A method for preparing titanium-based noble metal oxide coated electrode materials

Abstract

This invention belongs to the field of electrode material preparation technology and discloses a method for preparing a titanium-based noble metal oxide coated electrode material. The method includes pretreatment of a titanium substrate by sandblasting, acid etching, and surface cleaning; followed by constant current electrodeposition using ionic liquid electrodeposition solutions I and II, and high-temperature oxidation to form a Ta2O5 underlayer and an IrO2-Ta2O5 composite coating on the outside. The titanium-based noble metal oxide coated electrode material prepared by this invention exhibits good adhesion, good consistency in composition and structure, and a long service life.

Description

Technical Field

[0001] This invention belongs to the field of electrode material preparation technology. Specifically, it relates to a method for preparing a titanium-based noble metal oxide coated electrode material, and more particularly to a method for preparing a titanium-based IrO2-Ta2O5 coated electrode material for electrolytic copper foil. Background Technology

[0002] Titanium-based IrO2-Ta2O5 electrode materials possess advantages such as high electrocatalytic activity and long service life, making them suitable for applications in electrolytic copper foil, electroplating, and water treatment. Currently, the bottleneck for Ti / IrO2-Ta2O5 electrode materials is the non-uniformity of the overall product quality, which directly affects its service life and the quality of the cathode copper foil. The main method for industrial production of Ti / IrO2-Ta2O5 electrode materials utilizes coating oxidation, which inevitably results in poor adhesion and uneven coating thickness. Literature reports that tantalum underlayers can be prepared using methods such as molten salt immersion plating, magnetron sputtering, and plasma spraying to improve adhesion and coating uniformity; however, these methods involve expensive equipment, complex processes, and significant raw material waste, making them unsuitable for industrial production. Ionic liquids offer advantages such as low vapor pressure, good thermal stability, and a wide electrochemical window; however, composite coatings of Ta and Ir-Ta cannot be achieved through ionic liquid electrodeposition of aqueous solutions. Summary of the Invention

[0003] In view of the shortcomings of the prior art, the purpose of this invention is to propose a method for preparing Ta or Ir-Ta coatings by electrodeposition in ionic liquid solution, followed by oxidation to prepare titanium-based IrO2-Ta2O5 electrode materials.

[0004] To achieve the objectives of this invention, the inventors, through extensive experimental research and tireless exploration, finally screened out a suitable ionic liquid electrodeposition solution and obtained the following technical solution: a method for preparing a titanium-based noble metal oxide coated electrode material, the method comprising the following steps:

[0005] (1) The titanium substrate is subjected to surface pretreatment, the pretreatment including sandblasting, acid etching and surface cleaning;

[0006] (2) On the surface of the titanium substrate pretreated in step (1), a constant current electrodeposition and high-temperature oxidation are performed using ionic liquid electrodeposition solution I to form a Ta2O5 coating.

[0007] (3) On the surface of the Ta2O5 coating formed in step (2), constant current electrodeposition and high temperature oxidation are performed using ionic liquid electrodeposition solution II to form an external IrO2-Ta2O5 composite coating, and titanium-based noble metal oxide coating electrode material is obtained.

[0008] The ionic liquid electrodeposition solution I is prepared by mixing BMIPF6 ionic liquid and anhydrous tantalum pentachloride at a ratio of 1 L:

[0009] It is obtained by mixing and dissolving in a ratio of (2-20)g;

[0010] The ionic liquid electrodeposition solution II is obtained by mixing and dissolving BMIPF6 ionic liquid with anhydrous tantalum pentachloride and anhydrous iridium trichloride in a ratio of 1L:(2-20)g:(3-20)g.

[0011] It should be noted that the BMIPF6 ionic liquid described in this invention is 1-methyl-3-butylimidazolium hexafluorophosphate. The coating obtained from ionic liquid electrodeposition solution I is Ta, which is oxidized at 450-550℃ to obtain a Ta2O5 coating; the coating obtained from ionic liquid electrodeposition solution II is a Ta-Ir composite coating, which is oxidized at 450-550℃ to obtain an IrO2-Ta2O5 composite coating. The Ta2O5 coating serves as the bottom layer of the titanium-based noble metal oxide coating electrode material; the IrO2-Ta2O5 composite coating serves as the active coating of the titanium-based noble metal oxide coating electrode material.

