CN113881962A - Preparation method of high-conductivity Ir-Ta-Mn composite oxide coating anode - Google Patents

Preparation method of high-conductivity Ir-Ta-Mn composite oxide coating anode Download PDF

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CN113881962A
CN113881962A CN202111266660.0A CN202111266660A CN113881962A CN 113881962 A CN113881962 A CN 113881962A CN 202111266660 A CN202111266660 A CN 202111266660A CN 113881962 A CN113881962 A CN 113881962A
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solution
coating
conductivity
composite oxide
room temperature
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薛建超
冯庆
贾波
郝小军
窦泽坤
赵新泽
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Xian Taijin Industrial Electrochemical Technology Co Ltd
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    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
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Abstract

The invention belongs to the technical field of electrolytic copper foil, and relates to a preparation method of a high-conductivity Ir-Ta-Mn composite oxide coating anode, which specifically comprises the following steps: and carrying out surface treatment, coating active liquid and sintering on the titanium matrix. MnO with good stability is introduced into a traditional Ir-Ta system coatingxTo prepare active coating solutions due to MnOxThe coating has good catalytic activity, so that the conductivity of the coating is improved, and meanwhile, the Mn is used for replacing expensive Ir to make the surface of the Ir-Ta oxide coating porous, so that the exposed area of active sites in the coating is increased, the oxygen evolution potential of the coating is reduced, the content of Ir in the coating is reduced, and the production cost of the whole coating anode can be effectively reduced. The method is suitable for preparing the copper foil by electrolysis, and has the advantages of simple process, easy control and strong operabilityThe raw materials are easy to obtain and the cost is low.

Description

Preparation method of high-conductivity Ir-Ta-Mn composite oxide coating anode
Technical Field
The invention belongs to the technical field of electrolytic copper foil, relates to a coated anode for electrolytic copper foil, and particularly relates to a preparation method of a high-conductivity Ir-Ta-Mn composite oxide coated anode.
Background
The electrolytic copper foil is one of basic materials in the electronic industry, is mainly used for manufacturing Printed Circuit Boards (PCBs) and lithium ion batteries, and is widely applied to the fields of communication, medical treatment, aerospace, military, new energy and the like. The national implementation and popularization of key markets such as 5G, industrial internet, data center, new energy automobiles, intelligent internet automobiles and the like in the next three years are proposed in the development action plan of the basic electronic component industry. Meanwhile, in the new energy automobile industry planning, norway, finland, germany, uk, and france respectively announce that fuel vehicles were prohibited from being sold in full in 2025, 2030, 2040, and 2040. The market of new energy automobiles around the world enters a rapid development channel, so the demand of high-end electrolytic copper foil is very urgent. According to prediction, the demand of only lithium electrolytic copper foil in 2025 years is expected to reach 69.8 ten thousand tons. The production capacity of the copper foil is mainly concentrated in the United states, Japan and Asia before, the industry undergoes two times of large-scale production capacity transfer, and China gradually grows into the largest copper foil producing country all over the world. In the first ten copper foil manufacturers all over the world, seven enterprises are occupied by Chinese enterprises. The development of upstream industries is driven by huge market demands.
Currently, the iridium system is the most stable and oxygen evolution anode coating system with good electrocatalytic performance as Ti/Ir: ta is 7: 3. IrO is reported in literature2The anode has higher oxygen evolution electrocatalytic activity in an acidic medium, maintains higher stability, and has the best conductivity in noble metal oxides. And Ta2O5The inert component is doped into the coating, so that the stability of the active oxide is improved, and the service life of the active oxide is prolonged. However, the cost of Ir is high, and the current density is high when the copper foil is electrolyzed, so that the groove of the Ir-Ta noble metal coating anodeThe pressure is higher. Therefore, in order to meet the high requirements of the electrolytic preparation of copper foil, the anode coating material must be improved to reduce the Ir content in the coating, reduce the cost, and simultaneously improve the conductivity of the coating to reduce the energy consumption.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a high-conductivity Ir-Ta-Mn composite oxide coating anode, which introduces MnO with good stability into a traditional Ir-Ta system coatingxThe coating has better catalytic activity, so that the conductivity of the coating is improved, and the cost of the anode is reduced.
