Preparation method and application of fullerene-modified iridium-based composite coating titanium electrode

Abstract

This invention discloses a method for preparing and applying a fullerene-modified iridium-based composite coated titanium electrode, belonging to the field of titanium electrode preparation technology. The preparation method includes: pretreating the surface of a titanium substrate; completely dissolving an iridium source in an organic solvent, then adding a tantalum source and a titanium source and dissolving them completely; ultrasonically dispersing a fullerene in an organic solvent and adding it to the above solution, stirring until homogeneous to obtain an active liquid of fullerene-modified iridium-tantalum titanium oxide; brushing the prepared active liquid onto the pretreated titanium substrate surface, drying and sintering, then removing and cooling to room temperature; repeating the brushing, drying, and sintering process until all the active liquid is applied. This invention introduces fullerene, a zero-dimensional carbon material with excellent conductivity and corrosion resistance, to construct a highly efficient three-dimensional conductive network, improving catalytic reaction efficiency and the physical and chemical stability of the electrode under strong acid and strong oxidation conditions, thus significantly extending the electrode's lifespan.

Description

Technical Field

[0001] This invention belongs to the field of titanium electrode preparation technology, specifically relating to a method for preparing and applying a fullerene-modified iridium-based composite coated titanium electrode. Background Technology

[0002] In today's rapidly developing electronics and information industry, electrolytic copper foil is often referred to as the "neural network" for signal and power transmission and communication in electronic products. With the rapid development of emerging industries such as 5G communications, new energy vehicles, and artificial intelligence, the demand for high-performance copper foil is constantly increasing. Especially in the fields of lithium batteries, copper-clad laminates, and printed circuit boards, electrolytic copper foil, as a key material, enjoys strong market demand. Iridium-based coated titanium anodes, due to their excellent electrochemical activity and stability, are currently widely used in the field of electrolytic copper foil.

[0003] However, in an acidic oxygen evolution environment, the anode is subject to severe acid corrosion and the strong oxidizing properties of oxygen evolution, making it prone to loss. This loss manifests primarily as the dissolution of the anode surface active material, coating peeling, and passivation of the titanium substrate. Furthermore, the preparation of high-performance electrolytic copper foil inevitably requires a significant increase in the amount of organic additives used, which poses a considerable challenge to the stability of the titanium anode.

[0004] In view of this, the present invention is hereby proposed. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a method for preparing and applying a fullerene-modified iridium-based composite coated titanium electrode to improve the corrosion resistance of titanium electrodes.

[0006] To achieve the above objectives, the present invention provides the following technical solution: The preparation method of this fullerene-modified iridium-based composite coated titanium electrode, such as... Figure 1 As shown, the specific steps include: Step 1: Pre-treat the surface of the titanium substrate; Step 2: Dissolve the iridium source completely in organic solvent a, then add the tantalum source and titanium source. After complete dissolution, obtain iridium-tantalum-titanium oxide active liquid A; disperse the fullerene powder in organic solvent b to obtain a fullerene dispersion; add the fullerene dispersion to iridium-tantalum-titanium oxide active liquid A, stir evenly, and obtain fullerene-modified iridium-tantalum-titanium oxide active liquid B. Step 3: Apply the fullerene-modified iridium-tantalum titanium oxide active liquid B from Step 2 to the surface of the titanium substrate after pretreatment in Step 1, dry and sinter it, and then remove it and let it cool naturally to room temperature; repeat the above coating, drying and sintering process steps until all the fullerene-modified iridium-tantalum titanium oxide active liquid B is coated to obtain the target coated titanium electrode.

[0007] Specifically, the size of the titanium substrate in step 1 can be selected according to the actual application requirements of the electrode.

[0008] Specifically, the target coated titanium electrode obtained in step 3 is a fullerene-modified iridium-based composite coated titanium electrode, and more specifically, a fullerene-modified iridium-tantalum-titanium composite coated titanium electrode.

[0009] Furthermore, the concentration of the fullerene dispersion in step 2 is 0.3~0.6 g / L, and the fullerene dispersion accounts for 5~10% of the total volume of the fullerene-modified iridium-tantalum titanium oxide active liquid B.