[0012] More preferably, in the preparation method of the titanium-based noble metal oxide coated electrode material as described above, the Ir:Ta molar ratio in the IrO2-Ta2O5 composite coating is 7:(2-3).

[0013] More preferably, in the preparation method of the titanium-based noble metal oxide coated electrode material as described above, in the ionic liquid electrodeposition solution I described in step (2), the Ti / IrO2-Ta2O5 electrode material is used as the anode, the pure titanium plate is used as the cathode, and the distance between the anode and the cathode is 19-21 mm.

[0014] More preferably, in the preparation method of the titanium-based noble metal oxide coated electrode material as described above, the constant current density in step (2) is 0.05–0.50 mA / dm. 2 The voltage between the anode and cathode is 1.0–4.0V, the electrodeposition temperature is 60–80℃, and the electrodeposition time is 0.5–4h.

[0015] More preferably, in the preparation method of the titanium-based noble metal oxide coated electrode material as described above, in the ionic liquid electrodeposition solution II described in step (3), the Ti / IrO2-Ta2O5 electrode material prepared by the coating oxidation process is used as the anode, and the titanium-based Ta2O5 coated electrode material prepared in step (2) is used as the cathode, with a distance of 19-21 mm between the anode and the cathode.

[0016] More preferably, in the preparation method of the titanium-based noble metal oxide coated electrode material as described above, the constant current density in step (2) is 0.05–0.50 mA / dm. 2 The voltage between the anode and cathode is 1.0–4.0V, the electrodeposition temperature is 60–80℃, and the electrodeposition time is 0.5–12h.

[0017] More preferably, in the preparation method of the titanium-based noble metal oxide coated electrode material as described above, step (2) is repeated 2 to 4 times before step (3).

[0018] More preferably, the preparation method of the titanium-based noble metal oxide coated electrode material as described above is repeated step (3) 5 to 7 times.

[0019] More preferably, in the preparation method of the titanium-based noble metal oxide coated electrode material as described above, the high-temperature oxidation step in step (2) or step (3) is to wash the sample sequentially with anhydrous ethanol and pure water, then dry it at 100-125°C for 4-8 min, and then oxidize it in a muffle furnace at 450-550°C for 10-20 min.

[0020] More preferably, in the preparation method of the titanium-based noble metal oxide coated electrode material as described above, the Ti / IrO2-Ta2O5 electrode material is prepared by a coating oxidation process.

[0021] Compared with the prior art, the preparation method of the titanium-based noble metal oxide coated electrode material of the present invention has the following advantages and significant progress:

[0022] (1) The present invention utilizes ionic liquid solution electrodeposition to prepare a Ta coating with good adhesion and uniform thickness, and then obtains a Ta2O5 underlayer with good adhesion and uniform thickness after oxidation.

[0023] (2) The present invention prepares an Ir-Ta coating with good adhesion and uniform thickness on the surface of the Ta2O5 substrate, and then obtains an IrO2-Ta2O5 active coating with good adhesion and uniform thickness through oxidation.

[0024] (3) The titanium-based noble metal oxide coated electrode material prepared by the present invention has good adhesion, good consistency of composition and structure, and long service life. Attached Figure Description

[0025] Figure 1 The image shows an electron microscope (EM) image of the Ti / IrO2-Ta2O5 electrode material prepared in Example 3. Specific Implementation

[0026] The present invention will now be described in detail with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention. These all fall within the scope of protection of the present invention.

[0027] Example 1

[0028] S1: Add 250ml of BMIPF6 ionic liquid to a 500ml electrodeposition tank in a vacuum glove box, then add 0.6g of anhydrous TaCl5 salt to the solution. Stir at 1000r / min and heat the solution to 80℃ to completely dissolve the tantalum salt into the ionic liquid, which is the ionic liquid electrodeposition solution I.

[0029] S2: Use a 20mm*20mm Ti / IrO2-Ta2O5 electrode material as the anode and a 20*20mm pure titanium plate as the cathode. The anode surface is parallel to the cathode surface, and the distance between the anode and the cathode is 20mm.

[0030] S3: Constant current electrodeposition was performed in ionic liquid electrodeposition solution I at 80℃, with a cathode current density of 0.05 mA / dm³. 2 The voltage between the anode and cathode is approximately 1.8V;

[0031] S4: After electrodeposition for 3 hours, the substrate material was removed, rinsed with anhydrous ethanol and pure water in sequence, dried at 120°C for 5 minutes, and then oxidized in a muffle furnace at 500°C for 15 minutes to obtain the Ta2O5 bottom layer, and then cooled to room temperature in air.

