Method of making an ordered anode, ordered anode, and proton exchange membrane membrane electrode comprising the same

Abstract

The application discloses a preparation method of an ordered anode, the ordered anode and a proton exchange membrane membrane electrode comprising the same. The preparation method of the ordered anode comprises the following steps: modifying a titanium substrate by a deposition method or a sputtering method, and growing noble metal hemispherical cluster on the surface of the titanium substrate in an ordered manner at intervals to obtain a titanium substrate with modified noble metal cluster; and placing the titanium substrate with modified noble metal cluster in an iridium salt or ruthenium salt solution to perform an electrodeposition reaction, so that the oxide of iridium or the oxide of ruthenium is deposited on the noble metal cluster and the titanium substrate which is not modified by the noble metal cluster, thereby obtaining the ordered anode. The preparation method grows the noble metal hemispherical cluster on the surface of the titanium substrate, constructs an ordered substrate structure and increases the specific surface area of the substrate, then guides the oxide of iridium or the oxide of ruthenium to be deposited on the ordered substrate structure, forms a catalytic layer, effectively reduces the thickness of the catalytic layer, and improves the catalytic activity of the ordered anode.

Description

Technical Field

[0001] This invention relates to the field of electrode structure design technology, specifically to a method for preparing an ordered anode, the ordered anode, and a proton exchange membrane electrode containing the ordered anode. Background Technology

[0002] The oxygen evolution reaction (OER) plays a crucial role in the anode reactions of various electrochemical systems, such as water electrolysis for hydrogen production, rechargeable metal-air batteries, and renewable fuel cells. However, its relatively slow kinetics limit the potential for increased reaction efficiency. Proton exchange membrane electrolysis (PEMWE) technology offers advantages such as enabling water electrolysis at higher current densities and voltages, and producing hydrogen with higher purity, leading to its widespread research and application. However, the highly acidic and oxidizing environment near the anode places high demands on the catalysts selected for the OER.

[0003] Common improvement strategies include: 1) designing novel acidic catalysts; 2) controlling the morphology and form of the catalyst on the anode surface; and 3) establishing a dynamic equilibrium for catalyst conversion. Among these, controlling the morphology and form of the catalyst on the anode surface is considered a highly effective strategy. Currently, commonly used membrane electrode manufacturing processes include gas diffusion electrodes (GDE) and catalyst-coated membrane electrodes (CCM). The GDE process uses a gas diffusion layer as a substrate, directly coating the catalyst onto the gas diffusion layer, and then hot-pressing the GDE onto both sides of a proton exchange membrane to assemble the membrane electrode. This process results in a thicker catalyst layer, higher catalyst loading, and lower utilization. Furthermore, the contact between layers is not tight enough, leading to a higher interfacial resistance and lower overall membrane electrode performance. The CCM process is currently the more mainstream membrane electrode manufacturing process. Specifically, the CCM process coats the catalyst onto both sides of a proton exchange membrane, and then hot-presses the gas diffusion layer onto both sides of the CCM to assemble the membrane electrode. However, the CCM process produces membrane electrodes with poor catalyst layer stability, a complex manufacturing process, and still requires a relatively high loading of metallic iridium.

[0004] Therefore, there is an urgent need to find a new method that can reduce the dosage of the precious metal iridium and improve the utilization rate and stability of the catalyst. Summary of the Invention

[0005] To address the aforementioned technical problems, the present invention provides a method for preparing an ordered anode, an ordered anode, and a proton exchange membrane electrode comprising the same, in order to at least partially solve at least one of the aforementioned technical problems.

[0006] As an embodiment of one aspect of the present invention, a method for preparing an ordered anode is provided, comprising: modifying a titanium substrate by electroplating, chemical deposition or sputtering to grow noble metal hemispherical clusters at intervals on the surface of the titanium substrate to obtain a titanium substrate modified with noble metal clusters; placing the titanium substrate modified with noble metal clusters in an iridium salt or ruthenium salt solution to perform an electrodeposition reaction, so that iridium oxide or ruthenium oxide is deposited on the noble metal clusters and on the titanium substrate not modified with noble metal clusters to obtain an ordered anode.

