Fullerene-ir coated titanium anode and its preparation method and application

Abstract

This invention discloses a fullerene-Ir coated titanium anode, its preparation method, and its application, belonging to the field of iridium-based coated titanium electrode technology. The preparation method is as follows: fullerene is dissolved in an organic solvent, a precipitant is added, and after incubation, a mother liquor is obtained; ethylenediamine is added to the mother liquor, and after incubation, the lower precipitate is collected, washed, and dried to obtain fullerene nanoparticles; the fullerene nanoparticles are mixed and reacted with H2IrCl6·H2O / EG solution and sodium borohydride, centrifuged, and dried to obtain fullerene-Ir powder; the fullerene-Ir powder is dissolved in HCl solution, coated onto a pretreated substrate, and dried to obtain a fullerene-Ir coated anode. This invention significantly improves the hydrophilicity of fullerene. The prepared fullerene-Ir coated anode has a larger specific surface area and better conductivity than the traditional Ir-Ta coated anode, exhibiting a lower electrode potential and reducing reaction energy consumption.

Description

Technical Field

[0001] This invention mainly relates to the field of iridium-coated titanium electrode technology, specifically a fullerene-Ir coated titanium anode, its preparation method, and its application. Background Technology

[0002] Iridium-based coated titanium electrodes are among the most promising coated electrodes in the oxygen evolution reaction (OER) field. IrO2, as an excellent OER catalyst, remains stable in acidic solutions and exhibits good catalytic performance. However, pure IrO2 coatings are prone to peeling, resulting in short electrode lifespans and high costs. Therefore, Ta2O5 is introduced as an inert component of the coating to protect the active material IrO2. However, Ta2O5 only improves the adhesion between the coating and the substrate; it is not a catalytically active material and may even reduce the catalytic activity of the coating. Therefore, developing electrodes with good lifespan, low cost, and high coating performance has become a key research focus for scholars both domestically and internationally.

[0003] Titanium anodes were invented by the Dutch as early as the 1960s. Technicians in this field usually obtain improved titanium anodes by changing the type of metal salt, temperature, time, etc.

[0004] Carbon materials are a class of materials composed of nanoscale carbon structures, possessing excellent physicochemical properties and a wide range of applications. Their structural diversity and designability enable them to exhibit a variety of superior properties. Fullerenes, due to their high electron affinity and uniformly fluctuating lattice structure with large lattice distances, have become promising candidates for catalyst support materials. When anchored to metal nanoclusters / particles, these desirable surface properties can generate strong electronic and confinement effects, further creating different active sites. On the other hand, fullerenes are lightweight, have low density, large specific surface area, good electrical conductivity, and strong surface modifiability, leading to their application in many fields. The presence of π electron groups in fullerenes enhances intermolecular interactions; however, this also makes them difficult to dissolve in most common solvents. Traditional fullerenes are often limited by hydrophobicity and biocompatibility, and direct addition, pulverization, dissolution, or ultrasonication of general fullerenes cannot improve the performance or lifespan of titanium anodes, making it difficult to apply fullerenes to titanium electrode coatings. Summary of the Invention

[0005] This invention addresses the problem of overly simplistic solutions in existing technologies by providing a significantly different approach. It primarily offers a fullerene-Ir coated titanium anode, its preparation method, and its application. First, hydrophilic fullerene nanotubes are prepared. Then, using the hydrophilic fullerene as a framework, Ir clusters are anchored to synthesize fullerene-Ir powder, thereby obtaining a fullerene-Ir catalytic coating. This solves the technical problem mentioned in the background section regarding the difficulty of applying fullerenes to titanium electrode coatings.

[0006] The technical solution adopted by the present invention to solve the above-mentioned technical problems is as follows: A method for preparing a fullerene-Ir coated titanium anode includes the following steps: (1) Fullerene functionalization treatment: Fullerene powder is uniformly dissolved in an organic solvent, then a precipitant is added, and after cultivation, the mother liquor is obtained; (2) Functionalized fullerene reprocessing: Add ethylenediamine to the mother liquor and mix thoroughly. After culturing, remove the lower precipitate and wash it with the precipitant in step (1) and then dry it to obtain fullerene nanopowder. (3) Synthesis of fullerene-Ir: Take the fullerene nanopowder obtained in step (2), mix it with H2IrCl6·H2O / EG solution and sodium borohydride, and after the reaction is completed, centrifuge and dry it to obtain fullerene-Ir powder. (4) Preparation of fullerene-Ir coated anode: Dissolve the fullerene-Ir powder obtained in step (3) in HCl solution, then coat it on the pretreated substrate and dry it; until the Ir content reaches 14-22 g / cm2, the fullerene-Ir coated anode is finally obtained.

