CN114079071A - Preparation method and application of self-supporting membrane electrode - Google Patents
Preparation method and application of self-supporting membrane electrode Download PDFInfo
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Abstract
The invention belongs to the field of fuel cells, and particularly relates to a preparation method and application of a self-supporting membrane electrode. The method comprises the following steps: pretreating an electrode base layer; preparing a hydrophilic electrode substrate layer; with H2PtCl6Preparing an electrodeposition solution from powder, water and sulfuric acid; preparing a self-supporting electrode and a self-supporting membrane electrode; the self-supporting membrane electrode is prepared in an electrodeposition mode, so that the method is simple and easy to operate, has uniform deposition, and avoids the loss of noble metal catalyst in the traditional commercial catalyst spraying process; meanwhile, the lower limit potential is changed in an electrodeposition mode to obtain platinum particles with different shapes, so that the dissolution and Oswald aging of a platinum-based catalyst are effectively avoided, and the durability of the fuel cell is improved; and the redox reaction performance of the catalyst can be further enhanced. The self-supporting membrane electrode prepared by the invention is used for high-temperature proton exchange membrane fuel cells, and has wide application prospect.
Description
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to a preparation method of a self-supporting membrane electrode and application of the self-supporting membrane electrode in a high-temperature proton exchange membrane fuel cell.
Background
Proton Exchange Membrane Fuel Cells (PEMFC) are a highly efficient hydrogen energy conversion deviceChemical energy stored in hydrogen fuel and oxidant can be directly converted into electric energy by means of electrochemical reaction, and the electrochemical energy conversion device is regarded as an important approach for solving the problems of energy crisis and environmental pollution as a green and efficient energy conversion device, and has attracted extensive attention in recent years. The catalyst is one of the key materials of a Proton Exchange Membrane Fuel Cell (PEMFC), and has the functions of reducing the activation energy of the reaction, promoting the oxidation-reduction process of hydrogen and oxygen on an electrode and improving the reaction rate. Proton exchange membrane fuel cells are classified into low temperature proton exchange membrane fuel cells (LT-PEMFC) and high temperature proton exchange membrane fuel cells (HT-PEMFC). The reaction temperature of the low-temperature proton exchange membrane fuel cell is usually 60-80 ℃, liquid water is generated, flooding is easy to occur at the cathode of the cell, and the normal operation of the cell is seriously influenced. The reaction temperature of the high-temperature proton exchange membrane fuel cell is generally 140-180 ℃, water vapor is generated at the cathode, and the risk of flooding is avoided. Increasing operating temperatures is considered to be an ideal way to solve the major problems facing current pem fuel cells. Based on phosphoric acid (H)3PO4) Polybenzimidazole (PBI) doped high temperature proton exchange membrane fuel cells are currently the most successful systems. However, proton conductivity in high temperature membrane systems is dependent on the phosphoric acid electrolyte, and therefore a reasonable amount of phosphoric acid needs to be distributed throughout the membrane and electrode to maintain high proton conductivity. But due to a gas (e.g. O)2) The low solubility and diffusion rate in phosphoric acid, and the adsorption of phosphoric acid on the surface of the Pt catalyst, result in inefficient Oxygen Reduction Reaction (ORR) in the electrode and increased cost. And also easily causes the Pt catalyst to be aged under high temperature and strong acid conditions, resulting in a reduction in the life of the battery. And the spraying process used by the traditional commercial platinum-carbon catalyst (Pt/C) is complex, the used binder can cause the reduction of the active area of the catalyst and influence the performance of the battery, the loss amount is large in the process, and the binding force between the platinum catalyst and a substrate layer is not strong.