[0010] Furthermore, in step 2, the molar ratio of Ir, Ta and Ti in the iridium-tantalum-titanium oxide active solution A is (5.5~6.5):3:(0.5~1.5), and the total metal ion concentration is 0.2~0.3 mol / L.

[0011] Specifically, the total volume of the fullerene-modified iridium-tantalum titanium oxide active liquid B in step 2 can be determined according to the specific process requirements for the metal ion loading on the titanium electrode surface.

[0012] Furthermore, in step 2, organic solvents a and b are combinations of two or more of n-butanol, isopropanol, ethylene glycol, and ethanol.

[0013] Furthermore, in step 3, the drying temperature is 80~120℃, the drying time is 5~10min each time, the sintering temperature is 450~550℃, and the sintering time is 10~20min each time.

[0014] Furthermore, after the final application of the fullerene-modified iridium-tantalum titanium oxide active liquid B in step 3, the sintering time is 60~120 min.

[0015] Furthermore, the pretreatment steps in step 1 include cutting, sandblasting, pickling, rinsing, and air drying.

[0016] Specifically, pickling involves acid etching with a 10%~15% oxalic acid solution at a slight boiling state for 120~180 minutes.

[0017] Specifically, in step 2, the iridium source in the iridium-tantalum-titanium oxide active solution A is H2IrCl6·6H2O, the tantalum source is TaCl5, and the titanium source is tetrabutyl titanate.

[0018] Furthermore, the present invention also provides the application of titanium electrodes prepared by some or all of the preparation methods described above in the field of preparing electrolytic copper foil.

[0019] Compared with the prior art, the technical solution provided by the present invention has the following beneficial effects: 1. Based on the existing IrO2-Ta2O5 binary coating system, this invention introduces TiO2 as a third catalytic component. The incorporation of TiO2 can form a solid solution with IrO2, causing lattice expansion, stabilizing the crystal structure, and reducing the aggregation and loss of active components. TiO2 alters the internal stress and cracking behavior of the coating during the thermal decomposition preparation process, making the coating's unique "mud crack" microcrack network finer and more uniform, which can both increase the active area and slow down the direct penetration of the electrolyte into the substrate. The composite of TiO2 (n-type semiconductor), IrO2 (metal conductor), and Ta2O5 (insulator) forms an IrO2-Ta2O5-TiO2 ternary coating system, which can optimize the overall electronic conduction path of the coating and reduce charge transfer resistance. The above synergistic effects make the titanium electrode coating system more resistant to passivation and extend its lifespan, especially under harsh high-current environments.

[0020] 2. In this invention, fullerenes are used as zero-dimensional carbon materials to modify iridium-tantalum-titanium coatings (IrO2-Ta2O5-TiO2 ternary coating system). A small amount of fullerene is uniformly dispersed in the precursor solution to form a fullerene-IrO2-Ta2O5-TiO2 quaternary coating system, which is then coated onto the surface of a titanium substrate. The excellent electron affinity and strong metal-support interaction of fullerenes improve the durability of the electrode. Fullerenes possess a unique cage-like structure, and their carbon cage structure exhibits excellent chemical stability in acidic environments. When combined with metals such as iridium, tantalum, and titanium, they can act as "electron buffers," isolating and stabilizing metal oxide particles and delaying their aggregation and deactivation. Simultaneously, they can stabilize the valence state of surrounding metal species, reducing the excessive oxidation and dissolution of high-valence active components, thereby enhancing electrocatalytic activity.

[0021] 3. This invention constructs high-speed electron channels using fullerenes. Fullerenes possess excellent electron affinity and transport properties, enabling the creation of additional fast electron transport networks within the coating and optimizing charge transfer efficiency. Furthermore, the small amount of fullerene added in this invention serves only as an electron carrier modification; therefore, commercially available fullerene nanopowder can be directly used by dispersing it in an organic solvent. This reduces preparation steps while ensuring performance, facilitating industrialization.

[0022] In summary, fullerene-IrO 2- The Ta2O5-TiO2 quaternary coating system can further improve the overall performance of titanium electrodes, exhibiting higher electrochemical stability under harsh conditions (strong acid, high current, high dosage of organic additives), significantly extending service life, and reducing production costs. Attached Figure Description

[0023] The accompanying drawings are incorporated in and form part of this specification, and together with the description serve to explain the principles of the invention.

