A fence-type titanium-clad copper-based platinum-silver-zirconium-nano Ta2O5 gradient composite anode plate and its preparation method

Abstract

The present application relates to a kind of fence type titanium copper-based platinum-silver-zirconium-nano Ta2O5 Gradient composite anode plate and its preparation method, belong to hydrometallurgy electro-deposition technical field.The composite anode plate of the present application includes titanium copper-conducting beam and the fence type anode plate support fixedly arranged at the bottom end of titanium copper-conducting beam, fence type anode plate support includes tin immersion copper matrix, and titanium layer, Sn-Ru-Mn-SbOx Bottom layer, Pt-carbon nanotube-TaOx Middle layer and Pt-Ag-Zr-nano Ta2O5 Active layer are sequentially coated on tin immersion copper matrix;Fence type anode plate support is composed of horizontal titanium copper composite bar and several longitudinal titanium copper composite bars, and the top end of longitudinal titanium copper composite bar is fixedly arranged at the bottom end of titanium copper-conducting beam, and the bottom end of longitudinal titanium copper composite bar is fixedly connected with horizontal titanium copper composite bar.The composite anode plate of the present application compared with traditional lead silver multicomponent alloy, anode life is extended 1 times, the manganese dioxide particles on electrode surface is very few, tank voltage is reduced by more than 10%, current efficiency is increased by more than 3%, and cathode product quality is high.

Description

Technical Field

[0001] This invention relates to a fence-type titanium-clad copper-based platinum-silver-zirconium-nano Ta2O5 gradient composite anode plate and its preparation method, belonging to the field of hydrometallurgical electrowinning technology. Background Technology

[0002] Approximately 100% of manganese is extracted using hydrometallurgical techniques. Electrolytic manganese has low current efficiency, typically only reaching around 70%, and consumes nearly 6500 kWh of electricity per ton of electrolytic manganese product, making it a notorious "energy hog." Based on an annual domestic production of 1.4 million tons of manganese ingots, this would require nearly 9 billion kWh of electricity. In the electrolytic manganese production process, over 90% of the electricity consumption is concentrated in the electrolytic cell. During manganese electrolysis, the properties of the anode material directly affect indicators such as ion discharge potential, overpotential changes, current efficiency, energy consumption, anode lifespan, and cathode product quality. In the actual electrolytic manganese production process, a diaphragm bag is used to separate the anolyte and catholyte. Discharge at the anode produces oxygen or manganese dioxide, while manganese is deposited and hydrogen is evolved at the cathode.

[0003] Initially, graphite was used as the anode plate for electrolytic manganese production, but it was phased out due to its tendency to expand and detach during electrolysis. Currently, anode plates for electrolytic manganese typically use a quaternary alloy of lead, antimony, tin, and silver. Although lead alloys have strong corrosion resistance under normal conditions, they are less effective in chlorine-containing environments (Cl... - In the electrolysis of manganese sulfate (concentration greater than 1 g / L), the lead alloy anode plate has a service life of no more than 6 months and must be replaced periodically. Furthermore, when using lead alloy plates for electrolysis, the lead on the surface easily deposits as divalent lead ions at the cathode into the metallic manganese, reducing the purity of the electrolyzed manganese. Although titanium has moderate conductivity, it possesses high strength and strong corrosion resistance, being virtually unaffected by most organic acids such as dilute sulfuric acid, dilute hydrochloric acid, and chlorine, and its mass is much smaller than that of lead plates. However, pure titanium plates are prone to passivation at low temperatures, necessitating surface treatment. Moreover, titanium-based precious metal oxide coatings are expensive, resulting in a large initial investment for industrialization. Some reports have suggested using titanium-based manganese dioxide to replace precious metals; however, during use as an anode, the anode loses electrons and releases oxygen, which permeates into the electrode plate, increasing the oxygen content in the manganese dioxide coating and forming a passivation film on the titanium substrate. This passivation film not only has poor conductivity and increases the anode potential, but also increases energy consumption. Under the influence of an electric field, manganese ions in the anolyte produce manganese dioxide sludge on the anode surface. This sludge is firmly bonded to the manganese dioxide coating itself, causing the original coating to peel off during cleaning, exposing the titanium substrate. This leads to passivation of the titanium substrate and significantly reduces the lifespan of the electrode.

[0004] Platinum electrodes possess strong corrosion resistance and high catalytic activity. However, platinum resources are scarce and expensive, especially since the electrode material area required for industrial manganese electrolysis is very large, making direct use of pure platinum electrodes impractical in production. To reduce electrode costs and conserve platinum resources, platinum-plated materials are needed to replace pure platinum products. Titanium-based platinum electrodes, with their excellent corrosion resistance, have become the most promising electrode material among platinum-plated electrodes. However, platinum has a high oxygen evolution potential and high cell voltage. Furthermore, titanium substrates without an intermediate layer are prone to producing a semiconductor titanium dioxide oxide layer, resulting in poor coating adhesion and short service life, which cannot meet the requirements of practical applications in the electrochemical industry. Summary of the Invention

[0005] This invention addresses the problems existing in anode plates used in electrolytic manganese production by proposing a fence-type titanium-clad copper-based platinum-silver-zirconium-nano Ta2O5 gradient composite anode plate for manganese electrowinning and its preparation method. Compared with traditional lead-silver multi-element alloys, this fence-type titanium-clad copper-based platinum-silver-zirconium-nano Ta2O5 gradient composite anode plate, without changing the electrolytic cell structure, electrolyte composition, or operating specifications, extends the anode life by 100%, minimizes the amount of manganese dioxide particles coated on the electrode surface, reduces cell voltage by more than 10%, increases current efficiency by more than 3%, and produces high-quality cathode products.

[0006] A fence-type titanium-clad copper-based platinum-silver-zirconium-nano Ta2O5 gradient composite anode plate, comprising

[0007] The titanium-clad copper conductive beam 1 and the grid-type anode plate support 2 fixedly disposed at the bottom end of the titanium-clad copper conductive beam 1. The grid-type anode plate support 2 includes a tin-impregnated copper substrate, on which a titanium layer, a Sn-Ru-Mn-SbOx bottom layer 5, a Pt-carbon nanotube-TaOx intermediate layer 6 and a Pt-Ag-Zr-nano Ta2O5 active layer 7 are sequentially coated.

[0008] The grid-type anode plate support 2 consists of a transverse titanium-clad copper composite rod 4 and several longitudinal titanium-clad copper composite rods 3. The top end of the longitudinal titanium-clad copper composite rod 3 is fixedly set at the bottom end of the titanium-clad copper conductive beam 1, and the bottom end of the longitudinal titanium-clad copper composite rod 3 is fixedly connected to the transverse titanium-clad copper composite rod 4.

[0009] The molar ratio of Sn, Ru, Mn, and Sb in the Sn-Ru-Mn-SbOx bottom layer is 35-40:5-10:38-45:5-22; the molar ratio of Pt, carbon nanotubes, and Ta in the Pt-carbon nanotube-TaOx intermediate layer is 73-88:3-8:4-19; and the molar ratio of Pt, Ag, Zr, and Ta in the Pt-Ag-Zr-nano Ta2O5 active layer is 78-91:4-8:3-8:2-6.

[0010] Preferably, in the titanium-clad copper conductive beam 1, the copper cross-sectional height is 20-50 mm, the thickness is 5-20 mm, the tin layer thickness is 50-200 μm, the titanium layer thickness is 0.5-2 mm, and one end of the titanium-clad copper conductive beam exposes the copper conductive head.

[0011] Preferably, the tin layer thickness of the transverse titanium-coated copper composite rod 4 and the longitudinal titanium-coated copper composite rod 3 is 50-200 μm, the titanium layer thickness is 0.5-2 mm, the Sn-Ru-Mn-SbOx bottom layer thickness is 10-50 μm, the Pt-carbon nanotube-TaOx intermediate layer thickness is 1-10 μm, and the Pt-Ag-Zr-nano Ta2O5 active layer thickness is 1-10 μm.