Disclosure of Invention
The invention aims to overcome the defects of the traditional platinum-based catalyst electrode and provides a preparation method of a self-supporting membrane electrode and application of the self-supporting membrane electrode in a high-temperature proton exchange membrane fuel cell. The electrode uses the electrodeposition method to deposit the platinum particles with special shapes on the carbon paper, greatly reduces the platinum dosage in the catalyst, improves the utilization rate of the catalyst, realizes further improvement of catalytic performance compared with the traditional platinum-based catalyst, obtains the platinum particles with different shapes by changing the lower limit potential in the electrodeposition mode, is simple and easy to operate, avoids the loss of noble metal catalyst caused in spraying, does not use a binder, can expose more active sites, has uniform deposition, stronger bonding force between the catalyst and the carbon paper, reduces contact resistance, and is a potential fuel cell electrode.
The invention is realized by the following technical scheme, and the specific steps are as follows:
(1) pretreatment of the electrode base layer: cutting carbon paper or carbon cloth serving as an electrode substrate layer according to requirements, immersing the electrode substrate layer into acetone, heating and washing to remove surface dirt and functional groups, heating and washing, and performing ultrasonic washing in deionized water to remove acetone on the surface to obtain pretreated carbon paper or carbon cloth;
(2) preparing a hydrophilic electrode substrate layer: sulfuric acid A (H)2SO4) And nitric acid (HNO)3) Mixing to obtain mixed acid; then immersing the carbon paper or the carbon cloth pretreated in the step (1) into mixed acid for first ultrasonic treatment, then taking out the carbon paper or the carbon cloth, immersing the carbon paper or the carbon cloth into deionized water again for second ultrasonic treatment, washing the carbon paper or the carbon cloth with the deionized water for several times after ultrasonic treatment, and finally immersing the carbon paper or the carbon cloth into sulfuric acid B for later use;
(3) solution for deposition preparation: get H2PtCl6Diluting the powder with deionized water to obtain H2PtCl6Diluting the solution; sulfuric acid (98 wt%) was then added to the water, followed by H2PtCl6Diluting the solution, and uniformly mixing to obtain an electrodeposition solution;
(4) mounting three electrodes: sealing one side of the carbon paper or carbon cloth treated in the step (2), and then immersing the carbon paper or carbon cloth into the deposition solution prepared in the step (3) to obtain the treated carbon paper or carbon cloth; a saturated KOH electrode is used as a reference electrode, a Pt sheet is used as a counter electrode, and treated carbon paper or carbon cloth is fixed by using an electrode clamp in a three-electrode system;
(5) electro-deposition of a platinum catalyst with a special morphology: pouring the electrodeposition solution obtained in the step (3) into an electrolytic cell, and introducing high-purity N2Removing air in the solution, then immersing the carbon paper or carbon cloth fixed by the electrode clamp into the deposition solution of the electrolytic cell for deposition, and wrapping the part of the electrode clamp immersed into the solution to avoid platinum deposition on the electrode clamp; while maintaining high purity N during deposition2Introducing, taking out the carbon paper or the carbon cloth after deposition is finished, removing a covering material on the sealing surface of the carbon paper or the carbon cloth, washing with deionized water for a plurality of times, drying in an oven, and drying to obtain the self-supporting electrode;
(6) preparing a membrane electrode: and (5) taking the electrode as an anode and a cathode, separating the two electrodes by using a proton exchange membrane, and carrying out hot pressing to obtain the self-supporting membrane electrode.
Preferably, the heating washing time in the step (1) is 15-30min, and the heating temperature is kept at 30-70 ℃; the ultrasonic washing time is 15-60 min.
Preferably, the concentration of the sulfuric acid A in the step (2) is 98 wt%, and the concentration of the nitric acid is 68 wt%; the volume ratio of the sulfuric acid A to the nitric acid is 2: 1.
Preferably, the time of the first ultrasonic treatment in the step (2) is 20-90 min; the time of the first ultrasonic treatment is 15-60 min; the washing is carried out for 3 to 5 times; the final immersion was in sulfuric acid B, the concentration of which was 0.5M.
Preferably, said H in step (3)2PtCl6The dosage ratio of the powder to the deionized water is 1 g: 100 ml; the sulfuric acid is added into the water, and the concentration of the sulfuric acid is 98 wt%.