In order to achieve the purpose, the invention provides the following technical scheme:
the preparation method of the high-conductivity Ir-Ta-Mn composite oxide coating anode comprises the steps of pretreating a titanium substrate, and adding MnO into an Ir-Ta system coatingxPreparing active coating liquid, and painting and sintering.
Further, the preparation method specifically comprises the following steps:
1) pretreating a titanium substrate;
2) preparing an active masking liquid: weighing chloroiridic acid, dissolving the chloroiridic acid in an organic solvent, and stirring the chloroiridic acid at room temperature until the chloroiridic acid is completely dissolved to form a solution A; weighing tantalum pentachloride n-butyl alcohol solution, dissolving the tantalum pentachloride n-butyl alcohol solution in an organic solvent, and stirring the solution at room temperature until the tantalum pentachloride n-butyl alcohol solution is completely dissolved to form a solution B; weighing MnCl2·4H2Dissolving O in an organic solvent, and stirring at room temperature until the O is completely dissolved to form a solution C; uniformly mixing the solution A, the solution B and the solution C according to the molar ratio of 7:3 (0.5-6) to form a solution D, and storing for later use;
3) and (5) sintering.
Further, the organic solvent in the step 2) is any one of n-butanol, isopropanol and ethanol or a mixture thereof.
Further, the step 1) specifically 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 treated in the step 1.1);
1.3) soaking the titanium substrate with good shape correction in dilute hydrochloric acid, and then boiling in oxalic acid solution;
1.4) cleaning the titanium substrate treated in the step 1.3), taking out impurities remained on the surface, and airing for later use.
Furthermore, the sand for sand blasting is one or mixed sand of steel sand, brown corundum and white corundum, and the surface roughness Ra of the sand is less than 15 mu m.
Further, the concentration of the dilute hydrochloric acid is 3-15%, and the soaking time is 8-24 h.
Furthermore, the concentration of the oxalic acid solution is 5-10%, and the boiling time is 0.5-3 h.
Further, the step 3) specifically comprises the following steps:
3.1) brushing the prepared active masking liquid on the pretreated titanium substrate, naturally airing the titanium substrate, and putting the titanium substrate in an oven at 80 ℃ to completely volatilize the solvent;
3.2) placing the titanium substrate treated in the step 3.1) in a muffle furnace at the temperature of 450-550 ℃ for sintering for 10-20min, taking out, cooling to room temperature, and repeating the step 3.1) until the coating liquid is completely coated;
3.3) preserving the temperature of the coated titanium matrix in a muffle furnace at the temperature of 450-550 ℃ for 0.5-1.5h, taking out, and naturally cooling to room temperature to obtain the high-conductivity Ir-Ta-Mn composite oxide coating anode.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects: MnO with good stability is introduced into a traditional Ir-Ta system coatingxTo prepare active coating solutions due to MnOxThe coating has good catalytic activity, so that the conductivity of the coating is improved, and meanwhile, the Mn is used for replacing expensive Ir to make the surface of the Ir-Ta oxide coating porous, so that the exposed area of active sites in the coating is increased, the oxygen evolution potential of the coating is reduced, the content of Ir in the coating is reduced, and the production cost of the whole coating anode can be effectively reduced. In addition, the organic solvent adopts n-butanol solvent with higher viscosity, which can well control the diffusion rate of the solution, so that the noble metal active components are more uniformly dispersed on the surface of the titanium substrate.