[0007] After the functionalization process described in step (1), fullerenes can be reconstructed into rods, sheets, or blocks using a liquid-liquid interface precipitation method (different shapes are achieved by controlling the ratio of organic solvent and precipitant). The original fullerene particles or powders have a relatively large particle size and exhibit a blocky morphology, which is not conducive to the loading of the active metal Ir and subsequent catalytic reactions. The specific principle of step (1) is as follows: First, fullerenes are dissolved in solvents with high solubility, such as toluene, which are then a purple transparent solution. Subsequently, using alcohols as precipitants, isopropanol and other alcohol reagents are added, and the previously dissolved fullerenes precipitate out.

[0008] In step (2) above, the amino group on the ethylenediamine reacts with the carbon site on the fullerene to generate a certain N-substituted or amino-substituted fullerene, thereby ultimately improving hydrophilicity.

[0009] Original fullerenes consist entirely of carbon atoms and have virtually no interaction with water. The modification scheme described above primarily serves two purposes: ① It enhances the hydrophilic groups such as amino groups, enabling easier dispersion in water / alcohol without altering the structure. This allows the fullerene to be completely dispersed in a water-based Ir-containing solution in subsequent steps, achieving uniform loading; ② It creates sites on the fullerene that readily bind with Ir, facilitating the formation of a stable fullerene-Ir structure in subsequent steps.

[0010] The following reaction occurs in step (3) above: H2IrCl6·6H2O + NaBH4 = Ir + B(OH)3 + H2 + HCl + NaCl.

[0011] In step (3), the addition of sodium borohydride is also a crucial step. By controlling the ratio of sodium borohydride to Ir, it is ensured that the noble metal Ir can bind to the fullerene in the desired manner. This invention creatively alters the ability of fullerene to bind with Ir, thereby enabling Ir to be loaded onto the fullerene in a cluster form, thus achieving high activity.

[0012] Furthermore, in step (1), the fullerene can be any fullerene structure such as C20, C60, C70, C76, C80, etc.

[0013] Further, in step (1), the organic solvent is at least one of toluene, m-xylene, and mesitylene; the fullerene is dissolved in the organic solvent and the fullerene concentration is 0.1~5 mg / mL.

[0014] If too much organic solvent is used, the precipitate will not appear as desired, or the amount of precipitate will be very small, because fullerenes can still be dissolved in large quantities in toluene-based substances.

[0015] Further, in step (1), the precipitant is at least one of isopropanol, n-butanol, and methanol; the mass ratio of the precipitant to the organic solvent is 1:1 to 1:3.

[0016] If too much alcohol solvent is used, it will mainly affect the economy and practicality of the invention, but will not affect the performance.

[0017] Furthermore, in step (1), the incubation time is at least 24 hours.

[0018] Furthermore, in step (2), the amount of ethylenediamine added is 20-30% of the volume fraction of the mother liquor solution.

[0019] Furthermore, in step (2), the incubation time is 6-18 h.

[0020] Ethylenediamine is a crucial additive, determining the physical state of the fullerene after etching. Excessive ethylenediamine concentration or prolonged incubation time can cause irreversible structural changes in the fullerene, potentially destroying its original carbon chains and rendering it no longer a fullerene. Conversely, insufficient concentration or short incubation time may result in ineffective etching.

[0021] Furthermore, in step (2), the sample is washed 3-5 times with a precipitant.

[0022] Further, in step (3), fullerene nanotube powder is first added to ethanol and ultrasonically dispersed for 30 min; then 5 mL-9 mL of H2IrCl6·H2O / EG (1.0 M) solution is added (indicating that chloroiridium acid is dissolved in ethylene glycol and the concentration reaches 1 mol per liter), and the mixture is stirred for 12 h. The mass ratio of Ir to fullerene nanotube powder is 1:1 to 8:1; then 800-1500 mg of sodium borohydride is added, and the mixture is stirred for 12 h. The mass ratio of Ir to NaBH4 is 1:2 to 2:1, preferably 1:1-1.5:1; after the reaction is completed, the mixture is centrifuged and dried at 80 °C to obtain fullerene-Ir powder.

