CN114182307A - Preparation method of noble metal anode for electrolytic copper foil - Google Patents
Preparation method of noble metal anode for electrolytic copper foil Download PDFInfo
- Publication number
- CN114182307A CN114182307A CN202111390483.7A CN202111390483A CN114182307A CN 114182307 A CN114182307 A CN 114182307A CN 202111390483 A CN202111390483 A CN 202111390483A CN 114182307 A CN114182307 A CN 114182307A
- Authority
- CN
- China
- Prior art keywords
- solution
- copper foil
- electrolytic copper
- coating
- noble metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention belongs to the technical field of electrolytic copper foil, and relates to a preparation method of a noble metal anode for electrolytic copper foil. The method comprises the following steps: 1) pretreating the surface of the titanium substrate; 2) preparing a base solution: dissolving 20-40 mol percent of tantalum source and 60-90 mol percent of platinum source in an organic solvent in sequence, and stirring at normal temperature to form a base solution; 3) preparing an active solution: mixing and dissolving 60-80 mol percent of iridium source and 20-40 mol percent of tantalum source in an organic solvent, and stirring at normal temperature to form active liquid; 4) and (4) coating and sintering. According to the invention, the platinum-containing intermediate layer with good conductivity is introduced into the traditional iridium-tantalum system coating, so that the electron transmission efficiency between the substrate and the coating can be effectively improved, the passivation of the titanium substrate caused by charge accumulation is inhibited, and the service life of the anode is prolonged.
Description
Technical Field
The invention belongs to the technical field of electrolytic copper foil, relates to a noble metal anode, and particularly relates to a preparation method of a noble metal anode for electrolytic copper foil.
Background
The electrolytic copper foil is an important material for manufacturing copper clad laminates, printed circuit boards and lithium ion batteries. In the high-speed development of the electronic information industry, the electrolytic copper foil plays an important role in signal and power transmission and communication of electronic products. In an electrolytic copper foil production facility, an anode material is one of the most critical 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.
In the copper foil electrolysis process, the anode potential required for depositing copper is too high, so that the electric energy efficiency is low, 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 low 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
The present invention is directed to overcoming the above-mentioned disadvantages of the prior art and providing a method for preparing a noble metal anode for electrolytic copper foil to improve the service life of the anode for electrolytic copper foil and to obtain a lower electrolytic voltage.
In order to achieve the purpose, the invention provides the following technical scheme:
the preparation method of the noble metal anode for the electrolytic copper foil specifically comprises the following steps:
1) pretreating the surface of the titanium substrate;
2) preparing a base solution: dissolving 20-40 mol percent of tantalum source and 60-90 mol percent of platinum source in an organic solvent in sequence, and stirring at normal temperature to form a base solution;
3) preparing an active solution: mixing and dissolving 60-80 mol percent of iridium source and 20-40 mol percent of tantalum source in an organic solvent, and stirring at normal temperature to form active liquid;
4) coating and sintering: and (2) coating and sintering the surface of the titanium substrate pretreated in the step 1) with a base solution, and then coating and sintering the surface of the titanium substrate with an active solution.
Further, 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;
1.2) carrying out thermal sizing 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 concentration of 3-15% for 8-24 h, and then boiling in oxalic acid solution with the concentration of 5-10% for 0.5-3 h;
1.4) cleaning and airing the titanium substrate.
Further, in the step 1.1), sand blasting is carried out by using steel grit until the surface roughness Ra is less than 15 μm.
Further, the tantalum source in the step 2) and the step 3) is selected from any one of tantalum pentachloride n-butyl alcohol solution, tantalum butanediol and tantalum ethoxide.
Further, the platinum source in the step 2) is selected from any one of chloroplatinic acid, platinum tetrachloride and platinum oxide.
Further, the iridium source in the step 3) is selected from any one of chloro-iridic acid, iridium trichloride and bromoiridic acid.
Further, the organic solvent in the step 2) and the step 3) is any one or a mixture of n-butyl alcohol, isopropanol and ethanol.
