CN109023436B - Titanium-based β -MnO2-RuO2Composite coating anode plate and preparation method and application thereof - Google Patents

Titanium-based β -MnO2-RuO2Composite coating anode plate and preparation method and application thereof Download PDF

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CN109023436B
CN109023436B CN201810810563.5A CN201810810563A CN109023436B CN 109023436 B CN109023436 B CN 109023436B CN 201810810563 A CN201810810563 A CN 201810810563A CN 109023436 B CN109023436 B CN 109023436B
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陈步明
黄惠
郭忠诚
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KUNMING HENDERA SCIENCE AND TECHNOLOGY Co.,Ltd.
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Abstract

The invention relates to titanium-based β -MnO2‑RuO2The invention discloses a composite coating anode plate and a preparation method and application thereof, belonging to the technical field of anode plates in wet metallurgy and relating to titanium-based β -MnO2‑RuO2The composite coating anode plate comprises a titanium-clad copper conductive beam, a titanium mesh substrate, a silica gel sleeve and conductive heads, wherein the silica gel sleeve is sleeved at the left end and the right end of the titanium-clad copper conductive beam, the conductive heads are fixedly arranged at the bottom end of the titanium-clad copper conductive beam and are externally connected with a power supply, the titanium mesh substrate is fixedly arranged at the lower end of the titanium-clad copper conductive beam, and the titanium mesh substrate is sequentially coated with a gradient Ir-Ta-Sn-SbOx intermediate layer and β -MnO2‑RuO2Composite surface active layer titanium-based β -MnO of the present invention2‑RuO2The composite coating anode plate has excellent catalytic performance, long service life and low cell voltage in the electrolytic process, and effectively prevents TiO caused by the generation of oxygen in the use process of a titanium substrate2The generation of the film leads the titanium-based metal oxide anode to lose efficacy, is environment-friendly and overcomes the defect of overhigh cost of the noble metal oxide coating.

Description

Titanium-based β -MnO2-RuO2Composite coating anode plate and preparation method and application thereof
Technical Field
The invention relates to titanium-based β -MnO2-RuO2A composite coating anode plate and a preparation method and application thereof belong to the technical field of anode plates in wet metallurgy.
Background
Titanium-based metal oxide anodes, also known as "dimensionally Stable anodes" (DSA), generally use metal titanium as a substrate, and coat the surface of the substrate with a coating electrode of metal oxide with high catalytic activity by thermal decomposition, sol-gel or electrodeposition, etc. The research on DSA started in the middle of the 20 th century and has been widely used in electrochemical industries such as chlor-alkali industry, hydrometallurgy, electroplating, water treatment, electrosynthesis, and pollutant degradation. In the field of sewage treatment, the electrocatalytic oxidation method has strong oxidation and reduction capability and low chemical consumption, and can also recover valuable substances such as metals and the like. Therefore, the method is applied to the treatment of wastewater containing organic matters such as hydrocarbon, aldehyde, phenol, ether, alcohol, dye and the like, and particularly under the severe conditions of serious water pollution and water resource shortage in China, the treatment of sewage by an electrocatalytic oxidation method can bring huge economic and social benefits. DSA occupies most of the anode used for treating sewage by electrocatalytic oxidation at present. Except sewage treatment, in the field of waste battery recovery, the treatment problem of a large amount of scrapped lead-acid storage batteries is solved, and if scientific and reasonable treatment is not carried out, serious environmental damage and resource waste are caused. Therefore, how to clean and efficiently recycle the waste lead-acid storage battery becomes a current research focus, and the recycling of the waste lead-acid storage battery has important significance from the aspects of environmental protection and resource utilization. Relevant researches show that in an electrode system with DSA as an anode, waste lead plaster placed on a cathode plate can be directly reduced into metal lead, the method simplifies the recovery process of the waste lead plaster, completely avoids the discharge of pollutants such as lead dust, sulfur dioxide and the like generated in the pyrogenic recovery process in the whole process, has low consumption of chemical reagents, can be recycled after being filtered, and is suitable for large-scale production.
The research on DSA is mainly focused on the research on the oxide coating of noble metals such as ruthenium, iridium and the like, wherein the best coating of the oxygen evolution anode in the electrolysis industry is IrO2-Ta2O5The composite oxide coating has high oxygen evolution electrocatalytic activity and electrochemical stability in an aqueous solution, and can stably work in a solution with strong acidity and high current density. However, such electrodes have the disadvantages of high production cost and short service life, especially in the electrolysis of ammonium sulfate solution systems. In order to meet the demand of the electrolytic industry for DSA, it is urgently required to reduce the production cost of DSA, and thus researchers have conducted studies on base metal oxide coatings, among which tin-based and lead-based oxide coatings have been most studied. However, the problems of over-high cell voltage and short service life of the coating in the actual use process limit the large-scale popularization and application of the coating.
Disclosure of Invention
Aiming at the problems and the defects of the titanium-based metal oxide anode in the prior art, the invention provides titanium-based β -MnO2-RuO2The invention relates to a composite coating anode plate, a preparation method and application thereof, in particular to a titanium-based β -MnO2-RuO2The composite coating anode plate has excellent catalytic activity, long service life and low tank voltage in the electrolytic process, is suitable for extracting metal by electrolysis of an ammonium sulfate solution system, and has the titanium-based β -MnO2-RuO2On the basis of not changing the structure of the electrolytic cell, the composition of the electrolyte and the operation specification, the composite coating anode plate has the advantages of obviously improving the conductivity, reducing the cell voltage by 0.1V, reducing the material cost by 40 percent and reducing the electricity consumptionThe flow efficiency is improved by 1-3%, and the method can be applied to the electrochemical industry on a large scale.
Titanium-based β -MnO2-RuO2The composite coating anode plate comprises a titanium-clad copper conductive beam 1, a titanium mesh substrate 2, a silica gel sleeve 3 and conductive heads 4, wherein the silica gel sleeve 3 is sleeved at the left end and the right end of the titanium-clad copper conductive beam 1, copper is exposed at the bottom end of the titanium-clad copper conductive beam 1 to serve as the conductive heads 4, the conductive heads 4 are externally connected with a power supply, the titanium mesh substrate 2 is fixedly arranged at the lower end of the titanium-clad copper conductive beam 1, and the titanium mesh substrate 2 is sequentially coated with a gradient Ir-Ta-Sn-SbOx intermediate layer and β -MnO2-RuO2A composite surface active layer;
further, the thickness of the gradient Ir-Ta-Sn-SbOx intermediate layer is 5-20 mu m, β -MnO2-RuO2The thickness of the composite surface active layer is 50-200 mu m; the titanium mesh substrate 2 is of a net structure or a porous structure;
furthermore, the net of the net-shaped structure is rhombic and 1-3 mm thick; the pore diameter of the porous structure is 5-10mm, and the thickness is 2-6 mm.
