalyst slurry onto hydrophobic carbon paper of a surface microporous layer through an electrostatic spinning process, and drying at 40-60 ℃ to obtain the gas diffusion and catalysis layer integrated electrode.
Preferably, in the step a1, the mass fraction of the polytetrafluoroethylene emulsion is 2% to 20%; the immersion time is 5-10 min;
in the step A2, the adding amount of the carbon powder is 60-80% of the mass of the polytetrafluoroethylene emulsion solution during mixing; the drying process comprises the following steps: performing heat treatment in an inert atmosphere, wherein the heat treatment temperature is 250-450 ℃, the inert atmosphere comprises one of nitrogen, argon, helium, hydrogen-argon mixed gas and hydrogen-nitrogen mixed gas, and the mass fraction of the adopted polytetrafluoroethylene emulsion in the step is the same as that of the polytetrafluoroethylene emulsion in the step A1;
in the step A3, the rotation speed is 300rpm during stirring, and the stirring time is 12-36 h;
in the step A4, the rated operating voltage applied in the electrostatic spinning operation is 15-20 kV, the curing distance is 15-20 cm, the receiving time is 30-120min, and the flow rate of the slurry is 0.01-0.03 mL/min.
More preferably, in the step a1, the mass percentage of the polytetrafluoroethylene in the carbon paper is 5%.
More preferably, in the step a2, the preferable range of the heat treatment temperature is 350 to 360 ℃, and the preferable range of the heat treatment temperature is because: when the temperature is higher than 360 ℃, partial carbon powder is oxidized and collapsed; when the temperature is less than 350 ℃, polytetrafluoroethylene cannot be sufficiently dispersed.
More preferably, the amount of carbon powder added is 70% of the mass of the polytetrafluoroethylene emulsion solution, i.e., the mass ratio of carbon powder to PTFE emulsion is 7: 3.
Preferably, the catalyst is selected from one or a mixture of Pt/C catalyst, PtM/C alloy catalyst, platinum single-layer core-shell catalyst and non-platinum catalyst; the M comprises one or more of Fe, Co, Ni, Cu, Cr, Mn, Mo and V.
More preferably, the Pt/C catalyst comprises 40-60 wt% of Pt/C catalyst; the PtM/C alloy catalyst includes a PtCo/C alloy catalyst; the non-platinum catalyst is Fe-N-C or FeCo-N-C catalyst.
Preferably, the polymer binder is one or a mixture of polypyrrole (PPy), polyvinylpyrrolidone (PVP), Polythiophene (PTs), Polyaniline (PANI), and Polyacene (PAS).
Preferably, the dispersant comprises one or more of deionized water, ethanol and isopropanol.
Preferably, in the step a4, the electrostatic spinning spraying is completed by spraying for 2-4 times, and the voltage at the last spraying is 1.5-2.5 times of the rated operating voltage, wherein the spraying voltage at the first spraying is 100% of the rated operating voltage, and the spraying voltage at the last spraying is 1.5-2.5 times of the rated operating voltage.
In a second aspect, the invention provides a membrane electrode for a proton exchange membrane fuel cell, which is prepared by the above preparation method of the membrane electrode for the proton exchange membrane fuel cell, and comprises a cathode body diffusion catalysis layer integrated electrode, a proton exchange membrane and an anode gas diffusion catalysis layer integrated electrode.
Preferably, the thickness of the catalytic layer on the surface of the cathode and/or anode gas diffusion electrode is 5-20 μm, and the loading amount of Pt in the catalytic layer is 0.025-0.4 mg/cm2。
In a third aspect, the invention further provides a use of the membrane electrode for a proton exchange membrane fuel cell, which is used for the proton exchange membrane fuel cell.