Further, the step 4) of painting and sintering specifically comprises the following steps:
4.1) coating the prepared base solution on the pretreated titanium substrate, naturally drying the base solution, and putting the base solution 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 matrix in a muffle furnace at 450-520 ℃ for sintering for 50-75 min, taking out, and cooling to room temperature;
4.4) coating the prepared active liquid on the titanium substrate treated in the step 4.3), naturally airing, and putting in an oven at 60-100 ℃ to completely volatilize the solvent;
4.5) placing the titanium substrate treated in the step 4.4) in a muffle furnace at 450-520 ℃ for sintering for 10-25 min, taking out, and cooling to room temperature;
4.6) repeating the steps 4.4) and 4.5) until the active liquid is coated;
4.7) preserving 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: a platinum-containing intermediate layer with good conductivity is introduced into the traditional iridium-tantalum system coating, so that the coating has good electron conductivity, an effective charge conduction channel exists between a titanium substrate and an oxide coating, the voltage is reduced, and the passivation of the titanium substrate caused by the unfavorable charge conduction is inhibited; in addition, tantalum source prepared by the primer solution adopts tantalum ethoxide with better matching degree with platinum, thereby well controlling the uniform dispersion of platinum metal ions and leading precious metal active components to be more uniformly dispersed on the surface of the titanium matrix.
Drawings
FIG. 1 is a scanning electron microscope photograph of an anode of an electrolytic copper foil prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope photograph of an anode of an electrolytic copper foil prepared in example 2 of the present invention;
FIG. 3 is a scanning electron microscope photograph of an anode of an electrolytic copper foil prepared in example 3 of the present invention;
FIG. 4 is a scanning electron microscope photograph of an anode of an electrolytic copper foil prepared in example 4 of the present invention;
FIG. 5 is a scanning electron microscope photograph of an anode of an electrolytic copper foil prepared in example 5 of the present invention;
FIG. 6 is a scanning electron microscope photograph of an anode of an electrolytic copper foil prepared in example 6 of the present invention;
FIG. 7 is a graph showing the results of an enhanced lifetime test of an anode of an electrolytic copper foil manufactured by the manufacturing method provided in examples 1 to 6.
Detailed Description
The exemplary embodiments will be described herein in detail, and the embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. Rather, they are merely examples of methods consistent with certain aspects of the invention, as detailed in the appended claims.
In order to make those skilled in the art better understand the technical solution of the present invention, the following detailed description of the present invention is provided with reference to the accompanying drawings and examples.
The invention provides a preparation method of a noble metal anode for electrolytic copper foil, wherein a coating of a titanium anode is an Ir-Ta system noble metal coating added with a platinum intermediate layer, and the preparation method comprises the following specific 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: accurately weighing a certain amount of tantalum ethoxide solution, dissolving the tantalum ethoxide solution in a n-butyl alcohol solvent, and stirring the solution at room temperature until the tantalum ethoxide solution is completely dissolved to form a solution I; accurately weighing a certain amount of chloroplatinic acid according to the molar ratio of Ta to Pt (2-4) to (6-8), adding the chloroplatinic acid into the solution I, stirring at room temperature until the chloroplatinic acid is completely dissolved to form a primer solution A, and storing for later use;
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 (6-8) to (2-4), mixing and dissolving in a 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 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; and taking out and cooling, then 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 and cooling to room temperature for next coating, repeating the steps until the active liquid B is used up, and finally preserving the heat in the muffle furnace at 450-500 ℃ for 60min to prepare the Ir-Ta system noble metal oxide anode with the platinum-containing intermediate layer.
