Preparation method of anti-reverse electrode film electrode and application thereof

Abstract

The application discloses a preparation method of an anti-reverse electrode membrane and application thereof, and belongs to the technical field of hydrogen fuel cells. The preparation method comprises the following steps: first, preparing an anode first catalyst slurry and an anode second catalyst slurry respectively, then mixing to obtain a final anode catalyst slurry, simultaneously preparing a cathode catalyst layer slurry, and finally coating the anode and cathode catalyst slurries on both sides of a proton exchange membrane to obtain a membrane electrode. The anode catalyst layer prepared by the method adopts an IrRuO x / C catalyst and a polymethylacrylic acid sulfobetaine, a gradient collaborative catalytic interface layer is successfully constructed, the membrane electrode is provided with strong anti-reverse ability guarantee under complex working conditions, can work for a long time stably and continuously, the anti-reverse performance of the membrane electrode under complex working conditions is effectively improved, the reliability and service life of the fuel cell are provided with strong guarantee, and the application has remarkable practical application value and wide market promotion prospect.

Description

Technical Field

[0001] This invention belongs to the field of hydrogen fuel cell technology, specifically relating to a method for preparing an anti-reverse electrode membrane and its application. Background Technology

[0002] As a highly efficient and clean energy conversion device, fuel cells have broad application prospects in new energy vehicles, distributed energy storage, and power generation systems. However, when existing fuel cell membrane electrode assemblies encounter fuel starvation (insufficient hydrogen supply at the anode) during rapid load changes or low-temperature start-up, the anode potential rises sharply. This not only triggers the water electrolysis reaction but also significantly accelerates the electrochemical carbon corrosion process, thereby damaging the catalyst layer structure, causing platinum particles to detach from the carbon support, and ultimately leading to battery performance degradation, severely restricting the reliability and service life of fuel cells.

[0003] In existing technologies, most methods involve adding water electrolysis catalysts to the catalyst layer to improve the anti-reverse polarity performance of the membrane electrode assembly (MEA). However, this method suffers from problems such as poor catalyst layer dispersion and decreased MEA performance. Therefore, developing a novel anti-reverse polarity MEA assembly to meet the stable operation requirements of fuel cells under complex operating conditions while ensuring the catalytic activity of the MEA has become an urgent technical challenge. Summary of the Invention

[0004] Based on the above-mentioned technical problems, this invention proposes a method for preparing an anti-reverse polarity film electrode and its application.

[0005] The technical solution adopted in this invention is: This invention provides a method for preparing an anti-reverse polarity film electrode, comprising the following steps: S1 mixes Pt / C catalyst, perfluorosulfonic acid resin solution, water and ethanol evenly to obtain the first anode catalyst slurry; S2 involves dissolving chloroiridic acid and ruthenium chloride trihydrate in water, then mixing them with a graphitized carbon support solution and reacting. After the reaction is complete, the mixture is filtered and dried to obtain IrRuO. x / C catalyst powder; S3. Polymethacrylate sulfobetaine is dissolved in water until fully dissolved, followed by the addition of IrRuO obtained in step S2. x / C catalyst and ethanol are mixed evenly to obtain the second anode catalyst slurry; S4. The first anode catalyst slurry obtained in step S1 is mixed evenly with the second anode catalyst slurry obtained in step S3 to obtain the anode catalyst slurry. S5 involves uniformly mixing the Pt / C catalyst, perfluorosulfonic acid resin solution, water, and ethanol to obtain a cathode catalyst slurry (this step is the same as step S1). S6 The anode catalyst slurry obtained in step S4 and the cathode catalyst slurry obtained in step S5 are respectively coated on the anode side and cathode side of the proton exchange membrane to obtain the anti-reverse electrode membrane.

[0006] The anti-reverse electrode mainly consists of a proton exchange membrane, an anode catalyst layer, and a cathode catalyst layer. The proton exchange membrane separates the anode and cathode and conducts protons; the anode catalyst layer is coated on the anode side of the proton exchange membrane; and the cathode catalyst layer is coated on the cathode side of the proton exchange membrane.

[0007] Preferably, in step S1: the mass ratio of the Pt / C catalyst, perfluorosulfonic acid resin solution, water and ethanol is 15-30:35-50:160-200:150-170; the concentration of the perfluorosulfonic acid resin solution is 6%-10% (mass percentage).

[0008] Perfluorosulfonic acid resin solution refers to a uniform dispersion formed by dissolving perfluorosulfonic acid resin in water.