Another object of the present invention is to provide a titanium-based β -MnO2-RuO2The preparation method of the composite coating anode plate comprises the following specific steps:
(1) pretreatment of a titanium substrate: sequentially carrying out pretreatment of coarsening, oil removal, oxide film removal and acid pickling activation on the titanium mesh substrate;
(2) preparing a gradient Ir-Ta-Sn-SbOx interlayer: preparing a gradient Ir-Ta-Sn-SbOx intermediate layer on the titanium substrate pretreated in the step (1) by adopting a thermal decomposition method;
(3) preparation of β -MnO2-RuO2Preparing β -MnO on the gradient Ir-Ta-Sn-SbOx intermediate layer in the step (2) by adopting a thermal decomposition method2-RuO2Compounding the surface active layer to obtain titanium-based β -MnO2-RuO2A composite coating;
(4) titanium-based β -MnO in the step (3)2-RuO2The composite coating is welded at the lower end of the titanium-clad copper conductive beam, copper is milled at the bottom end of the titanium-clad copper conductive beam to be used as a conductive head, and the left end and the right end of the titanium-clad copper conductive beam are sleeved with silica gel sleeves to obtain the titanium-based β -MnO2-RuO2A composite coating anode plate;
in the step (1), the coarsening is sand blasting treatment by a sand blasting machine, and the oil removing is to place the titanium mesh substrate in NaOH solution with the mass percentage concentration of 10-30% to remove oil for 30-90 min; the step of removing the oxidation film is to place the deoiled titanium mesh substrate in a pickling solution to be soaked for 1-3 min to remove the oxidation film on the surface of the titanium mesh substrate, wherein the pickling solution is H2O/HNO3HF mixed acid solution, H2O、HNO3The volume ratio of HF to HF is (4-6): 3-5): 1; pickling and activating, namely placing the titanium mesh substrate without the oxide film in a hydrochloric acid solution with the mass percentage concentration of 10-30% for boiling for 2-3 h, taking out, washing with deionized water, and soaking in an oxalic acid solution with the mass percentage concentration of 1-5%;
the step (2) of preparing the gradient Ir-Ta-Sn-SbOx intermediate layer by a thermal decomposition method comprises the following specific steps: respectively dissolving five groups of tantalum pentachloride, chloroiridic acid, stannic chloride and antimony trichloride in concentrated hydrochloric acid, adding n-butyl alcohol solvent, and removing water from the solution by using a rotary evaporator to obtain precursor concentrated solution
Figure DEST_PATH_IMAGE002
Precursor concentrate
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Precursor concentrate
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Precursor concentrate
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Precursor concentrate
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(ii) a Concentrating the precursor
Figure 702061DEST_PATH_IMAGE002
Coating the titanium mesh substrate surface pretreated in the step (1), drying and sintering to obtain a coating
Figure 2593DEST_PATH_IMAGE002
(ii) a Concentrating the precursor
Figure 835419DEST_PATH_IMAGE004
Is applied to the coating
Figure 727152DEST_PATH_IMAGE002
Drying and sintering to obtain the coating
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(ii) a Concentrating the precursor
Figure 562701DEST_PATH_IMAGE006
Is applied to the coating
Figure 984455DEST_PATH_IMAGE004
Drying and sintering to obtain the coating
Figure 312668DEST_PATH_IMAGE006
(ii) a Concentrating the precursor
Figure 655925DEST_PATH_IMAGE008
Is applied to the coating
Figure 360576DEST_PATH_IMAGE006
Drying and sintering to obtain the coating
Figure 417262DEST_PATH_IMAGE008
(ii) a Concentrating the precursor
Figure 916377DEST_PATH_IMAGE010
Is applied to the coating
Figure 543667DEST_PATH_IMAGE008
Drying and sintering to obtain a gradient Ir-Ta-Sn-SbOx intermediate layer;
further, the precursor concentrated solution
Figure 786430DEST_PATH_IMAGE002
Moles of tantalum pentachloride, chloroiridate, tin tetrachloride and antimony trichlorideThe ratio of (52-60) to (22-26) to (16-20) to (2), and precursor concentrate
Figure 386038DEST_PATH_IMAGE004
The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is (40-46): 17-20): 34-38): 4, and the precursor concentrated solution
Figure 806786DEST_PATH_IMAGE006
The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is (32-36): 14-16): 42-48): 5, and the precursor concentrated solution
Figure 921373DEST_PATH_IMAGE008
The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is (26-30): 11-13): 52-56): 6, and the precursor concentrated solution
Figure 967826DEST_PATH_IMAGE010
The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is (10-16): 5-7): 68-76): 8; the drying temperature is 100-120 ℃, and the drying time is 1-5 min; the sintering temperature is 400-600 ℃, and the sintering time is 5-10 min; the distillation temperature of the rotary evaporator is 80-110 ℃, the rotating speed of the rotary distillation flask is 100-300 revolutions per time, the distillation vacuum degree is 0.05-1.2 Mpa, and the distillation time is 0.5-2.5 h;
β -MnO is prepared by adopting a thermal decomposition method in the step (3)2-RuO2The composite surface active layer comprises the specific steps of dissolving manganese chloride and ruthenium chloride in concentrated hydrochloric acid, sequentially adding nano cobaltosic oxide or nano silicon dioxide and n-butyl alcohol solvent, removing water of the solution by adopting a rotary evaporator to obtain precursor concentrated solution, uniformly coating the precursor concentrated solution on the gradient Ir-Ta-Sn-SbOx intermediate layer in the step (2), drying at the temperature of 100-120 ℃ for 1-5 min, sintering at the temperature of 200-300 ℃ for 5-10 min, repeating the coating and sintering processes for 20-30 times, and finally sintering at the temperature of 300-350 ℃ for 1-2 h to obtain β -MnO2-RuO2A composite surface active layer;
further, the total coating amount of the manganese chloride10 to 40mg/cm2The coating amount of ruthenium chloride is 5-10 mg/cm2；
Further, the nano cobaltosic oxide and the nano silicon dioxide are flaky particles, the particle sizes of the nano cobaltosic oxide particles and the nano silicon dioxide are 180-400 nm, and the nano cobaltosic oxide or the nano silicon dioxide is in the range of β -MnO2-RuO2The mass percentage content of the composite surface active layer is 0.1-5%;
further, in the step (3), the distillation temperature of the rotary evaporator is 80-110 ℃, the rotating speed of the rotary distillation flask is 100-300 revolutions per time, the vacuum degree of distillation is 0.05-1.2 Mpa, and the distillation time is 0.5-10 hours.
The titanium mesh substrate (2) is of a net-shaped structure or a hole-shaped structure, the mesh of the net-shaped structure is rhombic, and the thickness of the mesh is 1-3 mm; the pore diameter of the porous structure is 5-10mm, and the thickness is 2-6 mm.
The titanium-based β -MnO of the invention2-RuO2The composite coating anode plate is used as an anode plate for electrolyzing and extracting metal in an ammonium sulfate solution system.
The invention has the beneficial effects that:
(1) titanium-based β -MnO of the present invention2-RuO2The composite coating anode plate has excellent catalytic activity, long service life and low cell voltage in the electrolytic process, and is suitable for extracting metal by electrolysis of an ammonium sulfate solution system;
(2) titanium-based β -MnO of the present invention2-RuO2On the basis of not changing the structure of an electrolytic cell, the composition of an electrolyte and the operation specification, the conductivity of the composite coating anode plate is obviously improved, the cell voltage can be reduced by 0.1V, the material cost is reduced by 40%, the current efficiency is improved by 1-3%, and the composite coating anode plate can be used in the electrochemical industry on a large scale;
(3) the thermal decomposition oxide is distributed more uniformly, and the rapid and uniform coating can avoid the rapid oxidation of the titanium substrate due to water vapor;
(4) the gradient Ir-Ta-Sn-SbOx intermediate layer is introduced in a layered composite mode, so that the generation of oxygen in the use process of the titanium substrate is effectively prevented from causing TiO2The generation of the film leads the passivation failure of titanium-based metal oxide anode (DSA), prolongsThe service life of the electrode is prolonged, and the current conduction efficiency of the whole electrode is improved;
(5) the invention introduces β -MnO into the nanometer cobaltosic oxide particles or the nanometer silicon dioxide2-RuO2The internal stress in the plating layer is reduced, the generation of plating layer cracks is avoided, the conductivity and the corrosion resistance of the composite plating layer are greatly improved, and the service life of the anode is prolonged.
Drawings
FIG. 1 is a schematic structural view of titanium-based metal oxide anodes of examples 1 and 4 to 6;
wherein: 1-titanium-coated copper conductive beam, 2-titanium mesh substrate, 3-silica gel sleeve and 4-conductive head.
Detailed Description
The present invention will be further described with reference to the following embodiments.