Example 1
Referring to fig. 1, a scanning electron microscope image of an electrolytic copper foil anode 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 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 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: accurately weighing a certain amount of tantalum ethoxide solution, dissolving the tantalum ethoxide solution in a n-butyl alcohol solvent, and stirring the solution at room temperature until the tantalum ethoxide solution is completely dissolved to form a solution I; accurately weighing a certain amount of chloroplatinic acid according to the molar ratio of Ta to Pt which is 1:4, adding the chloroplatinic acid into the solution I, stirring at room temperature until the chloroplatinic acid is completely dissolved to form a base solution A, and storing for later use;
s3, 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 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; and taking out and cooling, then uniformly coating the prepared active liquid B on a titanium substrate, baking for 10-25 min in a muffle furnace at 450-500 ℃, taking out and cooling to room temperature for next coating, repeating the steps until the active liquid B is used up, and finally preserving the heat in the muffle furnace at 450-520 ℃ for 60min to prepare the Ir-Ta system noble metal oxide anode with the platinum-containing intermediate layer.
Example 2
In this example, referring to fig. 2, 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 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: accurately weighing a certain amount of tantalum ethoxide solution, dissolving the tantalum ethoxide solution in a n-butyl alcohol solvent, and stirring the solution at room temperature until the tantalum ethoxide solution is completely dissolved to form a solution I; accurately weighing a certain amount of chloroplatinic acid according to the molar ratio of Ta to Pt which is 1:3, adding the chloroplatinic acid into the solution I, stirring at room temperature until the chloroplatinic acid is completely dissolved to form a base solution A, and storing for later use;
s3, 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 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; and taking out and cooling, then uniformly coating the prepared active liquid B on a titanium substrate, baking for 10-25 min in a muffle furnace at 450-500 ℃, taking out and cooling to room temperature for next coating, repeating the steps until the active liquid B is used up, and finally preserving the heat in the muffle furnace at 450-520 ℃ for 60min to prepare the Ir-Ta system noble metal oxide anode with the platinum-containing intermediate layer.
Example 3
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 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: accurately weighing a certain amount of tantalum ethoxide solution, dissolving the tantalum ethoxide solution in a n-butyl alcohol solvent, and stirring the solution at room temperature until the tantalum ethoxide solution is completely dissolved to form a solution I; accurately weighing a certain amount of chloroplatinic acid according to the molar ratio of Ta to Pt which is 1:2, adding the chloroplatinic acid into the solution I, stirring at room temperature until the chloroplatinic acid is completely dissolved to form a base solution A, and storing for later use;
s3, 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 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 1 h; and taking out and cooling, then 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 and cooling to room temperature for next coating, repeating the steps until the active liquid B is used up, and finally preserving the 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.
Example 4
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 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: accurately weighing a certain amount of tantalum pentachloride solution, dissolving in an ethanol solvent, and stirring at room temperature until the tantalum pentachloride solution is completely dissolved to form a solution I; accurately weighing a certain amount of chloroplatinic acid according to the molar ratio of Ta to Pt which is 1:4, adding the chloroplatinic acid into the solution I, stirring at room temperature until the chloroplatinic acid is completely dissolved to form a base solution A, and storing for later use;
s3, 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 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; and taking out and cooling, then 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 and cooling to room temperature for next coating, repeating the steps until the active liquid B is used up, and finally preserving the 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.
Example 5
Referring to fig. 5, 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 according to the embodiment of the invention is a titanium anode coating with an Ir-Ta system noble metal coating with a platinum intermediate layer, 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: accurately weighing a certain amount of tantalum ethoxide solution, dissolving the tantalum ethoxide solution in an ethanol solvent, and stirring the solution at room temperature until the tantalum ethoxide solution is completely dissolved to form a solution I; accurately weighing a certain amount of chloroplatinic acid according to the molar ratio of Ta to Pt which is 1:4, adding the chloroplatinic acid into the solution I, stirring at room temperature until the chloroplatinic acid is completely dissolved to form a base solution A, and storing for later use;
s3, 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 6:4, 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; and taking out and cooling, then 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 and cooling to room temperature for next coating, repeating the steps until the active liquid B is used up, and finally preserving the 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.