Preferably, H in the electrodeposition solution in the step (3)2PtCl6In a concentration of 2mM, H2SO4The concentration of (3) is 0.5M.
Preferably, high purity N is introduced before the deposition in step (5)2The time of (2) is 20-60 min.
Preferably, the electrochemical workstation used for the deposition in the step (5) is idea 760E, and the parameter conditions of the deposition are as follows: nucleation potential ENat-1.3V for 0.2s, belowLimiting potential ELbetween-0.8V and 0.1V, the upper limit potential EU0.7-0.8V, deposition frequency of 10-50Hz, and deposition time of 10-15 min.
Preferably, the washing times in the step (5) are 3-5 times; the drying temperature is 60-70 ℃, and the drying time is 12-24 h.
The self-supporting membrane electrode prepared by the invention is used for high-temperature proton exchange membrane fuel cells.
Compared with the prior art, the invention has the following beneficial effects:
1. the method has the advantages that the method is simple and easy to operate through an electrodeposition mode, the deposition is uniform, and the loss of the noble metal catalyst in the traditional commercial catalyst spraying process is avoided; the catalyst is deposited on carbon paper after mixed acid hydrophilic treatment, the platinum catalyst with special morphology is a noble metal oxygen reduction catalyst with Oxygen Reduction Reaction (ORR) active sites, and can be used as a fuel cell catalyst to replace the traditional commercial platinum carbon catalyst (Pt/C) due to the electrocatalytic activity and high specific surface area of the platinum catalyst; moreover, the platinum catalyst with special morphology prepared by the electrodeposition method can further enhance the oxidation-reduction reaction performance of the catalyst.
2. The self-supporting membrane electrode prepared by the method does not need to use a binder, so that the binder is prevented from occupying active sites of the catalyst, the utilization rate of the catalyst is improved, and the performance is greatly improved.
3. The catalyst for preparing the self-supporting membrane electrode has various special shapes, such as nano flower shape and thorn shape, exposes a high-index crystal face, has electrochemical activity and high specific surface area, and improves the performance of the catalyst.
4. The lower limit potential is changed in an electrodeposition mode to obtain platinum particles with different shapes, so that the dissolution and Oswald aging of the platinum-based catalyst are effectively avoided, and the durability of the fuel cell is improved.
Drawings
FIG. 1 a is a SEM photograph of an electrodeposited free-standing film electrode prepared in example 1; b is an SEM picture of the electrodeposited free-standing film electrode prepared in example 2.
FIG. 2A is a CV diagram of an electrodeposited free standing film electrode prepared in example 1; b is a CV diagram of the electrodeposited free standing film electrode prepared in example 2.
FIG. 3 is a polarization diagram of a self-supporting membrane electrode.
Detailed Description
The present invention will be described in detail with reference to specific examples. 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 should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1:
and (3) electrodepositing a platinum catalyst fuel cell electrode with a nano flower-shaped special morphology, and performing a discharge test. The method mainly comprises the following steps:
(1) processing electrode substrate layer by cutting carbon paper into appropriate size of 1 × 2.5cm2Then washing in heated acetone for 15min to remove dirt and functional groups on the surface of the carbon paper, then ultrasonically washing in deionized water for 15min to wash off the acetone on the surface;
(2) preparing a hydrophilic electrode substrate layer: putting the carbon paper treated in the step (1) into H2SO4And HNO3In the mixed acid, the proportion of the mixed acid is 98 wt% of H2SO4：68wt％HNO3Ultrasonic treating for 30min at 2:1 in deionized water for 15min, washing with deionized water for 3 times, and placing at 0.5M H2SO4Preparing for later use;