[0012] Preferably, the length of the longitudinal titanium-clad copper composite rod 3 is 200-600 mm, and the length of the transverse titanium-clad copper composite rod 4 is 100-400 mm.

[0013] Preferably, the cross-sectional shapes of the transverse titanium-clad copper composite rod 4 and the longitudinal titanium-clad copper composite rod 3 are heterogeneous circular, serrated elliptical, or square.

[0014] The method for preparing the fence-type titanium-clad copper-based platinum-silver-zirconium-nano Ta2O5 gradient composite anode plate is characterized by the following specific steps:

[0015] 1) Preparation of titanium-clad copper conductive beams and titanium-clad copper composite rods: copper beams or rods are activated by immersing them in dilute HNO3 solution to obtain activated copper beams or rods. The surface of the activated copper beams or rods is coated with rosin flux, dried, and then immersed in tin-plating solution to obtain tin-plated copper beams or tin-plated copper rods. The inner wall of the titanium tube is treated with HNO3-HF solution, cleaned with deionized water, and dried to obtain pretreated titanium tubes. The pretreated titanium tubes are sleeved on tin-plated copper beams or tin-plated copper rods and drawn for composite. After hot rolling and cooling, they are sheared to obtain titanium-clad copper conductive beams or titanium-clad copper conductive rods.

[0016] 2) The main body of the fence-type anode plate support with the bottom layer is formed by welding titanium-clad copper composite rods. The fence-type anode plate support is immersed in NaOH solution for treatment, washed with deionized water and dried, then sandblasted and heat-treated, and then activated in hydrochloric acid solution to obtain the activated fence-type anode plate support. The surface of the activated fence-type anode plate support is coated with tin-ruthenium-manganese-antimony precursor liquid, dried and sintered at 400-700℃ for 8-12 min. The coating of tin-ruthenium-manganese-antimony precursor liquid and sintering process are repeated 1-5 times. Then it is sintered at 300-500℃ for 0.5-1 h to obtain the fence-type anode plate support with the bottom layer Sn-Ru-Mn-SbOx.

[0017] 3) The main body of the fence-type anode plate with the intermediate layer is coated: The surface of the fence-type anode plate main body with the bottom layer Sn-Ru-Mn-SbOx is coated with a platinum-tantalum precursor liquid containing carbon nanotubes. After drying, it is sintered at a temperature of 300-600℃ for 8-12 min. The coating and sintering process of platinum-tantalum precursor liquid containing carbon nanotubes are repeated 1-5 times. Then it is sintered at a temperature of 400-600℃ for 0.5-1 h to obtain the main body of the fence-type anode plate with the intermediate layer of Pt-carbon nanotube-TaOx.

[0018] 4) Pt-Ag-Zr-NanoTa2O5-coated fence-type anode plate support: Using a Pt-carbon nanotube-TaOx intermediate layer fence-type anode plate support as the cathode and platinum as the anode, the support is placed in a neutral platinum plating composite electroplating solution for composite electrodeposition. After washing with deionized water and drying, the active layer Pt-Ag-Zr-nanoTa2O5-coated fence-type anode plate support is obtained. The active layer Pt-Ag-Zr-nanoTa2O5-coated fence-type anode plate support is heat-treated at 400-600℃ for 1-3 hours in an argon protective atmosphere, then heated to 1000-1200℃ and held for 1-2 hours, and then cooled with the furnace to obtain a Pt-Ag-Zr-nanoTa2O5-coated active layer fence-type anode plate support.

[0019] 5) The grid-type anode plate bracket coated with Pt-Ag-Zr-nano Ta2O5 active layer is welded to the bottom of the titanium-clad copper conductive beam to achieve the metallurgical bonding of copper to copper and titanium to titanium, thus obtaining the grid-type titanium-clad copper-based platinum-silver-zirconium-nano Ta2O5 gradient composite anode plate.

[0020] In step (1), the concentration of the dilute HNO3 solution is 5-20 wt.%, the activation temperature is 40-60℃, and the activation time is 2-10 min; the rosin flux is composed of rosin grease, rosin oil, p-xylene, sodium dodecyl sulfate, salicylic acid, and anhydrous ethanol; the tin-immersion solution is a molten tin-aluminum alloy, the aluminum content in the tin-immersion solution is 1-5 wt.%, the immersion temperature is 200-400℃, and the immersion time is 0.5-10 min; the concentration of HNO3 in the HNO3-HF solution is 5-10 wt.%, and the concentration of HF is 5-10 wt.%; the hot rolling temperature is 500-700℃.

[0021] Step (2): The NaOH solution concentration is 10-20 wt.%, the treatment temperature is 50-80℃, and the time is 20-40 min; the heat treatment temperature is 400-700℃, and the time is 2-4 h; the hydrochloric acid solution concentration is 10-30 wt.%, the activation temperature is 80-100℃, and the activation time is 0.5-2 h; the tin-ruthenium-manganese-antimony precursor solution contains tin chloride, ruthenium chloride, manganese chloride, antimony chloride, and hydrochloric acid, and the solvent of the tin-ruthenium-manganese-antimony precursor solution is a mixture of isopropanol and n-butanol.

[0022] Step (3) The platinum-tantalum precursor solution contains chloroplatinic acid, tantalum chloride and carbon nanotubes, and the solvent of the platinum-tantalum precursor solution is n-butanol;

[0023] Step (4) The neutral platinum plating composite electroplating solution contains chloroplatinic acid, potassium citrate, sodium hypophosphite, Ag powder, nano Zr powder, and nano Ta2O5. The current density for composite electrodeposition is 1–10 A / dm³. 2 The temperature is 65-85℃ and the time is 10-80 minutes.

[0024] Preferably, in step (1), based on the mass of rosin flux as 100%, the composition is 10-20% rosin grease, 5-10% rosin oil, 60-70% p-xylene, 1-3% sodium dodecyl sulfate, 1-3% salicylic acid and 5-10% anhydrous ethanol.

[0025] In step (2), the concentrations of tin chloride, ruthenium chloride, manganese, and antimony in the tin-ruthenium-manganese-antimony precursor solution are 0.6–1.2 mol / L, ruthenium chloride, manganese chloride, antimony chloride, and hydrochloric acid, respectively.

[0026] In step (3), the concentration of chloroplatinic acid in the platinum-tantalum precursor solution is 0.1–0.5 mol / L, the concentration of tantalum chloride is 0.01–0.03 mol / L, and the concentration of carbon nanotubes is 0.01–1.0 g / L.

[0027] In step (4), the neutral platinum plating composite electroplating solution contains 10-40 g / L chloroplatinic acid, 100-300 g / L potassium citrate, 5-20 g / L sodium hypophosphite, 2-8 g / L Ag powder, 3-9 g / L nano Zr powder and 0.1-5 g / L nano Ta2O5.

[0028] Preferably, in step (3), the long diameter of the carbon nanotubes is 0.5 to 5 μm, in step (4), the Ag powder particles are flake-shaped or spherical with a particle size of 0.5 to 8 μm, the nano Zr powder particles are spherical with a particle size of 10 to 100 nm, and the nano Ta2O5 particles have a particle size of 50 to 200 nm.

[0029] The preparation method of Ag powder in step (4) is as follows:

[0030] S1. Under stirring conditions at a temperature of 0-20℃, the reducing agent solution is added dropwise to the silver ammonia solution, and the reaction is carried out at a pH of 9-11 for 10-120 min. The solid and liquid are then separated to obtain silver powder.

[0031] S2. Silver powder is soaked in oleic acid and then vacuum dried to obtain spherical silver powder;

[0032] The preparation method of Ag powder further includes: adding anhydrous ethanol and calcium stearate dispersant to the spherical silver powder in step S2, and ball milling for 10-20 hours to obtain flake Ag powder.