Example 6
Referring to fig. 6, 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 according to the present embodiment shows that a coating of a titanium anode is an Ir-Ta system noble metal coating with a platinum interlayer added thereto, and the 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 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: accurately weighing a certain amount of tantalum ethoxide solution, dissolving the tantalum ethoxide solution in an ethanol solvent, and stirring the solution at room temperature until the tantalum ethoxide solution is completely dissolved to form a solution I; accurately weighing a certain amount of chloroplatinic acid according to the molar ratio of Ta to Pt which is 1:4, adding the chloroplatinic acid into the solution I, stirring at room temperature until the chloroplatinic acid is completely dissolved to form a base solution A, and storing for later use;
s3, 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 8:2, 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; and taking out and cooling, then 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 and cooling to room temperature for next coating, repeating the steps until the active liquid B is used up, and finally preserving the 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.
1mol/L of H in the electrolyte2SO4The current density is 40000A/m2The results of the enhanced lifetime test of the anodes of electrolytic copper foil manufactured by the manufacturing methods provided in examples 1 to 6 under the electrolysis conditions of (1) are shown in FIG. 7. As can be seen from FIG. 7, the intermediate layer Pt/Ta ratio of 4:1 can achieve longer anode life with lower electrolysis voltage; when tantalum ethoxide was replaced with tantalum pentachloride according to example 4, the obtained anode had a short lifetime, which was not favorable for prolonging the electrode lifetime.
In conclusion, the method for preparing the iridium-tantalum system noble metal coating by using the platinum-containing intermediate layer with tantalum ethoxide as a tantalum source is adopted. IrO2-Ta2O5The coating is a semiconductor oxide, and has lower electron conduction and charge transmission efficiency compared with a titanium substrate, so that the introduction of the platinum-containing intermediate layer can effectively improve the conductivity of the coating and play a role in reducing voltage. Meanwhile, the high-efficiency charge conduction can also effectively relieve the passivation of the titanium matrix caused by charge accumulation between the Ti matrix and the oxide coating, and effectively prolong the service life of the noble metal oxide titanium anode.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention.
It is to be understood that the present invention is not limited to what has been described above, and that various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (8)
1. 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: dissolving 20-40 mol percent of tantalum source and 60-90 mol percent of platinum source in an organic solvent in sequence, and stirring at normal temperature to form a base solution;
3) preparing an active solution: mixing and dissolving 60-80 mol percent of iridium source and 20-40 mol percent of tantalum source in an organic solvent, and stirring at normal temperature to form active liquid;
4) coating and sintering: and (2) coating and sintering the surface of the titanium substrate pretreated in the step 1) with a base solution, and then coating and sintering the surface of the titanium substrate with an active solution.
2. The method for preparing a noble metal anode for electrolytic copper foil according to claim 1, 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;
1.2) carrying out thermal sizing 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 concentration of 3-15% for 8-24 h, and then boiling in oxalic acid solution with the concentration of 5-10% for 0.5-3 h;
1.4) cleaning and airing the titanium substrate.
3. The method for preparing a noble metal anode for electrolytic copper foil according to claim 2, wherein the step 1.1) is performed with sand blasting using steel grit until the surface roughness Ra <15 μm.
4. The method for preparing a noble metal anode for electrolytic copper foil according to claim 1, wherein the tantalum source of the step 2) and the step 3) is selected from any one of tantalum pentachloride n-butanol solution, tantalum butanediol, and tantalum ethoxide.
5. The method of manufacturing a noble metal anode for electrolytic copper foil according to claim 1, wherein the platinum source of the step 2) is selected from any one of chloroplatinic acid, platinum tetrachloride and platinum oxide.
6. The method of manufacturing a noble metal anode for electrolytic copper foil according to claim 1, wherein the iridium source of the step 3) is selected from any one of chloro-iridic acid, iridium trichloride and bromo-iridic acid.
7. The method for preparing a noble metal anode for electrolytic copper foil according to claim 1, wherein the organic solvent in the step 2) and the step 3) is selected from one of n-butanol, isopropanol, and ethanol, or a mixture thereof.