(3) solution for deposition preparation: fetch 1g H2PtCl6The powder was diluted with 100mL of deionized water to give 100mL of H2PtCl6Diluting the solution; then, 2.72mL of sulfuric acid (98 wt%) was added to 50mL of deionized water, and 10.34mL of the above H was added2PtCl6Uniformly mixing the diluent, and adding 37mL of deionized water to obtain an electrodeposition solution; electrodeposition solution of H2PtCl6In a concentration of 2mM, H2SO4The concentration of (A) is 0.5M;
(4) mounting three electrodes: sticking a Teflon adhesive tape on one side of the carbon paper subjected to hydrophilic treatment, and wrapping a raw adhesive tape on the part of the electrode clamp immersed in the solution to prevent platinum from depositing on the electrode clamp; fixing a graphite electrode clamp in a three-electrode system, taking a saturated KOH electrode as a reference electrode, and taking a Pt sheet as a counter electrode;
(5) electro-deposition of a platinum catalyst with a special morphology: pouring the electrodeposition solution obtained in the step (3) into an electrolytic cell, and introducing high-purity N for 30min2To drive out air from the solution and to maintain high purity N during deposition2(purity is more than 99.999 percent) is introduced, and the electrochemical workstation used is Ida 760E and nucleation potential ENA holding voltage of-1.3V for 0.2s, a lower limit potential ELis-0.35V, the upper limit potential EU0.75V, deposition frequency of 10Hz, and deposition time of 10 min; the platinum electrodeposited on the surface of the carbon paper shows a nano flower shape; taking down the deposited electrode from the electrode clamp, removing the Teflon adhesive tape, washing with deionized water for three times, and drying in an oven at 60 ℃ for 12 h; drying to obtain a self-supporting electrode which is a nano flower-shaped platinum particle electrode as shown in a picture a in figure 1;
(6) preparing a membrane electrode and assembling a battery: taking the nano flower-shaped platinum particle electrodes prepared in the step (5) as a cathode and an anode, and using 85 wt.% H in the middle3PO4Separating the treated AP-30 membrane, and hot-pressing for 5min by using a hot press to obtain a self-supporting membrane electrode;
(7) and (3) testing the discharge performance: after the membrane electrode was assembled in a single cell system, a discharge test was performed. The test conditions were: before the battery test, N is respectively used as the cathode and the anode2Purging was carried out for 15min each, with the flow rate controlled at 0.5 SLPM. The temperature of the cell was 160 ℃ at the time of cell testing. The flow rate of hydrogen was 0.2SLPM and the flow rate of oxygen was 0.4 SLPM. After normalization, the current density reaches the value under the working voltage of 0.6V
Power density up to
Example 2:
and (3) electrodepositing the spine-shaped platinum catalyst fuel cell electrode with the special morphology, and performing a discharge test. The method mainly comprises the following steps:
(1) processing electrode substrate layer by cutting carbon paper into appropriate size of 1 × 2.5cm2Then washing in heated acetone for 15min to remove dirt and functional groups on the surface of the carbon paper, then ultrasonically washing in deionized water for 15min to wash off the acetone on the surface;
(2) preparing a hydrophilic electrode substrate layer: putting the carbon paper treated in the step (1) into H2SO4And HNO3In the mixed acid, the proportion of the mixed acid is 98 wt% of H2SO4：68wt％HNO3Ultrasonic treating for 30min at 2:1 in deionized water for 15min, washing with deionized water for 3 times, and placing at 0.5M H2SO4Preparing for later use;
