CN114875458A - Noble metal anode for electrolytic copper foil and preparation method thereof - Google Patents
Noble metal anode for electrolytic copper foil and preparation method thereof Download PDFInfo
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Abstract
A noble metal anode for electrolytic copper foil and its preparing process, wherein the noble metal anode comprises titanium substrate sintered with g-C 3 N 4 An intermediate layer, and g-C 3 N 4 The iridium-tantalum system coating on the intermediate layer comprises the following preparation methods: (1) pretreating the surface of the titanium substrate; (2) preparation of g-C by pyrolysis 3 N 4 (ii) a (3) Preparing a base solution: 30-100 mg of g-C 3 N 4 Dissolving in 5ml of organic solvent, and stirring at room temperature to form a base solution; (4) preparing an active solution: mixing and dissolving 70 mol percent of iridium source and 30 mol percent of tantalum source in an organic solvent, and stirring at room temperature to form active liquid; (5) brushing and sintering;the invention introduces g-C with two-dimensional layered structure into the traditional iridium-tantalum system coating 3 N 4 The intermediate layer is prepared, so that the effective catalytic activity area of the coating can be effectively increased, and the electrochemical performance of the noble metal oxide titanium electrode can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of electrolytic copper foil, and particularly relates to a noble metal anode for electrolytic copper foil and a preparation method thereof.
Background
In the electrolytic copper foil production equipment, the anode material is one of the key components; after a series of changes of the traditional soluble anode, the lead anode and the like are carried out on the selection of the anode material, the noble metal coated titanium anode with stable size shows more excellent service performance. The preparation method of the electrolytic copper foil anode plate with the patent application number of CN201810529420.7 comprises the following steps: (1) selecting a titanium plate as a raw material; (6) preparing a noble metal solution; (7) coating the noble metal solution on the surface of the titanium plate substrate subjected to heat treatment for multiple times to form a coating with the thickness of 6-10 mu m; the product obtained by coating the noble metal solution on the surface of the matrix has low electric energy efficiency caused by overhigh anode potential required by copper deposition in the copper foil electrolysis process, and the cost is increased, which is an important problem in production. DSA with iridium tantalum oxide coating system has higher oxygen evolution electrocatalytic activity in an acid medium, keeps higher stability, can obtain lower overpotential in production, and is a popular anode at present. At present, because the current density required under the working condition of the electrolytic copper foil is higher, oxygen permeation is easy to occur in the iridium-tantalum system anode, so that the titanium matrix is oxidized, and the abnormal failure of the anode is caused.
Disclosure of Invention
In order to overcome the above-mentioned disadvantages of the prior art, it is an object of the present invention to provide a noble metal anode for electrolytic copper foil and a method for preparing the same, incorporating g-C having a two-dimensional layered structure 3 N 4 The intermediate layer is prepared, so that the effective catalytic active area of the coating can be effectively increased, the electrochemical performance of the noble metal oxide titanium electrode can be effectively improved, and the service life of the electrolytic copper foil anode can be prolongedAnd the lower electrolysis voltage is obtained.
In order to achieve the purpose, the invention provides the following technical scheme:
a noble metal anode for electrolytic copper foil comprises a titanium substrate sintered with g-C 3 N 4 An intermediate layer, and g-C 3 N 4 An iridium tantalum system coating over the intermediate layer.
Said g-C 3 N 4 g-C in the intermediate layer 3 N 4 One selected from melamine, cyanuric chloride, cyanamide, dicyanodiamine and urea is obtained by thermal decomposition.
The iridium-tantalum system coating comprises the following raw materials in a molar ratio: 60% -90% of iridium source and 10% -40% of tantalum source, wherein the tantalum source is selected from any one of tantalum pentachloride n-butyl alcohol solution, tantalum butanediol and tantalum ethoxide.
Said g-C 3 N 4 Thermal decomposition, in particular: heating to 510-610 ℃ at a heating rate of 1-10 ℃/min, calcining at a constant temperature for 1-4 h, naturally cooling, and grinding to obtain g-C 3 N 4 。
The g to C 3 N 4 The thickness of the intermediate layer is 0.5 to 1 μm.