[0009] Preferably, the platinum loading in the Pt / C catalyst is 40%-50%, where platinum loading refers to the mass percentage of platinum.

[0010] Preferably, in step S2, the mass ratio of chloroiridic acid, ruthenium chloride trihydrate, water, and graphitized carbon carrier solution is 9-11:8-12:38-42:40-50; and the concentration of the graphitized carbon carrier solution is 35%-45% (mass percentage).

[0011] Graphitized carbon carrier solution is a uniform suspension or dispersion formed by dispersing graphitized carbon carrier in water.

[0012] Preferably, in step S2, the reaction refers to a reaction at 70-90°C for 3.5-4.5 hours.

[0013] Preferably, the IrRuO x In the / C catalyst, x = 1.8-2.2.

[0014] Preferably, in step S3: IrRuO x The mass ratio of / C catalyst to polymethyl methacrylate sulfobetaine is 70-90:10-20.

[0015] More preferably, in step S3: IrRuO x The mass ratio of / C catalyst to polymethyl methacrylate sulfobetaine is 80-90:10-20.

[0016] Preferably, the anode catalyst slurry contains Pt / C catalyst and IrRuO x The mass ratio of the catalyst to the catalyst is 75-90:10-25.

[0017] Preferably, in step S5: the mass ratio of the Pt / C catalyst, perfluorosulfonic acid resin solution, water and ethanol is 15-30:35-50:160-200:150-170; the concentration of the perfluorosulfonic acid resin solution is 6%-10% (mass percentage).

[0018] Preferably, in step S6: the platinum loading on the anode side is 0.03-0.05 mg / cm³. 2 The platinum loading on the cathode side is 0.02-0.04 mg / cm³. 2 .

[0019] The present invention also provides the application of the anti-reverse polarity membrane electrode prepared by the above-described method in the preparation of hydrogen fuel cells.

[0020] The beneficial technical effects of the present invention are as follows: This invention provides a method for preparing a reverse polarity film electrode, by introducing IrRuO into the anode catalyst layer. x / C. The addition of polymethyl methacrylate sulfobetaine successfully constructed a cascaded synergistic catalytic interface layer, providing strong anti-reverse polarity capability for the membrane electrode under complex operating conditions. This ensures continuous and stable operation for extended periods, effectively improving the anti-reverse polarity performance of the membrane electrode under complex conditions. This provides a strong guarantee for the reliability and lifespan of the fuel cell, demonstrating significant practical application value and broad market prospects. Specifically: (1) The anode catalyst layer prepared in this invention uses a Pt / C catalyst and IrRuO, which has excellent anti-reverse polarity effect. x The catalyst was Pt / C and polymethyl methacrylate sulfonate betaine was added; polymethyl methacrylate sulfonate betaine has ionic conductivity and amphiphilicity, with its hydrophobic end tightly bound to the Pt / C catalyst and its hydrophilic end connected to IrRuO. x The / C catalyst forms a three-phase cascade synergistic catalytic interface layer, constructing an ordered material reaction channel. It can effectively inhibit carbon corrosion of the anode catalyst layer when hydrogen supply is insufficient, ensuring the reaction activity of the catalyst layer, and enabling the anti-reverse polarity reaction and hydrogen reduction catalytic reaction to proceed smoothly.

[0021] (2) In the preparation of the anode catalyst slurry, the present invention first prepares the first anode catalyst slurry and the second anode catalyst slurry separately, and then mixes them to obtain the final anode catalyst slurry. The above two-step mixing method can better facilitate the formation of a three-phase ladder synergistic catalytic interface layer and realize "ordered channel" and "reaction separation". At the same time, it can ensure that the raw materials are mixed more evenly and that polymethyl methacrylate sulfobetaine can be better dispersed in the slurry to play its role.

[0022] (3) This invention introduces IrRuO xThe / C catalyst, through the synergistic effect of Ir and Ru, significantly enhances the activity of water electrolysis and improves the anti-reverse polarity performance of the membrane electrode. At the same time, the low cost of Ru reduces the amount of precious metal Ir used, thereby lowering the raw material cost. Attached Figure Description

[0023] Figure 1 The reverse polarity curves are for the membrane electrodes prepared in Examples 1-3 and Comparative Example 1 of this invention. Detailed Implementation

[0024] The present invention will be further described below with reference to specific embodiments. Unless otherwise specified, all chemical reagents used in the embodiments of the present invention are obtained through conventional commercial means.

[0025] In the following examples, the Pt / C catalyst was purchased from Tanaka Precious Metals (TKK), model TEC10E50E, with a Pt loading of 50%.