Example 1 titanium-based β -MnO of this example, as shown in FIG. 12-RuO2The composite coating anode plate comprises a titanium-clad copper conductive beam 1, a titanium mesh substrate 2, a silica gel sleeve 3 and conductive heads 4, wherein the silica gel sleeve 3 is sleeved at the left end and the right end of the titanium-clad copper conductive beam 1, copper is exposed at the bottom end of the titanium-clad copper conductive beam 1 to serve as the conductive heads 4, the conductive heads 4 are externally connected with a power supply, the titanium mesh substrate 2 is fixedly arranged at the lower end of the titanium-clad copper conductive beam 1, and the titanium mesh substrate 2 is sequentially coated with a gradient Ir-Ta-Sn-SbOx intermediate layer and β -MnO2-RuO2The thickness of the gradient Ir-Ta-Sn-SbOx intermediate layer is 5 mu m, β -MnO2-RuO2The thickness of the composite surface active layer is 150 mu m; the titanium mesh substrate 2 is of a rhombic mesh structure and has the thickness of 2 mm;
titanium-based β -MnO2-RuO2The preparation method of the composite coating anode plate comprises the following specific steps:
(1) pretreatment of a titanium substrate: sequentially carrying out pretreatment of coarsening, oil removal, oxide film removal and acid washing activation on a titanium mesh substrate with the thickness of 2 mm; wherein the coarsening is sand blasting by a sand blasting machine, and the oil removing is that the titanium mesh substrate is placed in NaOH solution with the mass percentage concentration of 10% to remove oil for 90 min; the oxide film is removed by soaking the deoiled titanium mesh substrate in pickling solution for 1minAn oxide film on the surface of the titanium mesh substrate, wherein the pickling solution is H2O/HNO3HF mixed acid solution, H2O、HNO3And HF in a volume ratio of 4:5: 1; acid washing and activating, namely placing the titanium mesh substrate without the oxide film in a hydrochloric acid solution with the mass percentage concentration of 10% for boiling for 3 hours, taking out, washing with deionized water, and soaking in an oxalic acid solution with the mass percentage concentration of 1%;
(2) preparing a gradient Ir-Ta-Sn-SbOx interlayer: preparing a gradient Ir-Ta-Sn-SbOx intermediate layer on the titanium substrate pretreated in the step (1) by adopting a thermal decomposition method; the method for preparing the gradient Ir-Ta-Sn-SbOx intermediate layer by a thermal decomposition method comprises the following specific steps: respectively dissolving five groups of tantalum pentachloride, chloroiridic acid, stannic chloride and antimony trichloride in concentrated hydrochloric acid, adding n-butyl alcohol solvent, and removing water from the solution by using a rotary evaporator to obtain precursor concentrated solution
Figure 484258DEST_PATH_IMAGE002
Precursor concentrate
Figure 528438DEST_PATH_IMAGE004
Precursor concentrate
Figure 379588DEST_PATH_IMAGE006
Precursor concentrate
Figure 964153DEST_PATH_IMAGE008
Precursor concentrate
Figure 335092DEST_PATH_IMAGE010
(ii) a Concentrating the precursor
Figure 612489DEST_PATH_IMAGE002
Coating the titanium mesh substrate surface pretreated in the step (1), drying and sintering to obtain a coating
Figure 186821DEST_PATH_IMAGE002
(ii) a Concentrating the precursor
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Is applied to the coating
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Drying and sintering to obtain the coating
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(ii) a Concentrating the precursor
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Is applied to the coating
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Drying and sintering to obtain the coating
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(ii) a Concentrating the precursor
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Is applied to the coating
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Drying and sintering to obtain the coating
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(ii) a Concentrating the precursor
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Is applied to the coating
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Drying and sintering to obtain a gradient Ir-Ta-Sn-SbOx intermediate layer;
precursor concentrate in this example
Figure 395637DEST_PATH_IMAGE002
The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 56:24:18:2, and the precursor concentrated solution
Figure 929387DEST_PATH_IMAGE004
The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 42:18:36:4, and the precursor concentrated solution
Figure 239057DEST_PATH_IMAGE006
The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 35:15:45:5, and the precursor concentrated solution
Figure 200060DEST_PATH_IMAGE008
The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 28:12:54:6, and the precursor concentrated solution
Figure 910527DEST_PATH_IMAGE010
The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 14:6:72: 8; the drying temperature is 100 ℃, and the drying time is 5 min; the sintering temperature is 500 ℃, and the sintering time is 8 min; the distillation temperature of the rotary evaporator is 90 ℃, the rotating speed of the rotary distillation flask is 200 revolutions per time, the distillation vacuum degree is 0.098Mpa, and the distillation time is 1.0 h;
(3) preparation of β -MnO2-RuO2Preparing β -MnO on the gradient Ir-Ta-Sn-SbOx intermediate layer in the step (2) by adopting a thermal decomposition method2-RuO2Compounding the surface active layer to obtain titanium-based β -MnO2-RuO2Preparing β -MnO by thermal decomposition method2-RuO2The composite surface active layer comprises the following specific steps of dissolving manganese chloride and ruthenium chloride in concentrated hydrochloric acid, sequentially adding nano cobaltosic oxide and n-butyl alcohol solvent, removing water of the solution by using a rotary evaporator to obtain precursor concentrated solution, wherein the distillation temperature of the rotary evaporator is 90 ℃, the rotating speed of a rotary distillation flask is 200 revolutions/time, the distillation vacuum degree is 0.098Mpa, and the distillation time is 3.0h, uniformly coating the precursor concentrated solution on the gradient Ir-Ta-Sn-SbOx intermediate layer in the step (2), drying at the temperature of 100 ℃ for 5min, sintering at the temperature of 200 ℃ for 10min, repeating the coating and sintering processes for 20 times, and finally sintering at the temperature of 300 ℃ for 2h to obtain β -MnO2-RuO2A composite surface active layer;
the total coating amount of manganese chloride in this example was 20mg/cm2The coating amount of ruthenium chloride was 10mg/cm2；
In the embodiment, the nano cobaltosic oxide is flaky particles, the particle size of the nano cobaltosic oxide particles is 300nm, and the nano cobaltosic oxide is in the range of β -MnO2-RuO2The mass percentage content of the composite surface active layer is 0.1 percent;
(4) titanium-based β -MnO in the step (3)2-RuO2The composite coating is welded at the lower end of the titanium-clad copper conductive beam, copper is milled at the bottom end of the titanium-clad copper conductive beam to be used as a conductive head, and the left end and the right end of the titanium-clad copper conductive beam are sleeved with silica gel sleeves to obtain the titanium-based β -MnO2-RuO2A composite coating anode plate;
titanium-based β -MnO for metal of the embodiment2-RuO2The composite coating anode is used for electrolyzing and extracting metal in an ammonium sulfate solution system, metal manganese is electrodeposited in an anion membrane electrolytic bath under the electrolysis conditions that the concentration of manganese ions in a cathode manganese electrolyte is 40g/L, the concentration of ammonium sulfate is 60g/L, the electrolysis temperature is 30 ℃, the pH value is 6.50, the concentration of manganese ions in an anode electrolyte is 20g/L, the concentration of ammonium sulfate is 120g/L, sulfuric acid is 30 g/L, the electrolysis temperature is 30 ℃, and the titanium-based β -MnO is prepared by the method2-RuO2The electric efficiency of the composite coating anode is improved by 1 percent compared with that of the traditional titanium-based ruthenium-iridium-titanium oxide noble metal anode plate, and the TiO caused by the generation of oxygen in the use process of the titanium substrate is effectively prevented2The generation of the film leads the anode of the titanium-based metal oxide to lose efficacy, the voltage of the tank is low by 100mV, and the service life is prolonged by 1.5 times.