[0033] Preferably, the solvent of the reducing agent solution is anhydrous ethanol, and the reducing agent solution contains 1-20 ml / L of formaldehyde and 0.01-0.1 g / L of polyvinylpyrrolidone; the silver ammonia solution contains 6-10 g / L AgNO3, 2-4 g / L NaOH, and 30-100 ml / L of ammonia.

[0034] Preferably, the ball milling rate is 100–300 rpm.

[0035] The beneficial effects of this invention are:

[0036] (1) The fence-type titanium-coated copper-based platinum-silver-zirconium-nano Ta2O5 gradient composite anode plate of the present invention, compared with the traditional lead-silver multi-element alloy, without changing the structure of the electrolytic cell, the composition of the electrolyte and the operating specifications, has a doubled anode life, very few manganese dioxide particles on the electrode surface, a cell voltage reduction of more than 10%, a current efficiency improvement of more than 3%, and high cathode product quality.

[0037] (2) The fence-type titanium-clad copper-based platinum-silver-zirconium-nano Ta2O5 gradient composite anode plate of the present invention utilizes the high conductivity of copper and the strong corrosion resistance of titanium. The titanium-clad copper composite material is used to achieve the metallurgical welding of copper to copper and titanium to titanium, which greatly improves the conductivity of the entire anode and reduces the cell voltage of the electrode during the manganese electrowinning process. It has good conductivity, low cell voltage during electrolysis, long service life, less anode mud, and high cathode product quality.

[0038] (3) The present invention roughens the surface of the copper rod by drawing and sandblasts the titanium surface, thereby increasing the contact area and bonding force between the coating layers and extending the service life of the electrode.

[0039] (4) The bottom layer of this invention uses Sn-Ru-Mn-SbOx oxide, where Ru forms a solid solution with Ti and Sn with Ti, preventing the oxidation of titanium and thus reducing the interfacial resistance. The middle layer uses Pt-carbon nanotube-TaO. x This makes the coating easier to form a network structure and improves the conductivity of the coating, providing support for subsequent cathodic electrodeposition;

[0040] (5) The introduction of silver into the active layer Pt-Ag-Zr-nano Ta2O5 composite coating of the present invention not only improves the conductivity of the coating, but also enhances the electrocatalytic activity of the coating surface in sulfuric acid solution system; the introduction of nano-particle Zr gives the coating the characteristics of high temperature oxidation and hot corrosion resistance; the introduction of amorphous nano-Ta2O5 particles can make the entire coating have a high specific surface area under heat treatment; the synergistic effect between these particles greatly improves the electrocatalytic activity of the electrode. Attached Figure Description

[0041] Figure 1 A schematic diagram of the structure of a fence-type titanium-clad copper-based platinum-silver-zirconium-nano Ta2O5 gradient composite anode plate;

[0042] Figure 2 for Figure 1 A schematic diagram of the AA cross-section;

[0043] Figure 3 for Figure 1 BB cross-sectional diagram;

[0044] Figure 4 for Figure 1 A schematic diagram of the CC cross-section;

[0045] In the figure: 1-Titanium-clad copper beam, 2-Fence-type anode plate support, 3-Longitudinal titanium-clad copper composite rod, 4-Transverse titanium-clad copper composite rod, 5-Sn-Ru-Mn-SbOx bottom layer, 6-Pt-carbon nanotube-TaOx intermediate layer, 7-Pt-Ag-Zr-nano Ta2O5 active layer. Detailed Implementation

[0046] The present invention will be further described in detail below with reference to specific embodiments, but the scope of protection of the present invention is not limited to the content described.

[0047] This invention relates to a fence-type titanium-clad copper-based platinum-silver-zirconium-nano Ta₂O₅ gradient composite anode plate (see...). Figure 1-4 ),include

[0048] The titanium-clad copper conductive beam 1 and the grid-type anode plate support 2 fixedly disposed at the bottom end of the titanium-clad copper conductive beam 1. The grid-type anode plate support 2 includes a tin-impregnated copper substrate, on which a titanium layer, a Sn-Ru-Mn-SbOx bottom layer 5, a Pt-carbon nanotube-TaOx intermediate layer 6 and a Pt-Ag-Zr-nano Ta2O5 active layer 7 are sequentially coated.

[0049] The fence-type anode plate support 2 is composed of a transverse titanium-clad copper composite rod 4 and several longitudinal titanium-clad copper composite rods 3. The top end of the longitudinal titanium-clad copper composite rod 3 is fixedly set at the bottom end of the titanium-clad copper conductive beam 1, and the bottom end of the longitudinal titanium-clad copper composite rod 3 is fixedly connected to the transverse titanium-clad copper composite rod 4.

[0050] In the Sn-Ru-Mn-SbOx bottom layer, the molar ratio of Sn, Ru, Mn, and Sb is 35-40:5-10:38-45:5-22; in the Pt-carbon nanotube-TaOx intermediate layer, the molar ratio of Pt, carbon nanotube, and Ta is 73-88:3-8:4-19; and in the Pt-Ag-Zr-nano Ta2O5 active layer, the molar ratio of Pt, Ag, Zr, and Ta is 78-91:4-8:3-8:2-6.

[0051] In the titanium-clad copper conductive beam 1, the copper cross-sectional height is 20-50mm, the thickness is 5-20mm, the tin layer thickness is 50-200μm, the titanium layer thickness is 0.5-2mm, and one end of the titanium-clad copper conductive beam exposes the copper conductive head.

[0052] The tin layer thickness of the transverse titanium-coated copper composite rod 4 and the longitudinal titanium-coated copper composite rod 3 is 50-200 μm, the titanium layer thickness is 0.5-2 mm, the Sn-Ru-Mn-SbOx bottom layer thickness is 10-50 μm, the Pt-carbon nanotube-TaOx intermediate layer thickness is 1-10 μm, and the Pt-Ag-Zr-nano Ta2O5 active layer thickness is 1-10 μm.

[0053] The length of the longitudinal titanium-clad copper composite rod 3 is 200-600mm, and the length of the transverse titanium-clad copper composite rod 4 is 100-400mm.

[0054] The cross-sectional shapes of the transverse titanium-clad copper composite rod 4 and the longitudinal titanium-clad copper composite rod 3 are heterogeneous circular, serrated elliptical, or square.

[0055] This invention introduces silver to improve the conductivity of the coating, introduces Zr nanoparticles to give the coating resistance to high-temperature oxidation and hot corrosion, and introduces amorphous nano-Ta2O5 particles, which have a high specific surface area under heat treatment. The synergistic effect between these particles greatly improves the electrocatalytic activity of the electrode, resulting in a long service life and high electrolytic efficiency. Compared with traditional lead-silver multi-element alloys, without changing the electrolytic cell structure, electrolyte composition and operating specifications, the anode prepared by this invention has a lifespan that is twice as long. Due to the extremely low amount of manganese dioxide particles generated on the surface, the cell voltage is reduced by more than 10%, the current efficiency is increased by more than 3%, and the cathode product has high quality.

[0056] Example 1: This example uses a grid-type titanium-clad copper-based platinum-silver-zirconium-nano Ta2O5 gradient composite anode plate for manganese electrodeposition (see...). Figures 1-4 );

[0057] The titanium-clad copper conductive beam 1 is 800mm long. The copper substrate in the titanium-clad copper conductive beam 1 has a cross-sectional height of 20mm and a thickness of 5mm. The tin layer is 50μm thick, and the titanium layer is 0.5mm thick. One end of the titanium-clad copper conductive beam exposes a copper conductive head, which is 50mm long. The titanium-clad copper composite rod 3 has an heterogeneous circular cross-sectional shape, where the diameter of the heterogeneous circular copper is... The tin layer is 50 μm thick, the titanium layer is 0.5 mm thick, and the length of the titanium-coated copper composite rod 3 is 200 mm. The titanium-coated copper composite rod 4 has a square cross-section, with the major axis of the square copper section being 5 mm and the minor axis being 2 mm. The tin layer is 50 μm thick, the titanium layer is 0.5 mm thick, and the length of the titanium-coated copper composite rod 4 is 100 mm. The Sn-Ru-Mn-SbOx bottom layer is 10 μm thick, the Pt-carbon nanotube-TaOx intermediate layer is 1 μm thick, and the Pt-Ag-Zr-nano Ta2O5 active layer is 2 μm thick.