Drawings
FIG. 1 is a scanning electron microscope image of an anode of an Ir-Ta-Mn composite oxide prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of an anode of Ir-Ta-Mn composite oxide prepared in example 2 of the present invention;
FIG. 3 is a scanning electron microscope image of an anode of Ir-Ta-Mn composite oxide prepared in example 3 of the present invention;
FIG. 4 is a scanning electron microscope image of an anode of Ir-Ta-Mn composite oxide prepared in example 4 of the present invention;
FIG. 5 is a scanning electron microscope image of an anode of Ir-Ta-Mn composite oxide prepared in example 5 of the present invention;
FIG. 6 shows 4000A/m of coated anodes obtained in examples 1-5 in a 1mol/L sulfuric acid system2Strengthening the life test result;
FIG. 7 shows coated anodes obtained from examples 1-5 in H2SO4Results of EIS tests performed in solution (1.35V).
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 high-conductivity Ir-Ta-Mn composite oxide coating anode, wherein the coating of the titanium anode is an Ir-Ta system noble metal coating added with Mn, and the Mn source is MnCl2·4H2And O. Wherein, the addition amount (molar ratio) of Mn is determined by adding source substances into the coating according to the design, and the proportion is Ir: ta: mn is 7:3 (0.5-3.5);
the preparation method of the coating anode comprises the following steps:
1) titanium base treatment: degreasing and deoiling the titanium substrate by using a cleaning agent, pickling and etching;
2) preparing an active masking liquid: accurately weighing a certain amount of chloroiridic acid, dissolving in n-butanol solvent (stirring at room temperature to completely dissolve to form solution A; accurately weighing a certain amount of tantalum pentachloride n-butanol solution, dissolving in n-butanol solvent, stirring at room temperature to completely dissolve to form solution B; accurately weighing a certain amount of MnCl2·4H2Dissolving O in n-butanol solvent, and stirring at room temperature to dissolve completely to form solution C. A, B, C are evenly mixed according to the molar ratio of 7:3 (0.5-6) to form a solution D; storing for later use;
3) and (3) sintering: and uniformly coating the coating on a titanium substrate, baking the titanium substrate at 550 ℃ in a muffle furnace after drying for 10-20min, taking out the titanium substrate, cooling the titanium substrate to room temperature, coating the titanium substrate for the next time, repeating the work until the active coating liquid is used up, finally keeping the temperature in the muffle furnace at 550 ℃ at 450 ℃ for 0.5-1.5h, taking out the titanium substrate, and naturally cooling the titanium substrate to room temperature to obtain the high-conductivity Ir-Ta-Mn composite oxide coating anode.
Example 1
The embodiment provides a preparation method of an Ir-Ta composite oxide coating anode, which specifically comprises the following steps:
s1, carrying out oil removal and degreasing, sand blasting, thermal sizing, acid washing and cleaning treatment on the titanium matrix, and airing for later use;
s2, accurately weighing a certain amount of chloroiridic acid to be dissolved in n-butanol solvent (the concentration of metal ions is 0.3mol/L), and stirring at room temperature until the chloroiridic acid is completely dissolved to form a solution A; accurately weighing a certain amount of tantalum pentachloride n-butanol solution, dissolving the tantalum pentachloride n-butanol solution in n-butanol solvent (the concentration of metal ions is 0.3mol/L) and stirring the solution at room temperature until the solution is completely dissolved to form a solution B; uniformly mixing the solution A and the solution B according to the volume ratio of 7:3 to form a solution D, and storing for later use;
s3, uniformly coating the solution D on the treated titanium substrate to uniformly diffuse the coating liquid, and placing the titanium substrate in an oven at 80 ℃ to completely volatilize the solvent; then placing the mixture in a muffle furnace at 500 ℃, sintering for 15min, taking out, naturally cooling to room temperature, and repeating the steps until the coating liquid is completely coated; and finally, preserving the heat of the coated titanium substrate in a muffle furnace at 500 ℃ for 1h, taking out, naturally cooling to room temperature to obtain an Ir-Ta composite oxide coating anode (I), and taking a scanning electron microscope picture of the Ir-Ta composite oxide coating anode (I) as shown in figure 1.