Example 2 titanium-based β -MnO of this example2-RuO2The composite coating anode plate comprises a titanium-clad copper conductive beam, a titanium mesh substrate, a silica gel sleeve and conductive heads, wherein the silica gel sleeve is sleeved at the left end and the right end of the titanium-clad copper conductive beam, copper is exposed at the bottom end of the titanium-clad copper conductive beam to serve as the conductive heads, the conductive heads are externally connected with a power supply, the titanium mesh substrate is fixedly arranged at the lower end of the titanium-clad copper conductive beam, and the titanium mesh substrate is sequentially coated with a gradient Ir-Ta-Sn-SbOx intermediate layer and β -MnO2-RuO2The thickness of the gradient Ir-Ta-Sn-SbOx intermediate layer is 8 mu m, β -MnO2-RuO2The thickness of the composite surface active layer is 200 mu m; the titanium mesh substrate 2 is of a porous structure, the thickness is 5mm, and the aperture is 8 mm;
titanium-based β -MnO2-RuO2The preparation method of the composite coating anode plate comprises the following specific steps:
(1) pretreatment of a titanium substrate: sequentially carrying out pretreatment of coarsening, oil removal, oxide film removal and acid washing activation on a titanium mesh substrate with the thickness of 5mm and the aperture of 8 mm; wherein the coarsening is sand blasting by a sand blasting machine, and the oil removing is to place the titanium mesh substrate in NaOH solution with the mass percentage concentration of 15 percent to remove oil for 70 min; the step of removing the oxidation film is to put the deoiled titanium mesh substrate into a pickling solution to be soaked for 1.5min to remove the oxidation film on the surface of the titanium mesh substrate, wherein the pickling solution is H2O/HNO3HF mixed acid solution, H2O、HNO3And HF in a volume ratio of 5:5: 1; acid washing and activating, namely placing the titanium mesh substrate without the oxide film in a hydrochloric acid solution with the mass percentage concentration of 15% for boiling for 2.5h, taking out, washing with deionized water, and soaking in an oxalic acid solution with the mass percentage concentration of 2%;
(2) preparing a gradient Ir-Ta-Sn-SbOx interlayer: preparing a gradient Ir-Ta-Sn-SbOx intermediate layer on the titanium substrate pretreated in the step (1) by adopting a thermal decomposition method; the method for preparing the gradient Ir-Ta-Sn-SbOx intermediate layer by a thermal decomposition method comprises the following specific steps: respectively dissolving five groups of tantalum pentachloride, chloroiridic acid, stannic chloride and antimony trichloride in concentrated hydrochloric acid, adding n-butyl alcohol solvent, and removing water from the solution by using a rotary evaporator to obtain precursor concentrated solution
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Precursor concentrate
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Precursor concentrate
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Precursor concentrate
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Concentration of the precursorLiquid for treating urinary tract infection
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(ii) a Concentrating the precursor
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Coating the titanium mesh substrate surface pretreated in the step (1), drying and sintering to obtain a coating
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(ii) a Concentrating the precursor
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Is applied to the coating
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Drying and sintering to obtain the coating
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(ii) a Concentrating the precursor
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Is applied to the coating
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Drying and sintering to obtain the coating
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(ii) a Concentrating the precursor
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Is applied to the coating
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Drying and sintering to obtain the coating
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(ii) a Concentrating the precursor
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Is applied to the coating
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Drying and sintering to obtain a gradient Ir-Ta-Sn-SbOx intermediate layer;
precursor concentrate in this example
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The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 56:24:18:2, and the precursor concentrated solution
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The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 42:18:36:4, and the precursor concentrated solution
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The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 35:15:45:5, and the precursor concentrated solution
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The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 28:12:54:6, and the precursor concentrated solution
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The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 14:6:72: 8; the drying temperature is 110 ℃, and the drying time is 3 min; the sintering temperature is 400 ℃, and the sintering time is 10 min; the distillation temperature of the rotary evaporator is 80 ℃, the rotating speed of the rotary distillation flask is 300 r/t, the distillation vacuum degree is 0.05Mpa, and the distillation time is 0.5 h;
(3) preparation of β -MnO2-RuO2Preparing β -MnO on the gradient Ir-Ta-Sn-SbOx intermediate layer in the step (2) by adopting a thermal decomposition method2-RuO2Compounding the surface active layer to obtain titanium-based β -MnO2-RuO2Preparing β -MnO by thermal decomposition method2-RuO2Composite surface-active layer, in particularDissolving manganese chloride in concentrated hydrochloric acid, sequentially adding nano silicon dioxide and n-butanol solvent, removing water of the solution by using a rotary evaporator to obtain precursor concentrated solution, wherein the distillation temperature of the rotary evaporator is 80 ℃, the rotating speed of a rotary distillation flask is 300 revolutions per time, the distillation vacuum degree is 0.05Mpa, and the distillation time is 4.0h, uniformly coating the precursor concentrated solution on the gradient Ir-Ta-Sn-SbOx intermediate layer in the step (2), drying for 5min at the temperature of 100 ℃, sintering for 10min at the temperature of 200 ℃, repeating the coating and sintering processes for 25 times, and finally sintering for 1.5h at the temperature of 320 ℃ to obtain β -MnO2-RuO2A composite surface active layer;
the total coating amount of manganese chloride in this example was 25mg/cm2The coating amount of ruthenium chloride was 6mg/cm2；
In the embodiment, the nano silicon dioxide is flaky particles, the particle size of the nano silicon dioxide is 300nm, and the nano silicon dioxide is in the range of β -MnO2-RuO2The mass percentage content of the composite surface active layer is 1.5 percent;
(4) titanium-based β -MnO in the step (3)2-RuO2The composite coating is welded at the lower end of the titanium-clad copper conductive beam, copper is milled at the bottom end of the titanium-clad copper conductive beam to be used as a conductive head, and the left end and the right end of the titanium-clad copper conductive beam are sleeved with silica gel sleeves to obtain the titanium-based β -MnO2-RuO2A composite coating anode plate;
titanium-based β -MnO for metal of the embodiment2-RuO2The composite coating anode is used for electrolyzing and extracting metal in an ammonium sulfate solution system, metal manganese is electrodeposited in an anion membrane electrolytic bath under the electrolysis conditions that the concentration of manganese ions in a cathode manganese electrolyte is 40g/L, the concentration of ammonium sulfate is 60g/L, the electrolysis temperature is 30 ℃, the pH value is 6.50, the concentration of manganese ions in an anode electrolyte is 20g/L, the concentration of ammonium sulfate is 120g/L, sulfuric acid is 30 g/L, the electrolysis temperature is 30 ℃, and the titanium-based β -MnO is prepared by the method2-RuO2The electric efficiency of the composite coating anode is improved by 1.5 percent compared with that of the traditional titanium-based ruthenium-iridium-titanium oxide noble metal anode plate, and the TiO caused by the generation of oxygen in the use process of the titanium substrate is effectively prevented2The generation of the film leads the titanium-based metal oxide anode to be passivated and failed, and the tankThe voltage is reduced by 50mV, and the service life is prolonged by 2 times.
Example 3 titanium-based β -MnO of this example2-RuO2The composite coating anode plate comprises a titanium-clad copper conductive beam, a titanium mesh substrate, a silica gel sleeve and conductive heads, wherein the silica gel sleeve is sleeved at the left end and the right end of the titanium-clad copper conductive beam, copper is exposed at the bottom end of the titanium-clad copper conductive beam to serve as the conductive heads, the conductive heads are externally connected with a power supply, the titanium mesh substrate is fixedly arranged at the lower end of the titanium-clad copper conductive beam, and the titanium mesh substrate is sequentially coated with a gradient Ir-Ta-Sn-SbOx intermediate layer and β -MnO2-RuO2The thickness of the gradient Ir-Ta-Sn-SbOx intermediate layer is 15 mu m, β -MnO2-RuO2The thickness of the composite surface active layer is 150 mu m; the titanium mesh substrate 2 is of a porous structure, the thickness is 5mm, and the aperture is 8 mm;
titanium-based β -MnO2-RuO2The preparation method of the composite coating anode plate comprises the following specific steps:
(1) pretreatment of a titanium substrate: sequentially carrying out pretreatment of coarsening, oil removal, oxide film removal and acid washing activation on a titanium mesh substrate with the thickness of 5mm and the aperture of 8 mm; wherein the coarsening is sand blasting by a sand blasting machine, and the oil removing is to place the titanium mesh substrate in NaOH solution with the mass percentage concentration of 30 percent to remove oil for 30 min; the step of removing the oxidation film is to put the deoiled titanium mesh substrate into a pickling solution to be soaked for 3min to remove the oxidation film on the surface of the titanium mesh substrate, wherein the pickling solution is H2O/HNO3HF mixed acid solution, H2O、HNO3And HF in a volume ratio of 6:3: 1; acid washing and activating, namely placing the titanium mesh substrate without the oxide film in a hydrochloric acid solution with the mass percentage concentration of 30% for boiling for 2 hours, taking out, washing with deionized water, and soaking in an oxalic acid solution with the mass percentage concentration of 4%;
(2) preparing a gradient Ir-Ta-Sn-SbOx interlayer: preparing a gradient Ir-Ta-Sn-SbOx intermediate layer on the titanium substrate pretreated in the step (1) by adopting a thermal decomposition method; the method for preparing the gradient Ir-Ta-Sn-SbOx intermediate layer by a thermal decomposition method comprises the following specific steps: respectively dissolving five groups of tantalum pentachloride, chloroiridic acid, stannic chloride and antimony trichloride in concentrated hydrochloric acid, adding n-butyl alcohol solvent, and removing water from the solution by using a rotary evaporator to obtain precursor concentrated solution
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Precursor concentrate
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Precursor concentrate
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Precursor concentrate
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Precursor concentrate
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(ii) a Concentrating the precursor
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Coating the titanium mesh substrate surface pretreated in the step (1), drying and sintering to obtain a coating
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(ii) a Concentrating the precursor
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Is applied to the coating
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Drying and sintering to obtain the coating
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(ii) a Concentrating the precursor
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Is applied to the coating
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Drying and sintering to obtain the coating