[0007] According to some embodiments of the present invention, the noble metal includes platinum, gold, iridium, or ruthenium; the oxide of iridium includes: IrO. x Or IrO2; Ruthenium oxides include RuO2.

[0008] According to some embodiments of the present invention, before the ordered growth of noble metal clusters, the titanium substrate is pretreated, including: removing the oxide film attached to the surface of the crude titanium substrate by acid washing, followed by water washing and drying to obtain the titanium substrate.

[0009] According to some embodiments of the present invention, the orderly growth of noble metal hemispherical clusters on the surface of a titanium substrate by electroplating includes: using a titanium substrate as the working electrode, a crude titanium substrate as the counter electrode, and an SCE as the reference electrode, stirring the solution in a noble metal salt solution at a constant current of 5-15 mA for 3-10 min at 15-25°C to stably form noble metal hemispherical clusters; the noble metal salt includes: platinum salt, gold salt, iridium salt, or ruthenium salt.

[0010] According to some embodiments of the present invention, the electrodeposition reaction conditions are as follows: using a titanium substrate as the working electrode, a crude titanium substrate as the counter electrode, and an SCE as the reference electrode, at 15–25°C and 0.5–0.9V. SCE A constant voltage is applied to deposit iridium or ruthenium salt solutions for 8–12 min. The iridium salts include chloroiridium acid, iridium trichloride, or iridium tetrachloride; the ruthenium salts include ruthenium trichloride or ruthenium sulfate.

[0011] As another embodiment of the present invention, an ordered anode is provided, which is prepared by the preparation method described above.

[0012] As another embodiment of the present invention, a proton exchange membrane electrode is provided, comprising an ordered anode, a cathode and a proton exchange membrane located between the ordered anode and the cathode as described above; the ordered anode, the proton exchange membrane and the cathode are assembled by hot pressing.

[0013] According to some embodiments of the present invention, the cathode is prepared by the following method: ultrasonic homogenization of cathode ink containing Pt / C powder, wherein the ultrasonic frequency is 10-60 kHz and the ultrasonic time is 10-60 min; and the homogenized cathode ink is coated on carbon paper to obtain the cathode.

[0014] According to some embodiments of the present invention, the loading amount of Pt / C powder on carbon paper is 0.1–2 mg / cm³. 2 .

[0015] According to some embodiments of the present invention, the hot pressing temperature is 100-180°C, the hot pressing pressure is 390-450 psi, and the hot pressing time is 1-10 min.

[0016] Based on the above embodiments of the present invention, an ordered anode preparation method, an ordered anode, and a proton exchange membrane electrode containing the same are disclosed. The present invention involves the ordered growth of noble metal particles at intervals on the surface of a titanium substrate. Under the action of internal stress between the noble metal particles, the particles form stable hemispherical clusters, which constitute a modification layer. This further expands the specific surface area of ​​the titanium substrate and increases the specific surface area of ​​the iridium oxide or ruthenium oxide used as catalysts. This allows for high catalytic activity while reducing the loading of iridium oxide or ruthenium oxide, thereby improving the catalytic efficiency of the catalyst. The ordered anode constructed by the present invention, due to the ordered and uniform arrangement of the catalyst, provides pathways for electron and mass transport, significantly reducing mass transfer resistance and ohmic impedance, thus promoting higher catalytic activity. The ordered anode constructed by the present invention has a low electrode interface resistance, exhibiting good catalytic performance, good stability, and a long service life. Attached Figure Description

[0017] The present invention will be further described in detail below with reference to the accompanying drawings.

[0018] Figure 1 This is a flowchart of a method for preparing an ordered anode according to an embodiment of the present invention;

[0019] Figure 2 This is a schematic diagram of the surface microstructure of an ordered anode according to an embodiment of the present invention;

[0020] Figure 3 This is a schematic diagram of the proton exchange membrane electrode assembly process according to an embodiment of the present invention;

[0021] Figure 4 Histogram of platinum cluster size distribution after 15 minutes of chemical deposition on the ordered anode according to Example 1 of the present invention; and

[0022] Figure 5 This is a comparison chart of the electrochemical performance of different loaded electrodes according to Example 1 of the present invention.