(3) solution for deposition preparation: fetch 1g H2PtCl6The powder was diluted with 100mL of deionized water to give 100mL of H2PtCl6Diluting the solution; then, 2.72mL of sulfuric acid (98 wt%) was added to 50mL of deionized water, and 10.34mL of the above H was added2PtCl6Uniformly mixing the diluent, and adding 37mL of deionized water to obtain an electrodeposition solution; electrodeposition solution of H2PtCl6In a concentration of 2mM, H2SO4The concentration of (A) is 0.5M;
(4) mounting three electrodes: sticking a Teflon adhesive tape on one side of the carbon paper subjected to hydrophilic treatment, and wrapping a raw adhesive tape on the part of the electrode clamp immersed in the solution to prevent platinum from depositing on the electrode clamp; fixing a graphite electrode clamp in a three-electrode system, taking a saturated KOH electrode as a reference electrode, and taking a Pt sheet as a counter electrode;
(5) electro-deposition of a platinum catalyst with a special morphology: pouring the electrodeposition solution obtained in the step (3) into an electrolytic cell, and introducing high-purity N for 30min2To drive out air from the solution and to maintain high purity N during deposition2Introducing, using an electrochemical workstation of Ida 760E, nucleation potential ENA holding voltage of-1.3V for 0.2s, a lower limit potential ELis-0.4V, the upper limit potential EU0.75V, deposition frequency 10Hz, deposition time10 min; the platinum electrodeposited on the surface of the carbon paper shows a thorn shape; taking down the deposited electrode from the electrode clamp, removing the Teflon adhesive tape, washing with deionized water for three times, and drying in an oven at 60 ℃ for 12 h; drying to obtain a self-supporting electrode which is a thorn-shaped platinum particle electrode as shown in a picture a in figure 1;
(6) preparing a membrane electrode and assembling a battery: taking the spiny platinum particle electrode prepared in the step (5) as a cathode and an anode, and using 85 wt.% H in the middle3PO4Separating the treated AP-30 membrane, and hot-pressing for 5min by using a hot press to obtain a self-supporting membrane electrode;
(7) and (3) testing the discharge performance: after the membrane electrode was assembled in a single cell system, a discharge test was performed. The test conditions were: before the battery test, N is respectively used as the cathode and the anode2Purging was carried out for 15min each, with the flow rate controlled at 0.5 SLPM. The temperature of the cell was 160 ℃ at the time of cell testing. The flow rate of hydrogen was 0.2SLPM and the flow rate of oxygen was 0.4 SLPM. After normalization, the current density reaches the value under the working voltage of 0.6V
Power density up to
Comparative example 1:
high temperature proton exchange membrane fuel cells of conventional commercial platinum carbon catalyst (Pt/C) were prepared and subjected to discharge testing. The anode and cathode of the fuel cell both use conventional electrodes, and the main steps are as follows:
(1) and (3) treating the carbon paper: carbon paper (Dongli-060) was used for the gas diffusion layer. Firstly, decontaminating treatment is carried out, the carbon paper is soaked in acetone, heated and boiled for 15-20min, impurities on the surface and in holes of the carbon paper are removed, and the carbon paper is dried at 70 ℃. Then soaking the PTFE powder in a dispersion liquid of Polytetrafluoroethylene (PTFE) for hydrophobic treatment, taking out after a period of time, drying for 2h at 70 ℃, and then putting the PTFE powder in a muffle furnace at 370 ℃ for sintering for 30min to enable the content of the PTFE to reach 15-20 wt%;
(2) preparation of conventional electrode:
firstly, carbon powder (Vulcan XC-72R) and PTFE is dispersed in isopropanol dispersion liquid, is subjected to ultrasonic uniform spraying, is uniformly sprayed on carbon paper containing a hydrophobic layer, is dried for 2 hours at the temperature of 70 ℃, is then placed in a muffle furnace at the temperature of 370 ℃ for sintering for 30 minutes, is taken out, is cooled and is weighed to calculate to obtain the carbon powder loading capacity of 2-3 mg cm-2PTFE, C ═ 15% hydrophobic layer.