[0026] Example 1 Preparation of S1 anode first catalyst slurry Weigh 15g of anode Pt / C catalyst, 35g of perfluorosulfonic acid resin solution (mass fraction of 8.75%), 200g of water and 150g of ethanol and mix them evenly.

[0027] S2 IrRuO x Catalyst preparation Weigh 10g of chloroiridium acid (H₂IrCl₆) and 10g of ruthenium chloride (RuCl·3H₂O) into a beaker, and dissolve them completely in 40g of water. Weigh 40g of a well-dispersed graphitized carbon support solution (40% by mass), and mix it with the above solution by sonication. Pour the mixture into a three-necked flask and react for 4 hours at 90℃. After the reaction is complete, filter and dry to obtain IrRuO₂. x / C catalyst powder, x ranges from 1.8 to 2.2.

[0028] Preparation of S3 anode second catalyst slurry Weigh 0.5g of polymethacrylic acid sulfobetaine and dissolve it in 20g of water, then add 4.5g of IrRuO x / C catalyst and 40g ethanol are thoroughly mixed to obtain the second anode catalyst layer slurry.

[0029] Preparation of S4 anode catalyst slurry The first catalyst slurry of the anode containing Pt / C catalyst is mixed with IrRuO x The second catalyst slurry at the anode of the / C catalyst, in accordance with Pt / C and IrRuO x The anode catalyst slurry was obtained by thoroughly mixing and dispersing the catalyst at a mass ratio of 80:15 / C.

[0030] Preparation of S5 cathode catalyst slurry Weigh 15g of anode Pt / C catalyst, 35g of perfluorosulfonic acid resin solution (mass fraction of 8.75%), 200g of water and 150g of ethanol and mix them evenly.

[0031] Preparation of S6 anti-reverse film electrode The anode and cathode catalyst slurries were coated on both sides of the proton exchange membrane, respectively. The platinum loading of the anode catalyst was 0.05 mg / cm³. 2 The platinum loading of the cathode catalyst is 0.03 mg / cm³. 2 Thus, an anti-reverse polarization film electrode was obtained.

[0032] Example 2 Preparation of S1 anode first catalyst slurry Weigh 20g of anode Pt / C catalyst, 50g of perfluorosulfonic acid resin solution (mass fraction 8.75%), 180g of water and 150g of ethanol and mix them evenly.

[0033] S2 IrRuO x Catalyst preparation Weigh 10g of chloroiridium acid (H₂IrCl₆) and 12g of ruthenium chloride (RuCl·3H₂O) into a beaker, and dissolve them completely in 40g of water. Weigh 50g of a well-dispersed graphitized carbon support solution (40% by mass), and ultrasonically mix it with the above solution. Pour the mixture into a three-necked flask and react for 3.5 h at 80℃. After the reaction is complete, filter and dry to obtain IrRuO₂. x / C catalyst powder, x ranges from 1.8 to 2.2.

[0034] Preparation of S3 anode second catalyst slurry Weigh 0.5g of polymethacrylate sulfobetaine and dissolve it in 20g of water, then add 4g of IrRuO x The catalyst and 50g of ethanol were thoroughly mixed to obtain the second anode catalyst layer slurry.

[0035] Preparation of S4 anode catalyst slurry The first catalyst slurry of the anode containing Pt / C catalyst is mixed with IrRuO x The second catalyst slurry at the anode of the / C catalyst, in accordance with Pt / C and IrRuO x The anode catalyst slurry was obtained by thoroughly mixing and dispersing the catalyst at a mass ratio of 75:20 / C.

[0036] Preparation of S5 cathode catalyst slurry Weigh 20g of anode Pt / C catalyst, 50g of perfluorosulfonic acid resin solution (mass fraction of 8.75%), 180g of water and 150g of ethanol and mix them evenly.

[0037] Preparation of S6 anti-reverse film electrode The anode and cathode catalyst slurries were coated on both sides of the proton exchange membrane, respectively. The platinum loading of the anode catalyst was 0.05 mg / cm³. 2 The platinum loading of the cathode catalyst is 0.03 mg / cm³. 2 Thus, an anti-reverse polarization film electrode was obtained.

[0038] Example 3 Preparation of S1 anode first catalyst slurry Weigh 30g of anode Pt / C catalyst, 40g of perfluorosulfonic acid resin solution (mass fraction 8.75%), 160g of water and 170g of ethanol and mix them evenly.