8. The method for preparing a noble metal anode for electrolytic copper foil according to claim 1, wherein the step 4) of brushing and sintering specifically comprises:
4.1) coating the prepared base solution on the pretreated titanium substrate, naturally drying the base solution, and putting the base solution 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 matrix in a muffle furnace at 450-520 ℃ for sintering for 50-75 min, taking out, and cooling to room temperature;
4.4) coating the prepared active liquid on the titanium substrate treated in the step 4.3), naturally airing, and putting in an oven at 60-100 ℃ to completely volatilize the solvent;
4.5) placing the titanium substrate treated in the step 4.4) in a muffle furnace at 450-520 ℃ for sintering for 10-25 min, taking out, and cooling to room temperature;
4.6) repeating the steps 4.4) and 4.5) until the active liquid is coated;
4.7) preserving 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111390483.7A CN114182307A (en) | 2021-11-23 | 2021-11-23 | Preparation method of noble metal anode for electrolytic copper foil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111390483.7A CN114182307A (en) | 2021-11-23 | 2021-11-23 | Preparation method of noble metal anode for electrolytic copper foil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114182307A true CN114182307A (en) | 2022-03-15 |
Family
ID=80602363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111390483.7A Pending CN114182307A (en) | 2021-11-23 | 2021-11-23 | Preparation method of noble metal anode for electrolytic copper foil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114182307A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114752971A (en) * | 2022-04-11 | 2022-07-15 | 西安泰金工业电化学技术有限公司 | Preparation method of coated titanium anode with high electrolysis durability |
| CN114774998A (en) * | 2022-04-08 | 2022-07-22 | 西安泰金工业电化学技术有限公司 | Preparation method of low-noble-metal Ir-Ta composite oxide coating anode |
| CN114875458A (en) * | 2022-05-19 | 2022-08-09 | 西安泰金工业电化学技术有限公司 | Noble metal anode for electrolytic copper foil and preparation method thereof |
| CN114990604A (en) * | 2022-05-19 | 2022-09-02 | 西安泰金工业电化学技术有限公司 | PEM water electrolysis cell catalyst loaded diffusion layer and preparation method thereof |
| CN115198285A (en) * | 2022-07-14 | 2022-10-18 | 西安泰金工业电化学技术有限公司 | Preparation method of noble metal powder catalyst for hydrogen production by water electrolysis |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59150091A (en) * | 1983-01-31 | 1984-08-28 | Permelec Electrode Ltd | Electrode for electrolysis having durability and its production |
| JPH05255881A (en) * | 1992-03-11 | 1993-10-05 | Tdk Corp | Electrode for generation of oxygen and its production |
| JPH06330368A (en) * | 1993-05-20 | 1994-11-29 | Permelec Electrode Ltd | Electrode for electrolysis |
| JP2003183894A (en) * | 2001-12-11 | 2003-07-03 | Daiki Engineering Kk | Electrode for metal plating |
| CN102560561A (en) * | 2010-12-10 | 2012-07-11 | 上海太阳能工程技术研究中心有限公司 | DSA (Dimensionally Stable Anode) electrode and manufacturing method thereof |
| CN112795908A (en) * | 2020-12-18 | 2021-05-14 | 西安泰金工业电化学技术有限公司 | Preparation method of titanium anode with titanium-based coating |
-
2021
- 2021-11-23 CN CN202111390483.7A patent/CN114182307A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59150091A (en) * | 1983-01-31 | 1984-08-28 | Permelec Electrode Ltd | Electrode for electrolysis having durability and its production |
| JPH05255881A (en) * | 1992-03-11 | 1993-10-05 | Tdk Corp | Electrode for generation of oxygen and its production |
| JPH06330368A (en) * | 1993-05-20 | 1994-11-29 | Permelec Electrode Ltd | Electrode for electrolysis |
| JP2003183894A (en) * | 2001-12-11 | 2003-07-03 | Daiki Engineering Kk | Electrode for metal plating |
| CN102560561A (en) * | 2010-12-10 | 2012-07-11 | 上海太阳能工程技术研究中心有限公司 | DSA (Dimensionally Stable Anode) electrode and manufacturing method thereof |