Secondly, weighing a proper amount of 40 wt.% commercial platinum-carbon catalyst (Pt/C) and Nafion, dispersing the Pt/C and the Nafion in isopropanol dispersion liquid, ultrasonically and uniformly spraying the Pt/C and the Nafion on a hydrophobic layer in the first step, drying the hydrophobic layer for 2 hours at 70 ℃, taking out the hydrophobic layer, cooling, weighing and calculating to obtain the Pt catalyst loading capacity of 0.7mg cm-2A conventional electrode of (1);
(3) preparation of conventional membrane electrode and assembly of cell: taking two pieces of conventional electrodes prepared in the step (2) as a cathode and an anode of a battery respectively, and using 85 wt.% H in the middle3PO4Separating the treated AP-30 membrane, and hot-pressing for 5min by using a hot press to obtain a conventional membrane electrode;
(4) and (3) testing the discharge performance: after the membrane electrode was assembled in a single cell system, a discharge test was performed. The test conditions were: before the battery test, N is respectively used as the cathode and the anode2Purging was carried out for 15min each, with the flow rate controlled at 0.5 SLPM. The temperature of the cell was 160 ℃ at the time of cell testing. The flow rate of hydrogen was 0.2SLPM and the flow rate of oxygen was 0.4 SLPM. After normalization, the current density at 0.6V of the working voltage is
A power density of
The conventional Pt catalyst loading of the high-temperature proton exchange membrane fuel cell is 0.7mg cm-2The power density is 0.6-0.7W cm-2Normalized to Pt of unit mass and power density of 0.86-1W cm-2(ii) a Comparative example 1 normalized catalyst power density per unit mass at 0.6V operating voltage of
Example 2 normalized Unit mass at 0.6V operating VoltageHas a catalyst power density of
Power density increases
The power density is improved by 33 percent, the performance of the catalyst is obviously improved, and 75 percent of nano flower-shaped catalyst can reach the same power density as the traditional catalyst, so the utilization rate of the catalyst is greatly improved, and the cost of the fuel cell is greatly reduced because the platinum-based catalyst is high in price.
Compared with the traditional catalyst particles which are sprayed, the catalyst nanoparticles prepared by the electro-deposition method have stronger bonding force with carbon paper, so that the performance attenuation of the catalyst caused by dissolution, migration and agglomeration of the platinum nanoparticles can be effectively relieved in the application process, and the activity and stability of the catalyst are greatly improved. In addition, the catalyst with special morphology has high-index crystal faces, and the high-index crystal faces contain a large number of atomic steps so that the catalyst shows very good catalytic activity and stability, so that the synthetic Pt catalyst with the high-index crystal faces can greatly improve the catalytic performance of the Pt catalyst. The nano flower-shaped nano Pt particles have a polyhedral structure, so that the nano flower-shaped nano Pt particles are not easy to dissolve in an electrolyte, and can provide more adsorption sites in a limited space, so that the flower-shaped nano Pt particles show good durability and catalytic activity. Compared with the electrode prepared by the traditional spraying method, the self-supporting membrane electrode with the platinum catalyst with the special morphology prepared by the electrodeposition method has the advantages that the platinum catalyst is uniformly distributed, the binder is avoided, the binder does not occupy the active sites of the catalyst any more, so that more active sites of the catalyst are exposed, and the catalytic performance of the catalyst is further improved. The binding force of the self-supporting membrane electrode catalyst and the carbon paper is stronger than that of the traditional electrode, and the contact resistance of the catalyst and the carbon paper is reduced, so that the self-supporting membrane electrode of the nano flower-shaped catalyst in the embodiment 2 has obvious advantages compared with the traditional commercial catalyst electrode, and has great significance for the development of fuel cell electrodes.