In a fourth aspect, the invention further provides a proton exchange membrane fuel cell, which includes the membrane electrode for a proton exchange membrane fuel cell described above.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) the method overcomes the problems that in the prior art, the catalyst layer is hot-pressed on the proton exchange membrane through thermal transfer printing, the resistance of proton conduction is too large, and the discharge of water is not facilitated; the catalyst layer is directly spun on the MPL layer by an electrostatic spinning technology, the ionic resin solution can be uniformly wrapped on the surface of the catalyst, the thickness of the ionic resin solution wrapped on the surface of the catalyst can be controlled by adjusting the amount of the ionic resin solution, the mass transfer of protons and water is further improved, the catalyst slurry is spun on hydrophobic carbon paper with a surface microporous layer to form a gas diffusion catalyst layer integrated electrode, the catalyst layer is fibrous, the mass transfer problem of oxygen, protons and water is greatly improved, the catalyst layer which is suitable for various requirements and different thicknesses can be prepared, the utilization rate of the catalyst is improved, the porous structure of the catalyst layer can be adjusted by adjusting process parameters, and the performance of a fuel cell is improved;
(2) the catalyst layer is directly spun on the MPL layer by an electrostatic spinning technology, so that the MPL layer and the catalyst layer are contacted more closely, the contact resistance between the MPL layer and the catalyst layer is reduced, the voltage is increased, and the output power of the fuel cell is increased;
(3) the MPL layer on the carbon paper has proper thickness, pore structure and certain hydrophobicity by adjusting the type of solvent for preparing the MPL layer, the amount of PTFE and proper heat treatment temperature; the proportion of each component is reasonably adjusted, a proper binder is selected, and each parameter of electrostatic spinning is optimized, so that the membrane electrode for the proton exchange membrane fuel cell with higher performance is obtained conveniently.
(4) The pore size of the catalyst layer is directly controlled by adjusting the voltage of electrostatic spinning. The low voltage is adopted at one side close to the diffusion layer, so that the mass transfer resistance is reduced; one side of the proton membrane adopts high voltage, thereby reducing the proton conduction resistance and greatly improving the battery performance.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a graph illustrating the porosity of the catalytic layers of the membrane electrodes in examples 1-6 compared to comparative examples 1-6;
FIG. 2 is a graph illustrating the power density comparison of membrane electrodes in examples 1-6 versus comparative examples 1-6;
FIG. 3 is a diagram illustrating the structure of a membrane electrode assembly for a PEM fuel cell prepared in example 1 of the present invention;
FIG. 4 is an enlarged view of a portion of FIG. 3;
FIG. 5 is a partial enlarged view of FIG. 3 at B;
fig. 6 is a partially enlarged view of fig. 3 at C.
Detailed Description
The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. The present invention will be described in detail with reference to the following specific examples:
example 1
A preparation method of a membrane electrode of a proton exchange membrane fuel cell comprises the following steps:
A. preparing a microporous layer on the surface of the carbon paper, and preparing hydrophobic carbon paper: immersing carbon paper in 2 mass percent PTFE emulsion for pretreatment for 5min, taking out and drying, and repeating the operation until the percentage content of PTFE in the carbon paper reaches 5 percent to obtain the hydrophobic carbon paper;
preparation of a gas diffusion layer with an MPL layer grown on the surface of hydrophobic carbon paper: evenly mixing XC-72 with the mass ratio of 7:3 and 3 percent of PTFE emulsion, adding a proper amount of ethanol, evenly coating on the surface of the hydrophobic carbon paper after ultrasonic stirring, drying, processing at 350 ℃ for 60min under the protection of argon atmosphere, and cooling along with a furnace to obtain the carbon paper with the MPL layer.
B. Preparing catalyst slurry, namely dispersing 50% of Pt/C catalyst, Nafion and PVP in a mass ratio of 1:0.3:0.1 into 10mL/g of ethanol; the rotation speed is 300rpm, and the stirring is carried out for 36 hours, so as to obtain the catalyst slurry.
C. Preparing a gas diffusion electrode by adopting an electrostatic spinning technology, wherein the rated operating voltage is 20kV, the curing distance is 15cm, the receiving time is 120min, the flow rate of slurry is 0.02mL/min, the catalyst slurry is spun on the microporous layer on the surface of the carbon paper, the spraying voltage is set to be 35kV when the spraying is carried out for the last time, and the gas diffusion electrode is obtained by drying at 40 ℃ after the spraying is finished; the thickness of the catalytic layer on the surface of the prepared gas diffusion electrode is 16 mu m, and the loading capacity of the catalytic layer Pt is 0.4mg/cm2。
D. And assembling according to the structure of the cathode gas diffusion electrode-the proton exchange membrane-the anode gas diffusion electrode to obtain the membrane electrode of the proton exchange membrane fuel cell.