[0058] The carbon nanotubes have a major diameter of 1 μm, the Ag powder particles are spherical with a particle size of 1 μm, the Zr powder particles are spherical with a particle size of 10 nm, and the nano Ta2O5 particles have a particle size of 50 nm.

[0059] The molar ratio of Sn, Ru, Mn, and Sb in the Sn-Ru-Mn-SbOx bottom layer is 35:5:45:15; the molar ratio of Pt, carbon nanotubes, and Ta in the Pt-carbon nanotube-TaOx intermediate layer is 78:3:19; and the molar ratio of Pt, Ag, Zr, and Ta in the Pt-Ag-Zr-nano Ta2O5 active layer is 78:8:8:6.

[0060] A fence-type titanium-clad copper-based platinum-silver-zirconium-nano Ta₂O₅ gradient composite anode plate and its preparation method are described below:

[0061] 1) Preparation of titanium-clad copper conductive beams and titanium-clad copper composite rods: Copper beams or rods are immersed in a 5 wt.% dilute HNO3 solution and activated at 40℃ for 2 min to obtain activated copper beams or rods. The surface of the activated copper beams or rods is coated with a completely dissolved rosin flux at 50℃, wherein the rosin flux formula is 20 wt.% rosin grease, 8 wt.% rosin oil, 60 wt.% p-xylene, 1 wt.% sodium dodecyl sulfate, 1 wt.% salicylic acid, and 10 wt.% anhydrous ethanol. After drying at 100℃, they are immersed in a tin-plating solution at 200℃ for 1 min to obtain… The titanium tube is prepared by treating the inner wall of the titanium tube with HNO3-HF solution, cleaning it with deionized water, and drying it with hot air at 60°C. The pretreated titanium tube is then placed on the tin-plated copper beam or rod and drawn together using an extrusion drawing machine at a speed of 2 m / min. It is then hot-rolled in a spiral rolling process at 500°C and sheared after natural cooling to obtain the titanium-clad copper conductive beam or rod. The tin-plating solution is a molten tin-aluminum alloy with an aluminum content of 1 wt.% and an HNO3-HF solution with a concentration of 5 wt.% for both HNO3 and HF.

[0062] 2) The main body of the grid-type anode plate support is formed by welding titanium-copper composite rods to fix copper to copper and titanium to titanium in pairs by argon arc welding. The main body of the grid-type anode plate support is immersed in a 10wt.% NaOH solution at 50℃ for 20 min. After washing and drying with deionized water, the surface is sprayed with 20-mesh green silicon carbide sand and then heat-treated at 400℃ for 2 h. Finally, it is placed in a 10wt.% NaOH solution. In a % hydrochloric acid solution, an activated grid-type anode plate support body was obtained by activation at 80℃ for 0.5h. The surface of the activated grid-type anode plate support body was coated with a tin-ruthenium-manganese-antimony precursor liquid. After drying at 80℃, it was sintered at 400℃ for 8min. The coating of tin-ruthenium-manganese-antimony precursor liquid and sintering process were repeated once. Then, it was sintered at 300℃ for 0.5h to obtain a grid-type anode plate support body with a Sn-Ru-Mn-SbOx bottom layer.

[0063] The preparation method of the tin-ruthenium-manganese-antimony precursor solution is as follows: tin chloride, ruthenium chloride, manganese chloride, and antimony chloride are dissolved in concentrated hydrochloric acid, and a solvent (50% isopropanol + 50% n-butanol mixed solvent) is added. Water is removed using a rotary evaporator. The concentrations of tin chloride, ruthenium chloride, manganese chloride, and hydrochloric acid in the tin-ruthenium-manganese-antimony precursor solution are 0.6 mol / L, ruthenium chloride, manganese chloride, and antimony chloride, respectively, and 1.0 mol / L.

[0064] 3) The main body of the fence-type anode plate with the intermediate layer is coated with a platinum-tantalum precursor liquid containing carbon nanotubes. After drying at 80°C, it is sintered at 300°C for 8 min. The coating and sintering process of platinum-tantalum precursor liquid containing carbon nanotubes are repeated once. Then it is sintered at 400°C for 0.5 h to obtain the main body of the fence-type anode plate with the intermediate layer of Pt-carbon nanotube-TaOx.

[0065] The preparation method of platinum-tantalum precursor solution containing carbon nanotubes is as follows: chloroplatinic acid, tantalum chloride, and carbon nanotubes are added to n-butanol solvent and mixed evenly, and stirred at 40℃ for 0.5h using a rotary evaporator; the concentration of chloroplatinic acid in the platinum-tantalum precursor solution is 0.1mol / L, the concentration of tantalum chloride is 0.01mol / L, and the concentration of carbon nanotubes is 0.01g / L;

[0066] 4) Activated layer-coated fence-type anode plate support: Using a fence-type anode plate support with a Pt-carbon nanotube-TaOx intermediate layer as the cathode and platinum as the anode, it is placed in a neutral platinum plating composite electroplating solution at a temperature of 65℃ and a current density of 1A / dm³. 2 Composite electrodeposition was performed for 10 minutes under mechanical stirring speed of 100 rpm. The neutral platinum plating composite electroplating solution contained 10 g / L chloroplatinic acid, 100 g / L potassium citrate, 5 g / L sodium hypophosphite, 2 g / L Ag powder, 3 g / L nano Zr powder, 0.1 g / L nano Ta2O5, and the pH was adjusted to 7.0 with ammonia water. After washing with deionized water and drying, the active layer Pt-Ag-Zr-nano Ta2O5 fence-type anode plate support body was obtained. The active layer Pt-Ag-Zr-nano Ta2O5 fence-type anode plate support body was heat-treated at 400℃ for 1 hour in an argon protective atmosphere, and then heated to 1000℃ and held for 1 hour. After furnace cooling, the Pt-Ag-Zr-nano Ta2O5 active layer fence-type anode plate support body was obtained.

[0067] The silver powder was prepared as follows: At pH 9, the silver ammonia solution was at 20°C, and mechanically stirred at 100 rpm. A reducing agent solution was uniformly added dropwise to the silver ammonia solution and reacted for 10 minutes. After filtration, silver powder was obtained. This powder was then soaked in oleic acid and vacuum dried to obtain spherical silver powder. The silver ammonia solution contained 6 g / L AgNO3, 2 g / L NaOH, and 30 ml / L ammonia water. The reducing agent solution contained 1 ml / L formaldehyde (38%), 100 ml / L anhydrous ethanol, and 0.01 g / L polyvinylpyrrolidone (PVP).

[0068] 5) The grid-type anode plate bracket coated with Pt-Ag-Zr-nano Ta2O5 active layer is welded to the bottom end of the titanium-clad copper conductive beam to achieve the metallurgical bonding of copper to copper and titanium to titanium, thus obtaining the grid-type titanium-clad copper-based platinum-silver-zirconium-nano Ta2O5 gradient composite anode plate.

[0069] In this embodiment, the fence-type titanium-clad copper-based platinum-silver-zirconium-nano Ta₂O₅ gradient composite anode plate was prepared. Manganese was electrodeposited using a polyester fiber bag diaphragm in a manganese sulfate electrolyte. The electrolysis conditions were that the anolyte was Mn. 2+ 14-16 g / L, H2SO4 45-49 g / L, ammonium sulfate 110 g / L, chloride ion concentration 1 g / L, magnesium ion concentration 3 g / L and calcium ion concentration 1 g / L; the electrolytic cathode solution is Mn 2+ (16-18 g / L), ammonium sulfate 110 g / L, Cl - 923 mg / L, pH 6.5-7.0, cathode current density 340-380 A / m 2 Anode current density 680–760 A / m 2 Under otherwise unchanged conditions, its electrical efficiency is 3% higher than that of traditional lead-silver-tin-antimony multi-element alloy anode plates, the cell voltage can be reduced by 10%, the lifespan is doubled, and there are fewer manganese dioxide particles on the electrode surface.