Description of the drawings: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Claims (10)
1. The preparation method of the self-supporting membrane electrode is characterized by comprising the following steps:
(1) pretreatment of the electrode base layer: cutting carbon paper or carbon cloth serving as an electrode substrate layer according to requirements, and then soaking the electrode substrate layer into acetone for heating and washing; heating and washing, and then carrying out ultrasonic washing in deionized water to obtain pretreated carbon paper or carbon cloth;
(2) preparing a hydrophilic electrode substrate layer: mixing sulfuric acid A and nitric acid to obtain mixed acid; then immersing the carbon paper or the carbon cloth pretreated in the step (1) into mixed acid for first ultrasonic treatment, then taking out the carbon paper or the carbon cloth, immersing the carbon paper or the carbon cloth into deionized water again for second ultrasonic treatment, washing the carbon paper or the carbon cloth with the deionized water for several times after ultrasonic treatment, and finally immersing the carbon paper or the carbon cloth into sulfuric acid B for later use;
(3) solution for deposition preparation: get H2PtCl6Diluting the powder with deionized water to obtain H2PtCl6Diluting the solution; then adding sulfuric acid into water, then adding H2PtCl6Diluting the solution, and uniformly mixing to obtain an electrodeposition solution;
(4) mounting three electrodes: sealing one side of the carbon paper or carbon cloth treated in the step (2), and then immersing the carbon paper or carbon cloth into the deposition solution prepared in the step (3) to obtain the treated carbon paper or carbon cloth; a saturated KOH electrode is used as a reference electrode, a Pt sheet is used as a counter electrode, and treated carbon paper or carbon cloth is fixed by using an electrode clamp in a three-electrode system;
(5) pouring the electrodeposition solution obtained in the step (3) into an electrolytic cell, and introducing high-purity N2Removing air in the solution, then immersing the carbon paper or carbon cloth fixed by the electrode clamp into the deposition solution of the electrolytic cell for deposition, and wrapping the part of the electrode clamp immersed into the solution to avoid platinum deposition on the electrode clamp; while maintaining high purity N during deposition2Introducing, taking out the carbon paper or the carbon cloth after deposition is finished, removing a covering material on the sealing surface of the carbon paper or the carbon cloth, washing with deionized water for a plurality of times, drying in an oven, and drying to obtain the self-supporting electrode;
(6) preparing a membrane electrode: and (5) taking the electrode as an anode and a cathode, separating the two electrodes by using a proton exchange membrane, and carrying out hot pressing to obtain the self-supporting membrane electrode.
2. The method for preparing a self-supporting membrane electrode according to claim 1, wherein the heating and washing time in the step (1) is 15-30min, and the heating temperature is maintained at 30-70 ℃; the ultrasonic washing time is 15-60 min.
3. The method for preparing a self-supporting membrane electrode according to claim 1, wherein the concentration of sulfuric acid a in step (2) is 98 wt%, and the concentration of nitric acid is 68 wt%; the volume ratio of the sulfuric acid A to the nitric acid is 2: 1.
4. The method for preparing a self-supporting membrane electrode according to claim 1, wherein the time of the first ultrasonic treatment in the step (2) is 20 to 90 min; the time of the first ultrasonic treatment is 15-60 min; the washing is carried out for 3 to 5 times; the final immersion was in sulfuric acid B, the concentration of which was 0.5M.
5. The method for producing a self-supporting membrane electrode assembly according to claim 1, wherein the H in step (3)2PtCl6The dosage ratio of the powder to the deionized water is 1 g: 100 ml; the sulfuric acid is added into the water, and the concentration of the sulfuric acid is 98 wt%.
6. The method for preparing a self-supporting membrane electrode assembly according to claim 1, wherein H in the electrodeposition solution in the step (3)2PtCl6In a concentration of 2mM, H2SO4The concentration of (3) is 0.5M.
7. The method for preparing a self-supporting membrane electrode assembly according to claim 1, wherein high purity N is introduced before the deposition in step (5)2The time of (2) is 20-60 min.
8. The method for preparing a self-supporting membrane electrode according to claim 1, wherein the electrochemical workstation used for the deposition in the step (5) is Ida 760E, and the parameter conditions of the deposition are as follows: nucleation potential ENA holding voltage of-1.3V for 0.2s, a lower limit potential ELbetween-0.8V and 0.1V, the upper limit potential EU0.7-0.8V, deposition frequency of 10-50Hz, and deposition time of 10-15 min.
9. The method for preparing a self-supporting membrane electrode according to claim 1, wherein the washing in step (5) is performed 3 to 5 times; the drying temperature is 60-70 ℃, and the drying time is 12-24 h.
10. Use of a self-supporting membrane electrode prepared according to any one of claims 1 to 9, wherein the self-supporting membrane electrode is used in a high temperature proton exchange membrane fuel cell.
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