Wherein, fig. 3 illustrates the structure of the membrane electrode for proton exchange membrane fuel cell prepared in example 1 of the present invention.
As shown in fig. 3, in the present embodiment, the layered structure of the gas diffusion catalyst layer integrated electrode is a gas diffusion catalyst layer I, which includes a carbon paper layer II, a microporous layer III, and a catalyst layer IV. As for the specific structure of each layer, see fig. 4 to 6, wherein fig. 4 is a partial enlarged view of a portion a of fig. 3; FIG. 5 is a partial enlarged view of FIG. 3 at B;
fig. 6 is a partially enlarged view of fig. 3 at C.
As shown in fig. 3 and as necessary with reference to fig. 4 to 6, the layered structure of the integrated electrode of the gas diffusion catalyst layer of the embodiment is described, and the carbon paper layer II uses hydrophobic carbon paper as a base layer, and since the hydrophobic carbon paper is repeatedly immersed in the polytetrafluoroethylene emulsion, it can be seen from fig. 3 that PTFE particles are attached to the carbon fibers in the carbon paper layer II.
With continued reference to fig. 3, it can be seen that on the surface of the carbon paper layer II, a microporous layer III is formed. As can be seen from fig. 6, the microporous layer IIII is actually a hierarchical structure formed by the PTFE particles 1 wrapping the carbon particles 6, and micropores 5 are formed between the carbon particles 6 included in each PTFE particle 1, and the pore diameters of the micropores 5 are gradually increased toward the microporous layer.
As can be seen from fig. 3, the catalyst slurry was spun onto microporous layer III by an electrospinning technique to form final catalytic layer IV. As can be seen from fig. 5, in the catalytic layer IV, the catalyst particles 3 can be deposited on the electrospun fiber 4 by changing the voltage, and the catalytic layer IV with different pore sizes is formed.
Example 2
A preparation method of a membrane electrode of a proton exchange membrane fuel cell comprises the following steps:
A. preparing a microporous layer on the surface of the carbon paper, and preparing hydrophobic carbon paper: immersing the carbon paper in 20 mass percent PTFE emulsion for pretreatment for 5min, taking out and drying, and repeating the operation until the percentage content of PTFE in the carbon paper reaches 5 percent to obtain the hydrophobic carbon paper;
preparation of a gas diffusion layer with an MPL layer grown on the surface of hydrophobic carbon paper: and (3) mixing the following components in a mass ratio of 7:3 XC-72 and 3 percent PTFE emulsion are mixed evenly, a proper amount of ethanol is added, after ultrasonic stirring evenly, the mixture is evenly coated on the surface of the carbon paper subjected to hydrophobic treatment, and after drying, the carbon paper is treated for 60min at 350 ℃ under the protection of argon atmosphere and is cooled along with a furnace to obtain the carbon paper with the MPL layer.
B. Preparing catalyst slurry, namely dispersing 50% of Pt/C catalyst, Nafion and PPy in 10mL/g of ethanol according to the mass ratio of 1:0.7: 0.3; the rotation speed is 300rpm, and the stirring is carried out for 36 hours, so as to obtain the catalyst slurry.
C. Preparing a gas diffusion electrode by adopting an electrostatic spinning technology, wherein the rated operating voltage is 20kV, the curing distance is 18cm, the receiving time is 60min, the flow rate of slurry is 0.01mL/min, the catalyst slurry is spun on the microporous layer on the surface of the carbon paper, the spraying voltage is set to be 35kV when the spraying is carried out for the last time, and the gas diffusion electrode is obtained by drying at 40 ℃ after the spraying is finished; the thickness of the catalytic layer on the surface of the prepared gas diffusion electrode is 8 mu m, and the loading capacity of the catalytic layer Pt is 0.1mg/cm2。
D. And assembling according to the structure of the cathode gas diffusion electrode-the proton exchange membrane-the anode gas diffusion electrode to obtain the membrane electrode of the proton exchange membrane fuel cell.