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(ii) a Concentrating the precursor
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Is applied to the coating
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Drying and sintering to obtain the coating
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(ii) a Concentrating the precursor
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Is applied to the coating
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Drying and sintering to obtain a gradient Ir-Ta-Sn-SbOx intermediate layer;
precursor concentrate in this example
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The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 56:24:18:2, and the precursor concentrated solution
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The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 42:18:36:4, and the precursor concentrated solution
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The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 35:15:45:5, and the precursor concentrated solution
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The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 28:12:54:6, and the precursor concentrated solution
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The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 14:6:72: 8;the drying temperature is 120 ℃, and the drying time is 1 min; the sintering temperature is 600 ℃, and the sintering time is 5 min; the distillation temperature of the rotary evaporator is 110 ℃, the rotating speed of the rotary distillation flask is 250 r/t, the distillation vacuum degree is 1.2Mpa, and the distillation time is 2.5 h;
(3) preparation of β -MnO2-RuO2Preparing β -MnO on the gradient Ir-Ta-Sn-SbOx intermediate layer in the step (2) by adopting a thermal decomposition method2-RuO2Compounding the surface active layer to obtain titanium-based β -MnO2-RuO2Preparing β -MnO by thermal decomposition method2-RuO2The composite surface active layer comprises the following specific steps of dissolving manganese chloride in concentrated hydrochloric acid, sequentially adding nano cobaltosic oxide and n-butyl alcohol solvent, removing water of the solution by using a rotary evaporator to obtain precursor concentrated solution, wherein the distillation temperature of the rotary evaporator is 110 ℃, the rotating speed of a rotary distillation flask is 200 revolutions/time, the distillation vacuum degree is 1.2Mpa, and the distillation time is 10 hours, uniformly coating the precursor concentrated solution on the gradient Ir-Ta-Sn-SbOx intermediate layer obtained in the step (2), drying at the temperature of 120 ℃ for 2min, sintering at the temperature of 300 ℃ for 5min, repeating the coating and sintering processes for 30 times, and finally sintering at the temperature of 350 ℃ for 1 hour to obtain β -MnO2-RuO2A composite surface active layer;
the total coating amount of manganese chloride in this example was 30mg/cm2The coating amount of ruthenium chloride was 8mg/cm2；
In the embodiment, the nano cobaltosic oxide is flaky particles, the particle size of the nano cobaltosic oxide particles is 300nm, and the nano cobaltosic oxide is in the range of β -MnO2-RuO2The mass percentage content of the composite surface active layer is 5.0 percent;
(4) titanium-based β -MnO in the step (3)2-RuO2The composite coating is welded at the lower end of the titanium-clad copper conductive beam, copper is milled at the bottom end of the titanium-clad copper conductive beam to be used as a conductive head, and the left end and the right end of the titanium-clad copper conductive beam are sleeved with silica gel sleeves to obtain the titanium-based β -MnO2-RuO2A composite coating anode plate;
titanium-based β -MnO for metal of the embodiment2-RuO2Composite coatingThe anode is used for electrolytic extraction of metals in an ammonium sulfate solution system: in the solid-phase electrolysis recovery of waste lead-acid storage battery lead plaster, the electrolysis conditions are as follows: the cathode is a stainless steel cathode cylinder filled with lead paste, the concentration of ammonium sulfate in the catholyte is 80g/L, the concentration of sulfuric acid is 30 g/L, the concentration of ethylenediamine is 20g/L, the concentration of ammonium acetate is 180g/L, and the electrolysis temperature is 40 ℃; the anode current density is 600A/m2Titanium-based β -MnO of this example2-RuO2The electric efficiency of the composite coating anode is improved by 3 percent compared with the traditional titanium-based ruthenium-iridium-titanium oxide noble metal anode plate, and the TiO caused by the generation of oxygen in the use process of the titanium substrate is effectively prevented2The generation of the film leads the anode of the titanium-based metal oxide to lose efficacy, the voltage of the tank is low by 150mV, and the service life is prolonged by 3 times.
Example 4 titanium-based β -MnO of this example as shown in FIG. 12-RuO2The composite coating anode plate comprises a titanium-clad copper conductive beam 1, a titanium mesh substrate 2, a silica gel sleeve 3 and conductive heads 4, wherein the silica gel sleeve 3 is sleeved at the left end and the right end of the titanium-clad copper conductive beam 1, copper is exposed at the bottom end of the titanium-clad copper conductive beam 1 to serve as the conductive heads 4, the conductive heads 4 are externally connected with a power supply, the titanium mesh substrate 2 is fixedly arranged at the lower end of the titanium-clad copper conductive beam 1, and the titanium mesh substrate 2 is sequentially coated with a gradient Ir-Ta-Sn-SbOx intermediate layer and β -MnO2-RuO2The thickness of the gradient Ir-Ta-Sn-SbOx intermediate layer is 20 mu m, β -MnO2-RuO2The thickness of the composite surface active layer is 200 mu m; the titanium mesh substrate 2 is of a rhombic mesh structure and is 3mm thick;
titanium-based β -MnO2-RuO2The preparation method of the composite coating anode plate comprises the following specific steps:
(1) pretreatment of a titanium substrate: sequentially carrying out pretreatment of coarsening, oil removal, oxide film removal and acid washing activation on a titanium mesh substrate with the thickness of 3 mm; wherein the coarsening is sand blasting by a sand blasting machine, and the oil removing is to place the titanium mesh substrate in NaOH solution with the mass percentage concentration of 15 percent for oil removal for 40 min; the step of removing the oxidation film is to put the deoiled titanium mesh substrate into a pickling solution to be soaked for 2min to remove the oxidation film on the surface of the titanium mesh substrate, wherein the pickling solution is H2O/HNO3HF mixed acid solution, H2O、HNO3And HF in a volume ratio of 5:3: 1; acid picklingPlacing the titanium mesh substrate without the oxide film in a hydrochloric acid solution with the mass percentage concentration of 20% to boil for 2.5h, taking out the titanium mesh substrate, washing the titanium mesh substrate with deionized water, and soaking the titanium mesh substrate in an oxalic acid solution with the mass percentage concentration of 5%;
(2) preparing a gradient Ir-Ta-Sn-SbOx interlayer: preparing a gradient Ir-Ta-Sn-SbOx intermediate layer on the titanium substrate pretreated in the step (1) by adopting a thermal decomposition method; the method for preparing the gradient Ir-Ta-Sn-SbOx intermediate layer by a thermal decomposition method comprises the following specific steps: respectively dissolving five groups of tantalum pentachloride, chloroiridic acid, stannic chloride and antimony trichloride in concentrated hydrochloric acid, adding n-butyl alcohol solvent, and removing water from the solution by using a rotary evaporator to obtain precursor concentrated solution
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Precursor concentrate
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Precursor concentrate
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Precursor concentrate
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Precursor concentrate
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(ii) a Concentrating the precursor
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Coating the titanium mesh substrate surface pretreated in the step (1), drying and sintering to obtain a coating
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(ii) a Concentrating the precursor
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Is applied to the coating
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Drying in the upper partAnd sintering to obtain the coating
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(ii) a Concentrating the precursor
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Is applied to the coating
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Drying and sintering to obtain the coating
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(ii) a Concentrating the precursor
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Is applied to the coating
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Drying and sintering to obtain the coating
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(ii) a Concentrating the precursor
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Is applied to the coating
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Drying and sintering to obtain a gradient Ir-Ta-Sn-SbOx intermediate layer;
precursor concentrate in this example
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The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 52:26:20:2, and the precursor concentrated solution
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The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 40:19:37:4, and the precursor concentrated solution
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The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 32:15:48:5, and the precursor concentrated solution
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The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 26:13:55:6, and the precursor concentrated solution
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The molar ratio of the tantalum pentachloride to the chloroiridic acid to the tin tetrachloride to the antimony trichloride is 10:7:75: 8; the drying temperature is 110 ℃, and the drying time is 2 min; the sintering temperature is 500 ℃, and the sintering time is 7 min; the distillation temperature of the rotary evaporator is 100 ℃, the rotating speed of the rotary distillation flask is 200 revolutions per time, the distillation vacuum degree is 0.5Mpa, and the distillation time is 1.5 h;
(3) preparation of β -MnO2-RuO2Preparing β -MnO on the gradient Ir-Ta-Sn-SbOx intermediate layer in the step (2) by adopting a thermal decomposition method2-RuO2Compounding the surface active layer to obtain titanium-based β -MnO2-RuO2Preparing β -MnO by thermal decomposition method2-RuO2The composite surface active layer comprises the following specific steps of dissolving manganese chloride in concentrated hydrochloric acid, sequentially adding nano silicon dioxide and n-butanol solvent, removing water of the solution by using a rotary evaporator to obtain precursor concentrated solution, wherein the distillation temperature of the rotary evaporator is 100 ℃, the rotating speed of a rotary distillation flask is 200 revolutions/time, the distillation vacuum degree is 0.8Mpa, and the distillation time is 8 hours, uniformly coating the precursor concentrated solution on the gradient Ir-Ta-Sn-SbOx intermediate layer in the step (2), drying for 3 minutes at the temperature of 110 ℃, sintering for 8 minutes at the temperature of 250 ℃, repeating the coating and sintering processes for 28 times, and finally sintering for 1.5 hours at the temperature of 320 ℃ to obtain β -MnO2-RuO2A composite surface active layer;
the total coating amount of manganese chloride in this example was 40mg/cm2The coating amount of ruthenium chloride was 5mg/cm2；
In this example AThe nanometer silica is flaky, the particle diameter of the nanometer silica is 180nm, and the nanometer silica is β -MnO2-RuO2The mass percentage content of the composite surface active layer is 3.0 percent;
(4) titanium-based β -MnO in the step (3)2-RuO2The composite coating is welded at the lower end of the titanium-clad copper conductive beam, copper is milled at the bottom end of the titanium-clad copper conductive beam to be used as a conductive head, and the left end and the right end of the titanium-clad copper conductive beam are sleeved with silica gel sleeves to obtain the titanium-based β -MnO2-RuO2A composite coating anode plate;
titanium-based β -MnO for metal of the embodiment2-RuO2The composite coating anode can be used for electrolyzing and extracting metal in an ammonium sulfate solution system.