In the intermediate layer, g-C 3 N 4 The loading amount of (2) is 0.3-2.5 mg cm -2 。
The thickness of the catalytic active layer is 6-10 mu m, and IrO is used in the catalytic active layer 2 The loading capacity of the element Ir in the form is 0.5-3 mg cm -2 。
A preparation method of a noble metal anode for electrolytic copper foil specifically comprises the following steps:
(1) pretreating the surface of the titanium substrate;
(2) preparing a base solution: 30mg to 100mg of g-C 3 N 4 Dissolving in 5ml of organic solvent A, and stirring at room temperature to form a base solution;
(3) preparing an active solution: mixing and dissolving 60-90 mol percent of iridium source and 10-40 mol percent of tantalum source in an organic solvent B, and stirring at room temperature to form active liquid;
(4) and coating and sintering: and (2) firstly brushing and sintering the base solution on the surface of the titanium substrate pretreated in the step (1), and then brushing and sintering the active solution.
The step (1) of pretreating the surface of the titanium substrate specifically comprises the following steps:
(1.1) carrying out surface oil removal and sand blasting treatment on the titanium matrix until the surface roughness Ra is less than 15 mu m;
(1.2) carrying out thermal shape correction treatment on the titanium matrix subjected to sand blasting;
(1.3) soaking the titanium substrate with good shape correction in dilute hydrochloric acid with the mass concentration of 3-15% for 8-24 h, and then boiling in oxalic acid solution with the mass concentration of 5-10% for 0.5-3 h;
and (1.4) cleaning and airing the titanium substrate.
G to C in the step (2) 3 N 4 One selected from melamine, cyanuric chloride, cyanamide, dicyanodiamine and urea is obtained by thermal decomposition.
The organic solvent A in the step (2) is any one of n-butyl alcohol, ethylene glycol, dimethylformamide, nitrogen and nitrogen-dimethyl pyrrolidone or a mixture of n-butyl alcohol, ethylene glycol, dimethylformamide and nitrogen-dimethyl pyrrolidone in any proportion.
The tantalum source in the step (3) is selected from any one of tantalum pentachloride n-butyl alcohol solution, tantalum butanediol and tantalum ethoxide.
The organic solvent B in the step (3) is any one of n-butanol, isopropanol and ethanol or a mixture of n-butanol, isopropanol and ethanol in any proportion.
The step (4) of coating and sintering comprises the following steps:
(4.1) coating the pre-treated titanium substrate with the base solution prepared in the step (2) not less than twice, wherein the total thickness is 0.5-1 mu m, and the g-C 3 N 4 The loading amount of (2) is 0.3-2.5 mg cm -2 Naturally drying the mixture, and putting the dried mixture in an oven at 60-100 ℃ to completely volatilize the solvent;
(4.2) placing the titanium substrate treated in the step (4.1) in a muffle furnace at 450-520 ℃ for sintering for 10-25 min, taking out, and cooling to room temperature;
(4.3) repeating the step (4.1), placing the treated titanium substrate in a muffle furnace at 450-520 ℃ for sintering for 50-75 min, taking out, and cooling to room temperature;
(4.4) brushing the active liquid prepared in the step (3) on the titanium substrate treated in the step (4.3) for more than 15 times, wherein the thickness is 6-10 mu m, and the loading capacity of element Ir in the form of IrO2 is 0.5-3 mg cm < -2 >; naturally drying, and putting the dried product in an oven at 60-100 ℃ to completely volatilize the solvent;
(4.5) sintering the titanium substrate treated in the step (4.4) in a muffle furnace at 450-520 ℃ for 10-25 min, taking out, and cooling to room temperature;
(4.6) repeating the steps (4.4) and (4.5) until the active solution is brushed for more than 15 times;
(4.7) keeping the temperature of the coated titanium matrix in a muffle furnace at 450-500 ℃ for 30-90min, taking out, and naturally cooling to room temperature.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects: graphite-like phase carbon nitride (g-C) 3 N 4 ) The graphene-like two-dimensional planar structure has the advantages of no toxicity, no metal, low density, high thermal stability and chemical stability at room temperature, acid and alkali resistance, low price and the like. Introduction of g-C with good conductivity into traditional iridium-tantalum system coating 3 N 4 The intermediate layer has better electron conduction capability, so that an effective charge conduction channel exists between the titanium matrix and the oxide coating, the voltage is reduced, and the passivation of the titanium matrix caused by the unfavorable charge conduction is inhibited; in addition, two-dimensional lamellar g-C in priming solution 3 N 4 The attachment area of the noble metal oxide is greatly increased, so that the effective catalytic activity area is increased, and the catalytic activity of the electrode is improved.