Example 2
The embodiment provides a preparation method of a high-conductivity Ir-Ta-Mn composite oxide coating anode, which specifically comprises the following steps:
s1, carrying out oil removal and degreasing, sand blasting, thermal sizing, acid washing and cleaning treatment on the titanium matrix, and airing for later use;
s2, accurately weighing a certain amount of chloroiridic acid to be dissolved in n-butanol solvent (the concentration of metal ions is 0.3mol/L), and stirring at room temperature until the chloroiridic acid is completely dissolved to form a solution A; accurately weighing a certain amount of tantalum pentachloride n-butanol solution, dissolving the tantalum pentachloride n-butanol solution in n-butanol solvent (the concentration of metal ions is 0.3mol/L) and stirring the solution at room temperature until the solution is completely dissolved to form a solution B; accurately weighing a certain amount of MnCl2·4H2Dissolving O in n-butanol solvent (metal ion concentration of 0.3mol/L) and stirring at room temperature until completely dissolving to form solution C; uniformly mixing the solution A, the solution B and the solution C according to the volume ratio of 7:3:0.5 to form a solution D; storing for later use;
s3, uniformly coating the solution D on the treated titanium substrate to uniformly diffuse the coating liquid, and placing the titanium substrate in an oven at 80 ℃ to completely volatilize the solvent; then placing the mixture in a muffle furnace at 500 ℃, sintering for 15min, taking out, naturally cooling to room temperature, and repeating the steps until the coating liquid is completely coated; and finally, preserving the heat of the coated titanium substrate in a muffle furnace at 500 ℃ for 1h, taking out, naturally cooling to room temperature to obtain a high-conductivity Ir-Ta-Mn composite oxide coating anode (II), wherein a scanning electron microscope picture of the anode (II) is shown in figure 2.
Example 3
The embodiment provides a preparation method of a high-conductivity Ir-Ta-Mn composite oxide coating anode, which specifically comprises the following steps:
s1, carrying out oil removal and degreasing, sand blasting, thermal sizing, acid washing and cleaning treatment on the titanium matrix, and airing for later use;
s2, accurately weighing a certain amount of chloroiridic acid to be dissolved in n-butanol solvent (the concentration of metal ions is 0.3mol/L), and stirring at room temperature until the chloroiridic acid is completely dissolved to form a solution A; accurately weighing a certain amount of tantalum pentachloride n-butanolDissolving the solution in n-butanol solvent (metal ion concentration is 0.3mol/L) and stirring at room temperature until the solution is completely dissolved to form a solution B; accurately weighing a certain amount of MnCl2·4H2Dissolving O in n-butanol solvent (metal ion concentration of 0.3mol/L) and stirring at room temperature until completely dissolving to form solution C; uniformly mixing the solution A, the solution B and the solution C according to the volume ratio of 7:3:1.5 to form a solution D; storing for later use;
s3, uniformly coating the solution D on the treated titanium substrate to uniformly diffuse the coating liquid, and placing the titanium substrate in an oven at 80 ℃ to completely volatilize the solvent; then placing the mixture in a muffle furnace at 500 ℃, sintering for 15min, taking out, naturally cooling to room temperature, and repeating the steps until the coating liquid is completely coated; and finally, preserving the heat of the coated titanium substrate in a muffle furnace at 500 ℃ for 1h, taking out, naturally cooling to room temperature to obtain a high-conductivity Ir-Ta-Mn composite oxide coating anode (III), wherein a scanning electron microscope picture of the anode (III) is shown in figure 3.
