Method for manufacturing interface-enhanced anode plate and titanium-based lead dioxide anode plate

Abstract

The manufacturing method of the disclosed interface-enhanced anode plate comprises the following steps: carrying out sand blasting and acid pickling on the surface of the doped titanium substrate; snSO, HSO, gelatin and thiourea are selected as deposition liquid, electro-deposition is conducted on the surface of the doped titanium substrate, and ZnSO is added into the deposition liquid to continue electro-deposition; an electrolyte containing NHF and citric acid is selected, the workpiece is used as an anode to be subjected to oxidation treatment in the electrolyte, then the workpiece is placed in alkali liquor to be subjected to alkali etching treatment, and finally the workpiece is subjected to thermocuring treatment. Pb (NO), nanometer TaO5, Cu (NO). 3HO and PVP-K30 are selected as deposition liquid, and electro-deposition is carried out on the surface of a workpiece. The disclosed titanium-based lead dioxide anode plate sequentially comprises a doped titanium substrate, a SnO intermediate layer and a nano-modified beta-PbO active layer from inside to outside, the SnO intermediate layer and the doped titanium substrate are combined to form a first enhanced interface, and the SnO intermediate layer and the nano-modified beta-PbO active layer are combined to form a second enhanced interface. The anode plate has higher coating bonding strength and longer service life.

Description

Technical Field

[0001] This invention belongs to the field of anode plates, specifically relating to a method for manufacturing an interface-enhanced anode plate and a titanium-based lead dioxide anode plate. Background Technology

[0002] Titanium-based lead dioxide anodes are a novel electrode material with α-PbO2 and β-PbO2 coatings as its core, primarily used in... Electrochemical Industry Organic matter electrolysis, wastewater treatment and lead-acid batteries In fields such as positive electrode.

[0003] In existing technologies, titanium-based lead dioxide anodes typically enhance adhesion and conductivity by combining an intermediate layer of tin-antimony oxide with an active layer. This intermediate layer is prepared through thermal decomposition after coating. However, with industrial development, titanium-based lead dioxide anode plates produced using this traditional method no longer meet customer needs. The bonding strength between the active layer and the titanium substrate still needs improvement. Furthermore, after prolonged use, the coating is prone to cracking, allowing electrolyte to seep through the cracks and contact the titanium substrate, causing oxidation of the substrate surface and further reducing coating adhesion. In severe cases, coating peeling may occur. Summary of the Invention

[0004] To further improve the bonding strength of the coating on the surface of titanium-based lead dioxide anode plates and to solve the problems of easy oxidation of the substrate and easy cracking of the coating, this invention provides a method for manufacturing an interface-reinforced anode plate, which includes the following steps:

[0005] S1. Sandblasting and acid washing are performed on the surface of the titanium-doped substrate to form a pit structure on the substrate and increase the surface area.

[0006] S2. Select a deposition solution containing 48-55 g / L SnSO4, 50-70 g / L H2SO4, 0.8-2 g / L gelatin, and 0.03-0.1 g / L thiourea. Electrodeposit on the surface of a doped titanium substrate at 20-25℃ and a current density of 7-12 mA / cm². Then, add ZnSO4 to the deposition solution to make it contain 13-18 g / L ZnSO4, and continue electrodeposition at a current density of 12-16 mA / cm². This stepwise electrodeposition allows Sn to be deposited first in the surface pits of the doped titanium substrate to form the first reinforcing interface. After adjusting the electrodeposition solution, Sn-Zn alloy deposition continues to form on the surface.

[0007] S3. Select an electrolyte containing 0.2-0.4 mol / L NH4F and 0.05-0.2 mol / L citric acid, with a water-ethylene glycol volume ratio of 6-8:3. Use the workpiece obtained in step S2 as the anode and a titanium-based platinum-plated sheet as the cathode. Treat the workpiece in the electrolyte at 15-25V for 4-8 min, then at 40-45V for 10-15 min. During this electrochemical process, in the Sn-Zn alloy on the workpiece surface, Zn dissolves as a sacrificial phase to form pore nuclei, and Sn is oxidized to SnO2. After anodizing, place the workpiece in an alkaline solution for alkaline etching to dissolve residual Zn and deepen the pores. Finally, heat-solidify the workpiece at 260-300℃ for 15-30 min under an argon inert atmosphere to stabilize the SnO2 lattice, ultimately obtaining a porous SnO2 intermediate layer.