Drawings
FIG. 1 shows g-C prepared by thermal decomposition according to the present invention 3 N 4 X-ray electron diffraction pattern of (a).
FIG. 2 is a scanning electron microscope photograph of an anode of an electrolytic copper foil prepared in accordance with one embodiment of the present invention.
FIG. 3 is a scanning electron microscope photograph of an anode of an electrolytic copper foil prepared in example two of the present invention.
FIG. 4 is a scanning electron microscope photograph of an anode of an electrolytic copper foil prepared in example III of the present invention.
FIG. 5 is a scanning electron microscope photograph of an anode of an electrolytic copper foil according to comparative example of the present invention.
FIG. 6 is a graph showing electrocatalytic properties of anodes of electrolytic copper foils prepared by the preparation methods provided in example 2 and comparative example one.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example one
A noble metal anode for electrolytic copper foil comprises a titanium substrate sintered with g-C 3 N 4 An intermediate layer, and an iridium tantalum system coating.
Said g-C 3 N 4 g-C in the intermediate layer 3 N 4 Selected from melamine, and is obtained by thermal decomposition of melamine at 600 ℃ for 2 h.
The iridium-tantalum system coating comprises the following raw materials in a molar ratio: 70% of an iridium source selected from chloroiridic acid and 30% of a tantalum source; the tantalum source is selected from tantalum pentachloride n-butyl alcohol solution.
The preparation method of the noble metal anode of the embodiment specifically includes:
s1, pretreating the surface of the titanium substrate:
s1.1, carrying out surface oil removal and sand blasting treatment on a titanium matrix;
s1.2, carrying out thermal sizing treatment on the titanium matrix subjected to sand blasting;
s1.3, soaking the titanium substrate with the corrected shape in dilute hydrochloric acid with the mass concentration of 10% for 15 hours, and then boiling the titanium substrate in oxalic acid solution with the mass concentration of 8% for 2 hours;
s1.4, cleaning and airing the titanium substrate;
s2, preparation g-C 3 N 4 :: weighing a certain amount of melamine, placing the melamine in a crucible, placing the crucible in a muffle furnace, heating to 600 ℃ at a heating rate of 1 ℃/min, preserving heat for 2 hours, and cooling with the furnace to obtain the required g-C 3 N 4 (ii) a Referring to FIG. 1, FIG. 1 is a graph showing g-C prepared by a thermal decomposition method 3 N 4 X-ray electron diffraction pattern of (a).