[0023] [Explanation of Labels in the Attached Image]

[0024] 1- Noble metal clusters;

[0025] Oxides of 2-iridium or oxides of ruthenium;

[0026] 3-Proton exchange membrane;

[0027] 4-Gas diffusion layer;

[0028] 5-Ordered anode;

[0029] 6-Cathode;

[0030] 7-Septum;

[0031] 8-Proton exchange membrane electrode;

[0032] A-Hot pressing treatment. Detailed Implementation

[0033] In the process of realizing this invention, it was discovered that by coating the catalyst onto an ordered nanostructure, the electrode can exhibit an ordered structure, which can further reduce the catalyst loading and reduce the mass transfer resistance.

[0034] In view of this, the present invention proposes a method for preparing an ordered anode, an ordered anode and a proton exchange membrane electrode containing the ordered anode. First, an ordered substrate structure is constructed by modifying the surface of a titanium substrate, and then a catalyst is guided to grow on the ordered substrate to prepare an ordered anode. This method can improve the catalytic activity of the ordered anode while reducing the thickness of the catalyst layer and the catalyst loading.

[0035] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below with reference to specific embodiments and accompanying drawings.

[0036] However, it should be understood that these descriptions are exemplary only and are not intended to limit the scope of the invention. In the following detailed description, numerous specific details are set forth to provide a thorough understanding of the embodiments of the invention for ease of explanation. However, it will be apparent that one or more embodiments may be practiced without these specific details. Furthermore, descriptions of well-known technologies are omitted in the following description to avoid unnecessarily obscuring the concepts of this application.

[0037] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. The term "comprising" as used herein indicates the presence of features, steps, or operations, but does not exclude the presence or addition of one or more other features.

[0038] When using expressions such as "at least one of A, B, and C," the expression should generally be interpreted in accordance with the meaning commonly understood by a person skilled in the art (e.g., "a system having at least one of A, B, and C" should include, but is not limited to, systems having A alone, having B alone, having C alone, having A and B, having A and C, having B and C, and / or having A, B, and C, etc.). Similarly, when using expressions such as "at least one of A, B, or C," the expression should generally be interpreted in accordance with the meaning commonly understood by a person skilled in the art (e.g., "a system having at least one of A, B, or C" should include, but is not limited to, systems having A alone, having B alone, having C alone, having A and B, having A and C, having B and C, and / or having A, B, and C, etc.).

[0039] All terms used herein (including technical and scientific terms) have the meanings commonly understood by those skilled in the art, unless otherwise defined. It should be noted that the terms used herein are to be interpreted in a manner consistent with the context of this specification, and not in an idealized or overly rigid way.

[0040] Figure 1 This is a flowchart of a method for preparing an ordered anode according to an embodiment of the present invention. Figure 2 This is a schematic diagram of the surface microstructure of an ordered anode according to an embodiment of the present invention.

[0041] According to some embodiments of the present invention, the present invention provides a method for preparing an ordered anode, referring to... Figures 1-2 As shown, it includes steps S101 to S102.

[0042] In step S101, the titanium substrate is modified by electroplating, chemical deposition or sputtering to grow noble metal hemispherical clusters at intervals on the surface of the titanium substrate, thereby obtaining a titanium substrate modified with noble metal clusters 1.

[0043] In step S102, the titanium substrate modified with noble metal cluster 1 is placed in an iridium salt or ruthenium salt solution to perform an electrodeposition reaction, so that iridium oxide or ruthenium oxide 2 is deposited on the noble metal cluster 1 and on the titanium substrate not modified with noble metal cluster 1, thereby obtaining an ordered anode.

[0044] According to some embodiments of the present invention, by orderly growing noble metal particles at intervals on the surface of a titanium substrate, the noble metal particles can form stable hemispherical clusters under the action of mutual internal stress between the particles. These hemispherical clusters are referred to as noble metal cluster 1. This increases the specific surface area of ​​the titanium substrate and enhances the specific surface area of ​​the iridium oxide or ruthenium oxide 2 used as a catalyst. This allows for higher catalytic activity while reducing the loading of iridium oxide or ruthenium oxide 2, thereby improving the catalytic efficiency of the catalyst. The catalyst in the ordered anode constructed in this invention is also uniformly arranged in an ordered manner, providing pathways for electron and mass transport, significantly reducing mass transfer resistance and ohmic impedance, and further contributing to higher catalytic activity.