[0024] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, for those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0025] Figure 1 A flowchart illustrating the preparation method of a fullerene-modified iridium-based composite coated titanium electrode provided by this invention; Figure 2 A scanning electron microscope image of the fullerene-modified iridium-based composite coated titanium electrode provided in Example 1 of the present invention; Figure 3 A scanning electron microscope image of the fullerene-modified iridium-based composite coated titanium electrode provided in Example 2 of the present invention; Figure 4 A scanning electron microscope image of the fullerene-modified iridium-based composite coated titanium electrode provided in Embodiment 3 of the present invention; Figure 5 A scanning electron microscope image of the fullerene-modified iridium-based composite coated titanium electrode provided in Example 4 of the present invention; Figure 6 Scanning electron microscope image of an iridium-based composite coated titanium electrode provided for comparison; Figure 7 This is a comparison chart of the enhanced life test results of the samples prepared in Examples 1-4 and the comparative examples of the present invention. Detailed Implementation

[0026] Exemplary embodiments will now be described in detail. The embodiments described below are not representative of all embodiments consistent with this invention. Rather, they are merely examples consistent with some aspects of the invention as detailed in the appended claims.

[0027] This invention provides a method for preparing a fullerene-modified iridium-based composite coated titanium electrode, the method comprising: Step 1: Pretreatment of the titanium substrate surface: Select a titanium sheet as the substrate. The pretreatment includes cutting, sandblasting, acid pickling, rinsing, and natural drying. Through this series of pretreatments, a rough, clean, and highly active titanium substrate is finally obtained, laying the foundation for subsequent coating and sintering. Acid pickling refers to acid etching with a 10%~15% oxalic acid solution under a slightly boiling state for 120~180 minutes.

[0028] Step 2, Preparation of the active solution: Add the iridium source (H₂IrCl₆·6H₂O) to organic solvent a (a combination of two or more of n-butanol, isopropanol, ethylene glycol, and ethanol), and stir for 30-60 minutes until completely dissolved. Then add the tantalum source (TaCl₅) and the titanium source (tetrabutyl titanate), and stir again for 30-60 minutes until completely dissolved to obtain an iridium-tantalum-titanium oxide active solution A with a total metal ion concentration of 0.2-0.3 mol / L, wherein the molar ratio of Ir, Ta, and Ti is (5.5-6.5):3:( 0.5~1.5); Add fullerene powder to organic solvent b (a combination of two or more of n-butanol, isopropanol, ethylene glycol, and ethanol), and disperse it uniformly by ultrasonication for 30~60 min to obtain a fullerene dispersion with a concentration of 0.3~0.6 g / L; Add the fullerene dispersion to iridium tantalum titanium oxide active liquid A, so that the fullerene dispersion accounts for 5~10% of the total volume of the final fullerene-modified iridium tantalum titanium oxide active liquid B, and stir for 30~60 min to mix evenly to obtain fullerene-modified iridium tantalum titanium oxide active liquid B.

[0029] Step 3, coating, drying and sintering: The fullerene-modified iridium-tantalum titanium oxide active liquid B prepared in Step 2 is uniformly coated onto the surface of the titanium substrate after the pretreatment in Step 1. After drying at 80~120℃ for 5~10 min, it is sintered at 450~550℃ for 10~20 min. The above coating process is repeated until all the active liquid is coated. After the last coating of fullerene-modified iridium-tantalum titanium oxide active liquid B, the sintering time is 60~120 min. Then it is taken out and naturally cooled to room temperature to obtain the fullerene-modified iridium-based composite coated titanium electrode.

[0030] The fullerene-modified iridium-based composite coated titanium electrode prepared in this invention is mainly used as the anode in the production of electrolytic copper foil.

[0031] To enable those skilled in the art to better understand the technical solutions of the present invention, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments.

[0032] Example 1 This embodiment provides a method for preparing a fullerene-modified iridium-based composite coated titanium electrode, specifically including the following steps: Step 1: Pre-treatment of the titanium substrate surface: Select a 10cm×10cm titanium sheet as the substrate. The surface pre-treatment of the titanium substrate includes cutting, sandblasting, acid pickling, rinsing, and natural drying. Among them, acid pickling is carried out by acid etching with a 15% oxalic acid solution under a slight boiling state for 120 minutes.