Example 4
The embodiment provides a preparation method of a high-conductivity Ir-Ta-Mn composite oxide coating anode, which specifically comprises the following steps:
s1, carrying out oil removal and degreasing, sand blasting, thermal sizing, acid washing and cleaning treatment on the titanium matrix, and airing for later use;
s2, accurately weighing a certain amount of chloroiridic acid to be dissolved in n-butanol solvent (the concentration of metal ions is 0.3mol/L), and stirring at room temperature until the chloroiridic acid is completely dissolved to form a solution A; accurately weighing a certain amount of tantalum pentachloride n-butanol solution, dissolving the tantalum pentachloride n-butanol solution in n-butanol solvent (the concentration of metal ions is 0.3mol/L) and stirring the solution at room temperature until the solution is completely dissolved to form a solution B; accurately weighing a certain amount of MnCl2·4H2Dissolving O in n-butanol solvent (metal ion concentration of 0.3mol/L) and stirring at room temperature until completely dissolving to form solution C; uniformly mixing the solution A, the solution B and the solution C according to the volume ratio of 7:3:2.5 to form a solution D; storing for later use;
s3, uniformly coating the solution D on the treated titanium substrate to uniformly diffuse the coating liquid, and placing the titanium substrate in an oven at 80 ℃ to completely volatilize the solvent; then placing the mixture in a muffle furnace at 500 ℃, sintering for 15min, taking out, naturally cooling to room temperature, and repeating the steps until the coating liquid is completely coated; and finally, preserving the heat of the coated titanium substrate in a muffle furnace at 500 ℃ for 1h, taking out, naturally cooling to room temperature to obtain the high-conductivity Ir-Ta-Mn composite oxide coating anode (IV), wherein a scanning electron microscope picture of the anode is shown in figure 4.
Example 5
The embodiment provides a preparation method of a high-conductivity Ir-Ta-Mn composite oxide coating anode, which specifically comprises the following steps:
s1, carrying out oil removal and degreasing, sand blasting, thermal sizing, acid washing and cleaning treatment on the titanium matrix, and airing for later use;
s2, accurately weighing a certain amount of chloroiridic acid to be dissolved in n-butanol solvent (the concentration of metal ions is 0.3mol/L), and stirring at room temperature until the chloroiridic acid is completely dissolved to form a solution A; accurately weighing a certain amount of tantalum pentachloride n-butanol solution, dissolving the tantalum pentachloride n-butanol solution in n-butanol solvent (the concentration of metal ions is 0.3mol/L) and stirring the solution at room temperature until the solution is completely dissolved to form a solution B; accurately weighing a certain amount of MnCl2·4H2Dissolving O in n-butanol solvent (metal ion concentration of 0.3mol/L) and stirring at room temperature until completely dissolving to form solution C; uniformly mixing the solution A, the solution B and the solution C according to the volume ratio of 7:3:3.5 to form a solution D; and (5) storing for later use.
S3, uniformly coating the solution D on the treated titanium substrate to uniformly diffuse the coating liquid, and placing the titanium substrate in an oven at 80 ℃ to completely volatilize the solvent; then placing the mixture in a muffle furnace at 500 ℃, sintering for 15min, taking out, naturally cooling to room temperature, and repeating the steps until the coating liquid is completely coated; and finally, preserving the heat of the coated titanium substrate in a muffle furnace at 500 ℃ for 1h, taking out, naturally cooling to room temperature to obtain the high-conductivity Ir-Ta-Mn composite oxide coating anode (V), wherein a scanning electron microscope image of the anode (V) is shown in figure 5.
The composite oxide coating anodes prepared in the above examples 1 to 5 were placed in 1mol/L of H2SO4The electrolytic copper foil experiment is carried out in the electrolyte to obtain the enhanced life cell pressure of each example, the specific data is shown in the following table 1, and the test result is shown in the figure 6.
TABLE 1 shows the enhanced life slot pressures of examples 1-5
Example 1 Example 2 Example 3 Example 4 Example 5
Groove pressure 7.87V 7.67V 6.95V 6.8V 6.72V
The experimental results show that the method of the invention adopts the Ir-Ta-Mn system noble metal coating with Mn replacing Ir, and Mn has the function of refining iridium oxide crystal grains, so that the active component amount can be improved, and the anodic oxygen evolution potential can be reduced; meanwhile, the surface of the coating is in a porous shape, as shown in FIG. 7, FIG. 7 shows that the anode of the Ir-Ta-Mn composite oxide coating is in H2SO4EIS tests carried out in a solution (1.35V) show that the prepared Ir-Ta-Mn composite oxide coating anode has a porous structure and increases the exposed area of active sites in the coating. Furthermore, since IrO2·Ta2O5The mixed crystal material belongs to p-type conductivity, and is oxidized by adding Mn metalThe compound can improve the anode conduction process by forming electron holes; at the same time by introducing MnOxThe manufacturing cost of the anode is reduced, and the market demand can be better met.