Example 3
A preparation method of a membrane electrode of a proton exchange membrane fuel cell comprises the following steps:
A. preparing a microporous layer on the surface of the carbon paper, and preparing hydrophobic carbon paper: immersing carbon paper in 10% of PTFE emulsion for pretreatment for 10min, taking out and drying, and repeating the operation until the percentage content of PTFE in the carbon paper reaches 5% to obtain the hydrophobic carbon paper;
preparation of a gas diffusion layer with an MPL layer grown on the surface of hydrophobic carbon paper: evenly mixing XC-72 with the mass ratio of 7:3 and 3 percent of PTFE emulsion, adding a proper amount of ethanol, evenly coating on the surface of the hydrophobic carbon paper after ultrasonic stirring, drying, processing at 450 ℃ for 60min under the protection of argon atmosphere, and cooling along with a furnace to obtain the carbon paper with the MPL layer.
B. Preparing catalyst slurry, namely dispersing 50% of Pt/C catalyst, Nafion and PVP with the mass ratio of 1:0.4:0.1 into a mixed solvent of water and alcohol with the mass ratio of 10 mL/g; the rotation speed is 300rpm, and the stirring is carried out for 24 hours, so as to obtain the catalyst slurry.
C. Preparing a gas diffusion electrode by adopting an electrostatic spinning technology, wherein the rated operating voltage is 18kV, the curing distance is 20cm, the receiving time is 60min, the flow rate of slurry is 0.03mL/min, the catalyst slurry is spun on the microporous layer on the surface of the carbon paper, the spraying voltage is set to be 32kV when the spraying is carried out for the last time, and the gas diffusion electrode is obtained by drying at 40 ℃ after the spraying is finished; the thickness of the catalytic layer on the surface of the prepared gas diffusion electrode is 14 mu m, and the loading capacity of the catalytic layer Pt is 0.3mg/cm2。
D. And assembling according to the structure of the cathode gas diffusion electrode-the proton exchange membrane-the anode gas diffusion electrode to obtain the membrane electrode of the proton exchange membrane fuel cell.
Example 4
A preparation method of a membrane electrode of a proton exchange membrane fuel cell comprises the following steps:
A. preparing a microporous layer on the surface of the carbon paper, and preparing hydrophobic carbon paper: immersing carbon paper in 2 mass percent PTFE emulsion for pretreatment for 5min, taking out and drying, and repeating the operation until the percentage content of PTFE in the carbon paper reaches 5 percent to obtain the hydrophobic carbon paper;
preparation of a gas diffusion layer with an MPL layer grown on the surface of hydrophobic carbon paper: evenly mixing XC-72 with the mass ratio of 7:3 and 3 percent of PTFE emulsion, adding a proper amount of ethanol, evenly coating on the surface of the hydrophobic carbon paper after ultrasonic stirring, drying, processing at 250 ℃ for 60min under the protection of argon atmosphere, and cooling along with a furnace to obtain the carbon paper with the MPL layer.
B. Preparing catalyst slurry, namely dispersing a PtNi/C catalyst, Nafion and PVP with the mass ratio of 1:0.7:0.3 into a mixed solvent of water and ethanol of 10 mL/g; the rotation speed is 300rpm, and the stirring is carried out for 24 hours, so as to obtain the catalyst slurry.
C. Preparation of gas diffusion electrodes by means of electrostaticsSpinning technology, wherein the rated operating voltage is 18kV, the curing distance is 15cm, the receiving time is 30min, the flow rate of slurry is 0.03mL/min, the catalyst slurry is spun on the microporous layer on the surface of the carbon paper, the spraying voltage is set to be 32kV when the spraying is carried out for the last time, and the gas diffusion electrode is obtained after the drying at 40 ℃ after the spraying is finished; the thickness of the catalytic layer on the surface of the prepared gas diffusion electrode is 7 mu m, and the loading capacity of the catalytic layer Pt is 0.15mg/cm2。
D. And assembling according to the structure of the cathode gas diffusion electrode-the proton exchange membrane-the anode gas diffusion electrode to obtain the membrane electrode of the proton exchange membrane fuel cell.