[0008] S4. Select a deposition solution containing 170-200 g / L Pb(NO3)2, 7-15 g / L nano-Ta2O5 (average particle size 60 nm), 3-8 g / L Cu(NO3)2·3H2O, and 0.5-2 g / L PVP-K30. Electrodeposit the solution on the surface of the workpiece obtained in step S3 at 60-70℃ and a current density of 15-25 mA / cm². In this deposition solution, Cu(NO3)2·3H2O is a grain refiner, and PVP-K30 can prevent the agglomeration of nanoparticles. During electrodeposition, PbO2 is first deposited on the pore walls of the SnO2 intermediate layer, and nano-Ta2O5 fills the grain boundaries in the pores to form a second reinforcing interface. Then, PbO2 and Ta2O5 continue to co-deposit to form a nano-modified β-PbO2 active layer.

[0009] Furthermore, the doped titanium substrate is made by adding 3-5 wt% tantalum powder and 1-3 wt% niobium powder to titanium powder, and then hot isostatically pressing it at 950-1000℃ and 120-150MPa for 2-3 hours to form a plate. In this way, the Ti matrix and the Ta and Nb dopants form a solid solution, which, in addition to improving the conductivity of the matrix, mainly inhibits the oxidative growth of TiO2 at the interface.

[0010] Preferably, in step S1, the sandblasting uses 120-180 mesh white corundum, and the pressure of the compressed air driving the abrasive is 0.5-0.8 MPa; the pickling uses a compound solution containing 8-12 wt% oxalic acid and 1-3 wt% hydrofluoric acid, and the pickling temperature is 65-75℃; such surface pitting treatment can greatly increase the surface area of ​​the doped titanium substrate, creating conditions for the subsequent formation of the first reinforcing interface and improving the bonding strength with the intermediate layer.

[0011] Preferably, in step S3, the alkaline solution contains 30-40 g / L NaOH, 10-20 g / L sodium gluconate, and 0.5-2 g / L hexamethylenetetramine. The alkaline etching treatment is performed at a temperature of 40-50°C for 2-5 minutes. Hexamethylenetetramine acts as a corrosion inhibitor and can form an adsorption protective film on the SnO2 surface to prevent excessive loss of SnO2.

[0012] The titanium-based lead dioxide anode plate prepared by the above method comprises, from the inner layer to the outer layer, a doped titanium substrate, a SnO2 intermediate layer and a nano-modified β-PbO2 active layer. The SnO2 intermediate layer and the doped titanium substrate are bonded to form a first reinforcing interface, and the SnO2 intermediate layer and the nano-modified β-PbO2 active layer are bonded to form a second reinforcing interface.

[0013] Preferably, the thickness of the doped titanium substrate is 2 mm, and by controlling the parameters and processing time of each of the above-mentioned fabrication steps, the thickness of the first reinforcing interface is 1.5-2.5 μm, the thickness of the SnO2 intermediate layer is 25-35 μm, the thickness of the second reinforcing interface is 5-8 μm, and the thickness of the nano-modified β-PbO2 active layer is 180-220 μm.

[0014] Through the above technical solutions, the present invention has at least the following beneficial effects:

[0015] The method for fabricating an interface-enhanced anode plate described in this application involves a combination of increasing the bonding surface area through pit treatment on the surface of a doped titanium substrate, a stepwise electrodeposition of the intermediate layer, and a combination of electrochemical anodizing to create pores on the surface of the intermediate layer and filling the grain boundaries within the pores with nano-Ta2O5. This results in a titanium-based lead dioxide anode plate with a first and a second reinforcing interface, leading to stronger coating adhesion.