[0032] S5: Add 250ml of BMIPF6 ionic liquid to a 500ml electrodeposition tank in a vacuum glove box, then add 0.6g of anhydrous TaCl5 salt and 0.8g of anhydrous IrCl3 salt to the solution. Stir at 1000r / min and heat the solution to 80℃ to completely dissolve the tantalum salt into the ionic liquid, which is the ionic liquid electrodeposition solution II.

[0033] S6: The sample obtained in S4 was electrodeposited in ionic liquid electrodeposition solution II at 80℃ for 6 hours, then taken out and rinsed with anhydrous ethanol and pure water in sequence. After drying at 120℃ for 5 minutes, it was oxidized in a muffle furnace at 500℃ for 15 minutes and then cooled to room temperature to obtain Ti / IrO2-Ta2O5 electrode material 1.

[0034] Example 2

[0035] S1: Add 250ml of BMIPF6 ionic liquid to a 500ml electrodeposition tank in a vacuum glove box, then add 0.6g of anhydrous TaCl5 salt to the solution. Stir at 1000r / min and heat the solution to 80℃ to completely dissolve the tantalum salt into the ionic liquid, which is the ionic liquid electrodeposition solution I.

[0036] S2: Use a 20mm*20mm Ti / IrO2-Ta2O5 electrode material as the anode and a 20*20mm pure titanium plate as the cathode. The anode surface is parallel to the cathode surface, and the distance between the anode and the cathode is 20mm.

[0037] S3: Constant current electrodeposition in ionic liquid electrodeposition solution I at 80℃, with a cathode current density of 0.05 mA / dm³. 2 The voltage between the anode and cathode is approximately 1.8V;

[0038] S4: After electrodepositing in ionic liquid electrodeposition solution I at 80℃ for 1 hour, the substrate material was removed, rinsed with anhydrous ethanol and pure water in sequence, dried at 120℃ for 5 minutes, and then oxidized in a muffle furnace at 500℃ for 15 minutes to obtain the Ta2O5 bottom layer, and air-cooled to room temperature.

[0039] S5: Repeat step S4 3 times to obtain the Ta2O5 bottom layer;

[0040] S6: Add 250ml of BMIPF6 ionic liquid to a 500ml electrodeposition tank in a vacuum glove box, then add 0.6g of anhydrous TaCl5 salt and 0.8g of anhydrous IrCl3 salt to the solution. Stir at 1000r / min and heat the solution to 80℃ to completely dissolve the tantalum salt into the ionic liquid, which is the ionic liquid electrodeposition solution II.

[0041] S7: The sample obtained in S5 was electrodeposited in ionic liquid electrodeposition solution II at 80℃ for 6 hours, then taken out, rinsed with anhydrous ethanol and pure water in sequence, dried at 120℃ for 5 minutes, and then oxidized in a muffle furnace at 500℃ for 15 minutes. After air cooling to room temperature, Ti / IrO2-Ta2O5 electrode material 2 can be obtained.

[0042] Example 3

[0043] S1: Add 250ml of BMIPF6 ionic liquid to a 500ml electrodeposition tank in a vacuum glove box, then add 0.6g of anhydrous TaCl5 salt to the solution. Stir at 1000r / min and heat the solution to 80℃ to completely dissolve the tantalum salt into the ionic liquid, which is the ionic liquid electrodeposition solution I.

[0044] S2: Use a 20mm*20mm Ti / IrO2-Ta2O5 electrode material as the anode and a 20*20mm pure titanium plate as the cathode. The anode surface is parallel to the cathode surface, and the distance between the anode and the cathode is 20mm.

[0045] S3: Constant current electrodeposition in ionic liquid electrodeposition solution I at 80℃, with a cathode current density of 0.05 mA / dm³. 2 The voltage between the anode and cathode is approximately 1.8V;

[0046] S4: After electrodeposition for 1 hour, the substrate material was removed, rinsed with anhydrous ethanol and pure water in sequence, dried at 120°C for 5 minutes, and then oxidized in a muffle furnace at 500°C for 15 minutes to obtain the Ta2O5 bottom layer, and then cooled to room temperature in air.