S3, preparing a base solution A: weighing 30mg g-C 3 N 4 Dissolving in 2.5ml of ethylene glycol and 2.5ml of DMF solution, stirring at room temperature until the mixture is completely dissolved to form a base solution A, and storing for later use;
s4, preparing active liquid B: weighing chloroiridic acid and tantalum pentachloride n-butyl alcohol solution according to the molar ratio of Ir to Ta to 7:3, mixing and dissolving in n-butyl alcohol solvent, stirring at room temperature until the chloroiridic acid and the tantalum pentachloride n-butyl alcohol solution are completely dissolved to form active liquid B, and storing for later use;
s5, coating and sintering: uniformly coating the prepared base solution A on a titanium substrate, drying, sintering in a muffle furnace at 450-480 ℃ for 15min, taking out, cooling, coating in the next step, drying, sintering at 450-480 ℃ for 60min, and coating a g-C3N4 layer to a thickness of 0.5 mu m; and taking out and cooling, then uniformly coating the prepared active liquid B on a titanium substrate, baking for 15min in a muffle furnace at 450-500 ℃ after drying, taking out and cooling to room temperature for next coating, repeating the step for 16 times, wherein the coating thickness is 6 mu m, and finally preserving the heat in the muffle furnace at 480-520 ℃ for 60min to prepare the Ir-Ta system noble metal oxide anode with the g-C3N 4-containing intermediate layer. A scanning electron micrograph of the obtained electrolytic copper foil anode is shown in FIG. 2.
Example two
The embodiment of the noble metal anode for the electrolytic copper foil comprises a titanium substrate, wherein g-C is sintered on the titanium substrate 3 N 4 An intermediate layer, and an iridium tantalum system coating.
Said g-C 3 N 4 g-C in the intermediate layer 3 N 4 Selected from cyanamide, and is obtained by thermal decomposition of cyanamide at 600 ℃ for 2 h.
The iridium-tantalum system coating comprises the following raw materials in a molar ratio: 60% of an iridium source selected from chloroiridic acid and 40% of a tantalum source; the tantalum source is selected from tantalum pentachloride n-butanol solution.
Referring to fig. 3, a scanning electron microscope image of an anode of an electrolytic copper foil prepared by the method for preparing a noble metal anode for electrolytic copper foil, in this example, a coating of a titanium anode is an Ir-Ta system noble metal coating with a platinum interlayer added thereto, and the preparation method specifically includes:
s1, pretreating the surface of the titanium substrate:
s1.1, carrying out surface oil removal and sand blasting treatment on a titanium matrix;
s1.2, carrying out thermal sizing treatment on the titanium matrix subjected to sand blasting;
s1.3, soaking the titanium substrate with good shape in dilute hydrochloric acid with the mass concentration of 3% for 8 hours, and then boiling in oxalic acid solution with the mass concentration of 5% for 0.5 hour;
s1.4, cleaning and airing the titanium substrate;
s2, preparation g-C 3 N 4 Weighing a certain amount of cyanamide, placing into a crucible, placing into a muffle furnace, heating to 600 deg.C at a heating rate of 1 deg.C/min, maintaining for 2 hr, and cooling to obtain the required g-C 3 N 4 ；
S3, preparing a base solution A: accurately weighing 50mg g-C 3 N 4 Dissolving in 2.5ml of ethylene glycol and 2.5ml of DMF solution, stirring at room temperature until the mixture is completely dissolved to form a base solution A, and storing for later use;
s4, preparing active liquid B: weighing chloroiridic acid and tantalum pentachloride n-butyl alcohol solution according to the molar ratio of Ir to Ta to 6:4, mixing and dissolving in n-butyl alcohol solvent, stirring at room temperature until the mixture is completely dissolved to form active liquid B, and storing for later use;
s5, coating and sintering: uniformly coating the prepared base solution A on a titanium substrate, drying, sintering in a muffle furnace at 480-520 ℃ for 10min, taking out, cooling, coating in the next step, drying, sintering at 480-520 ℃ for 60min, and coating a g-C3N4 layer to a thickness of 1 mu m; taking out and cooling, then uniformly coating the prepared active liquid B on a titanium substrate, baking for 10min in a muffle furnace at 450-500 ℃, taking out and cooling to room temperature for next coating, repeating the coating step of the active liquid B for 20 times, wherein the coating thickness is 10 mu m, and finally preserving the heat in the muffle furnace at 450-480 ℃ for 60min to prepare the Ir-Ta system noble metal oxide anode with the platinum-containing middle layer.