[0016] In addition, its doped titanium substrate forms a solid solution with Ta and Nb dopants, which can inhibit the oxidative growth of TiO2 at the substrate interface. Furthermore, its nano-modified β-PbO2 active layer is more dense, which can resist cracking and toughen the substrate, making it more difficult for the electrolyte to penetrate into the titanium surface. This further avoids the reduction in coating adhesion caused by oxidation of the titanium substrate surface.

[0017] In summary, compared with titanium-based lead dioxide anode plates prepared by traditional methods, the product of this application has higher coating bonding strength and longer service life. Detailed Implementation

[0018] The present invention will be further illustrated by the following examples.

[0019] Example 1

[0020] This embodiment of a method for manufacturing an interface-enhanced anode plate includes the following steps:

[0021] S1. Sandblasting and acid washing are performed on the surface of the titanium-doped substrate to form a pit structure on the substrate and increase the surface area.

[0022] S2. A deposition solution containing 53 g / L SnSO4, 60 g / L H2SO4, 1.3 g / L gelatin, and 0.03 g / L thiourea was selected. Electrodeposition was performed on the surface of a doped titanium substrate at 23°C and a current density of 9 mA / cm². ZnSO4 was then added to the deposition solution to make it contain 16 g / L ZnSO4, and electrodeposition continued at a current density of 14 mA / cm². This stepwise electrodeposition allowed Sn to first deposit in the surface pits of the doped titanium substrate to form the first reinforcing interface. After adjusting the electrodeposition solution, Sn-Zn alloy deposition continued to form on the surface.

[0023] S3. Select a solution containing 0.3 mol / L NH4F and 0.13 mol / L citric acid, with a water-ethylene glycol volume ratio of 7:3 as the electrolyte. Use the workpiece obtained in step S2 as the anode and a titanium-based platinum-plated sheet as the cathode. Treat the workpiece in the electrolyte at 20V for 6 min, then at 42V for 12 min. During this electrochemical process, in the Sn-Zn alloy on the workpiece surface, Zn dissolves as a sacrificial phase to form pore nuclei, and Sn is oxidized to SnO2. After anodizing, place the workpiece in an alkaline solution for alkaline etching to dissolve the residual Zn and deepen the pores. Finally, heat-solidify the workpiece at 280℃ for 20 min under an argon inert atmosphere to stabilize the SnO2 lattice, ultimately obtaining a porous SnO2 intermediate layer.

[0024] S4. Select a deposition solution containing 185 g / L Pb(NO3)2, 11 g / L nano Ta2O5 (average particle size 60 nm), 5 g / L Cu(NO3)2·3H2O, and 1.3 g / L PVP-K30. Electrodeposition is performed on the surface of the workpiece obtained in step S3 at 65 °C and a current density of 20 mA / cm². In this deposition solution, Cu(NO3)2·3H2O is a grain refiner, and PVP-K30 can prevent the agglomeration of nanoparticles. During electrodeposition, PbO2 is first deposited on the pore walls of the SnO2 intermediate layer, while nano Ta2O5 fills the grain boundaries in the pores to form a second reinforcing interface. Then, PbO2 and Ta2O5 continue to co-deposit to form a nano-modified β-PbO2 active layer.

[0025] The aforementioned doped titanium substrate is made by adding 4wt% tantalum powder and 2wt% niobium powder to titanium powder, and then hot isostatically pressing it at 980℃ and 130MPa for 2.5h to form a plate. In this way, the Ti matrix and the Ta and Nb dopants form a solid solution, which, in addition to improving the conductivity of the matrix, mainly inhibits the oxidative growth of TiO2 at the interface.

[0026] In step S1, the sandblasting uses 150-mesh white corundum, and the pressure of the compressed air driving the abrasive is 0.7 MPa; the pickling uses a compound solution containing 10 wt% oxalic acid and 2 wt% hydrofluoric acid, and the pickling temperature is 70°C; such surface pitting treatment can greatly increase the surface area of ​​the doped titanium substrate, creating conditions for the formation of the first reinforcing interface and improving the bonding strength with the intermediate layer.