[0070] Example 2: This example uses a grid-type titanium-clad copper-based platinum-silver-zirconium-nano Ta2O5 gradient composite anode plate for manganese electrowinning (see...). Figures 1-4 );

[0071] The titanium-clad copper conductive beam 1 is 1200mm long. The copper substrate in the titanium-clad copper conductive beam 1 has a cross-sectional height of 50mm and a thickness of 20mm. The tin layer is 200μm thick, and the titanium layer is 2mm thick. One end of the titanium-clad copper conductive beam exposes a copper conductive head, which is 200mm long. The titanium-clad copper composite rod 3 has an heterogeneous circular cross-sectional shape, where the diameter of the heterogeneous circular copper is... The tin layer is 200 μm thick, the titanium layer is 2 mm thick, and the length of the titanium-coated copper composite rod 3 is 600 mm. The cross-sectional shape of the titanium-coated copper composite rod 4 is elliptical, with the major axis of the elliptical copper cross-section being 12 mm and the minor axis being 6 mm. The tin layer is 200 μm thick, the titanium layer is 2 mm thick, and the length of the titanium-coated copper composite rod 4 is 400 mm. The Sn-Ru-Mn-SbOx bottom layer is 50 μm thick, the Pt-carbon nanotube-TaOx intermediate layer is 10 μm thick, and the Pt-Ag-Zr-nano Ta2O5 active layer is 10 μm thick.

[0072] The carbon nanotubes have a long diameter of 5 μm, the Ag powder particles are plate-shaped with a particle size of 8 μm, the Zr powder particles are spherical with a particle size of 100 nm, and the nano Ta2O5 particles have a particle size of 200 nm.

[0073] The molar ratio of Sn, Ru, Mn, and Sb in the Sn-Ru-Mn-SbOx bottom layer is 40:5:45:10; the molar ratio of Pt, carbon nanotubes, and Ta in the Pt-carbon nanotube-TaOx intermediate layer is 88:3:9; and the molar ratio of Pt, Ag, Zr, and Ta in the Pt-Ag-Zr-nano Ta2O5 active layer is 91:4:3:2.

[0074] A fence-type titanium-clad copper-based platinum-silver-zirconium-nano Ta₂O₅ gradient composite anode plate and its preparation method are described below:

[0075] 1) Preparation of titanium-clad copper conductive beams and titanium-clad copper composite rods: Copper beams or rods are immersed in a 20 wt.% dilute HNO3 solution and activated at 60℃ for 10 min to obtain activated copper beams or rods. The surface of the activated copper beams or rods is coated with a completely dissolved rosin flux at 80℃, wherein the rosin flux formula is 15 wt.% rosin grease, 8 wt.% rosin oil, 70 wt.% p-xylene, 1 wt.% sodium dodecyl sulfate, 1 wt.% salicylic acid, and 5 wt.% anhydrous ethanol. After drying at 200℃, they are immersed in a tin-plating solution at 200℃ for 10 min to obtain… Tin-plated copper beams or rods are produced. The inner wall of a titanium tube is treated with HNO3-HF solution, cleaned with deionized water, and dried with hot air at 100°C to obtain a pretreated titanium tube. This pretreated titanium tube is then fitted onto a tin-plated copper beam or rod and drawn together using an extrusion drawing machine at a speed of 10 m / min. It is then hot-rolled in a spiral rolling process at 700°C, and after natural cooling, sheared to obtain a titanium-clad copper conductive beam or rod. The tin-plating solution is a molten tin-aluminum alloy with an aluminum content of 5 wt.%, and the HNO3-HF solution contains 10 wt.% HNO3 and 10 wt.% HF.

[0076] 2) The main body of the grid-type anode plate support is formed by welding titanium-clad copper composite rods together to fix copper to copper and titanium to titanium in pairs by argon arc welding. The main body of the grid-type anode plate support is immersed in a 20wt.% NaOH solution at 80℃ for 40 min. After washing and drying with deionized water, the surface is sprayed with 100-mesh green silicon carbide sand, and then heat-treated at 700℃ for 4 h. Finally, it is immersed in a 30wt.% NaOH solution. In a 0.% hydrochloric acid solution, the activated grid-type anode plate support body was obtained by activation at 100℃ for 2 hours. The surface of the activated grid-type anode plate support body was coated with tin-ruthenium-manganese-antimony precursor liquid. After drying at 100℃, it was sintered at 400℃ for 12 minutes. The coating and sintering process of tin-ruthenium-manganese-antimony precursor liquid were repeated 5 times. Then, it was sintered at 500℃ for 1 hour to obtain the Sn-Ru-Mn-SbOx grid-type anode plate support body with a bottom layer.

[0077] The preparation method of the tin-ruthenium-manganese-antimony precursor solution is as follows: tin chloride, ruthenium chloride, manganese chloride, and antimony chloride are dissolved in concentrated hydrochloric acid, and a solvent (50% isopropanol + 50% n-butanol mixed solvent) is added. Water is removed using a rotary evaporator. The concentrations of tin chloride, ruthenium chloride, manganese chloride, and antimony chloride in the tin-ruthenium-manganese-antimony precursor solution are 1.2 mol / L, ruthenium chloride, manganese chloride, and antimony chloride, respectively, and hydrochloric acid, respectively, are 5.0 mol / L.

[0078] 3) The main body of the fence-type anode plate with the intermediate layer is coated with a platinum-tantalum precursor liquid containing carbon nanotubes. After drying at 100℃, it is sintered at 600℃ for 12 min. The coating and sintering process of platinum-tantalum precursor liquid containing carbon nanotubes are repeated 5 times. Then, it is sintered at 600℃ for 1 h to obtain the main body of the fence-type anode plate with the intermediate layer of Pt-carbon nanotube-TaOx.

[0079] The preparation method of platinum-tantalum precursor solution containing carbon nanotubes is as follows: chloroplatinic acid, tantalum chloride, and carbon nanotubes are added to n-butanol solvent and mixed evenly, and stirred at 60℃ for 2 hours using a rotary evaporator; the concentration of chloroplatinic acid in the platinum-tantalum precursor solution is 0.5 mol / L, the concentration of tantalum chloride is 0.06 mol / L, and the concentration of carbon nanotubes is 0.21 g / L;

[0080] 4) Activated layer-coated fence-type anode plate support: Using a fence-type anode plate support with a Pt-carbon nanotube-TaOx intermediate layer as the cathode and platinum as the anode, it is placed in a neutral platinum plating composite electroplating solution at a temperature of 85℃ and a current density of 10A / dm³. 2 Composite electrodeposition was performed for 80 minutes under mechanical stirring at 300 rpm. The neutral platinum plating composite electroplating solution contained 40 g / L chloroplatinic acid, 300 g / L potassium citrate, 20 g / L sodium hypophosphite, 8 g / L Ag powder, 9 g / L nano Zr powder, 5 g / L nano Ta2O5, and the pH was adjusted to 8.0 with ammonia. After washing with deionized water and drying, the active layer Pt-Ag-Zr-nano Ta2O5 fence-type anode plate support body was obtained. The active layer Pt-Ag-Zr-nano Ta2O5 fence-type anode plate support body was heat-treated at 600℃ for 3 hours in an argon protective atmosphere, and then heated to 1200℃ and held for 2 hours. After furnace cooling, the Pt-Ag-Zr-nano Ta2O5 active layer fence-type anode plate support body was obtained.