EXAMPLE III
The embodiment of the noble metal anode for the electrolytic copper foil comprises a titanium substrate, wherein g-C is sintered on the titanium substrate 3 N 4 An intermediate layer which is a layer of a polymer,and iridium-tantalum system coatings.
Said g-C 3 N 4 g-C in the intermediate layer 3 N 4 Selected from urea, and is obtained by thermal decomposition of urea at 600 ℃ for 2 h.
The iridium-tantalum system coating comprises the following raw materials in a molar ratio: 90% of an iridium source selected from chloroiridic acid and 10% of a tantalum source; the tantalum source is selected from tantalum pentachloride n-butanol solution.
In this example, referring to fig. 4, a scanning electron microscope image of an anode of an electrolytic copper foil prepared by the method for preparing a noble metal anode for electrolytic copper foil, a coating of a titanium anode is an Ir-Ta system noble metal coating added with a platinum interlayer, and the preparation method specifically includes:
s1, pretreating the surface of the titanium substrate:
s1.1, carrying out surface oil removal and sand blasting treatment on a titanium matrix;
s1.2, carrying out thermal sizing treatment on the titanium matrix subjected to sand blasting;
s1.3, soaking the titanium substrate with good shape correction in dilute hydrochloric acid with the mass concentration of 15% for 24 hours, and then boiling in oxalic acid solution with the mass concentration of 10% for 3 hours;
s1.4, cleaning and airing the titanium substrate;
s2, preparation g-C 3 N 4 Weighing a certain amount of urea, placing into a crucible, placing into a muffle furnace, heating to 600 deg.C at a heating rate of 1 deg.C/min, maintaining for 2 hr, and cooling to obtain the required g-C 3 N 4 ；
S3, preparing a base solution A: accurately weighing 100mg g-C 3 N 4 Dissolving in 2.5ml of ethylene glycol and 2.5ml of DMF solution, stirring at room temperature until the mixture is completely dissolved to form a base solution A, and storing for later use;
s4, preparing active liquid B: accurately weighing a certain amount of chloroiridic acid and tantalum pentachloride n-butyl alcohol solution according to the molar ratio of Ir to Ta to 9:1, mixing and dissolving in a n-butyl alcohol solvent, stirring at room temperature until the solution is completely dissolved to form an active liquid B, and storing for later use;
s5, coating and sintering: uniformly coating the prepared base solution A on a titanium substrate, drying, sintering for 25min at 460-500 ℃ in a muffle furnace, taking out, cooling, coating the base solution A, drying, sintering for 1h at 480-520 ℃, coating the g-C3N4 layer with the thickness of 0.8 mu m, and coating the g-C3N4 with the load of 1.5mg cm < -2 >; and taking out and cooling, then uniformly coating the prepared active liquid B on a titanium substrate, baking for 25min in a muffle furnace at 450-520 ℃, taking out and cooling to room temperature for next coating, repeating the coating step of the active liquid B for 18 times, wherein the coating thickness is 8 mu m, and finally preserving the heat in the muffle furnace at 450-480 ℃ for 60min to prepare the Ir-Ta system noble metal oxide anode with the platinum-containing intermediate layer.