[0039] S2 IrRuO x Catalyst preparation Weigh 10g of chloroiridium acid (H₂IrCl₆) and 9g of ruthenium chloride (RuCl·3H₂O) into a beaker, and dissolve them completely in 40g of water. Weigh 50g of a well-dispersed graphitized carbon support solution (40% by mass), and ultrasonically mix it with the above solution. Pour the mixture into a three-necked flask and react for 4.5 hours at 70℃. After the reaction is complete, filter and dry to obtain IrRuO₂. x / C catalyst powder, x ranges from 1.8 to 2.2.

[0040] Preparation of S3 anode second catalyst slurry Weigh 0.6g of polymethacrylic acid sulfobetaine and dissolve it in 15g of water, then add 3.5g of IrRuO x / C catalyst and 30g ethanol are thoroughly mixed to obtain the second anode catalyst layer slurry.

[0041] Preparation of S4 anode catalyst slurry The first catalyst slurry of the anode containing Pt / C catalyst is mixed with IrRuO x The second catalyst slurry at the anode of the / C catalyst, in accordance with Pt / C and IrRuO x The anode catalyst slurry was obtained by thoroughly mixing and dispersing the catalyst at a mass ratio of 90:10 / C.

[0042] Preparation of S5 cathode catalyst slurry Weigh 30g of anode Pt / C catalyst, 40g of perfluorosulfonic acid resin solution (mass fraction of 8.75%), 160g of water and 170g of ethanol and mix them evenly.

[0043] Preparation of S6 anti-reverse film electrode The anode and cathode catalyst slurries were coated on both sides of the proton exchange membrane, respectively. The platinum loading of the anode catalyst was 0.04 mg / cm³. 2 The platinum loading of the cathode catalyst is 0.03 mg / cm³. 2 Thus, an anti-reverse polarization film electrode was obtained.

[0044] Comparative Example 1 Preparation of S1 anode first catalyst slurry Weigh 15g of anode Pt / C catalyst, 35g of perfluorosulfonic acid resin solution (mass fraction 8.75%), 200g of water and 150g of ethanol and mix them evenly.

[0045] S2 IrRuO x Catalyst preparation Weigh 10g of chloroiridium acid (H₂IrCl₆) and 10g of ruthenium chloride (RuCl·3H₂O) into a beaker, and dissolve them completely in 40g of water. Weigh 40g of a well-dispersed graphitized carbon support solution (40% by mass), and ultrasonically mix it with the above solution. Pour the mixture into a three-necked flask and react for 4 hours at 90℃. After the reaction is complete, filter and dry to obtain IrRuO₂. x / C catalyst powder, x ranges from 1.8 to 2.2.

[0046] Preparation of S3 anode second catalyst slurry Weigh out 4.5g of IrRuO x The catalyst C is thoroughly mixed with 40g of ethanol and 20g of water to obtain the second anode catalyst layer slurry.

[0047] Preparation of S4 anode catalyst slurry The first catalyst slurry of the anode containing Pt / C catalyst is mixed with IrRuO x The second catalyst slurry at the anode of the / C catalyst, in accordance with Pt / C and IrRuO x The anode catalyst slurry was obtained by thoroughly mixing and dispersing the catalyst at a mass ratio of 80:15 / C.

[0048] Preparation of S5 cathode catalyst slurry Weigh 15g of anode Pt / C catalyst, 35g of perfluorosulfonic acid resin solution (mass fraction of 8.75%), 200g of water and 150g of ethanol and mix them evenly.

[0049] Preparation of S6 anti-reverse film electrode The anode and cathode catalyst slurries were coated on both sides of the proton exchange membrane, respectively. The platinum loading of the anode catalyst was 0.05 mg / cm³. 2 The platinum loading of the cathode catalyst is 0.03 mg / cm³. 2 Thus, an anti-reverse polarization film electrode was obtained.

[0050] Test Analysis The membrane electrodes prepared in Examples 1-3 and Comparative Example 1 were subjected to reverse polarity tests, and the test results are as follows: Figure 1 As shown. The results indicate that the membrane electrodes prepared in Examples 1-3 exhibit excellent anti-reverse polarity time, proving the feasibility of the anti-reverse polarity membrane electrode preparation method provided by this invention; the innovative preparation method of this invention introduces IrRuO into the anode catalyst layer. x / C. The addition of polymethyl methacrylate sulfobetaine successfully constructed a cascade synergistic catalytic interface layer, providing strong anti-reverse polarity capability for the membrane electrode under complex operating conditions. It can work stably for a long time, effectively improving the anti-reverse polarity performance of the membrane electrode under complex operating conditions, providing strong support for the reliability and service life of fuel cells, and has significant practical application value and broad market promotion prospects.