Example 5 titanium-based β -MnO of this example as shown in FIG. 12-RuO2The composite coating anode plate comprises a titanium-clad copper conductive beam 1, a titanium mesh substrate 2, a silica gel sleeve 3 and conductive heads 4, wherein the silica gel sleeve 3 is sleeved at the left end and the right end of the titanium-clad copper conductive beam 1, copper is exposed at the bottom end of the titanium-clad copper conductive beam 1 to serve as the conductive heads 4, the conductive heads 4 are externally connected with a power supply, the titanium mesh substrate 2 is fixedly arranged at the lower end of the titanium-clad copper conductive beam 1, and the titanium mesh substrate 2 is sequentially coated with a gradient Ir-Ta-Sn-SbOx intermediate layer and β -MnO2-RuO2The thickness of the gradient Ir-Ta-Sn-SbOx intermediate layer is 16 mu m, β -MnO2-RuO2The thickness of the composite surface active layer is 150 mu m; the titanium mesh substrate 2 is of a rhombic mesh structure and has the thickness of 2.5 mm;
titanium-based β -MnO2-RuO2The preparation method of the composite coating anode plate comprises the following specific steps:
(1) pretreatment of a titanium substrate: sequentially carrying out pretreatment of coarsening, oil removal, oxide film removal and acid washing activation on a titanium mesh substrate with the thickness of 2.5 mm; wherein the coarsening is sand blasting by a sand blasting machine, and the oil removing is to place the titanium mesh substrate in NaOH solution with the mass percentage concentration of 20 percent to remove oil for 50 min; the step of removing the oxidation film is to put the deoiled titanium mesh substrate into a pickling solution to be soaked for 2.5min to remove the oxidation film on the surface of the titanium mesh substrate, wherein the pickling solution is H2O/HNO3HF mixed acid solution, H2O、HNO3And volume ratio of HFIs 6:4: 1; acid washing and activating, namely placing the titanium mesh substrate without the oxide film in 25 mass percent hydrochloric acid solution for boiling for 2.3h, taking out, washing with deionized water, and soaking in 3 mass percent oxalic acid solution;
(2) preparing a gradient Ir-Ta-Sn-SbOx interlayer: preparing a gradient Ir-Ta-Sn-SbOx intermediate layer on the titanium substrate pretreated in the step (1) by adopting a thermal decomposition method; the method for preparing the gradient Ir-Ta-Sn-SbOx intermediate layer by a thermal decomposition method comprises the following specific steps: respectively dissolving five groups of tantalum pentachloride, chloroiridic acid, stannic chloride and antimony trichloride in concentrated hydrochloric acid, adding n-butyl alcohol solvent, and removing water from the solution by using a rotary evaporator to obtain precursor concentrated solution
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Precursor concentrate
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Precursor concentrate
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Precursor concentrate
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Precursor concentrate
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(ii) a Concentrating the precursor
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Coating the titanium mesh substrate surface pretreated in the step (1), drying and sintering to obtain a coating
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(ii) a Concentrating the precursor
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Is applied to the coating
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Drying and sintering to obtain the coating
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(ii) a Concentrating the precursor
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Is applied to the coating
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Drying and sintering to obtain the coating
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(ii) a Concentrating the precursor
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Is applied to the coating
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Drying and sintering to obtain the coating
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(ii) a Concentrating the precursor
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Is applied to the coating
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Drying and sintering to obtain a gradient Ir-Ta-Sn-SbOx intermediate layer;
precursor concentrate in this example
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The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 54:25:19:2, and the precursor concentrated solution
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The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 43:19:34:4, and the precursor concentrated solution
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The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 34:16:45:5, and the precursor concentrated solution
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The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 27:13:54:6, and the precursor concentrated solution
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The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 12:7:73: 8; the drying temperature is 110 ℃, and the drying time is 2 min; the sintering temperature is 400 ℃, and the sintering time is 10 min; the distillation temperature of the rotary evaporator is 100 ℃, the rotating speed of the rotary distillation flask is 250 r/t, the distillation vacuum degree is 0.5Mpa, and the distillation time is 2.0 h;
(3) preparation of β -MnO2-RuO2Preparing β -MnO on the gradient Ir-Ta-Sn-SbOx intermediate layer in the step (2) by adopting a thermal decomposition method2-RuO2Compounding the surface active layer to obtain titanium-based β -MnO2-RuO2Preparing β -MnO by thermal decomposition method2-RuO2The composite surface active layer comprises the following specific steps of dissolving manganese chloride in concentrated hydrochloric acid, sequentially adding nano cobaltosic oxide and n-butyl alcohol solvent, removing water of the solution by using a rotary evaporator to obtain precursor concentrated solution, wherein the distillation temperature of the rotary evaporator is 100 ℃, the rotating speed of a rotary distillation flask is 200 revolutions/time, the distillation vacuum degree is 0.50Mpa, and the distillation time is 6 hours, uniformly coating the precursor concentrated solution on the gradient Ir-Ta-Sn-SbOx intermediate layer in the step (2), drying at the temperature of 110 ℃ for 4 minutes, sintering at the temperature of 250 ℃ for 7 minutes, repeating the coating and sintering processes for 30 times, and finally sintering at the temperature of 350 ℃ for 1.2 hours to obtain β -MnO2-RuO2A composite surface active layer;
the total coating amount of manganese chloride in this example was 35mg/cm2The coating amount of ruthenium chloride was 7mg/cm2；
In the embodiment, the nano cobaltosic oxide is flaky particles, the particle size of the nano cobaltosic oxide particles is 400nm, and the nano cobaltosic oxide is in the range of β -MnO2-RuO2The mass percentage content of the composite surface active layer is 1.0 percent;
(4) titanium-based β -MnO in the step (3)2-RuO2The composite coating is welded at the lower end of the titanium-clad copper conductive beam, copper is milled at the bottom end of the titanium-clad copper conductive beam to be used as a conductive head, and the left end and the right end of the titanium-clad copper conductive beam are sleeved with silica gel sleeves to obtain the titanium-based β -MnO2A composite coating anode plate;
titanium-based β -MnO for metal of the embodiment2-RuO2The composite coating anode can be used for electrolyzing and extracting metal in an ammonium sulfate solution system.