| CN112795908A (en) * | 2020-12-18 | 2021-05-14 | 西安泰金工业电化学技术有限公司 | Preparation method of titanium anode with titanium-based coating |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114774998A (en) * | 2022-04-08 | 2022-07-22 | 西安泰金工业电化学技术有限公司 | Preparation method of low-noble-metal Ir-Ta composite oxide coating anode |
| CN114752971A (en) * | 2022-04-11 | 2022-07-15 | 西安泰金工业电化学技术有限公司 | Preparation method of coated titanium anode with high electrolysis durability |
| CN114875458A (en) * | 2022-05-19 | 2022-08-09 | 西安泰金工业电化学技术有限公司 | Noble metal anode for electrolytic copper foil and preparation method thereof |
| CN114990604A (en) * | 2022-05-19 | 2022-09-02 | 西安泰金工业电化学技术有限公司 | PEM water electrolysis cell catalyst loaded diffusion layer and preparation method thereof |
| CN115198285A (en) * | 2022-07-14 | 2022-10-18 | 西安泰金工业电化学技术有限公司 | Preparation method of noble metal powder catalyst for hydrogen production by water electrolysis |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114182307A (en) | Preparation method of noble metal anode for electrolytic copper foil | |
| CN112647086B (en) | Titanium fiber felt anode diffusion layer for PEM water electrolysis cell and preparation method and application thereof | |
| CN111170415A (en) | Titanium oxide/ruthenium oxide composite electrode and preparation method and application thereof | |
| CN105239094A (en) | Graphene and lanthanum-doped modified titanium-based lead dioxide electrode and preparation method thereof | |
| CN113690455B (en) | Long-life anode electrode material and preparation method thereof | |
| EP0027367A1 (en) | Method of manufacture of catalytic electrodes with coatings comprising platinum group electrocatalysts | |
| CN113881978A (en) | Preparation method of low-cost titanium-based coating titanium anode | |
| CN112663124B (en) | Preparation method of precious metal anode for horizontal electroplating of PCB | |
| CN113881962A (en) | Preparation method of high-conductivity Ir-Ta-Mn composite oxide coating anode | |
| CN104846398B (en) | A kind of titanium-based TiNx/IrO2‑Ta2O5Coated anode | |
| CN104846399B (en) | A kind of titanium-based TiNx/TiO2-RuO2Nano coating anode | |
| CN104962948B (en) | A kind of titanium-based TiNx/IrO2‑Ta2O5Nano coating anode | |
| CN114774998A (en) | Preparation method of low-noble-metal Ir-Ta composite oxide coating anode | |
| CN114164419B (en) | Method for preparing platinum active layer on anode plate by thermal decomposition method | |
| CN114990679B (en) | Preparation method of oxygen-evolving titanium anode | |
| CN115613083A (en) | Titanium anode for copper plating field, preparation method and copper plating equipment | |
| CN114592218B (en) | Titanium-based anode and preparation method and application thereof | |
| CN114540824B (en) | Method for regenerating titanium anode plate by using waste acid solution | |
| CN112725831B (en) | Improve Ti/RuO 2 -TiO 2 Sintering process for anode electrocatalytic activity and stability | |
| CN114016007A (en) | Preparation method of titanium-based insoluble anode for acid tinning | |
| CN114875458B (en) | Noble metal anode for electrolytic copper foil and preparation method thereof | |
| KR100523591B1 (en) | Electrode and its manufacturing method using rare earth element | |
| JP2013237934A (en) | Method for manufacturing anticorrosive conductive coating material | |
| CN113755872B (en) | Preparation method of high-stability titanium-based lead dioxide electrode | |
| CN118854280A (en) | Noble metal anode for electrolytic copper foil and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 710299 No. 15, west section of Xijin Road, Jingwei Industrial Park, Xi'an Economic and Technological Development Zone, Xi'an City, Shaanxi Province Applicant after: Xi'an Taijin Xinneng Technology Co.,Ltd. Address before: 710299 No. 15, west section of Xijin Road, Jingwei Industrial Park, Xi'an Economic and Technological Development Zone, Xi'an City, Shaanxi Province Applicant before: XI'AN TAIJIN INDUSTRIAL ELECTROCHEMICAL TECHNOLOGY Co.,Ltd. |
|
| CB02 | Change of applicant information |