[0033] Step 2, Preparation of active solution: Using a pipette, transfer 5 mL of n-butanol and 5 mL of isopropanol separately, mix them, and stir evenly on a magnetic stirrer to obtain organic solvent a. Prepare a solution with a total metal ion concentration of 0.2 mol / L and a molar ratio of Ir, Ta, and Ti of 5.5:3:1.5. Add H₂IrCl₆·6H₂O to organic solvent a and stir on a magnetic stirrer for 30 min until completely dissolved. Then add TaCl₅ and tetrabutyl titanate, and stir again for 30 min until completely dissolved to obtain iridium-tantalum-titanium oxide active solution A. Prepare a solution with a fullerene concentration of 0.3 g / L. Add fullerene powder to organic solvent b (a mixture of ethanol and isopropanol), and disperse evenly by ultrasonication for 30 min to obtain a fullerene dispersion. The solution was prepared by making the fullerene dispersion account for 10% of the total volume of the final fullerene-modified iridium-tantalum-titanium oxide active solution B. The fullerene dispersion was added to the iridium-tantalum-titanium oxide active solution A and stirred for 60 minutes to mix evenly, thus obtaining the fullerene-modified iridium-tantalum-titanium oxide active solution B.

[0034] Step 3, Coating, Drying, and Sintering: Using a wool brush, apply an appropriate amount of fullerene-modified iridium-tantalum titanium oxide active liquid B evenly to the surface of the titanium sheet after the pretreatment in Step 1. Place it on a heating table and dry it at 100°C for 5 minutes. Immediately transfer it to a muffle furnace for sintering at 500°C for 15 minutes. After completion, remove the sample and allow it to cool naturally to room temperature. Repeat the above coating process until all the active liquid is applied. After the final application of fullerene-modified iridium-tantalum titanium oxide active liquid B, sinter for 90 minutes. Then remove it and allow it to cool naturally to room temperature to obtain a fullerene-modified iridium-based composite coated titanium electrode. See the scanning electron microscope image for details. Figure 2 .

[0035] Example 2 This embodiment provides a method for preparing a fullerene-modified iridium-based composite coated titanium electrode, specifically including the following steps: Step 1: Pre-treatment of the titanium substrate surface: Select a 10cm×10cm titanium sheet as the substrate. The surface pre-treatment of the titanium substrate includes cutting, sandblasting, acid pickling, rinsing, and natural drying. Among them, acid pickling is carried out by acid etching with a 10% oxalic acid solution under a slight boiling state for 180 minutes.

[0036] Step 2, Preparation of active solutions: Using a pipette, transfer 2.5 mL of ethanol, 2.5 mL of ethylene glycol, and 5 mL of isopropanol, mix them, and stir evenly on a magnetic stirrer to obtain organic solvent a. Prepare a solution with a total metal ion concentration of 0.25 mol / L and a molar ratio of Ir, Ta, and Ti of 6:3:1. Add H₂IrCl₆·6H₂O to organic solvent a and stir on a magnetic stirrer for 45 min until completely dissolved. Then add TaCl₅ and tetrabutyl titanate, and stir again for 45 min until completely dissolved to obtain iridium-tantalum titanium oxide active solution A. Prepare a solution with a fullerene concentration of 0.4 g / L. Add fullerene powder to organic solvent b (a mixture of n-butanol and isopropanol), and disperse evenly by ultrasonication for 45 min to obtain a fullerene dispersion. The solution was prepared by making the fullerene dispersion account for 7.5% of the total volume of the final fullerene-modified iridium-tantalum-titanium oxide active solution B. The fullerene dispersion was added to the iridium-tantalum-titanium oxide active solution A and stirred for 45 minutes to mix evenly to obtain the fullerene-modified iridium-tantalum-titanium oxide active solution B.