Example 5
A preparation method of a membrane electrode of a proton exchange membrane fuel cell comprises the following steps:
A. preparing a microporous layer on the surface of the carbon paper, and preparing hydrophobic carbon paper: immersing the carbon paper in 20 mass percent PTFE emulsion for pretreatment for 8min, taking out and drying, and repeating the operation until the percentage content of PTFE in the carbon paper reaches 5 percent to obtain the hydrophobic carbon paper;
preparation of Gas Diffusion Layer (GDL) with MPL layer grown on surface of hydrophobic carbon paper: evenly mixing XC-72 with the mass ratio of 6:4 and 3 percent of PTFE emulsion, adding a proper amount of ethanol, evenly coating on the surface of the hydrophobic carbon paper after ultrasonic stirring, drying, processing at 350 ℃ for 60min under the protection of argon atmosphere, and cooling along with a furnace to obtain the carbon paper with the MPL layer.
B. Preparing catalyst slurry, namely dispersing 50% of PtCo/C catalyst, Nafion and PTs in 15mL/g ethanol according to the mass ratio of 1:0.4: 0.2; the rotation speed is 300rpm, and the stirring is carried out for 12 hours, so as to obtain the catalyst slurry.
C. Preparing a gas diffusion electrode by adopting an electrostatic spinning technology, wherein the rated operating voltage is 15kV, the curing distance is 18cm, the receiving time is 30min, the flow rate of slurry is 0.01mL/min, the catalyst slurry is spun on the microporous layer on the surface of the carbon paper, the spraying voltage is set to be 28kV when the last spraying is carried out, and the gas diffusion electrode is obtained by drying at 40 ℃ after the spraying is finished; the thickness of the catalytic layer on the surface of the prepared gas diffusion electrode is 5 mu m, and the loading capacity of Pt in the catalytic layer is 0.025mg/cm2。
D. And assembling according to the structure of the cathode gas diffusion electrode-the proton exchange membrane-the anode gas diffusion electrode to obtain the membrane electrode of the proton exchange membrane fuel cell.
Example 6
A preparation method of a membrane electrode of a proton exchange membrane fuel cell comprises the following steps:
A. preparing a microporous layer on the surface of the carbon paper, and preparing hydrophobic carbon paper: immersing carbon paper in 10 mass percent PTFE emulsion for pretreatment for 8min, taking out and drying, and repeating the operation until the percentage content of PTFE in the carbon paper reaches 6 percent to obtain the hydrophobic carbon paper;
preparation of a gas diffusion layer with an MPL layer grown on the surface of hydrophobic carbon paper: evenly mixing XC-72 with the mass ratio of 8:2 and 3 percent of PTFE emulsion, adding a proper amount of ethanol, evenly coating on the surface of the hydrophobic carbon paper after ultrasonic stirring, drying, processing at 350 ℃ for 60min under the protection of argon atmosphere, and cooling along with a furnace to obtain the carbon paper with the MPL layer.
B. Preparing catalyst slurry, namely dispersing 50% of PtCo/C catalyst, Nafion and PAS in 10mL/g ethanol according to the mass ratio of 1:0.3: 0.1; the rotation speed is 300rpm, and the stirring is carried out for 36 hours, so as to obtain the catalyst slurry.
C. Preparing a gas diffusion electrode by adopting an electrostatic spinning technology, wherein the rated operating voltage is 15kV, the curing distance is 20cm, the receiving time is 120min, the flow rate of slurry is 0.02mL/min, the catalyst slurry is spun on the microporous layer on the surface of the carbon paper, the spraying voltage is set to be 28kV when the spraying is carried out for the last time, and the gas diffusion electrode is obtained by drying at 40 ℃ after the spraying is finished; the thickness of the catalytic layer on the surface of the prepared gas diffusion electrode is 20 mu m, and the loading capacity of the catalytic layer Pt is 0.4mg/cm2。
D. And assembling according to the structure of the cathode gas diffusion electrode-the proton exchange membrane-the anode gas diffusion electrode to obtain the membrane electrode of the proton exchange membrane fuel cell.
Comparative example 1
A preparation method of a membrane electrode of a proton exchange membrane fuel cell is different from that of example 1 only in the preparation of a microporous layer on the surface of carbon paper in the step A and the preparation of hydrophobic carbon paper: and immersing the carbon paper in 2 mass percent PTFE emulsion for pretreatment for 5min, taking out and drying, and repeating the operation until the percentage content of PTFE in the carbon paper reaches 2 percent to obtain the hydrophobic carbon paper.