[0047] S5: Repeat step S4 3 times to obtain the Ta2O5 bottom layer;

[0048] S6: Add 250ml of BMIPF6 ionic liquid to a 500ml electrodeposition tank in a vacuum glove box, then add 0.6g of anhydrous TaCl5 salt and 0.8g of anhydrous IrCl3 salt to the solution. Stir at 1000r / min and heat the solution to 80℃ to completely dissolve the tantalum salt into the ionic liquid, which is the ionic liquid electrodeposition solution II.

[0049] S7: The sample obtained in S5 is electrodeposited in ionic liquid electrodeposition solution II at 80℃ for 1 hour, then taken out and rinsed with anhydrous ethanol and pure water in sequence. After drying at 120℃ for 5 minutes, it is oxidized in a muffle furnace at 500℃ for 15 minutes and then cooled to room temperature to obtain the IrO2-Ta2O5 coating.

[0050] S8: Repeat step S7 6 times to obtain Ti / IrO2-Ta2O5 electrode material 3 (e.g. Figure 1 (As shown).

[0051] The enhanced lifespans of electrode materials 1, 2, and 3 obtained in Examples 1, 2, and 3 were 10.2 days, 13.5 days, and 20.5 days, respectively.

[0052] Example 4 (using ionic liquid BMIPF4 instead of BMIPF6)

[0053] S1: Add 250ml of BMIPF4 ionic liquid to a 500ml electrodeposition tank in a vacuum glove box, then add 0.6g of anhydrous TaCl5 salt to the solution. Stir at 1000r / min and heat the solution to 80℃ to completely dissolve the tantalum salt into the ionic liquid, which is the ionic liquid electrodeposition solution I.

[0054] S2: Use a 20mm*20mm Ti / IrO2-Ta2O5 electrode material as the anode and a 20*20mm pure titanium plate as the cathode. The anode surface is parallel to the cathode surface, and the distance between the anode and the cathode is 20mm.

[0055] S3: Constant current electrodeposition in ionic liquid electrodeposition solution I at 80℃, with a cathode current density of 0.05 mA / dm³. 2 The voltage between the anode and cathode is approximately 1.8V;

[0056] S4: After electrodeposition for 1 hour, the substrate material was removed, rinsed with anhydrous ethanol and pure water in sequence, dried at 120°C for 5 minutes, and then oxidized in a muffle furnace at 500°C for 15 minutes to obtain the Ta2O5 bottom layer, and then cooled to room temperature in air.

[0057] S5: Repeat step S4 3 times to obtain the Ta2O5 bottom layer;

[0058] S6: Add 250 ml of BMIPF4 ionic liquid to a 500 ml electrodeposition tank in a vacuum glove box, then add 0.6 g of anhydrous TaCl5 salt and 0.8 g of anhydrous IrCl3 salt to the solution. Stir at 1000 r / min and heat the solution to 80 °C to completely dissolve the tantalum salt into the ionic liquid, which is the ionic liquid electrodeposition solution II.

[0059] S7: The sample obtained from S5 was electrodeposited in ionic liquid electrodeposition solution II at 80℃ for 1 hour, then taken out, rinsed with anhydrous ethanol and pure water in sequence, dried at 120℃ for 5 minutes, and then oxidized in a muffle furnace at 500℃ for 15 minutes. After air cooling to room temperature, the IrO2-Ta2O5 coating was obtained.

[0060] S8: Repeat step S7 6 times to obtain Ti / IrO2-Ta2O5 electrode material 4.

[0061] The enhanced lifetime analysis showed that the enhanced lifetime of electrode material 4 obtained in Example 4 was 16.2 days, which was less than the 20.5 days of electrode material 3.

[0062] Example 5

[0063] Example 5 describes the preparation of a Ti / IrO2-Ta2O5 electrode material with the same noble metal Ir and Ta content as in Example 3 using a coating process. The specific implementation steps are as follows:

[0064] S1: Coat the surface of the titanium substrate with a 0.20 mol / L solution of tantalum pentachloride, n-butanol, and n-butanol three times. The coating should be fully wetted. The oxidation temperature is 500℃ and the oxidation time is 15 min.

[0065] S2: Apply 0.20 mol of IrCl3 + tantalum pentachloride n-butanol solution / L + n-butanol + isopropanol solution to the sample obtained in S1 three times. The coating should be fully moistened. The oxidation temperature is 500℃ and the oxidation time is 15 min. The molar ratio of IrCl3 to tantalum pentachloride is 1:1.