[0037] Step 3, Coating, Drying, and Sintering: Using a wool brush, apply an appropriate amount of fullerene-modified iridium-tantalum titanium oxide active liquid B evenly to the surface of the titanium sheet after the pretreatment in Step 1. Place it on a heating table and dry it at 120°C for 10 minutes. Immediately transfer it to a muffle furnace for sintering at 480°C for 15 minutes. After completion, remove the sample and allow it to cool naturally to room temperature. Repeat the above coating process until all the active liquid is applied. After the final application of fullerene-modified iridium-tantalum titanium oxide active liquid B, sinter for 120 minutes. Then remove it and allow it to cool naturally to room temperature to obtain a fullerene-modified iridium-based composite coated titanium electrode. See the scanning electron microscope image for details. Figure 3 .

[0038] Example 3 This embodiment provides a method for preparing a fullerene-modified iridium-based composite coated titanium electrode, specifically including the following steps: Step 1: Pre-treatment of the titanium substrate surface: Select a 10cm×10cm titanium sheet as the substrate. The surface pre-treatment of the titanium substrate includes cutting, sandblasting, acid pickling, rinsing, and natural drying. Among them, acid pickling is performed by acid etching with a 12.5% ​​oxalic acid solution under a slight boiling state for 150 minutes.

[0039] Step 2, Preparation of active solution: Using a pipette, transfer 5 mL of ethylene glycol and 5 mL of isopropanol separately, mix, and stir evenly on a magnetic stirrer to obtain organic solvent a. Prepare a solution with a total metal ion concentration of 0.3 mol / L and a molar ratio of Ir, Ta, and Ti of 6.5:3:0.5. Add H₂IrCl₆·6H₂O to organic solvent a and stir on a magnetic stirrer for 60 min until completely dissolved. Then add TaCl₅ and tetrabutyl titanate, and stir again for 60 min until completely dissolved to obtain iridium-tantalum titanium oxide active solution A. Prepare a solution with a fullerene concentration of 0.5 g / L. Add fullerene powder to organic solvent b (a mixture of n-butanol, isopropanol, and ethylene glycol), and disperse evenly by ultrasonication for 60 min to obtain a fullerene dispersion. The solution was prepared by adding the fullerene dispersion to the iridium tantalum titanium oxide active solution A and stirring for 60 minutes to mix evenly, thus obtaining the fullerene-modified iridium tantalum titanium oxide active solution B.

[0040] Step 3, Coating, Drying, and Sintering: Using a wool brush, apply an appropriate amount of fullerene-modified iridium-tantalum titanium oxide active liquid B evenly to the surface of the titanium sheet after the pretreatment in Step 1. Place it on a heating table and dry it at 80°C for 7.5 min. Immediately transfer it to a muffle furnace for sintering at 520°C for 12 min. After completion, remove the sample and allow it to cool naturally to room temperature. Repeat the above coating process until all the active liquid is applied. After the final application of fullerene-modified iridium-tantalum titanium oxide active liquid B, sinter for 90 min. Then remove it and allow it to cool naturally to room temperature to obtain a fullerene-modified iridium-based composite coated titanium electrode. See the scanning electron microscope image for details. Figure 4 .

[0041] Example 4 This embodiment provides a method for preparing a fullerene-modified iridium-based composite coated titanium electrode, specifically including the following steps: Step 1: Pre-treatment of the titanium substrate surface: Select a 10cm×10cm titanium sheet as the substrate. The surface pre-treatment of the titanium substrate includes cutting, sandblasting, acid pickling, rinsing, and natural drying. Among them, acid pickling is carried out by acid etching with a 15% oxalic acid solution under a slight boiling state for 120 minutes.

[0042] Step 2, Preparation of active solution: Using a pipette, transfer 5 mL of ethylene glycol and 5 mL of n-butanol separately, mix them, and stir evenly on a magnetic stirrer to obtain organic solvent a. Prepare a solution with a total metal ion concentration of 0.25 mol / L and a molar ratio of Ir, Ta, and Ti of 6:3:1. Add H₂IrCl₆·6H₂O to organic solvent a and stir on a magnetic stirrer for 30 min until completely dissolved. Then add TaCl₅ and tetrabutyl titanate, and stir again for 30 min until completely dissolved to obtain iridium-tantalum-titanium oxide active solution A. Prepare a solution with a fullerene concentration of 0.6 g / L. Add fullerene powder to organic solvent b (a mixture of n-butanol and ethylene glycol), and disperse evenly by ultrasonication for 45 min to obtain a fullerene dispersion. The solution was prepared by making the fullerene dispersion account for 7.5% of the total volume of the final fullerene-modified iridium-tantalum-titanium oxide active solution B. The fullerene dispersion was added to the iridium-tantalum-titanium oxide active solution A and stirred for 45 minutes to mix evenly to obtain the fullerene-modified iridium-tantalum-titanium oxide active solution B.