[0023] The reason for using ethylene glycol in this step is that: ① chloroiridic acid can be dissolved in ethylene glycol; ② ethylene glycol has good water solubility, a wide operating temperature range (-13 to 197°C), and low volatility.

[0024] Furthermore, the substrate used in step (4) is any valve-type metal selected from titanium, tantalum, or niobium, and it will form a dense oxide film under oxidation potential without dissolution; the substrate is plate-shaped, mesh-shaped, or tubular. The pretreatment is as follows: the substrate cut to a fixed size is sandblasted, etched, cleaned, and dried.

[0025] Furthermore, in step (4), the coating method is any one of spraying, brushing, or sputtering.

[0026] Furthermore, in step (4), the drying temperature after coating is 80-150℃.

[0027] The present invention also provides a fullerene-Ir coated titanium anode, which is prepared by the above-described preparation method, and the fullerene-Ir coated titanium anode has an electrolysis life greater than 1850h and a cell voltage less than 3.6V.

[0028] The present invention also provides applications of the above-mentioned fullerene-Ir coated titanium anode, which include, but are not limited to, applications in electrolytic copper foil, electrolytic chlorine production, water treatment, seawater desalination, and printed circuit board manufacturing.

[0029] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) This invention reconstructs fullerenes from zero-dimensional to multi-dimensional by functionalizing them (first dissolving them in an organic solvent, then precipitating them with a precipitant, and then etching them with ethylenediamine). This overcomes the hydrophobicity of the original fullerene without altering its basic structure, significantly improving its hydrophilicity. This allows the fullerene to be completely dispersed in an Ir-containing solution dominated by water in subsequent steps, achieving uniform loading. Simultaneously, the functionalization process creates sites on the fullerene that readily bind with Ir, facilitating the formation of a stable fullerene-iridium structure. In other words, this invention creatively alters the binding ability of fullerenes. Furthermore, by applying the improved hydrophilicity of fullerenes to titanium anodes, this invention achieves a cross-disciplinary composite method that not only improves the cell voltage of titanium anodes (reducing energy consumption) but also significantly enhances their lifespan (reducing operating costs).

[0030] (2) In this invention, after obtaining the modified fullerene, it is reacted with H2IrCl6·H2O / EG solution and sodium borohydride, and the ratio of sodium borohydride to Ir is controlled to ensure that the noble metal Ir can be loaded onto the fullerene in the form of clusters, thereby achieving high activity. Too much sodium borohydride will result in an overly vigorous reaction. For the sake of saving dosage and safety, a safer dosage is given in this application. Too little sodium borohydride will lead to incomplete reaction, and the Ir in chloroiridium acid will not be able to react completely with sodium borohydride, ultimately leading to a decrease in performance.

[0031] (3) In this invention, the fullerene-Ir powder is dissolved in an HCl solution, then coated onto a pretreated substrate and dried to obtain a fullerene-Ir coating, thus synthesizing a novel iridium-based catalytic coating. This coating combines the advantages of fullerenes with those of iridium coatings. Compared with traditional Ir-Ta coating anodes, the fullerene-Ir coated anode prepared by this invention has a larger specific surface area, better conductivity, more active sites, and a lower electrode potential, which can reduce reaction energy consumption and lower costs.

[0032] The present invention will be explained in detail below with reference to the accompanying drawings and specific embodiments. Attached Figure Description

[0033] Figure 1 Scanning electron microscope (SEM) images of the fullerene nanorods prepared in Examples 1 to 5.

[0034] Figure 2 The images are scanning electron microscope (SEM) images of the fullerene nanotubes prepared in Examples 1 to 5.

[0035] Figure 3 The images show the scanning electron microscope (SEM) spectra of the initial fullerenes at different magnifications, where (a) is at 100 μm magnification and (b) is at 40 μm magnification.

[0036] Figure 4 The X-ray diffraction data are compared between the original fullerene powder and the powder after hydrophilicity improvement and ethylenediamine etching in the examples.

[0037] Figure 5 The figures show the cyclic voltammetry curves of Examples 1 to 5 and Comparative Examples 1 to 3.

[0038] Figure 6 The figures show the polarization curves of Examples 1 to 5 and Comparative Examples 1 to 3.