Comparative example 1
The comparative example shows a scanning electron microscope image of an anode of electrolytic copper foil prepared by the method for preparing a noble metal anode for electrolytic copper foil, referring to fig. 5, a coating of a titanium anode is an Ir-Ta system noble metal coating added with a platinum interlayer, and the preparation method specifically comprises the following steps:
s1, pretreating the surface of the titanium substrate:
s1.1, carrying out surface oil removal and sand blasting treatment on a titanium matrix;
s1.2, carrying out thermal sizing treatment on the titanium matrix subjected to sand blasting;
s1.3, soaking the titanium substrate with good shape correction in dilute hydrochloric acid with the concentration of 3-15% for 8-24 hours, and then boiling in oxalic acid solution with the concentration of 5-10% for 0.5-3 hours;
s1.4, cleaning and airing the titanium substrate;
s2, preparing a base solution A: 2.5ml of ethylene glycol and 2.5ml of DMF are mixed evenly to form a base solution A which is stored for standby, and the difference from the invention lies in that g-C in the invention is not added 3 N 4 ；
S3, preparing active liquid: accurately weighing a certain amount of chloroiridic acid and tantalum pentachloride n-butyl alcohol solution according to the molar ratio of Ir to Ta to 7:3, mixing and dissolving in a n-butyl alcohol solvent, stirring at room temperature until the solution is completely dissolved to form an active liquid B, and storing for later use;
s4, coating and sintering: uniformly coating the prepared base solution A on a titanium substrate, drying, sintering in a muffle furnace at 450-520 ℃ for 10-25 min, taking out, cooling, coating, drying, and sintering at 450-520 ℃ for 60 min; taking out, cooling, uniformly coating the prepared active liquid B on a titanium substrate, baking for 10-25 min in a muffle furnace at 450-520 ℃, taking out, cooling to room temperature, coating for the next time, repeating the steps until the active liquid B is used up, and finally preserving heat in the muffle furnace at 450-520 ℃ for 60min to prepare the Ir-Ta system noble metal oxide anode with the platinum-containing interlayer.
And (3) performance testing: h in the electrolyte is 0.5mol/L 2 SO 4 The electrolytic copper foil anode prepared by the preparation method provided by the second embodiment and the first embodiment is a working electrode, and the electro-catalysis performance of the sample is tested in an electrochemical workstation under a three-electrode system. As can be seen from FIG. 6, 50mg g-C was added to the intermediate layer 3 N 4 The catalytic activity of the electrode can be effectively improved, and the overpotential of the OER reaction is reduced. Meanwhile, as can be seen from FIGS. 2 to 5, g-C 3 N 4 The addition of the catalyst obviously influences the surface appearance of the noble metal oxide catalyst, and more needle-shaped solutions are obtained, which is beneficial to improving the catalytic performance of the electrode.
In summary, the present invention employs pyrogenically prepared g-C 3 N 4 Method for producing iridium-tantalum system noble metal coating for intermediate layer, g-C 3 N 4 Has a graphite-like layered structure, good thermal stability and chemical stability, no toxicity, rich sources and simple preparation and molding process. The two-dimensional layered structure is used as the middle layer, so that the catalytic activity area can be effectively increased, the electrochemical performance of the noble metal anode is optimized, and the service life is prolonged.
Claims (10)
1. The noble metal anode for the electrolytic copper foil is characterized by comprising a titanium matrix, wherein g-C is sintered on the titanium matrix 3 N 4 An intermediate layer, and g-C 3 N 4 An iridium tantalum system coating over the intermediate layer.
2. The noble metal anode for electrolytic copper foil according to claim 1Characterized by that said g-C 3 N 4 g-C in the intermediate layer 3 N 4 One selected from melamine, cyanuric chloride, cyanamide, dicyanodiamine and urea is obtained by thermal decomposition;
g to C 3 N 4 Thermal decomposition, in particular: heating to 510-610 ℃ at a heating rate of 1-10 ℃/min, calcining at a constant temperature for 1-4 h, naturally cooling, and grinding to obtain g-C 3 N 4 。
3. The noble metal anode for electrolytic copper foil as claimed in claim 1, wherein said iridium-tantalum system coating layer has a raw material molar ratio of: 60% -90% of iridium source and 10% -40% of tantalum source, wherein the tantalum source is selected from any one of tantalum pentachloride n-butyl alcohol solution, tantalum butanediol and tantalum ethoxide.