[0081] The preparation method of silver powder is as follows: Under the conditions of pH 11, silver ammonia solution temperature 0℃, and mechanical stirring at 1000 rpm, the reducing agent solution is uniformly added dropwise to the silver ammonia solution and reacted for 120 min. After filtration, silver powder is obtained, which is then soaked in oleic acid and vacuum dried to obtain spherical silver powder. The silver ammonia solution contains 10 g / L AgNO3, 4 g / L NaOH, and 100 ml / L ammonia water, while the reducing agent solution contains 20 ml / L formaldehyde (38%), 300 ml / L anhydrous ethanol, and 0.1 g / L polyvinylpyrrolidone (PVP). 100 g of spherical silver powder is weighed and added at a material-to-particle ratio of 1:5. Stainless steel balls were added to 300ml of ethanol and 3g of calcium stearate dispersant. The ball milling time was 20h and the ball milling speed was 300rpm to obtain flake silver powder with an average particle size of 8μm.

[0082] 5) The grid-type anode plate bracket coated with Pt-Ag-Zr-nano Ta2O5 active layer is welded to the bottom end of the titanium-clad copper conductive beam to achieve the metallurgical bonding of copper to copper and titanium to titanium, thus obtaining the grid-type titanium-clad copper-based platinum-silver-zirconium-nano Ta2O5 gradient composite anode plate.

[0083] In this embodiment, the fence-type titanium-clad copper-based platinum-silver-zirconium-nano Ta₂O₅ gradient composite anode plate was prepared. Manganese was electrodeposited using a polyester fiber bag diaphragm in a manganese sulfate electrolyte. The electrolysis conditions were that the anolyte was Mn. 2+ 14-16 g / L, H2SO4 45-49 g / L, ammonium sulfate 110 g / L, chloride ion concentration 0.8 g / L; the electrolytic cathode solution is Mn 2+ (16-18 g / L), ammonium sulfate 110 g / L, Cl - 923 mg / L, pH 6.5-7.0, cathode current density 340-380 A / m 2 Anode current density 680–760 A / m 2 Under otherwise unchanged conditions, its electrical efficiency is 4% higher than that of traditional lead-silver-tin-antimony multi-element alloy anode plates, the cell voltage can be reduced by 12%, the lifespan can be extended by 1.5 times, and there are fewer manganese dioxide particles on the electrode surface.

[0084] Example 3: This example uses a grid-type titanium-clad copper-based platinum-silver-zirconium-nano Ta2O5 gradient composite anode plate for manganese electrowinning (see...). Figures 1-4 );

[0085] The titanium-clad copper conductive beam 1 is 1000mm long. The copper substrate in the titanium-clad copper conductive beam 1 has a cross-sectional height of 40mm and a thickness of 16mm. The tin layer is 100μm thick, and the titanium layer is 1.5mm thick. One end of the titanium-clad copper conductive beam exposes a copper conductive head, which is 200mm long. The titanium-clad copper composite rod 3 has an heterogeneous circular cross-sectional shape, where the diameter of the heterogeneous circular copper is... The tin layer is 100 μm thick, the titanium layer is 1.5 mm thick, and the length of the titanium-coated copper composite rod 3 is 400 mm. The cross-sectional shape of the titanium-coated copper composite rod 4 is elliptical, with the major axis of the elliptical copper cross-section being 10 mm and the minor axis being 4 mm. The tin layer is 100 μm thick, the titanium layer is 1.5 mm thick, and the length of the titanium-coated copper composite rod 4 is 200 mm. The Sn-Ru-Mn-SbOx bottom layer is 30 μm thick, the Pt-carbon nanotube-TaOx intermediate layer is 5 μm thick, and the Pt-Ag-Zr-nano Ta2O5 active layer is 5 μm thick.

[0086] The carbon nanotubes have a long diameter of 2 μm, the Ag powder particles are plate-shaped with a particle size of 5 μm, the Zr powder particles are spherical with a particle size of 50 nm, and the nano Ta2O5 particles have a particle size of 100 nm.

[0087] The molar ratio of Sn, Ru, Mn, and Sb in the Sn-Ru-Mn-SbOx bottom layer is 40:8:42:10; the molar ratio of Pt, carbon nanotubes, and Ta in the Pt-carbon nanotube-TaOx intermediate layer is 82:5:13; and the molar ratio of Pt, Ag, Zr, and Ta in the Pt-Ag-Zr-nano Ta2O5 active layer is 83:6:5:6.

[0088] A fence-type titanium-clad copper-based platinum-silver-zirconium-nano Ta₂O₅ gradient composite anode plate and its preparation method are described below:

[0089] 1) Preparation of titanium-clad copper conductive beams and titanium-clad copper composite rods: Copper beams or rods are immersed in a 15 wt.% dilute HNO3 solution and activated at 50℃ for 6 min to obtain activated copper beams or rods. The surface of the activated copper beams or rods is coated with a completely dissolved rosin flux at 60℃, wherein the rosin flux formula is 20 wt.% rosin grease, 8 wt.% rosin oil, 65 wt.% p-xylene, 1 wt.% sodium dodecyl sulfate, 1 wt.% salicylic acid, and 5 wt.% anhydrous ethanol. After drying at 160℃, they are immersed in a tin-plating solution at 300℃ for 6 min to obtain… The titanium tube is prepared by treating the inner wall of the titanium tube with HNO3-HF solution, cleaning it with deionized water, and drying it with hot air at 80°C. The pretreated titanium tube is then placed on the tin-plated copper beam or rod and drawn together using an extrusion drawing machine at a speed of 5 m / min. It is then hot-rolled in a spiral rolling process at 600°C and sheared after natural cooling to obtain the titanium-clad copper conductive beam or rod. The tin-plating solution is a molten tin-aluminum alloy with an aluminum content of 3 wt.% and an HNO3 concentration of 6 wt.% and an HF concentration of 6 wt.% in the HNO3-HF solution.

[0090] 2) The main body of the grid-type anode plate support is formed by welding titanium-clad copper composite rods together to fix copper to copper and titanium to titanium in pairs by argon arc welding. The grid-type anode plate support is then immersed in a 15wt.% NaOH solution at 60℃ for 30 minutes. After washing and drying with deionized water, the surface is sprayed with 60-mesh green silicon carbide sand, and then heat-treated at 600℃ for 3 hours. Finally, it is immersed in a 20wt.% NaOH solution. In a 0.% hydrochloric acid solution, the activated grid-type anode plate support body was obtained by activation at 100℃ for 2 hours. The surface of the activated grid-type anode plate support body was coated with tin-ruthenium-manganese-antimony precursor liquid. After drying at 100℃, it was sintered at 500℃ for 10 minutes. The coating and sintering process of tin-ruthenium-manganese-antimony precursor liquid were repeated 3 times. Then, it was sintered at 400℃ for 1 hour to obtain the grid-type anode plate support body with Sn-Ru-Mn-SbOx coating bottom layer.

[0091] The preparation method of the tin-ruthenium-manganese-antimony precursor solution is as follows: tin chloride, ruthenium chloride, manganese chloride, and antimony chloride are dissolved in concentrated hydrochloric acid, and a solvent (50% isopropanol + 50% n-butanol mixed solvent) is added. Water is removed using a rotary evaporator. The concentrations of tin chloride, ruthenium chloride, manganese chloride, and antimony chloride in the tin-ruthenium-manganese-antimony precursor solution are 0.9 mol / L, ruthenium chloride, 1.0 mol / L, 0.2 mol / L, and hydrochloric acid, respectively.

[0092] 3) The main body of the fence-type anode plate with the intermediate layer is coated with a platinum-tantalum precursor liquid containing carbon nanotubes. After drying at 100℃, it is sintered at 500℃ for 10 min. The coating and sintering process of platinum-tantalum precursor liquid containing carbon nanotubes are repeated 3 times. Then it is sintered at 450℃ for 1 h to obtain the main body of the fence-type anode plate with the intermediate layer of Pt-carbon nanotube-TaOx.