[0039] Figure 7 This is a schematic diagram of the structure of fullerene combined with Ir clusters in this invention. Detailed Implementation

[0040] To facilitate understanding of the present invention, a more comprehensive description of the present invention will be given below with reference to the accompanying drawings, which illustrate several embodiments of the present invention. However, the present invention can be implemented in different forms and is not limited to the embodiments described in the text. Rather, these embodiments are provided to make the disclosure of the present invention more thorough and complete.

[0041] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly associated with those skilled in the art to which this invention pertains. The terminology used herein in the specification of this invention is for the purpose of describing particular embodiments and is not intended to limit the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0042] Example 1: A method for preparing a fullerene-Ir coated titanium anode: (1) First, weigh 320 mg of fullerene C60 powder, grind it and dissolve it in 80 ml of m-xylene solution. Then, place the resulting solution in a 5°C ice-water bath and sonicate it for 1 h to accelerate the dissolution of fullerene in the solvent. Slowly pour 80 ml of isopropanol solution into the sonicated solution and place the resulting mixed solution in a 25°C constant temperature incubator for 24 h to obtain the mother liquor.

[0043] (2) Add 25% ethylenediamine to the mother liquor, sonicate for 2 h, and then incubate at 25℃ for 12 h. Then centrifuge the mother liquor at 5000 rpm for 5 min to collect the lower precipitate, wash the lower precipitate three times with isopropanol and dry it to obtain fullerene nanotube powder.

[0044] (3) Take 300 mg of the powder obtained in step (2), add 40 ml of ethanol, mix and sonicate for 30 min, then add 5 mL of H2IrCl6·H2O / EG (1M) solution to obtain a mixture, and keep the mixture stirred for 12 h. Subsequently, add 800 mg of sodium borohydride to the above mixture, and keep the mixture stirred for 12 h. Then centrifuge to collect the sample, and dry it in an oven at 80℃ for 12 h to obtain fullerene-Ir powder. The structural diagram of fullerene combined with Ir clusters is shown below. Figure 7 As shown.

[0045] (4) Titanium substrate pretreatment: The sample was cut to size using a shearing machine, with the titanium plate cut to 100*100 mm. Then, the substrate was sandblasted using 18-24 mesh steel grit at a pressure of 0.5 MPa to give the substrate surface a certain roughness. After sandblasting, it was etched with an HCl solution of approximately 20-26 wt% for 20-35 min, and finally rinsed with pure water and dried for later use.

[0046] (5) Preparation of fullerene-Ir coated titanium anode: Take 100 mg of the fullerene-Ir powder prepared in step (3) and dissolve it in 20 ml of HCl solution. Disperse it ultrasonically for 30 min and coat it evenly on the titanium plate pretreated in step (4) with a roller brush. Dry it in an oven at 150℃ for 1 h. Repeat ten times until the Ir content reaches 14 g / cm2, and finally obtain the anode product.

[0047] Example 2: This example provides a method for preparing a fullerene-Ir coated titanium anode, which is basically the same as that in Example 1, except that: in step (3), the amount of H2IrCl6·H2O / EG (1.0 M) solution added is 7 mL, and the amount of sodium borohydride added is 1000 mg. In step (5), the coating is performed until the Ir content reaches 18 g / cm2.

[0048] Example 3: This example provides a method for preparing a fullerene-Ir coated titanium anode, which is basically the same as that in Example 1, except that: in step (3), the amount of H2IrCl6·H2O / EG (1.0 M) solution added is 9 mL, and the amount of sodium borohydride added is 1500 mg. In step (5), the coating is performed until the Ir content reaches 22 g / cm2.

[0049] Example 4: This example provides a method for preparing a fullerene-Ir coated titanium anode, which is basically the same as that in Example 2, except that: in step (5), 150 mg of the fullerene-Ir powder prepared in step (3) is dissolved in 20 ml of HCl solution and ultrasonically dispersed for 30 min. It is then uniformly coated onto the pretreated titanium plate in step (4) using a roller brush and dried in an oven at 150°C for 1 h. This process is repeated until the Ir content reaches 18 g / cm2, and the anode product is finally obtained.

[0050] Example 5: This example provides a method for preparing a fullerene-Ir coated titanium anode, which is basically the same as that in Example 2, except that: in step (5), 200 mg of the fullerene-Ir powder prepared in step (3) is dissolved in 20 ml of HCl solution and ultrasonically dispersed for 30 min. It is then uniformly coated onto the pretreated titanium plate in step (4) using a roller brush and dried in an oven at 150°C for 1 h. This process is repeated until the Ir content reaches 18 g / cm2, and the anode product is finally obtained.