[0043] Step 3, Coating, Drying, and Sintering: Using a wool brush, apply an appropriate amount of fullerene-modified iridium-tantalum titanium oxide active liquid B evenly to the surface of the titanium sheet after the pretreatment in Step 1. Place it on a heating table and dry it at 100℃ for 5 minutes, then immediately transfer it to a muffle furnace for sintering at 550℃ for 15 minutes. After completion, remove the sample and allow it to cool naturally to room temperature. Repeat the above coating process until all the active liquid is applied. After the final application of fullerene-modified iridium-tantalum titanium oxide active liquid B, sinter for 60 minutes, then remove it and allow it to cool naturally to room temperature to obtain a fullerene-modified iridium-based composite coated titanium electrode. See the scanning electron microscope image for details. Figure 5 .

[0044] Comparative example (without fullerene modification) This comparative example provides a method for preparing an iridium-based composite coated titanium electrode, specifically including the following steps: Step 1: Pre-treatment of the titanium substrate surface: Select a 10cm×10cm titanium sheet as the substrate. The surface pre-treatment of the titanium substrate includes cutting, sandblasting, acid pickling, rinsing, and natural drying. Among them, acid pickling is carried out by acid etching with a 15% oxalic acid solution under a slight boiling state for 120 minutes.

[0045] Step 2, Preparation of the active solution: 5 mL of n-butanol and 5 mL of isopropanol were pipetted separately, mixed, and stirred evenly on a magnetic stirrer to obtain an organic solvent. A solution was prepared with a total metal ion concentration of 0.2 mol / L and a molar ratio of Ir, Ta, and Ti of 5.5:3:1.5. H₂IrCl₆·6H₂O was added to the organic solvent and stirred on a magnetic stirrer for 30 min until completely dissolved. Then, TaCl₅ and tetrabutyl titanate were added, and the mixture was stirred again for 30 min until completely dissolved to obtain the iridium-tantalum titanium oxide active solution.

[0046] Step 3, Coating, Drying, and Sintering: Using a wool brush, apply an appropriate amount of iridium-tantalum titanium oxide active liquid evenly to the surface of the titanium sheet after the pretreatment in Step 1. Place it on a heating table and dry it at 100°C for 5 minutes. Immediately transfer it to a muffle furnace for sintering at 450°C for 10 minutes. After completion, remove the sample and allow it to cool naturally to room temperature. Repeat the above coating process until all the active liquid is applied. After the final application of the iridium-tantalum titanium oxide active liquid, sinter for 90 minutes. Then remove it and allow it to cool naturally to room temperature to obtain an iridium-based composite coated titanium electrode. See the scanning electron microscope image for details. Figure 6 .

[0047] contrast Figures 2-6 It can be observed that after the introduction of fullerene modification, the uniformly dispersed carbon-based micro- and nano-structures in the components can serve as nucleation sites, effectively improving the crystal clusters generated by IrO2 segregation on the coating surface and enhancing the consistency of the coating microstructure. After fullerene modification, the coating surface becomes rougher, generating a unique microcrack network, effectively increasing the specific surface area, thereby significantly improving the electrochemical performance.

[0048] To further verify the effectiveness of the technical solution of the present invention, the inventors tested the performance of the iridium-based composite coated titanium electrodes prepared in Examples 1-4 and the comparative example, using a 1 mol / L sulfuric acid solution as the electrolyte, and subjected the titanium electrodes prepared in Examples 1-4 and the comparative example to a 4 A / cm test. 2 Enhanced lifetime testing at current density; test results are available in [link to relevant documentation]. Figure 7 Analysis shows that, under a voltage of 20V, the titanium electrode prepared in the comparative example has an operating life of only about 450 hours, while that in Example 1 can reach nearly 1200 hours, which is about 167% longer.