[0045] According to some embodiments of the present invention, the noble metal includes platinum, gold, iridium, or ruthenium; the oxide of iridium includes: IrO. x Or IrO2; ruthenium oxides include RuO2. When platinum, gold, iridium, or ruthenium are ordered and grown as noble metal clusters 1, noble metal clusters 1 can significantly improve the catalytic activity of the titanium substrate and promote the anodic oxidation reaction. Using noble metal clusters 1 can provide good electrochemical active sites, which is beneficial for reducing the reaction initiation voltage and increasing the reaction rate, thereby improving the efficiency of the anodic oxidation process. Noble metal clusters 1 can effectively improve the surface conductivity of the titanium substrate. In the preparation of ordered anodes, good surface conductivity can accelerate the charge transfer reaction and improve the efficiency of subsequent anodic oxidation processes. In addition, using noble metal clusters 1 can regulate the size and morphology of the grain growth of subsequent iridium oxide or ruthenium oxide 2 catalysts, which is beneficial for the orderly and uniform arrangement of catalysts on both the noble metal clusters 1 and the unmodified titanium substrate.

[0046] It should be noted that in the iridium catalyst used in this invention, IrO x is amorphous iridium oxide, where x has no specifically defined value.

[0047] According to some embodiments of the present invention, before the ordered growth of noble metal clusters 1, the titanium substrate is pretreated, including: removing the oxide film adhering to the surface of the crude titanium substrate by acid washing, followed by water washing and drying to obtain the titanium substrate. During processing and transportation, the crude titanium substrate may react with atmospheric oxygen, and this oxide film may contain impurities and contaminants, interfering with the oxidation reaction in the subsequent ordered anode preparation process and affecting the quality and performance of the subsequent catalyst. Acid washing can form a clean titanium substrate surface, thereby improving the efficiency of the subsequent anodic oxidation reaction.

[0048] According to some embodiments of the present invention, the orderly growth of noble metal hemispherical clusters on the surface of a titanium substrate by electroplating includes: using the titanium substrate as the working electrode, using a crude titanium substrate as the counter electrode, and using SCE as the reference electrode, under conditions of 15–25°C, for example, 15°C, 16°C, 17°C, 18°C, 19°C, 20°C, 21°C, 22°C, 23°C, 24°C, or 25°C, but not limited thereto. A constant current of 5–15 mA is used, for example, 5 mA, 6 mA, 7 mA, 8 mA, 9 mA, 10 mA, 11 mA, 12 mA, 13 mA, 14 mA, or 15 mA, but not limited thereto. The solution is stirred in a noble metal salt solution for 3–10 min, for example, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, or 10 min, but not limited to these, to stably form noble metal clusters 1. The noble metal salts include platinum salts, gold salts, iridium salts, or ruthenium salts. A titanium substrate is used as the working electrode, which is the primary electrode for the electrochemical reaction. The titanium substrate provides the reaction site and can directly react with the chemical substances in the reaction solution. The surface state and material of the titanium substrate directly affect the reaction process and results. A crude titanium substrate is used as the counter electrode to provide a current relative to the titanium substrate, maintaining the electroneutrality of the reaction solution. A saturated calomel solution (SCE) is used as the reference electrode to provide a stable standard potential reference. The potential on the titanium substrate is determined by the potential difference between the reference electrode and the titanium substrate. The SCE includes a saturated calomel solution, and a stable potential is maintained by the potential of the calomel-calomel ion system in the saturated calomel solution. Using a constant current provides greater stability, resulting in a more uniform morphology after deposition, which is more conducive to the formation of ordered noble metal clusters 1.

[0049] According to some embodiments of the present invention, the electrodeposition reaction conditions are as follows: using a titanium substrate as the working electrode, a crude titanium substrate as the counter electrode, and an SCE as the reference electrode, at a temperature of 15–25°C, for example, 15°C, 16°C, 17°C, 18°C, 19°C, 20°C, 21°C, 22°C, 23°C, 24°C, or 25°C, but not limited thereto. The voltage is 0.5–0.9V. SCE A constant voltage, for example, could be 0.5V. SCE 0.6V SCE 0.7V SCE 0.8V SCE or 0.9V SCE However, this is not a limitation. Deposition treatment in iridium or ruthenium salt solutions for 8–12 minutes, for example, 8 min, 9 min, 10 min, 11 min, or 12 min, is not limited to this. Iridium salts include chloroiridium acid, iridium trichloride, or iridium tetrachloride; ruthenium salts include ruthenium trichloride or ruthenium sulfate.