[0093] The preparation method of platinum-tantalum precursor solution containing carbon nanotubes is as follows: chloroplatinic acid, tantalum chloride, and carbon nanotubes are added to n-butanol solvent and mixed evenly, and stirred at 50℃ for 1 h using a rotary evaporator; the concentration of chloroplatinic acid in the platinum-tantalum precursor solution is 0.3 mol / L, the concentration of tantalum chloride is 0.05 mol / L, and the concentration of carbon nanotubes is 0.3 g / L;

[0094] 4) Grid-type anode plate support with an active layer: The main body of the grid-type anode plate support with a Pt-carbon nanotube-TaOx intermediate layer is used as the cathode, and platinum is used as the anode. It is placed in a neutral platinum plating composite electroplating solution at a temperature of 75℃ and a current density of 5A / dm³. 2 Composite electrodeposition was performed for 40 minutes under mechanical stirring at 200 rpm. The neutral platinum plating composite electroplating solution contained 30 g / L chloroplatinic acid, 200 g / L potassium citrate, 10 g / L sodium hypophosphite, 5 g / L Ag powder, 6 g / L nano Zr powder, 2 g / L nano Ta2O5, and the pH was adjusted to 7.5 with ammonia. After washing with deionized water and drying, the active layer Pt-Ag-Zr-nano Ta2O5 fence-type anode plate support body was obtained. The active layer Pt-Ag-Zr-nano Ta2O5 fence-type anode plate support body was heat-treated at 500℃ for 2 hours in an argon protective atmosphere, and then heated to 1100℃ and held for 2 hours. After furnace cooling, the Pt-Ag-Zr-nano Ta2O5 active layer fence-type anode plate support body was obtained.

[0095] The preparation method of silver powder is as follows: Under the conditions of pH 10, silver ammonia solution temperature 5℃, and mechanical stirring at 500 rpm, the reducing agent solution is uniformly added dropwise to the silver ammonia solution and reacted for 60 min. After filtration, silver powder is obtained, which is then soaked in oleic acid and vacuum dried to obtain spherical silver powder. The silver ammonia solution contains 8 g / L AgNO3, 3 g / L NaOH, and 70 ml / L ammonia water, while the reducing agent solution contains 10 ml / L formaldehyde (38%), 200 ml / L anhydrous ethanol, and 0.05 g / L polyvinylpyrrolidone (PVP). 100 g of spherical silver powder is weighed and added at a material-to-particle ratio of 1:10. Stainless steel balls were added to 300 mL of ethanol and 3 g of calcium stearate dispersant. The ball milling time was 20 h and the ball milling speed was 300 rpm to obtain flake silver powder with an average particle size of 5 μm.

[0096] 5) The grid-type anode plate bracket coated with Pt-Ag-Zr-nano Ta2O5 active layer is welded to the bottom end of the titanium-clad copper conductive beam to achieve the metallurgical bonding of copper to copper and titanium to titanium, thus obtaining the grid-type titanium-clad copper-based platinum-silver-zirconium-nano Ta2O5 gradient composite anode plate.

[0097] In this embodiment, the fence-type titanium-clad copper-based platinum-silver-zirconium-nano Ta₂O₅ gradient composite anode plate was prepared. Manganese was electrodeposited using a polyester fiber bag diaphragm in a manganese sulfate electrolyte. The electrolysis conditions were that the anolyte was Mn. 2+ 14-16 g / L, H2SO4 45-49 g / L, ammonium sulfate 110 g / L, chloride ion concentration 0.8 g / L; the electrolytic cathode solution is Mn 2+ (16-18 g / L), ammonium sulfate 110 g / L, Cl - 923 mg / L, pH 6.5-7.0, cathode current density 340-380 A / m 2 Anode current density 680–760 A / m 2 Under otherwise unchanged conditions, its electrical efficiency is 4% higher than that of traditional lead-silver-tin-antimony multi-element alloy anode plates, the cell voltage can be reduced by 20%, the lifespan is extended by 2 times, and there are very few manganese dioxide particles on the electrode surface.

[0098] The specific embodiments of the present invention have been described in detail above. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention.

Claims

1. A grid-type titanium-clad copper-based platinum-silver-zirconium-nano Ta₂O₅ gradient composite anode plate, characterized in that: It includes a titanium-clad copper conductive beam and a grid-type anode plate support fixed to the bottom end of the titanium-clad copper conductive beam; the grid-type anode plate support is composed of a transverse titanium-clad copper composite rod and several longitudinal titanium-clad copper composite rods, the top end of the longitudinal titanium-clad copper composite rod is fixed to the bottom end of the titanium-clad copper conductive beam, and the bottom end of the longitudinal titanium-clad copper composite rod is fixedly connected to the transverse titanium-clad copper composite rod. Its preparation method is as follows: 1) Activate copper beams or rods by immersing them in dilute HNO3 solution. Coat the surface of the activated copper beams or rods with rosin flux, dry them, and then immerse them in tin plating solution to obtain tin-plated copper beams or tin-plated copper rods. Treat the inner wall of a titanium tube with HNO3-HF solution, clean it with deionized water and blow it dry to obtain a pretreated titanium tube. Put the pretreated titanium tube on the tin-plated copper beams or tin-plated copper rods and draw them together. After hot rolling and cooling, shear them to obtain titanium-clad copper conductive beams or titanium-clad copper composite rods. 2) The titanium-clad copper composite rod is welded to form a grid-type anode plate support body. The grid-type anode plate support body is immersed in NaOH solution for treatment. After washing and drying with deionized water, it is sandblasted and heat-treated. Then it is activated in hydrochloric acid solution to obtain an activated grid-type anode plate support body. The surface of the activated grid-type anode plate support body is coated with a tin-ruthenium-manganese-antimony precursor liquid containing tin chloride, ruthenium chloride, manganese chloride, antimony chloride and hydrochloric acid. After drying, it is sintered at a temperature of 400~700℃ for 8~12 min. The coating of tin-ruthenium-manganese-antimony precursor liquid and sintering process are repeated 1~5 times. Then it is sintered at a temperature of 300~500℃ for 0.5~1 h to obtain a grid-type anode plate support body with a Sn-Ru-Mn-SbOx coating bottom layer. 3) Coat the surface of the Sn-Ru-Mn-SbOx-coated bottom layer of the fence-type anode plate support body with a platinum-tantalum precursor liquid containing chloroplatinic acid, tantalum chloride and carbon nanotubes. After drying, sinter at 300~600℃ for 8~12 min. Repeat the coating and sintering process of platinum-tantalum precursor liquid containing carbon nanotubes 1~5 times. Then sinter at 400~600℃ for 0.5~1 h to obtain the Pt-carbon nanotube-TaOx intermediate layer fence-type anode plate support body. 4) Using a Pt-carbon nanotube-TaOx interlayer fence-type anode plate support as the cathode and platinum as the anode, the plate is placed in a neutral platinum plating composite electroplating solution containing chloroplatinic acid, potassium citrate, sodium hypophosphite, Ag powder, nano Zr powder and nano Ta2O5 for composite electrodeposition. After washing with deionized water and drying, a platinum-silver-zirconium-nano Ta2O5 fence-type anode plate support with an active layer is obtained. The platinum-silver-zirconium-nano Ta2O5 fence-type anode plate support is heat-treated at 400~600℃ for 1~3h in an argon protective atmosphere, then heated to 1000~1200℃ and held for 1~2h, and cooled with the furnace to obtain a platinum-silver-zirconium-nano Ta2O5 active layer fence-type anode plate support. 5) Weld the platinum-silver-zirconium-nano Ta2O5 active layer-coated grid-type anode plate bracket to the bottom of the titanium-coated copper conductive beam.