[0027] In step S3, the alkaline solution contains 35 g / L NaOH, 15 g / L sodium gluconate, and 0.8 g / L hexamethylenetetramine. The alkaline etching treatment is performed at a temperature of 45°C for 4 minutes. Hexamethylenetetramine acts as a corrosion inhibitor and can form an adsorption protective film on the SnO2 surface to prevent excessive loss of SnO2.

[0028] The titanium-based lead dioxide anode plate prepared by the above method comprises, from the inner layer to the outer layer, a doped titanium substrate, a SnO2 intermediate layer, and a nano-modified β-PbO2 active layer. The SnO2 intermediate layer and the doped titanium substrate bond to form a first reinforcing interface, and the SnO2 intermediate layer and the nano-modified β-PbO2 active layer bond to form a second reinforcing interface. The thickness of the doped titanium substrate is 2 mm. Through parameter control and processing time control in each of the above fabrication steps, the thickness of the first reinforcing interface is 2.2 μm, the thickness of the SnO2 intermediate layer is 30 μm, the thickness of the second reinforcing interface is 7 μm, and the thickness of the nano-modified β-PbO2 active layer is 208 μm.

[0029] Example 2

[0030] This embodiment of a method for manufacturing an interface-enhanced anode plate includes the following steps:

[0031] S1. Sandblasting and acid washing are performed on the surface of the titanium-doped substrate to form a pit structure on the substrate and increase the surface area.

[0032] S2. A deposition solution containing 48 g / L SnSO4, 50 g / L H2SO4, 0.8 g / L gelatin, and 0.06 g / L thiourea was selected. Electrodeposition was performed on the surface of a doped titanium substrate at 20°C and a current density of 12 mA / cm². ZnSO4 was then added to the deposition solution to make it contain 13 g / L ZnSO4, and electrodeposition continued at a current density of 16 mA / cm². This stepwise electrodeposition allowed Sn to first deposit in the surface pits of the doped titanium substrate to form the first reinforcing interface. After adjusting the electrodeposition solution, Sn-Zn alloy deposition continued to form on the surface.

[0033] S3. Select a solution containing 0.4 mol / L NH4F and 0.05 mol / L citric acid, with a water-ethylene glycol volume ratio of 8:3 as the electrolyte. Use the workpiece obtained in step S2 as the anode and a titanium-based platinum-plated sheet as the cathode. Treat the workpiece in the electrolyte at 25V for 4 min, then at 40V for 15 min. During this electrochemical process, in the Sn-Zn alloy on the workpiece surface, Zn dissolves as a sacrificial phase to form pore nuclei, and Sn is oxidized to SnO2. After anodizing, place the workpiece in an alkaline solution for alkaline etching to dissolve the residual Zn and deepen the pores. Finally, heat-solidify the workpiece at 300℃ for 15 min under an argon inert atmosphere to stabilize the SnO2 lattice, ultimately obtaining a porous SnO2 intermediate layer.

[0034] S4. Select a deposition solution containing 200 g / L Pb(NO3)2, 7 g / L nano-Ta2O5 (average particle size of 60 nm), 3 g / L Cu(NO3)2·3H2O, and 0.5 g / L PVP-K30. Electrodeposit the solution at 70 °C on the surface of the workpiece obtained in step S3 with a current density of 15 mA / cm². In this deposition solution, Cu(NO3)2·3H2O is a grain refiner, and PVP-K30 can prevent the agglomeration of nanoparticles. During electrodeposition, PbO2 is first deposited on the pore walls of the SnO2 intermediate layer, while nano-Ta2O5 fills the grain boundaries in the pores to form a second reinforcing interface. Then, PbO2 and Ta2O5 continue to co-deposit to form a nano-modified β-PbO2 active layer.