[0050] According to another aspect of the present invention, the present invention also provides an ordered anode, which is prepared by the preparation method described above.

[0051] According to some embodiments of the present invention, the ordered anode constructed by the present invention has a low electrode interface resistance, and can exhibit good catalytic performance while having good stability and a long service life.

[0052] According to another embodiment of the present invention, a proton exchange membrane electrode 8 is also provided, comprising an ordered anode 5, a cathode 6 as described above, and a proton exchange membrane 3 located between the ordered anode 5 and the cathode 6. The ordered anode 5, the proton exchange membrane 3, and the cathode 6 are assembled by a hot-pressing process A.

[0053] Figure 3 This is a schematic diagram of the proton exchange membrane electrode assembly process according to an embodiment of the present invention. Figure 3 As shown, the ordered anode 5, proton exchange membrane 3, gas diffusion layer 4, diaphragm 7 and cathode 6 are assembled into a "sandwich" structure proton exchange membrane electrode 8 by hot pressing A. In use, it can exhibit high catalytic activity and long life when the loading of iridium oxide or ruthenium oxide 2 is low, which is beneficial to its superior performance in subsequent proton exchange membrane water electrolysis cells and renewable fuel cells.

[0054] According to some embodiments of the present invention, the cathode 6 is prepared by the following method: ultrasonic homogenization of cathode ink containing Pt / C powder, wherein the ultrasonic frequency is 10-60 kHz and the ultrasonic time is 10-60 min; the homogenized cathode ink is coated on carbon paper to obtain the cathode 6.

[0055] According to some embodiments of the present invention, the ultrasonic frequency may be, for example, 10 kHz, 20 kHz, 30 kHz, 40 kHz, 50 kHz or 60 kHz, but is not limited thereto. The ultrasonic duration may be, for example, 10 min, 20 min, 30 min, 40 min, 50 min or 60 min, but is not limited thereto.

[0056] According to some embodiments of the present invention, the loading amount of Pt / C powder on carbon paper is 0.1–2 mg / cm³. 2 For example, it can be 0.1 mg / cm³ 2 0.5 mg / cm 2 1mg / cm 2 1.5 mg / cm 2 or 2mg / cm 2 However, this is not the limit.

[0057] According to some embodiments of the present invention, the temperature of hot pressing treatment A is 100-180°C, the pressure of hot pressing treatment is 390-450 psi, and the time of hot pressing treatment A is 1-10 min.

[0058] According to some embodiments of the present invention, the temperature of hot pressing A can be, for example, 100°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, or 180°C, but is not limited thereto. The pressure of hot pressing A can be, for example, 390 psi, 400 psi, 410 psi, 420 psi, 430 psi, 440 psi, or 450 psi, but is not limited thereto. The hot pressing time can be, for example, 1 min, 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, or 10 min, but is not limited thereto.

[0059] The present invention will be further illustrated below by way of comparative examples, embodiments, accompanying drawings, and related test experiments and results. In the following detailed description, numerous specific details are set forth to provide a comprehensive understanding of the embodiments of the invention for ease of explanation. However, it will be apparent that one or more embodiments may be practiced without these specific details. Moreover, the details in the following embodiments can be arbitrarily combined to form other feasible embodiments without conflict.

[0060] It should be noted that the specific embodiments described below are merely illustrative examples, and the scope of protection of this invention is not limited thereto. The chemicals and raw materials used in the following embodiments are analytical grade, commercially available conventional chemicals, and do not require further processing.