[0066] S3: Coat the sample obtained in S2 with an oxidation solution of 0.20 mol IrCl3 + tantalum pentachloride n-butanol / L + n-butanol + isopropanol six times. The coating should be saturated and moist. The oxidation temperature is 500℃. The oxidation time for the first five oxidations is 15 min, and the molar ratio of IrCl3 to tantalum pentachloride is 7:3. The oxidation time for the sixth oxidation is 30 min, and Ti / IrO2-Ta2O5 electrode material 5 can be obtained.

[0067] The enhanced lifetime analysis showed that the enhanced lifetime of electrode material 5 obtained in Example 5 was 18.3 days, which was less than the 20.5 days of electrode material 3.

Claims

1. A method for preparing a titanium-based noble metal oxide coated electrode material, characterized in that, The method includes the following steps: (1) The titanium substrate is subjected to surface pretreatment, which includes sandblasting, acid etching and surface cleaning; (2) On the surface of the titanium substrate pretreated in step (1), a constant current electrodeposition and high-temperature oxidation are performed using ionic liquid electrodeposition solution I to form a Ta2O5 coating; (3) On the surface of the Ta2O5 coating formed in step (2), constant current electrodeposition and high temperature oxidation are performed using ionic liquid electrodeposition solution II to form an external IrO2-Ta2O5 composite coating, and titanium-based noble metal oxide coating electrode material is obtained. The ionic liquid electrodeposition solution I is prepared by mixing and dissolving BMIPF6 ionic liquid with anhydrous tantalum pentachloride at a ratio of 1L:(2.0~20)g; The ionic liquid electrodeposition solution II is obtained by mixing and dissolving BMIPF6 ionic liquid with anhydrous tantalum pentachloride and anhydrous iridium trichloride in a ratio of 1L:(2~20)g:(3~20)g.

2. The method for preparing the titanium-based noble metal oxide coated electrode material according to claim 1, characterized in that, The IrO2-Ta2O5 composite coating has an Ir:Ta molar ratio of 7:(2~3).

3. The method for preparing the titanium-based noble metal oxide coated electrode material according to claim 1, characterized in that, In the ionic liquid electrodeposition solution I described in step (2), Ti / IrO2-Ta2O5 electrode material is used as the anode and pure titanium plate is used as the cathode. The distance between the anode and the cathode is 19~21 mm.

4. The method for preparing the titanium-based noble metal oxide coated electrode material according to claim 3, characterized in that, The constant current density in step (2) is 0.05~0.50 mA / dm. 2 The voltage between the anode and cathode is 1.0~4.0V, the electrodeposition temperature is 60~80℃, and the electrodeposition time is 0.5~4h.

5. The method for preparing the titanium-based noble metal oxide coated electrode material according to claim 1, characterized in that, In the ionic liquid electrodeposition solution II described in step (3), the Ti / IrO2-Ta2O5 electrode material prepared by the coating oxidation process is used as the anode, and the titanium-based Ta2O5 coated electrode material prepared in step (2) is used as the cathode. The distance between the anode and the cathode is 19~21 mm.

6. The method for preparing the titanium-based noble metal oxide coated electrode material according to claim 5, characterized in that, The constant current density in step (2) is 0.05~0.50 mA / dm. 2 The voltage between the anode and cathode is 1.0~4.0V, the electrodeposition temperature is 60~80℃, and the electrodeposition time is 0.5~12h.

7. The method for preparing the titanium-based noble metal oxide coated electrode material according to claim 1, characterized in that, Before step (3), repeat step (2) 2 to 4 times.

8. The method for preparing the titanium-based noble metal oxide coated electrode material according to claim 1, characterized in that, Repeat step (3) 5 to 7 times.

9. The method for preparing the titanium-based noble metal oxide coated electrode material according to claim 1, characterized in that, The high-temperature oxidation step described in step (2) or step (3) involves rinsing the sample sequentially with anhydrous ethanol and pure water, drying it at 100-125°C for 4-8 minutes, and then oxidizing it in a muffle furnace at 450-550°C for 10-20 minutes.

10. The method for preparing the titanium-based noble metal oxide coated electrode material according to claim 3, characterized in that, The Ti / IrO2-Ta2O5 electrode material is prepared by a coating oxidation process.

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