[0035] The aforementioned doped titanium substrate is made by adding 3wt% tantalum powder and 1wt% niobium powder to titanium powder, and then hot isostatically pressing it at 950℃ and 150MPa for 3 hours to form a plate. In this way, the Ti matrix and the Ta and Nb dopants form a solid solution, which, in addition to improving the conductivity of the matrix, mainly inhibits the oxidative growth of TiO2 at the interface.

[0036] In step S1, the sandblasting uses 180-mesh white corundum, and the pressure of the compressed air driving the abrasive is 0.5 MPa; the pickling uses a compound solution containing 8 wt% oxalic acid and 1 wt% hydrofluoric acid, and the pickling temperature is 65°C; such surface pitting treatment can greatly increase the surface area of ​​the doped titanium substrate, creating conditions for the formation of the first reinforcing interface and improving the bonding strength with the intermediate layer.

[0037] In step S3, the alkaline solution contains 30 g / L NaOH, 10 g / L sodium gluconate, and 0.5 g / L hexamethylenetetramine. The alkaline etching treatment is performed at a temperature of 40°C for 5 minutes. Hexamethylenetetramine acts as a corrosion inhibitor and can form an adsorption protective film on the SnO2 surface to prevent excessive loss of SnO2.

[0038] The titanium-based lead dioxide anode plate prepared by the above method comprises, from the inner layer to the outer layer, a doped titanium substrate, a SnO2 intermediate layer, and a nano-modified β-PbO2 active layer. The SnO2 intermediate layer and the doped titanium substrate bond to form a first reinforcing interface, and the SnO2 intermediate layer and the nano-modified β-PbO2 active layer bond to form a second reinforcing interface. The thickness of the doped titanium substrate is 2 mm. Through control of the parameters and processing time in each of the above fabrication steps, the thickness of the first reinforcing interface is 1.5 μm, the thickness of the SnO2 intermediate layer is 35 μm, the thickness of the second reinforcing interface is 5 μm, and the thickness of the nano-modified β-PbO2 active layer is 180 μm.

[0039] Example 3

[0040] This embodiment of a method for manufacturing an interface-enhanced anode plate includes the following steps:

[0041] S1. Sandblasting and acid washing are performed on the surface of the titanium-doped substrate to form a pit structure on the substrate and increase the surface area.

[0042] S2. A deposition solution containing 55 g / L SnSO4, 70 g / L H2SO4, 2 g / L gelatin, and 0.1 g / L thiourea was selected. Electrodeposition was performed on the surface of a doped titanium substrate at 25°C and a current density of 7 mA / cm². ZnSO4 was then added to the deposition solution to make it contain 18 g / L ZnSO4, and electrodeposition continued at a current density of 12 mA / cm². This stepwise electrodeposition allowed Sn to first deposit in the surface pits of the doped titanium substrate to form the first reinforcing interface. After adjusting the electrodeposition solution, Sn-Zn alloy deposition continued to form on the surface.

[0043] S3. Select a solution containing 0.2 mol / L NH4F and 0.2 mol / L citric acid, with a water-ethylene glycol volume ratio of 6:3 as the electrolyte. Use the workpiece obtained in step S2 as the anode and a titanium-based platinum-plated sheet as the cathode. Treat the workpiece in the electrolyte at 15V for 8 min, then at 45V for 10 min. During this electrochemical process, in the Sn-Zn alloy on the workpiece surface, Zn dissolves as a sacrificial phase to form pore nuclei, and Sn is oxidized to SnO2. After anodizing, place the workpiece in an alkaline solution for alkaline etching to dissolve the residual Zn and deepen the pores. Finally, heat-solidify the workpiece at 260℃ for 30 min under an argon inert atmosphere to stabilize the SnO2 lattice, ultimately obtaining a porous SnO2 intermediate layer.