[0049] In summary, the method for preparing the fullerene-modified iridium-based composite coated titanium electrode provided by this invention, compared with conventional methods, allows for the construction of a highly efficient three-dimensional conductive network by introducing fullerene, a zero-dimensional carbon material with excellent conductivity. This reduces the internal resistance of the electrode, thereby accelerating the charge transfer rate and improving the catalytic reaction efficiency. Simultaneously, fullerenes possess excellent mechanical strength and corrosion resistance, particularly in acidic environments, which enhances the physical and chemical stability of the entire electrode under strong acid and strong oxidizing conditions, significantly extending the electrode's lifespan.

[0050] The above description is merely a specific embodiment of the present invention, enabling those skilled in the art to understand or implement the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention.

[0051] It should be understood that the present invention is not limited to the content already described above, and various modifications and changes can be made without departing from its scope. The scope of the present invention is limited only by the appended claims.

Claims

1. A method for preparing a fullerene-modified iridium-based composite coated titanium electrode, characterized in that, The preparation method includes the following steps: Step 1: Pre-treat the surface of the titanium substrate; Step 2: Dissolve the iridium source completely in organic solvent a, then add the tantalum source and titanium source. After complete dissolution, obtain iridium-tantalum-titanium oxide active liquid A; disperse the fullerene powder in organic solvent b to obtain a fullerene dispersion; add the fullerene dispersion to iridium-tantalum-titanium oxide active liquid A, stir evenly, and obtain fullerene-modified iridium-tantalum-titanium oxide active liquid B. Step 3: Apply the fullerene-modified iridium-tantalum titanium oxide active liquid B to the surface of the titanium substrate after pretreatment in Step 1, dry and sinter it, and then remove it and let it cool naturally to room temperature; repeat the above coating, drying and sintering process steps until all the fullerene-modified iridium-tantalum titanium oxide B active liquid is coated to obtain the target coated titanium electrode.

2. The method for preparing a fullerene-modified iridium-based composite coated titanium electrode according to claim 1, characterized in that, In step 2, the concentration of the fullerene dispersion is 0.3~0.6 g / L, and the fullerene dispersion accounts for 5~10% of the total volume of the fullerene-modified iridium-tantalum titanium oxide active liquid B.

3. The method for preparing a fullerene-modified iridium-based composite coated titanium electrode according to claim 1, characterized in that, In step 2, the molar ratio of Ir, Ta and Ti in the iridium-tantalum-titanium oxide active solution A is (5.5~6.5):3:(0.5~1.5), and the total metal ion concentration is 0.2~0.3 mol / L.

4. The method for preparing a fullerene-modified iridium-based composite coated titanium electrode according to claim 1, characterized in that, In step 2, organic solvents a and b are two or more combinations of n-butanol, isopropanol, ethylene glycol, and ethanol.

5. The method for preparing a fullerene-modified iridium-based composite coated titanium electrode according to claim 1, characterized in that, In step 3, the drying temperature is 80~120℃, the drying time is 5~10min each time, the sintering temperature is 450~550℃, and the sintering time is 10~20min each time.

6. The method for preparing a fullerene-modified iridium-based composite coated titanium electrode according to claim 5, characterized in that, After the final application of the fullerene-modified iridium-tantalum titanium oxide active liquid B in step 3, the sintering time is 60~120 min.

7. The method for preparing a fullerene-modified iridium-based composite coated titanium electrode according to claim 1, characterized in that, The pretreatment in step 1 includes cutting, sandblasting, pickling, rinsing, and air drying. The pickling is performed by acid etching with a 10% to 15% oxalic acid solution under a slightly boiling state for 120 to 180 minutes.

8. The method for preparing a fullerene-modified iridium-based composite coated titanium electrode according to claim 1, characterized in that, In step 2, the iridium source in the iridium-tantalum-titanium oxide active solution A is H2IrCl6·6H2O, the tantalum source is TaCl5, and the titanium source is tetrabutyl titanate.

9. The application of the fullerene-modified iridium-based composite coated titanium electrode prepared by the preparation method according to any one of claims 1 to 8 in the field of preparing electrolytic copper foil.

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