Example 6 titanium-based β -MnO of this example as shown in FIG. 12-RuO2The composite coating anode plate comprises a titanium-clad copper conductive beam 1, a titanium mesh substrate 2, a silica gel sleeve 3 and conductive heads 4, wherein the silica gel sleeve 3 is sleeved at the left end and the right end of the titanium-clad copper conductive beam 1, copper is exposed at the bottom end of the titanium-clad copper conductive beam 1 to serve as the conductive heads 4, the conductive heads 4 are externally connected with a power supply, the titanium mesh substrate 2 is fixedly arranged at the lower end of the titanium-clad copper conductive beam 1, and the titanium mesh substrate 2 is sequentially coated with a gradient Ir-Ta-Sn-SbOx intermediate layer and β -MnO2-RuO2The thickness of the gradient Ir-Ta-Sn-SbOx intermediate layer is 14 mu m, β -MnO2-RuO2The thickness of the composite surface active layer is 180 mu m; the titanium mesh substrate 2 is of a rhombic mesh structure and is 3mm thick;
titanium-based β -MnO2-RuO2The preparation method of the composite coating anode plate comprises the following specific steps:
(1) pretreatment of a titanium substrate: sequentially carrying out pretreatment of coarsening, oil removal, oxide film removal and acid washing activation on a titanium mesh substrate with the thickness of 3 mm; wherein the coarsening is sand blasting by a sand blasting machine, and the oil removing is to place the titanium mesh substrate in NaOH solution with the mass percentage concentration of 25% for oil removing for 50 min; the step of removing the oxidation film is to put the deoiled titanium mesh substrate into a pickling solution to be soaked for 2.5min to remove the oxidation film on the surface of the titanium mesh substrate, wherein the pickling solution is H2O/HNO3HF mixed acid solution, H2O、HNO3And HF in a volume ratio of 6:3: 1; acid washing and activating, namely placing the titanium mesh substrate without the oxide film in 25 mass percent hydrochloric acid solution for boiling for 2.4h, taking out, washing with deionized water, and soaking in 2 mass percent oxalic acid solution;
(2) preparing a gradient Ir-Ta-Sn-SbOx interlayer: preparing a gradient Ir-Ta-Sn-SbOx intermediate layer on the titanium substrate pretreated in the step (1) by adopting a thermal decomposition method; the method for preparing the gradient Ir-Ta-Sn-SbOx intermediate layer by a thermal decomposition method comprises the following specific steps: respectively dissolving five groups of tantalum pentachloride, chloroiridic acid, stannic chloride and antimony trichloride in concentrated hydrochloric acid, adding n-butyl alcohol solvent, and removing water from the solution by using a rotary evaporator to obtain precursor concentrated solution
Figure 203787DEST_PATH_IMAGE002
Precursor concentrate
Figure 308009DEST_PATH_IMAGE004
Precursor concentrate
Figure 995342DEST_PATH_IMAGE006
Precursor concentrate
Figure 323555DEST_PATH_IMAGE008
Precursor concentrate
Figure 729129DEST_PATH_IMAGE010
(ii) a Concentrating the precursor
Figure 918933DEST_PATH_IMAGE002
Coating the titanium mesh substrate surface pretreated in the step (1), drying and sintering to obtain a coating
Figure 460773DEST_PATH_IMAGE002
(ii) a Concentrating the precursor
Figure 163149DEST_PATH_IMAGE004
Is applied to the coating
Figure 790440DEST_PATH_IMAGE002
Drying and sintering to obtain the coating
Figure 33202DEST_PATH_IMAGE004
(ii) a Concentrating the precursor
Figure 209975DEST_PATH_IMAGE006
Is applied to the coating
Figure 879990DEST_PATH_IMAGE004
Drying and sintering to obtain the coating
Figure 728998DEST_PATH_IMAGE006
(ii) a Concentrating the precursor
Figure 775451DEST_PATH_IMAGE008
Is applied to the coating
Figure 495145DEST_PATH_IMAGE006
Drying and sintering to obtain the coating
Figure 86795DEST_PATH_IMAGE008
(ii) a Concentrating the precursor
Figure 688678DEST_PATH_IMAGE010
Is applied to the coating
Figure 273243DEST_PATH_IMAGE008
Drying and sintering to obtain a gradient Ir-Ta-Sn-SbOx intermediate layer;
precursor concentrate in this example
Figure 644181DEST_PATH_IMAGE002
The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 60:22:16:2, and the precursor concentrated solution
Figure 859262DEST_PATH_IMAGE004
The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 45:17:34:4, and the precursor concentrated solution
Figure 191849DEST_PATH_IMAGE006
The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 36:14:45:5, and the precursor concentrated solution
Figure 580105DEST_PATH_IMAGE008
The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 30:11:53:6, and the precursor concentrated solution
Figure 71129DEST_PATH_IMAGE010
The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is 16:5:71: 8; the drying temperature is 100 ℃, and the drying time is 5 min; the sintering temperature is 400 ℃, and the sintering time is 10 min; the distillation temperature of the rotary evaporator is 110 ℃, the rotating speed of the rotary distillation flask is 300 r/t, the distillation vacuum degree is 0.05Mpa, and the distillation time is 0.5 h;
(3) preparation of β -MnO2-RuO2Preparing β -MnO on the gradient Ir-Ta-Sn-SbOx intermediate layer in the step (2) by adopting a thermal decomposition method2-RuO2Compounding the surface active layer to obtain titanium-based β -MnO2-RuO2Preparing β -MnO by thermal decomposition method2-RuO2The composite surface active layer comprises the following specific steps of dissolving manganese chloride in concentrated hydrochloric acid, sequentially adding nano cobaltosic oxide and n-butanol solvent, removing water of the solution by using a rotary evaporator to obtain a precursor concentrated solution, wherein the distillation temperature of the rotary evaporator is 90 ℃, the rotating speed of a rotary distillation flask is 200 revolutions/time, the distillation vacuum degree is 0.12Mpa, and the distillation time is 3.5 hours, uniformly coating the precursor concentrated solution on the gradient Ir-Ta-Sn-SbOx intermediate layer obtained in the step (2), drying at the temperature of 110 ℃ for 3min, sintering at the temperature of 220 ℃ for 9min, repeating the coating and sintering processes for 28 times, and finally sintering at the temperature of 340 ℃ for 1.6 hours to obtain β -MnO2-RuO2A composite surface active layer;
the total coating amount of manganese chloride in this example was 10mg/cm2The coating amount of ruthenium chloride was 9mg/cm2；
In the embodiment, the nano cobaltosic oxide is flaky particles, the particle size of the nano cobaltosic oxide particles is 180-400 nm, and the nano cobaltosic oxide is in the range of β -MnO2-RuO2The mass percentage content of the composite surface active layer is 2.5 percent;
(4) titanium-based β -MnO in the step (3)2-RuO2The composite coating is welded at the lower end of the titanium-clad copper conductive beam, copper is milled at the bottom end of the titanium-clad copper conductive beam to be used as a conductive head, and the left end and the right end of the titanium-clad copper conductive beam are sleeved with silica gel sleeves to obtain the titanium-based β -MnO2-RuO2A composite coating anode plate;
titanium-based β -MnO for metal of the embodiment2-RuO2The composite coating anode can be used for electrolyzing and extracting metal in an ammonium sulfate solution system.

Claims (13)

1. Titanium-based β -MnO2-RuO2The composite coating anode plate is characterized by comprising a titanium-clad copper conductive beam (1), a titanium mesh substrate (2), a silica gel sleeve (3) and conductive heads (4), wherein the silica gel sleeve (3) is sleeved at the left end and the right end of the titanium-clad copper conductive beam (1), copper is exposed at the bottom end of the titanium-clad copper conductive beam (1) to serve as the conductive heads (4), the conductive heads (4) are externally connected with a power supply, the titanium mesh substrate (2) is fixedly arranged at the lower end of the titanium-clad copper conductive beam (1), and the titanium mesh substrate (2) is sequentially coated with a gradient Ir-Ta-Sn-SbOx intermediate layer and β -MnO2-RuO2The composite surface active layer is characterized in that the gradient Ir-Ta-Sn-SbOx intermediate layer is an Ir-Ta-Sn-SbOx intermediate layer from inside to outside in sequence
Figure DEST_PATH_IMAGE001
Ir-Ta-Sn-SbOx intermediate layer
Figure 305764DEST_PATH_IMAGE002
Ir-Ta-Sn-SbOx intermediate layer
Figure DEST_PATH_IMAGE003
Ir-Ta-Sn-SbOx intermediate layer
Figure 482668DEST_PATH_IMAGE004
Ir-Ta-Sn-SbOx intermediate layer
Figure DEST_PATH_IMAGE005
Intermediate layer of Ir-Ta-Sn-SbOx
Figure 325859DEST_PATH_IMAGE001
Wherein the molar ratio of Ta, Ir, Sn and Sb is (52-60): (22-26): 16-20): 2, Ir-Ta-Sn-SbOx intermediate layer
Figure 373449DEST_PATH_IMAGE002
Wherein the molar ratio of Ta, Ir, Sn and Sb is (40-46): 17-20): 34-38): 4, Ir-Ta-Sn-SbOx intermediate layer
Figure 948787DEST_PATH_IMAGE003
Wherein the molar ratio of Ta, Ir, Sn and Sb is (32-36): (14-16): 42-48): 5, Ir-Ta-Sn-SbOx intermediate layer
Figure 347407DEST_PATH_IMAGE004
Wherein the molar ratio of Ta, Ir, Sn and Sb is (26-30): (11-13): 52-56): 6, Ir-Ta-Sn-SbOx intermediate layer
Figure 666393DEST_PATH_IMAGE005
The molar ratio of Ta, Ir, Sn and Sb is (10-16): 5-7): 68-76): 8.
2. The titanium-based β -MnO of claim 12-RuO2The composite coating anode plate is characterized in that the thickness of the gradient Ir-Ta-Sn-SbOx intermediate layer is 5-20 mu m, β -MnO2-RuO2The thickness of the composite surface active layer is 50-200 mu m; the titanium mesh substrate (2) is of a net structure or a porous structure.