[0044] S4. Select a deposition solution containing 170 g / L Pb(NO3)2, 15 g / L nano Ta2O5 (average particle size 60 nm), 8 g / L Cu(NO3)2·3H2O, and 2 g / L PVP-K30. Electrodeposit the solution on the surface of the workpiece obtained in step S3 at 60 °C and a current density of 25 mA / cm². In this deposition solution, Cu(NO3)2·3H2O is a grain refiner, and PVP-K30 can prevent the agglomeration of nanoparticles. During electrodeposition, PbO2 is first deposited on the pore walls of the SnO2 intermediate layer. Nano Ta2O5 fills the grain boundaries in the pores to form a second reinforcing interface. Then, PbO2 and Ta2O5 continue to co-deposit to form a nano-modified β-PbO2 active layer.

[0045] The aforementioned doped titanium substrate is made by adding 5 wt% tantalum powder and 3 wt% niobium powder to titanium powder, and then hot isostatically pressing it at 1000℃ and 120MPa for 2 hours to form a plate. In this way, the Ti matrix and the Ta and Nb dopants form a solid solution, which, in addition to improving the conductivity of the matrix, mainly inhibits the oxidative growth of TiO2 at the interface.

[0046] In step S1, the sandblasting uses 120-mesh white corundum, and the pressure of the compressed air driving the abrasive is 0.8 MPa; the pickling uses a compound solution containing 12 wt% oxalic acid and 3 wt% hydrofluoric acid, and the pickling temperature is 75°C; such surface pitting treatment can greatly increase the surface area of ​​the doped titanium substrate, creating conditions for the formation of the first reinforcing interface and improving the bonding strength with the intermediate layer.

[0047] In step S3, the alkaline solution contains 40 g / L NaOH, 20 g / L sodium gluconate, and 2 g / L hexamethylenetetramine. The alkaline etching treatment is performed at a temperature of 50°C for 2 minutes. Hexamethylenetetramine acts as a corrosion inhibitor and can form an adsorption protective film on the SnO2 surface to prevent excessive loss of SnO2.

[0048] The titanium-based lead dioxide anode plate prepared by the above method comprises, from the inner layer to the outer layer, a doped titanium substrate, a SnO2 intermediate layer, and a nano-modified β-PbO2 active layer. The SnO2 intermediate layer and the doped titanium substrate bond to form a first reinforcing interface, and the SnO2 intermediate layer and the nano-modified β-PbO2 active layer bond to form a second reinforcing interface. The thickness of the doped titanium substrate is 2 mm. Through control of the parameters and processing time in each of the above fabrication steps, the thickness of the first reinforcing interface is 2.5 μm, the thickness of the SnO2 intermediate layer is 25 μm, the thickness of the second reinforcing interface is 8 μm, and the thickness of the nano-modified β-PbO2 active layer is 220 μm.

[0049] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Based on the present invention, and through the above description, those skilled in the art can make various changes and modifications without departing from the technical concept of 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.

[0050] Comparative Example

[0051] A titanium-based lead dioxide anode plate with a tin-antimony oxide intermediate layer, prepared by conventional methods, was used as a comparative example. The specific method is as follows:

[0052] S1. After removing oxides and oil stains from the 2mm thick titanium substrate with acid and alkali solutions, rinse it clean and set it aside for later use.

[0053] S2. Mix n(SnCl2·2H2O) and n(SbCl3) in a ratio of 10:1 and dissolve them in isopropanol to prepare a coating solution. Apply the solution to a titanium substrate, dry it, and then oxidize it at 500℃ for 2 hours in an oxygen atmosphere to obtain a SnO2-Sb2O3 intermediate layer with a thickness of about 35μm.

[0054] S3. Coat the Sb-SnO2 intermediate layer with a saturated Pb(NO3)2 aqueous solution containing a small amount of n-butanol. After drying for 10 min, transfer it to a muffle furnace at 500℃ for thermal decomposition for 10 min. Repeat this process 10 times, and extend the time to 1 h for the last time to obtain a PbO2 active layer with a thickness of about 215 μm.