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 high-conductivity Ir-Ta-Mn composite oxide coating anode is characterized in that a titanium matrix is pretreated, and MnO is added into an Ir-Ta system coatingxPreparing active coating liquid, and painting and sintering.
2. The preparation method of the high-conductivity Ir-Ta-Mn composite oxide coated anode according to claim 1, characterized in that it comprises the following steps:
1) pretreating a titanium substrate;
2) preparing an active masking liquid: weighing chloroiridic acid, dissolving the chloroiridic acid in an organic solvent, and stirring the chloroiridic acid at room temperature until the chloroiridic acid is completely dissolved to form a solution A; weighing tantalum pentachloride n-butyl alcohol solution, dissolving the tantalum pentachloride n-butyl alcohol solution in an organic solvent, and stirring the solution at room temperature until the tantalum pentachloride n-butyl alcohol solution is completely dissolved to form a solution B; weighing MnCl2·4H2Dissolving O in an organic solvent, and stirring at room temperature until the O is completely dissolved to form a solution C; uniformly mixing the solution A, the solution B and the solution C according to the molar ratio of 7:3 (0.5-6) to form a solution D, and storing for later use;
3) and (5) sintering.
3. The method for preparing the high-conductivity Ir-Ta-Mn composite oxide coated anode according to claim 2, wherein the organic solvent in the step 2) is any one of n-butanol, isopropanol, ethanol or a mixture thereof.
4. The method for preparing the high-conductivity Ir-Ta-Mn composite oxide coated anode according to claim 2, wherein the step 1) specifically 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 treated in the step 1.1);
1.3) soaking the titanium substrate with good shape correction in dilute hydrochloric acid, and then boiling in oxalic acid solution;
1.4) cleaning the titanium substrate treated in the step 1.3), taking out impurities remained on the surface, and airing for later use.
5. The method for preparing the high-conductivity Ir-Ta-Mn composite oxide coating anode according to claim 4, wherein the sand for sand blasting is one or a mixed sand of steel sand, brown corundum and white corundum, and the surface roughness Ra of the sand is less than 15 μm.
6. The method for preparing the high-conductivity Ir-Ta-Mn composite oxide coated anode according to claim 4, wherein the concentration of the dilute hydrochloric acid is 3 to 15 percent, and the soaking time is 8 to 24 hours.
7. The method for preparing the high-conductivity Ir-Ta-Mn composite oxide coated anode according to claim 4, wherein the oxalic acid solution has a concentration of 5 to 10% and a boiling time of 0.5 to 3 hours.
8. The method for preparing the high-conductivity Ir-Ta-Mn composite oxide coated anode according to claim 2, wherein said step 3) comprises the following steps:
3.1) brushing the prepared active masking liquid on the pretreated titanium substrate, naturally airing the titanium substrate, and putting the titanium substrate in an oven at 80 ℃ to completely volatilize the solvent;
3.2) placing the titanium substrate treated in the step 3.1) in a muffle furnace at the temperature of 450-550 ℃ for sintering for 10-20min, taking out, cooling to room temperature, and repeating the step 3.1) until the coating liquid is completely coated;
3.3) preserving the temperature of the coated titanium matrix in a muffle furnace at the temperature of 450-550 ℃ for 0.5-1.5h, taking out, and naturally cooling to room temperature to obtain the high-conductivity Ir-Ta-Mn composite oxide coating anode.
CN202111266660.0A 2021-10-28 2021-10-28 Preparation method of high-conductivity Ir-Ta-Mn composite oxide coating anode Pending CN113881962A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
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
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