2. The grid-type titanium-clad copper-based platinum-silver-zirconium-nano Ta₂O₅ gradient composite anode plate according to claim 1, characterized in that: In the Sn-Ru-Mn-SbOx bottom layer, the molar ratio of Sn, Ru, Mn, and Sb is 35-40:5-10:38-45:5-22; in the Pt-carbon nanotube-TaOx intermediate layer, the molar ratio of Pt, carbon nanotube, and Ta is 73-88:3-8:4-19; and in the platinum-silver-zirconium-nano Ta2O5 active layer, the molar ratio of Pt, Ag, Zr, and Ta is 78-91:4-8:3-8:2-6.

3. The method for preparing the fence-type titanium-clad copper-based platinum-silver-zirconium-nano Ta₂O₅ gradient composite anode plate according to claim 1 or 2, characterized in that, The specific steps are as follows: 1) Activate copper beams or rods by immersing them in dilute HNO3 solution. Coat the surface of the activated copper beams or rods with rosin flux, dry them, and then immerse them in tin plating solution to obtain tin-plated copper beams or tin-plated copper rods. Treat the inner wall of a titanium tube with HNO3-HF solution, clean it with deionized water and blow it dry to obtain a pretreated titanium tube. Put the pretreated titanium tube on the tin-plated copper beams or tin-plated copper rods and draw them together. After hot rolling and cooling, shear them to obtain titanium-clad copper conductive beams or titanium-clad copper composite rods. 2) The titanium-clad copper composite rod is welded to form a grid-type anode plate support body. The grid-type anode plate support body is immersed in NaOH solution for treatment. After washing and drying with deionized water, it is sandblasted and heat-treated. Then it is activated in hydrochloric acid solution to obtain an activated grid-type anode plate support body. The surface of the activated grid-type anode plate support body is coated with a tin-ruthenium-manganese-antimony precursor liquid containing tin chloride, ruthenium chloride, manganese chloride, antimony chloride and hydrochloric acid. After drying, it is sintered at a temperature of 400~700℃ for 8~12 min. The coating of tin-ruthenium-manganese-antimony precursor liquid and sintering process are repeated 1~5 times. Then it is sintered at a temperature of 300~500℃ for 0.5~1 h to obtain a grid-type anode plate support body with a Sn-Ru-Mn-SbOx coating bottom layer. 3) Coat the surface of the Sn-Ru-Mn-SbOx-coated bottom layer of the fence-type anode plate support body with a platinum-tantalum precursor liquid containing chloroplatinic acid, tantalum chloride and carbon nanotubes. After drying, sinter at 300~600℃ for 8~12 min. Repeat the coating and sintering process of platinum-tantalum precursor liquid containing carbon nanotubes 1~5 times. Then sinter at 400~600℃ for 0.5~1 h to obtain the Pt-carbon nanotube-TaOx intermediate layer fence-type anode plate support body. 4) Using a Pt-carbon nanotube-TaOx interlayer fence-type anode plate support as the cathode and platinum as the anode, the plate is placed in a neutral platinum plating composite electroplating solution containing chloroplatinic acid, potassium citrate, sodium hypophosphite, Ag powder, nano Zr powder and nano Ta2O5 for composite electrodeposition. After washing with deionized water and drying, a platinum-silver-zirconium-nano Ta2O5 fence-type anode plate support with an active layer is obtained. The platinum-silver-zirconium-nano Ta2O5 fence-type anode plate support is heat-treated at 400~600℃ for 1~3h in an argon protective atmosphere, then heated to 1000~1200℃ and held for 1~2h, and cooled with the furnace to obtain a platinum-silver-zirconium-nano Ta2O5 active layer fence-type anode plate support. 5) Weld the platinum-silver-zirconium-nano Ta2O5 active layer-coated grid-type anode plate bracket to the bottom of the titanium-coated copper conductive beam.

4. The preparation method of the fence-type titanium-clad copper-based platinum-silver-zirconium-nano Ta₂O₅ gradient composite anode plate according to claim 3, characterized in that: Step 1) The concentration of the dilute HNO3 solution is 5~20 wt.%, the activation temperature is 40~60℃, and the activation time is 2~10 min; the rosin flux is composed of rosin grease, rosin oil, p-xylene, sodium dodecyl sulfate, salicylic acid, and anhydrous ethanol; the tin immersion bath is a molten tin-aluminum alloy with an aluminum content of 1~5 wt.%, an immersion temperature of 200~400℃, and an immersion time of 0.5~10 min; the concentration of HNO3 in the HNO3-HF solution is 5~10 wt.%, and the concentration of HF is 5~10 wt.%; the hot rolling temperature is 500~700℃. Step 2) The NaOH solution concentration is 10~20 wt.%, the treatment temperature is 50~80℃, and the time is 20~40 min; the heat treatment temperature is 400~700℃, and the time is 2~4 h; the hydrochloric acid solution concentration is 10~30 wt.%, the activation temperature is 80~100℃, and the activation time is 0.5~2 h; the solvent for the tin-ruthenium-manganese-antimony precursor solution is a mixture of isopropanol and n-butanol. Step 3) The solvent for the platinum-tantalum precursor solution is n-butanol; Step 4) The current density for composite electrodeposition is 1~10 A / dm. 2 The temperature is 65~85℃ and the time is 10~80min.

5. The method for preparing the fence-type titanium-clad copper-based platinum-silver-zirconium-nano Ta₂O₅ gradient composite anode plate according to claim 4, characterized in that: In step 1), based on the mass of rosin flux as 100%, the composition is as follows: rosin grease 10-20%, rosin oil 5-10%, p-xylene 60-70%, sodium dodecyl sulfate 1-3%, salicylic acid 1-3%, and anhydrous ethanol 5-10%. In step 2), the concentrations of tin chloride, ruthenium chloride, manganese chloride, and antimony chloride in the tin-ruthenium-manganese-antimony precursor solution are 0.6-1.2 mol / L, ruthenium chloride, 0.09-0.18 mol / L, manganese chloride, 0.8-1.6 mol / L, antimony chloride, 0.1-0.2 mol / L, and hydrochloric acid, respectively, are 1-5 mol / L. In step 3), the concentrations of chloroplatinic acid, tantalum chloride, and carbon nanotubes in the platinum-tantalum precursor solution are 0.1–0.5 mol / L, 0.01–0.03 mol / L, and 0.01–1.0 g / L, respectively. In step 4), the neutral platinum plating composite electroplating solution contains 10~40g / L chloroplatinic acid, 100~300g / L potassium citrate, 5~20g / L sodium hypophosphite, 2~8g / L Ag powder, 3~9g / L nano Zr powder and 0.1~5g / L nano Ta2O5.

6. The method for preparing the fence-type titanium-clad copper-based platinum-silver-zirconium-nano Ta₂O₅ gradient composite anode plate according to claim 4 or 5, characterized in that: The preparation method of Ag powder in step 4) is as follows: S1. Under the conditions of 0~20℃ and stirring, the reducing agent solution is added dropwise to the silver ammonia solution, and the reaction is carried out at pH 9~11 for 10~120 min. The solid and liquid are separated to obtain silver powder. S2. Silver powder is soaked in oleic acid and then vacuum dried to obtain spherical silver powder.

7. The method for preparing the fence-type titanium-clad copper-based platinum-silver-zirconium-nano Ta₂O₅ gradient composite anode plate according to claim 6, characterized in that: The reducing agent solution is in the form of anhydrous ethanol and contains 1-20 ml / L of formaldehyde and 0.01-0.1 g / L of polyvinylpyrrolidone; the silver ammonia solution contains 6-10 g / L AgNO3, 2-4 g / L NaOH, and 30-100 ml / L ammonia.

8. The method for preparing the fence-type titanium-clad copper-based platinum-silver-zirconium-nano Ta₂O₅ gradient composite anode plate according to claim 6, characterized in that: Step S2 is followed by adding anhydrous ethanol and calcium stearate as milling aids to the spherical silver powder from step S2, and milling for 10-20 hours to obtain flake-shaped Ag powder.

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