[0061] Example 1

[0062] A chloroplatinic acid solution was prepared and magnetically stirred for 24 hours to ensure homogeneity. An Ir precursor solution was prepared and magnetically stirred for 72 hours to ensure homogeneity. Titanium felt was used as the anode substrate, first acid-washed and then rinsed thoroughly with deionized water. The acid-washed titanium felt was used as the working electrode, the untreated crude Ti felt as the counter electrode, and SCE as the reference electrode. Electrodeposition was performed at room temperature with a constant current of 10 mA for 5 minutes while maintaining continuous stirring. After deposition, the electrodepositor was rinsed with deionized water and then immersed in the Ir precursor solution. Electrodeposition was then carried out at room temperature with a voltage of 0.7 V. SCE A constant voltage was applied for 10 minutes, and after deposition, the anode was rinsed with deionized water to complete the preparation process of the ordered anode.

[0063] The current density and the loading of platinum and iridium oxides were tested for electrodeposition treatments of different durations, and the test results are shown in Table 1 below.

[0064] Table 1. Current density test results of anodes with different electrodeposition durations and loading of platinum and iridium oxides.

[0065]

[0066] As shown in Table 1, with the extension of deposition time, the deposition rate is relatively faster, and there are more nucleation sites. Therefore, the loading of platinum and iridium dioxide both increase, and the total loading also shows an upward trend. However, when the deposition time exceeds 12 minutes, the loading of platinum does not increase further. This is because platinum clusters do not grow indefinitely. Figure 4 This is a histogram showing the platinum cluster size distribution after 15 minutes of chemical deposition using the ordered anode according to Example 1 of the present invention. Figure 4 As shown, this verifies that platinum clusters will not grow further after reaching a certain radius.

[0067] Pt / C powder was formulated as cathode ink, which was then ultrasonically homogenized at 40 kHz for 30 min. The homogenized ink was then uniformly coated onto carbon paper, with the Pt / C loading controlled at 0.4 mg / cm³. 2 This completes the cathode preparation process.

[0068] The anode, proton exchange membrane, and cathode are arranged in sequence and subjected to hot pressing at 110°C and 395 psi. After 1 minute, they are allowed to cool naturally to complete the assembly of the membrane electrode.

[0069] The loading of iridium dioxide was tested on the platinum anodes deposited in Example 1, as well as on the anodes coated with iridium dioxide using the CCM process and the anodes deposited directly on the titanium felt. Figure 5 This is a comparison graph showing the electrochemical performance of different loaded electrodes according to Example 1 of the present invention. Figure 5 As shown, when coating iridium dioxide using the CCM process, the amount of iridium used is relatively the highest, at 0.347 mg, and the current density of the resulting membrane electrode is relatively low. However, when depositing iridium dioxide on platinum using the method of the present invention, the amount of iridium used is relatively smaller, and the current density of the resulting membrane electrode is relatively higher, indicating that the membrane electrode obtained by the preparation method of the present invention has the best performance.

[0070] Example 2

[0071] An Au precursor solution was prepared and magnetically stirred for 24 hours to ensure homogeneity. An Ir precursor solution was prepared and magnetically stirred for 72 hours to ensure homogeneity. Ti felt was used as the anode substrate, acid-washed, and then rinsed thoroughly with deionized water. The acid-washed titanium felt was used as the working electrode, the untreated crude Ti felt as the counter electrode, and SCE as the reference electrode. Electrodeposition was performed at room temperature with a constant current of 10 mA for 5 minutes while maintaining continuous stirring. After deposition, the electrodepositor was rinsed with deionized water and then immersed in the Ir precursor solution. Electrodeposition was then carried out at room temperature with a voltage of 0.7 V. SCE A constant voltage was applied for 10 minutes, and after deposition, the anode was rinsed with deionized water to complete the preparation process of the ordered anode.

[0072] Pt / C powder was formulated as cathode ink, which was then ultrasonically homogenized at 40 kHz for 30 min. The homogenized ink was then uniformly coated onto carbon paper, with the Pt / C loading controlled at 0.45 mg / cm³. 2 This completes the cathode preparation process.

[0073] The anode, proton exchange membrane, and cathode are arranged in sequence and hot-pressed at 115°C and 390 psi. After 1 minute, they are allowed to cool naturally to complete the assembly of the membrane electrode.