Comparative example 2
A method for preparing a membrane electrode of a proton exchange membrane fuel cell, which is different from the method of example 2 only in the step a of preparing a gas diffusion layer with an MPL layer growing on the surface of hydrophobic carbon paper): evenly mixing XC-72 with the mass ratio of 9:1 and 3 percent of PTFE emulsion, adding a proper amount of ethanol, evenly coating on the surface of the hydrophobic carbon paper after ultrasonic stirring, drying, processing at 350 ℃ for 60min under the protection of argon atmosphere, and cooling along with a furnace to obtain the carbon paper with the MPL layer.
Comparative example 3
A method for preparing a membrane electrode of a proton exchange membrane fuel cell, which is different from the method of example 3 only in the preparation of catalyst slurry in the step B: dispersing 50% of Pt/C catalyst, Nafion and PVP with the mass ratio of 1:0.9:0.5 into a mixed solvent of water and alcohol with the mass ratio of 10 mL/g; the rotation speed is 300rpm, and the stirring is carried out for 24 hours, so as to obtain the catalyst slurry.
Comparative example 4
A preparation method of a membrane electrode of a proton exchange membrane fuel cell is different from the preparation method of example 4 only in the preparation of catalyst slurry in the step B: dispersing 50% of Pt/C catalyst, Nafion and PVP with the mass ratio of 1:0.7:0.3 into a mixed solvent of water and alcohol of 2 mL/g; the rotation speed is 300rpm, and the stirring is carried out for 24 hours, so as to obtain the catalyst slurry.
Comparative example 5
A proton exchange membrane fuel cell membrane electrode preparation method, only lie in the preparation of step C gas diffusion electrode with the difference of example 5, adopt the electrostatic spinning technology, the rated operating voltage is 30kV, the solidification distance is 18cm, the receiving time is 30min, the flowrate of the thick liquids is 0.01mL/min, spin catalyst thick liquids to the carbon paper surface microporous layer, the spraying process voltage keeps the preparation method of the membrane electrode, the voltage of spraying processKeeping the voltage of 30kV unchanged, and drying at 40 ℃ after spraying to obtain a gas diffusion electrode; the thickness of the catalytic layer on the surface of the prepared gas diffusion electrode is 3 mu m, and the loading capacity of the catalytic layer Pt is 0.05mg/cm2。
Comparative example 6
A preparation method of a proton exchange membrane fuel cell membrane electrode, which is different from the embodiment 6 only in the preparation of a gas diffusion electrode in the step C, wherein an electrostatic spinning technology is adopted, the rated operating voltage is 15kV, the curing distance is 5cm, the receiving time is 120min, the flow rate of slurry is 0.02mL/min, catalyst slurry is spun on a microporous layer on the surface of carbon paper, the spraying voltage is set to be 28kV when the spraying is carried out for the last time, and the gas diffusion electrode is obtained after the drying at 40 ℃ after the spraying is finished; the thickness of the catalytic layer on the surface of the prepared gas diffusion electrode is 20 mu m, and the loading capacity of the catalytic layer Pt is 0.3mg/cm2。
Tables of data on evaluation criteria for examples 1 to 6 and comparative examples 1 to 6 can be seen in fig. 1 and 2, in which fig. 1 illustrates the porosity of the catalytic layers of the membrane electrodes in examples 1 to 6 and comparative examples 1 to 6, as measured by mercury intrusion; FIG. 2 is a graph showing the power density of the membrane electrode in examples 1 to 6 compared with that in comparative examples 1 to 6, which was measured at 25cm2Active area single cell.
As shown in FIG. 1, the porosity of examples 1-6 was tested to be 0.56-0.77, while the porosity of comparative examples 1-6 was tested to be 0.3-0.42.
As shown in FIG. 2, the power density of the pairs of examples 1 to 6 was 0.05 to 0.06gPt/kW and that of comparative examples 1 to 6 was 0.18 to 0.27gPt/kW, as obtained by the test.