[0051] Example 6: This example provides a method for preparing a fullerene-Ir coated titanium anode, which is basically the same as that in Example 1, except that: in step (1), the organic solvent is toluene; the precipitant is n-butanol; In step (2), the amount of ethylenediamine added is 20% of the volume fraction of the mother liquor solution; the incubation time is 6 h; In step (3), the amount of H2IrCl6·H2O / EG (1.0 M) solution added is 6 mL; the amount of sodium borohydride added is 1200 mg; In step (5), the drying temperature after coating is 80°C.

[0052] Example 7: This example provides a method for preparing a fullerene-Ir coated titanium anode, which is basically the same as that in Example 1, except that: in step (1), the organic solvent is mesitylene; and the precipitant is methanol. In step (2), the amount of ethylenediamine added is 30% of the volume fraction of the mother liquor solution; the incubation time is 18 h; In step (3), the amount of H2IrCl6·H2O / EG (1.0 M) solution added is 9 mL; the amount of sodium borohydride added is 1500 mg; In step (4), the drying temperature after coating is 120°C.

[0053] Comparative Example 1: This comparative example provides a method for preparing an IrO2-Ta2O5 coated titanium anode. Iridic acid (H2IrCl6·H2O) and TaCl5 n-butanol solution were added to the n-butanol solvent at a molar ratio of Ir:Ta = 70:30, resulting in a coating concentration of 0.3 mol / L. Then, following the preparation method of Example 1, a metal oxide coating was prepared on the titanium substrate obtained in step (4), ensuring an Ir content of 14 g / cm2. This resulted in an IrO2-Ta2O5 coated titanium anode without added graphene, which served as a comparative sample for the anode material in this example.

[0054] Comparative Example 2: This comparative example provides a method for preparing an IrO2-Ta2O5 coated titanium anode. Iridic acid (H2IrCl6·H2O) and TaCl5 n-butanol solution were added to the n-butanol solvent at a molar ratio of Ir:Ta = 70:30, resulting in a coating concentration of 0.3 mol / L. Following the preparation method of Example 2, a metal oxide coating was prepared on the titanium substrate obtained in step (4), ensuring an Ir content of 18 g / cm2. This resulted in an IrO2-Ta2O5 coated titanium anode without added graphene, which served as a comparative sample for the anode material in this example.

[0055] Comparative Example 3: This comparative example provides a method for preparing an IrO2-Ta2O5 coated titanium anode. Iridic acid (H2IrCl6·H2O) and TaCl5 n-butanol solution were added to the n-butanol solvent at a molar ratio of Ir:Ta = 70:30, resulting in a coating concentration of 0.3 mol / L. Following the preparation method of Example 3, a metal oxide coating was prepared on the titanium substrate obtained in step (4), ensuring an Ir content of 22 g / cm2. This resulted in an IrO2-Ta2O5 coated titanium anode without added graphene, which served as a comparative sample for the anode material in this example.

[0056] The performance of the above embodiments and comparative examples will be studied below. 1. The morphology of the prepared fullerene nanorods, nanotubes, and initial fullerenes in Example 1 above was observed using scanning electron microscopy. Their morphologies are shown below. Figures 1-3 As shown in the attached figures (data represents length, not diameter), the prepared nanorods exhibit varying uniformity in size, with diameters ranging from 669.2 nm to 1.121 μm. The etched nanotubes show some breakage but retain their tubular morphology well, with diameters ranging from 723.2 nm to 1.005 μm. The initial fullerenes were blocky; after adding an alcohol precipitant, [the desired shape / structure] was successfully prepared. Figure 1 The nanorods shown were subsequently etched by ethylenediamine and transformed into... Figure 2The image shows "some fractures but well-preserved tubular morphology". The slight fragmentation is due to microscopic damage to the structure. While the overall carbon chain remains intact, a small portion is replaced by nitrogen or amino groups, thus endowing the fullerene with the ability to bind with Ir.

[0057] 2. In Example 1 above, X-ray diffraction data of the original fullerene powder and the powder of the present invention after hydrophilicity improvement and ethylenediamine etching were observed, such as... Figure 4 As shown.