[0074] Example 3

[0075] A chloroplatinic acid solution was prepared and magnetically stirred for 24 hours to ensure homogeneity. A Ru precursor solution was prepared and magnetically stirred for 72 hours to ensure homogeneity. Titanium felt was used as the anode substrate, first acid-washed and then rinsed with deionized water. The acid-washed titanium felt was used as the working electrode, the untreated crude Ti felt as the counter electrode, and SCE as the reference electrode. Electrodeposition was performed at room temperature with a constant current of 10 mA for 5 minutes while maintaining continuous stirring. After deposition, the electrodepositor was rinsed with deionized water and then immersed in the Ru precursor solution. Electrodeposition was then carried out at room temperature with a voltage of 0.7 V. SCE A constant voltage was applied for 10 minutes, and after deposition, the anode was rinsed with deionized water to complete the preparation process of the ordered anode.

[0076] Pt / C powder was formulated as cathode ink, which was then ultrasonically homogenized at 40 kHz for 30 min. The homogenized ink was then uniformly coated onto carbon paper, with the Pt / C loading controlled at 0.5 mg / cm³. 2 This completes the cathode preparation process.

[0077] The anode, proton exchange membrane, and cathode are arranged in sequence and subjected to hot pressing at 120°C and 400 psi. After 1 minute, they are allowed to cool naturally to complete the assembly of the membrane electrode.

[0078] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing an ordered anode, comprising: A titanium substrate is modified by electroplating, and noble metal hemispherical clusters are grown at intervals and in an orderly manner on the surface of the titanium substrate to obtain a titanium substrate modified with noble metal clusters. as well as The titanium substrate modified with noble metal clusters is placed in an iridium salt or ruthenium salt solution and an electrodeposition reaction is performed, so that iridium oxide or ruthenium oxide is deposited on the noble metal clusters and on the titanium substrate not modified with noble metal clusters, thereby obtaining the ordered anode; Before the ordered growth of noble metal clusters, the titanium substrate is pretreated, including: removing the oxide film attached to the surface of the crude titanium substrate by acid pickling, followed by water washing and drying to obtain the titanium substrate. The orderly growth of noble metal hemispherical clusters on the surface of a titanium substrate by electroplating includes: Using a titanium substrate as the working electrode, a crude titanium substrate as the counter electrode, and an SCE as the reference electrode, the noble metal salt solution is stirred for 3-10 minutes at a constant current of 5-15 mA under conditions of 15-25°C to stably form the noble metal hemispherical clusters; wherein the noble metal salt includes: platinum salt, gold salt, iridium salt, or ruthenium salt.

2. The preparation method according to claim 1, wherein, The precious metals include platinum, gold, iridium, or ruthenium; The iridium oxide includes: IrO x Or IrO2; The oxides of ruthenium include RuO2.

3. The preparation method according to claim 1, wherein, The conditions for the electrodeposition reaction are as follows: Using a titanium substrate as the working electrode, a crude titanium substrate as the counter electrode, and SCE as the reference electrode, the electrode was applied at 15–25 °C with a voltage of 0.5–0.9 V. SCE A constant voltage is applied to deposit iridium or ruthenium salt solutions for 8-12 minutes, wherein the iridium salt includes chloroiridium acid, iridium trichloride, or iridium tetrachloride; and the ruthenium salt includes ruthenium trichloride or ruthenium sulfate.

4. An ordered anode, prepared by the preparation method according to any one of claims 1 to 3.

5. A proton exchange membrane electrode, comprising an ordered anode, a cathode, and a proton exchange membrane located between the ordered anode and the cathode as described in claim 4; wherein, The ordered anode, the proton exchange membrane, and the cathode are assembled by hot pressing.

6. The proton exchange membrane electrode according to claim 5, wherein, The cathode is prepared by the following method: The cathode ink containing Pt / C powder was homogenized by ultrasonication, wherein the ultrasonic frequency was 10~60kHz and the ultrasonic time was 10~60min. The homogenized cathode ink is coated onto carbon paper to obtain the cathode.

7. The proton exchange membrane electrode according to claim 6, wherein, The loading amount of Pt / C powder on the carbon paper is 0.1~2 mg / cm³. 2 .

8. The proton exchange membrane electrode according to claim 5, wherein, The hot pressing treatment is performed at a temperature of 100~180℃, at a pressure of 390~450psi, and for a time of 1~10min.

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