[0055] The coating bond strength of each specimen in the examples and comparative examples was measured according to ASTM D4541;

[0056] Electrode accelerated life test: Using a copper sheet as the cathode, the samples prepared in each example and comparative example were used as the anodes, with an electrode spacing of 20 mm. The test was conducted at 50 °C in a 1.0 mol / L H₂SO₄ solution at a current of 40 mA / cm². 2 Electrolysis is performed with a constant current. When the cell voltage rises sharply to exceed the initial voltage by 10V, the electrolysis time at this point is the accelerated life of the electrode. The anode plate is then removed, cleaned, and its surface coating condition is observed.

[0057] The performance test results are shown in Table 1. As can be seen from Table 1, the products of each embodiment of the technical solution of this application have better coating bonding strength and longer service life.

[0058] Table 1:

[0059]

Claims

1. A method for manufacturing an interface-enhanced anode plate, characterized in that, Includes the following steps: S1. The surface of the doped titanium substrate is sandblasted and then acid-washed; S2. Select a deposition solution containing 48-55 g / L SnSO4, 50-70 g / L H2SO4, 0.8-2 g / L gelatin and 0.03-0.1 g / L thiourea. Electrodeposit on the surface of a doped titanium substrate at 20-25℃ and a current density of 7-12 mA / cm². Then add ZnSO4 to the deposition solution to make it contain a ZnSO4 concentration of 13-18 g / L, and continue electrodeposition at a current density of 12-16 mA / cm². S3. Select an electrolyte containing 0.2-0.4 mol / L NH4F and 0.05-0.2 mol / L citric acid, with a water-ethylene glycol volume ratio of 6-8:

3. Use the workpiece obtained in step S2 as the anode and a titanium-based platinum-plated sheet as the cathode. Treat the workpiece in the electrolyte at 15-25V for 4-8 min, then at 40-45V for 10-15 min. After anodizing, place the workpiece in an alkaline solution for alkaline etching. Finally, heat-cure the workpiece at 260-300℃ for 15-30 min under an inert atmosphere. S4. Select a deposition solution containing 170-200 g / L Pb(NO3)2, 7-15 g / L nano Ta2O5, 3-8 g / L Cu(NO3)2·3H2O and 0.5-2 g / L PVP-K30, and perform electrodeposition on the surface of the workpiece obtained in step S3 at 60-70℃ and a current density of 15-25 mA / cm².

2. The method for manufacturing an interface-enhanced anode plate according to claim 1, characterized in that: The doped titanium substrate is a plate made by adding 3-5 wt% tantalum powder and 1-3 wt% niobium powder to titanium powder, and then hot isostatically pressing it at 950-1000℃ and 120-150MPa for 2-3 hours.

3. A method for manufacturing an interface-enhanced anode plate according to claim 1 or 2, characterized in that: In step S1, the sandblasting uses 120-180 mesh white corundum, and the pressure of the compressed air driving the sand is 0.5-0.8 MPa; the pickling uses a compound solution containing 8-12 wt% oxalic acid and 1-3 wt% hydrofluoric acid, and the pickling temperature is 65-75℃.

4. A method for manufacturing an interface-enhanced anode plate according to claim 1 or 2, characterized in that: In step S3, the alkaline solution contains 30-40 g / L NaOH, 10-20 g / L sodium gluconate, and 0.5-2 g / L hexamethylenetetramine. The alkaline etching treatment is performed at a temperature of 40-50°C for 2-5 minutes.

5. A titanium-based lead dioxide anode plate, characterized in that: It is prepared by the method according to any one of claims 2-4, and comprises, from the inner layer to the outer layer, a doped titanium substrate, a SnO2 intermediate layer and a nano-modified β-PbO2 active layer, wherein the SnO2 intermediate layer and the doped titanium substrate are bonded to form a first reinforcing interface, and the SnO2 intermediate layer and the nano-modified β-PbO2 active layer are bonded to form a second reinforcing interface.

6. A titanium-based lead dioxide anode plate according to claim 5, characterized in that: The thickness of the first reinforcing interface is 1.5-2.5 μm, the thickness of the SnO2 intermediate layer is 25-35 μm, the thickness of the second reinforcing interface is 5-8 μm, and the thickness of the nano-modified β-PbO2 active layer is 180-220 μm.

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