[0058] Depend on Figure 4 As can be seen, compared with the original fullerene powder, the diffraction peak positions of the powder processed by this invention change, indicating that etching may have broken the original relatively regular structure, generating more surface active sites or defects. More active sites can improve catalytic efficiency. Furthermore, the broadening of the diffraction peaks indicates a reduction in crystallinity. Lower crystallinity allows the fullerene powder to better integrate with the titanium substrate, enhancing interfacial adhesion and improving the overall performance of the titanium anode.

[0059] 3. Electrochemical tests were performed on the products of the above embodiments and comparative examples: Electrochemical measurements were performed in a three-electrode electrolytic cell. The working electrode had a test area of ​​1 cm², the auxiliary electrode was a platinum electrode, and the reference electrode was a saturated calomel electrode. The electrolyte was a 0.5 M sulfuric acid solution. Cyclic voltammetry was performed in the range of 0–1.2 V at a scan rate of 20 mV·s⁻¹ for 20 cycles. Integration was performed only on the voltammetric curve from the last cycle. Figure 5 The cyclic voltammetry curves are for Examples 1 to 5 and Comparative Examples 1 to 3. Figure 6 The polarization curves are for Examples 1 to 5 and Comparative Examples 1 to 3.

[0060] Depend on Figure 5 It can be seen that the cyclic voltammetry curves of Examples 1 to 5 are all larger than the areas of Comparative Examples 1 to 3. Among them, the cyclic curve area of ​​Example 3 is the largest, with the most active sites, which greatly improves the electrocatalytic activity of the anode.

[0061] Oxygen evolution polarization curves are an important method for evaluating anodic electrocatalytic activity. Figure 6 It can be seen that as the iridium weight increases, the oxygen evolution activity increases accordingly. Comparing Examples 1 to 3 and Comparative Examples 1 to 3, it can be seen that when the iridium weight is the same, under the same oxygen evolution potential, the exchange current density of the Examples is greater than that of the Comparative Examples, and the oxygen evolution activity is better. This indicates that compared with the traditional IrO2-Ta2O5 coating, the fullerene-Ir coating has more catalytic active sites and higher electrocatalytic activity.

[0062] 4. Perform a tank pressure test on the coated titanium anode prepared in the embodiments of the present invention: The method is as follows: The prepared coated titanium anode and titanium cathode are placed in an H2SO4 electrolyte with a concentration of 20% and electrolysis is carried out by DC power supply. The temperature is a constant water bath temperature of 50℃, the anode current density is 0.5 A / cm2, the electrode spacing is 3.3 cm, and the electrode area is 1 cm2. The cell voltage is monitored at the beginning of electrolysis.

[0063] The stability of the anode was evaluated using an enhanced electrolysis life test. Enhanced electrolysis life tests were conducted on Examples 1 to 5 and Comparative Examples 1 to 3: The coated titanium anode prepared above was processed into samples with an electrode area of ​​1 cm², a pure titanium sheet was used as the cathode, the electrode spacing was 1 cm, the current density was 5 Acm⁻², the temperature was controlled at 40 °C, and the time taken for the electrolysis voltage to increase by 5 V relative to the initial electrolysis value in a 20 wt% H₂SO₄ electrolytic solution was defined as the enhanced electrode life. The obtained electrolysis lifespans and corresponding cell voltages are shown in Table 1.

[0064] Table 1 Performance Comparison of Examples and Comparative Examples Example 1 / 1986 3.52 Example 2 Increased Ir content 2031 3.48 Example 3 The Ir content increased again 2468 3.54 Example 4 The coating concentration was increased, and the Ir content was the same as in Example 2. 2560 3.41 Example 5 The coating concentration was increased again, with the Ir content the same as in Example 2. 2685 3.31 Comparative Example 1 <![CDATA[IrO2-Ta2O5 coating, with the Ir content being the same as in Example 1]]> 1432 3.89 Comparative Example 2 <![CDATA[IrO2-Ta2O5 coating, Ir content same as in Example 2]]> 1625 3.78 Comparative Example 3 <![CDATA[IrO2-Ta2O5 coating, with the Ir content being the same as that in Example 3]]> 1588 3.82 Comparing Examples 1 to 3 with Comparative Examples 1 to 3, it can be seen that: under the condition of ensuring the same Ir content in the coating, the cell voltage of the examples is significantly reduced and the lifespan is longer, indicating that the fullerene-Ir coating has a significant effect on reducing electrode potential and improving the conductivity of the material.