3. The titanium-based β -MnO of claim 22-RuO2The composite coating anode plate is characterized in that: the net with the net-shaped structure is rhombic and 1-3 mm thick; the pore diameter of the porous structure is 5-10mm, and the thickness is 2-6 mm。
4. The titanium-based β -MnO of claim 12-RuO2The preparation method of the composite coating anode plate is characterized by comprising the following specific steps:
(1) pretreatment of a titanium substrate: sequentially carrying out pretreatment of coarsening, oil removal, oxide film removal and acid pickling activation on the titanium mesh substrate;
(2) preparing a gradient Ir-Ta-Sn-SbOx interlayer: preparing a gradient Ir-Ta-Sn-SbOx intermediate layer on the titanium substrate pretreated in the step (1) by adopting a thermal decomposition method;
(3) preparation of β -MnO2-RuO2Preparing β -MnO on the gradient Ir-Ta-Sn-SbOx intermediate layer in the step (2) by adopting a thermal decomposition method2-RuO2Compounding the surface active layer to obtain titanium-based β -MnO2-RuO2A composite coating;
(4) titanium-based β -MnO in the step (3)2-RuO2The composite coating is welded at the lower end of the titanium-clad copper conductive beam, copper is milled at the bottom end of the titanium-clad copper conductive beam to be used as a conductive head, and the left end and the right end of the titanium-clad copper conductive beam are sleeved with silica gel sleeves to obtain the titanium-based β -MnO2-RuO2An anode plate with a composite coating.
5. The titanium-based β -MnO of claim 42-RuO2The preparation method of the composite coating anode plate is characterized by comprising the following steps: in the step (1), the coarsening is sand blasting treatment by a sand blasting machine, and the oil removing is to place the titanium mesh substrate in NaOH solution with the mass percentage concentration of 10-30% to remove oil for 30-90 min; the step of removing the oxidation film is to place the deoiled titanium mesh substrate in a pickling solution to be soaked for 1-3 min to remove the oxidation film on the surface of the titanium mesh substrate, wherein the pickling solution is H2O/HNO3HF mixed acid solution, H2O、HNO3The volume ratio of HF to HF is (4-6): 3-5): 1; the pickling activation is to place the titanium mesh substrate without the oxide film in a hydrochloric acid solution with the mass percentage concentration of 10-30% to boil for 2-3 hours, take out the titanium mesh substrate, wash the titanium mesh substrate with deionized water, and soak the titanium mesh substrate in an oxalic acid solution with the mass percentage concentration of 1-5%.
6. The titanium-based β -MnO of claim 42-RuO2The preparation method of the composite coating anode plate is characterized by comprising the following steps: the thermal decomposition method in the step (2) is used for preparing the gradient Ir-Ta-Sn-SbOx intermediate layer, and the specific steps are as follows: respectively dissolving five groups of tantalum pentachloride, chloroiridic acid, stannic chloride and antimony trichloride in concentrated hydrochloric acid, adding n-butyl alcohol solvent, and removing water from the solution by using a rotary evaporator to obtain precursor concentrated solution
Figure 568490DEST_PATH_IMAGE006
Precursor concentrate
Figure DEST_PATH_IMAGE007
Precursor concentrate
Figure 642625DEST_PATH_IMAGE008
Precursor concentrate
Figure DEST_PATH_IMAGE009
Precursor concentrate
Figure 528542DEST_PATH_IMAGE010
(ii) a Concentrating the precursor
Figure 447956DEST_PATH_IMAGE006
Coating the titanium mesh substrate surface pretreated in the step (1), drying and sintering to obtain a coating
Figure 470139DEST_PATH_IMAGE006
(ii) a Concentrating the precursor
Figure 387279DEST_PATH_IMAGE007
Is applied to the coating
Figure 760492DEST_PATH_IMAGE006
Drying and sintering to obtain the coating
Figure 218018DEST_PATH_IMAGE007
(ii) a Concentrating the precursor
Figure 32390DEST_PATH_IMAGE008
Is applied to the coating
Figure 182749DEST_PATH_IMAGE007
Drying and sintering to obtain the coating
Figure 777678DEST_PATH_IMAGE008
(ii) a Concentrating the precursor
Figure 242157DEST_PATH_IMAGE009
Is applied to the coating
Figure 707774DEST_PATH_IMAGE008
Drying and sintering to obtain the coating
Figure 294613DEST_PATH_IMAGE009
(ii) a Concentrating the precursor
Figure 111259DEST_PATH_IMAGE010
Is applied to the coating
Figure 113850DEST_PATH_IMAGE009
And drying and sintering to obtain the gradient Ir-Ta-Sn-SbOx intermediate layer.
7. The titanium-based β -MnO of claim 62-RuO2The preparation method of the composite coating anode plate is characterized by comprising the following steps: precursor concentrated solution
Figure 965132DEST_PATH_IMAGE006
The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is (52-60): 22-26): 16-20): 2, and the precursor concentrated solution
Figure 660555DEST_PATH_IMAGE007
The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is (40-46): 17-20): 34-38): 4, and the precursor concentrated solution
Figure 698918DEST_PATH_IMAGE008
The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is (32-36): 14-16): 42-48): 5, and the precursor concentrated solution
Figure 567517DEST_PATH_IMAGE009
The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is (26-30): 11-13): 52-56): 6, and the precursor concentrated solution
Figure 476567DEST_PATH_IMAGE010
The molar ratio of the tantalum pentachloride to the chloroiridic acid to the stannic chloride to the antimony trichloride is (10-16): 5-7): 68-76): 8; the drying temperature is 100-120 ℃, and the drying time is 1-5 min; the sintering temperature is 400-600 ℃, and the sintering time is 5-10 min; the distillation temperature of the rotary evaporator is 80-110 ℃, the rotating speed of the rotary distillation flask is 100-300 revolutions per time, the distillation vacuum degree is 0.05-1.2 Mpa, and the distillation time is 0.5-2.5 h.
8. The titanium-based β -MnO of claim 42-RuO2The preparation method of the composite coating anode plate is characterized in that β -MnO is prepared by adopting a thermal decomposition method in the step (3)2-RuO2The composite surface active layer comprises the specific steps of dissolving manganese chloride and ruthenium chloride in concentrated hydrochloric acid, sequentially adding nano cobaltosic oxide or nano silicon dioxide and n-butyl alcohol solvent, removing water of the solution by adopting a rotary evaporator to obtain precursor concentrated solution, uniformly coating the precursor concentrated solution on the gradient Ir-Ta-Sn-SbOx intermediate layer in the step (2), drying at the temperature of 100-120 ℃ for 1-5 min, sintering at the temperature of 200-300 ℃ for 5-10 min, repeating the coating and sintering processes for 20-30 times, and finally sintering at the temperature of 300-350 ℃ for 1-2 h to obtain β -MnO2-RuO2And compounding the surface active layer.
9. The titanium-based β -MnO of claim 82-RuO2The preparation method of the composite coating anode plate is characterized by comprising the following steps: the coating amount of the manganese chloride is 10-40 mg/cm2The coating amount of ruthenium chloride is 5-10 mg/cm2。
10. The titanium-based β -MnO of claim 82-RuO2The preparation method of the composite coating anode plate is characterized in that the nano cobaltosic oxide and the nano silicon dioxide are flaky particles, the particle sizes of the nano cobaltosic oxide particles and the nano silicon dioxide are 180-400 nm, and the nano cobaltosic oxide or the nano silicon dioxide is in the range of β -MnO2-RuO2The mass percentage content of the composite surface active layer is 0.1-5%.
11. The titanium-based β -MnO of claim 82-RuO2The preparation method of the composite coating anode plate is characterized by comprising the following steps: the distillation temperature of the rotary evaporator is 80-110 ℃, the rotating speed of the rotary distillation flask is 100-300 revolutions per time, the distillation vacuum degree is 0.05-1.2 Mpa, and the distillation time is 0.5-10 h.
12. The titanium-based β -MnO of claim 42-RuO2The preparation method of the composite coating anode plate is characterized by comprising the following steps: the titanium mesh substrate (2) is of a net-shaped structure or a porous structure, the mesh of the net-shaped structure is rhombic, and the thickness of the mesh is 1-3 mm; the pore diameter of the porous structure is 5-10mm, and the thickness is 2-6 mm.
13. The titanium-based β -MnO of claim 12-RuO2The composite coating anode plate is used as an anode plate for electrolyzing and extracting metal in an ammonium sulfate solution system.
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