4. The noble metal anode for electrolytic copper foil as claimed in claim 1, wherein the g-C is 3 N 4 The thickness of the middle layer is 0.5-1 μm; in the intermediate layer, g-C 3 N 4 The loading amount of (2) is 0.3-2.5 mg cm -2 。
5. The noble metal anode for electrolytic copper foil according to claim 1, wherein the thickness of the catalytic active layer is 6 to 10 μm, and IrO is used as the active material in the catalytic active layer 2 The loading capacity of the element Ir in the form is 0.5-3 mg cm -2 。
6. A preparation method of a noble metal anode for electrolytic copper foil is characterized by comprising the following steps:
(1) pretreating the surface of the titanium substrate;
(2) preparing a base solution: 30mg to 100mg of g-C 3 N 4 Dissolving in 5ml of organic solvent A, and stirring at room temperature to form a base solution;
(3) preparing an active solution: mixing and dissolving 60-90 mol percent of iridium source and 10-40 mol percent of tantalum source in an organic solvent B, and stirring at room temperature to form active liquid;
(4) and coating and sintering: and (2) firstly brushing and sintering the base solution on the surface of the titanium substrate pretreated in the step (1), and then brushing and sintering the active solution.
7. The method for preparing a noble metal anode for electrolytic copper foil according to claim 6, wherein the step (1) of pretreating the surface of the titanium substrate comprises:
(1.1) carrying out surface oil removal and sand blasting treatment on the titanium matrix until the surface roughness Ra is less than 15 mu m;
(1.2) carrying out thermal shape correction treatment on the titanium matrix subjected to sand blasting;
(1.3) soaking the titanium substrate with good shape correction in dilute hydrochloric acid with the mass concentration of 3-15% for 8-24 h, and then boiling in oxalic acid solution with the mass concentration of 5-10% for 0.5-3 h;
and (1.4) cleaning and airing the titanium substrate.
8. The method for preparing a noble metal anode for electrolytic copper foil according to claim 6, wherein g-C in the step (2) 3 N 4 One selected from melamine, cyanuric chloride, cyanamide, dicyanodiamine and urea is obtained by thermal decomposition;
the organic solvent A in the step (2) is any one of n-butyl alcohol, ethylene glycol, dimethylformamide, nitrogen and nitrogen-dimethyl pyrrolidone or a mixture of n-butyl alcohol, ethylene glycol, dimethylformamide and nitrogen-dimethyl pyrrolidone in any proportion.
9. The method for preparing a noble metal anode for electrolytic copper foil according to claim 6, wherein the tantalum source of the step (3) is selected from any one of tantalum pentachloride n-butanol solution, tantalum butanediol, tantalum ethoxide;
the organic solvent B in the step (3) is any one of n-butanol, isopropanol and ethanol or a mixture of n-butanol, isopropanol and ethanol in any proportion.
10. The method for preparing a noble metal anode for electrolytic copper foil according to claim 6, wherein the step (4) of brushing and sintering specifically comprises:
(4.1) coating the pretreated titanium substrate with the base solution prepared in the step (2) not less than twice, wherein the total thickness is 0.5-1 mu m, and g-C 3 N 4 The load of (2) is 0.3-2.5 mg cm -2 Naturally drying the mixture, and putting the dried mixture in an oven at 60-100 ℃ to completely volatilize the solvent;
(4.2) placing the titanium substrate treated in the step (4.1) in a muffle furnace at 450-520 ℃ for sintering for 10-25 min, taking out, and cooling to room temperature;
(4.3) repeating the step (4.1), placing the treated titanium substrate in a muffle furnace at 450-520 ℃ for sintering for 50-75 min, taking out, and cooling to room temperature;
(4.4) coating the active liquid prepared in the step (3) on the titanium substrate treated in the step (4.3), wherein the total thickness is 6-10 mu m, and the loading amount of element Ir existing in the form of IrO2 is 0.5-3 mg cm < -2 >; naturally drying, and putting the dried product in an oven at 60-100 ℃ to completely volatilize the solvent;
(4.5) sintering the titanium substrate treated in the step (4.4) in a muffle furnace at 450-520 ℃ for 10-25 min, taking out, and cooling to room temperature;
(4.6) repeating the steps (4.4) and (4.5) until the active solution is brushed for more than 15 times;
(4.7) keeping the temperature of the coated titanium matrix in a muffle furnace at 450-500 ℃ for 30-90min, taking out, and naturally cooling to room temperature.
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