[0065] Comparing Examples 2, 4, and 5, it can be seen that as the coating concentration increases, the cell voltage decreases and the anode lifespan improves. This indicates that the carbon material composite anode fullerene-Ir coating prepared in this invention can significantly improve the stability of the anode and extend its service life while reducing the cell voltage.

[0066] The underlying principle is as follows: During the anodic reaction, the valence state of the catalytically active sites tends to shift to a higher valence state. Fullerenes, as structurally stable acceptors capable of accepting six electrons, actively transfer electrons from the Ir surface to the fullerene during the electrochemical reaction, thereby achieving a stable high valence state for Ir and extending its lifespan. Furthermore, fullerenes disperse Ir and expose it to the material surface, unlike traditional materials where a large amount of active material is buried and unable to function, thus reducing the cell voltage. The lifespan of this invention is greater than 1850 hours, and the cell voltage is less than 3.6V.

[0067] The above description is only a preferred embodiment of the present invention and is 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.

[0068] The present invention has been described by way of example in conjunction with the accompanying drawings. Obviously, the specific implementation of the present invention is not limited to the above-described manner. Any non-substantial improvement made by adopting the inventive concept and technical solution of the present invention, or the direct application of the inventive concept and technical solution of the present invention to other occasions without modification, shall be within the protection scope of the present invention.

Claims

1. A method for preparing a fullerene-Ir coated titanium anode, characterized in that: Includes the following steps: (1) Fullerene functionalization treatment: Fullerene powder is uniformly dissolved in an organic solvent, then a precipitant is added, and after cultivation, the mother liquor is obtained; (2) Functionalized fullerene reprocessing: Add ethylenediamine to the mother liquor and mix thoroughly. After culturing, remove the lower precipitate and wash it with the precipitant in step (1) and then dry it to obtain fullerene nanotube powder. (3) Synthesis of fullerene-Ir: Take the fullerene nanotube powder obtained in step (2), mix it with H2IrCl6·H2O / EG solution and sodium borohydride, and after the reaction is completed, centrifuge and dry it to obtain fullerene-Ir powder. (4) Preparation of fullerene-Ir coated anode: Dissolve the fullerene-Ir powder obtained in step (3) in HCl solution, then coat it on the pretreated substrate and dry it; until the Ir content reaches 14-22 g / cm2, the fullerene-Ir coated anode is finally obtained.

2. The method for preparing a fullerene-Ir coated titanium anode according to claim 1, characterized in that: In step (1), the organic solvent is at least one of toluene, m-xylene, and mesitylene; the fullerene is dissolved in the organic solvent and the fullerene concentration is 0.1~5 mg / L.

3. The method for preparing a fullerene-Ir coated titanium anode according to claim 1, characterized in that: In step (1), the precipitant is at least one of isopropanol, n-butanol, and methanol; the mass ratio of the precipitant to the organic solvent is 1:1 to 1:

3.

4. The method for preparing a fullerene-Ir coated titanium anode according to claim 1, characterized in that: In step (1), the incubation time is at least 24 hours.

5. The method for preparing a fullerene-Ir coated titanium anode according to claim 4, characterized in that: In step (2), the amount of ethylenediamine added is 20-30% of the volume fraction of the mother liquor solution.

6. The method for preparing a fullerene-Ir coated titanium anode according to claim 1, characterized in that: In step (2), the incubation time is 6-18 h.

7. The method for preparing a fullerene-Ir coated titanium anode according to claim 1, characterized in that: In step (3), fullerene nanotube powder is first added to ethanol and ultrasonically dispersed; then H2IrCl6·H2O / EG solution is added and mixed evenly, with the mass ratio of Ir to fullerene nanotube powder being 1:1~8:1; then sodium borohydride is added and mixed evenly, with the mass ratio of Ir to NaBH4 being 1:2~2:1; after the reaction is completed, the mixture is centrifuged and dried at 80℃ to obtain fullerene-Ir powder.

8. The method for preparing a fullerene-Ir coated titanium anode according to claim 1, characterized in that: In step (4), the drying temperature after coating is 80-150℃.

9. A fullerene-Ir coated titanium anode, characterized in that: It is prepared by the preparation method described in any one of claims 1-8.

10. An application of the fullerene-Ir coated titanium anode of claim 9, characterized in that: It is used in electrolytic copper foil, electrolytic chlorine production, water treatment, seawater desalination, and printed circuit board manufacturing.

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