It can be seen by comparing examples 1-6 with comparative examples 1-6 that the membrane electrode catalytic layers made according to the present invention are significantly optimized with respect to porosity, Pt loading required per kilowatt power density.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (10)
1. A preparation method of a membrane electrode for a proton exchange membrane fuel cell is characterized by comprising the following steps:
step A: spinning catalyst slurry onto a microporous layer on the surface of hydrophobic carbon paper by adopting a variable voltage electrostatic spinning process to obtain a gas diffusion and catalysis layer integrated electrode, wherein the gas diffusion and catalysis layer integrated electrode has a hierarchical structure with different pore sizes by controlling the change of voltage;
and B: and assembling the gas diffusion catalyst layer integrated electrode, the proton exchange membrane and the gas diffusion catalyst layer integrated electrode according to the assembling sequence, and preparing the membrane electrode for the proton exchange membrane fuel cell by a hot pressing or cold pressing process after assembling.
2. The preparation method according to claim 1, wherein the step a specifically comprises the steps of:
step A1: immersing the carbon paper in the polytetrafluoroethylene emulsion, taking out and drying, immersing in the polytetrafluoroethylene emulsion again, taking out and drying for a plurality of times until the mass percent of the polytetrafluoroethylene in the carbon paper is 5-6%, thus obtaining hydrophobic carbon paper;
step A2: mixing carbon powder and polytetrafluoroethylene emulsion, uniformly coating the mixture on the surface of hydrophobic carbon paper, and drying to obtain hydrophobic carbon paper with a microporous layer on the surface;
step A3: dispersing a catalyst, an ionic resin solution and a high-molecular adhesive in a dispersing agent according to the mass ratio of 1:0.3: 0.1-1: 0.7:0.3, and stirring to obtain catalyst slurry, wherein the addition amount of the dispersing agent is 5-15 mL/g of the mass of the catalyst;
and A4, spraying the prepared catalyst slurry onto hydrophobic carbon paper of a surface microporous layer through an electrostatic spinning process, and drying at 40-60 ℃ to obtain the gas diffusion and catalysis layer integrated electrode.
3. The preparation method according to claim 2, wherein in the step A1, the mass fraction of the polytetrafluoroethylene emulsion is 2-20%; the immersion time is 5-10 min;
in the step A2, the adding amount of the carbon powder is 60-80% of the mass of the polytetrafluoroethylene emulsion solution during mixing; the drying process comprises the following steps: performing heat treatment in an inert atmosphere, wherein the heat treatment temperature is 250-450 ℃, the inert atmosphere comprises one of nitrogen, argon, helium, hydrogen-argon mixed gas and hydrogen-nitrogen mixed gas, and the mass fraction of the adopted polytetrafluoroethylene emulsion in the step is the same as that of the polytetrafluoroethylene emulsion in the step A1;
in the step A3, the rotation speed is 300rpm during stirring, and the stirring time is 12-36 h;
in the step A4, the rated operating voltage applied in the electrostatic spinning operation is 15-20 kV, the curing distance is 15-20 cm, the receiving time is 30-120min, and the flow rate of the slurry is 0.01-0.03 mL/min.
4. The preparation method according to claim 2, wherein the catalyst is one or more selected from a Pt/C catalyst, a PtM/C alloy catalyst, a platinum single-layer core-shell catalyst and a non-platinum catalyst; the M comprises one or more of Fe, Co, Ni, Cu, Cr, Mn, Mo and V.
5. The preparation method according to claim 2, wherein the polymer binder is one or more of polypyrrole, polyvinylpyrrolidone, polythiophene, polyaniline and polyacene.
6. The preparation method of claim 2, wherein the dispersant comprises one or more of deionized water, ethanol and isopropanol.
7. The method according to claim 2, wherein in the step A4, the electrostatic spinning spraying is performed 2-4 times, and the voltage of the last spraying is 1.5-2.5 times of the rated operation voltage.
8. A membrane electrode for a proton exchange membrane fuel cell, which is prepared by the preparation method of the membrane electrode for the proton exchange membrane fuel cell according to any one of claims 1 to 7, and comprises a cathode body diffusion catalysis layer integrated electrode, a proton exchange membrane and an anode gas diffusion catalysis layer integrated electrode.
9. The membrane electrode for proton exchange membrane fuel cell according to claim 7, wherein the thickness of the catalytic layer on the surface of the cathode and/or anode gas diffusion electrode is 5 to 20 μm, and the loading amount of Pt in the catalytic layer is 0.025 to 0.4mg/cm2。
10. A pem fuel cell comprising a pem fuel cell membrane electrode assembly according to claim 8 or 9.
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