[0051] Comparative Example 1 did not contain polymethacrylate sulfobetaine, although IrRuO2 was added. x The Pt / C catalyst exhibits excellent anti-reverse polarity, but the resulting membrane electrode exhibits a short anti-reverse polarity time and poor performance. The main reason is that the absence of polymethyl methacrylate sulfobetaine prevents the formation of a three-phase ladder interface, leading to poor catalyst dispersion and a disordered reaction pathway. This causes interference between the anti-reverse polarity reaction and the hydrogen reduction catalytic reaction, resulting in accelerated Pt / C corrosion and increased IrRuO₂ content. x The anti-reverse polarity activity of carbon cannot be fully utilized, which further leads to an increase in anodic potential, triggers water electrolysis reaction, significantly exacerbates the process of electrochemical carbon corrosion, and ultimately leads to a deterioration in the anti-reverse polarity effect.

[0052] For any parts not mentioned in the above embodiments, existing technologies can be adopted or referenced.

[0053] Of course, the above description is not intended to limit the present invention, and the present invention is not limited to the above embodiments. Any changes, modifications, additions or substitutions made by those skilled in the art within the scope of the present invention should be protected by the present invention.

Claims

1. A method for preparing an anti-reverse polarity film electrode, characterized in that, Includes the following steps: S1 mixes Pt / C catalyst, perfluorosulfonic acid resin solution, water and ethanol evenly to obtain the first anode catalyst slurry; S2 chloroiridic acid and ruthenium chloride trihydrate are added to water and dissolved thoroughly, then mixed with a solution of graphitized carbon carrier and reacted, after which the reaction is filtered and dried to obtain IrRuO x / C catalyst powder; S3. Polymethacrylate sulfobetaine is dissolved in water until fully dissolved, followed by the addition of IrRuO obtained in step S2. x / C catalyst and ethanol are mixed evenly to obtain the second catalyst slurry for the anode; S4. The first anode catalyst slurry obtained in step S1 is mixed evenly with the second anode catalyst slurry obtained in step S3 to obtain the anode catalyst slurry. S5 mixes Pt / C catalyst, perfluorosulfonic acid resin solution, water and ethanol evenly to obtain cathode catalyst slurry; S6 The anode catalyst slurry obtained in step S4 and the cathode catalyst slurry obtained in step S5 are respectively coated on the anode side and cathode side of the proton exchange membrane to obtain the anti-reverse electrode membrane.

2. The method for preparing an anti-reverse polarity film electrode according to claim 1, characterized in that, In step S1: the mass ratio of the Pt / C catalyst, perfluorosulfonic acid resin solution, water and ethanol is 15-30:35-50:160-200:150-170; the concentration of the perfluorosulfonic acid resin solution is 6%-10%.

3. The method for preparing an anti-reverse polarity film electrode according to claim 1, characterized in that, The platinum loading in the Pt / C catalysts is 40%-50%.

4. The method for preparing an anti-reverse polarity film electrode according to claim 1, characterized in that, In step S2: the mass ratio of chloroiridic acid, ruthenium chloride trihydrate, water and graphitized carbon carrier solution is 9-11:8-12:38-42:40-50; the concentration of graphitized carbon carrier solution is 35%-45%.

5. The method for preparing an anti-reverse polarity film electrode according to claim 1, characterized in that, In step S2: the reaction refers to the reaction at 70-90℃ for 3.5-4.5h.

6. The method for preparing an anti-reverse polarity film electrode according to claim 1, characterized in that, The IrRuO x In the / C catalyst, x = 1.8-2.

2.

7. The method for preparing an anti-reverse polarity film electrode according to claim 1, characterized in that, In step S3: IrRuO x The mass ratio of / C catalyst to polymethyl methacrylate sulfobetaine is 70-90:10-20.

8. The method for preparing an anti-reverse polarity film electrode according to claim 1, characterized in that, The Pt / C catalyst and IrRuO in the anode catalyst slurry x The mass ratio of the catalyst to the catalyst is 75-90:10-25.

9. The method for preparing an anti-reverse polarity film electrode according to claim 1, characterized in that, In step S6: the platinum loading on the anode side is 0.03-0.05 mg / cm³. 2 The platinum loading on the cathode side is 0.02-0.04 mg / cm³. 2 .

10. The application of the anti-reverse polarity film electrode prepared by the method of any one of claims 1-9 in the preparation of hydrogen fuel cells.

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