CN117758332A - Electrolytic anode based on micro-arc oxidation technology and preparation method thereof - Google Patents
Electrolytic anode based on micro-arc oxidation technology and preparation method thereof Download PDFInfo
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- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
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- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 14
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 19
- 238000005238 degreasing Methods 0.000 claims description 19
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- 229910052741 iridium Inorganic materials 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 229910052715 tantalum Inorganic materials 0.000 claims description 9
- 238000005530 etching Methods 0.000 claims description 8
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
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- 150000007513 acids Chemical class 0.000 claims description 3
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- 239000003054 catalyst Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
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- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
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- 239000011248 coating agent Substances 0.000 abstract description 32
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
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- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- KFVUXNKQQOUCAH-UHFFFAOYSA-N butan-1-ol;propan-2-ol Chemical compound CC(C)O.CCCCO KFVUXNKQQOUCAH-UHFFFAOYSA-N 0.000 description 1
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- UHWHMHPXHWHWPX-UHFFFAOYSA-J dipotassium;oxalate;oxotitanium(2+) Chemical compound [K+].[K+].[Ti+2]=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UHWHMHPXHWHWPX-UHFFFAOYSA-J 0.000 description 1
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- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses an electrolytic anode based on micro-arc oxidation technology and a preparation method thereof, wherein the electrolytic anode comprises three parts: insoluble valve metal or valve metal alloy substrate, valve metal oxide intermediate layer, noble metal oxide catalytic layer. The intermediate layer is prepared on the surface of the valve metal or valve metal alloy matrix by a micro-arc oxidation technology, and the catalytic layer is prepared by a method of circularly coating noble metal solution and sintering at high temperature. The oxide intermediate layer prepared by utilizing the micro-arc oxidation technology grows on the surface of the base metal in situ, has a honeycomb surface, has extremely strong binding force with the base and the catalytic layer, and can effectively inhibit the oxidation and passivation of the base and prevent the coating from falling off, thereby prolonging the service life of the electrode. In addition, the middle layer with the special structure provides a framework for the catalytic layer, so that the number of catalytic active sites of the catalytic layer is obviously increased, the prepared electrode has low electrode potential, and the power consumption in the actual electrolysis process is reduced, thereby reducing the use cost of the anode.
Description
Technical Field
The invention relates to the technical field of electrolytic anodes, in particular to an electrolytic anode based on a micro-arc oxidation technology and a preparation method thereof, which are particularly suitable for the field of electrolytic anodes with long service life, strong corrosion resistance and high bearable current density.
Background
At present, electrodes for forming a coating layer by coating noble metal solution on the surfaces of other valve metal substrates such as metal titanium and the like are widely applied to the fields of chemical industry, metal foil production, electroplating, water treatment and the like. Many of the above fields are where an anode is oxidized during electrolysis in the presence of sulfuric acid or the like for the purpose of cathodic reduction, and an anode material having high corrosion resistance, low electrode potential and good electrolytic durability is required for industrial application. In IrO 2 +Ta 2 O 5 The titanium anode with the mixed oxide as the coating has high current density bearing capacity, lower electrode potential and excellent chemical stability, and is proved to be one of oxygen evolution anodes most suitable for the electrolysis industry.
However, the iridium tantalum coating titanium anode still has a certain defect in practical application, taking the electrolytic copper foil industry as an example, along with rapid development of technology and continuous increase of production requirements, the anode current density is obviously increased, the reaction rate of the anode surface is accelerated, and the generated gas amount is obviously increased, so that the bubbles generated by the gassing reaction on the surface of the coating form a larger mechanical impact effect on the surface of the coating, and finally, the coating with a large number of tortoise cracks can be easily stressed and peeled off, thereby reducing the service life and failure of the anode. According to researches, the surface of the anode matrix is modified, and the preparation of a proper intermediate layer can effectively improve the bonding capability of a coating and a base material and prolong the service life of the anode.
Micro-arc oxidation is a novel surface treatment technology developed on the basis of anodic oxidation, and the principle is that an oxide film is formed on the surface of an alloy by in-situ growth of plasmas generated by high-frequency pulse current. The micro-arc oxidation film layer has the characteristics of high hardness, high wear resistance, high heat resistance, good corrosion resistance and the like, the whole film layer is honeycomb-shaped, and a large number of discharge micropores are uniformly distributed in the film layer and serve as channels for generating gas through current and reaction. Because the micro-arc oxidation film layer has the structure, the honeycomb structure of the film layer can be used as the adhesion ground of a framework and other modified substances, and the materials can show different performances according to the different attached substances.
Therefore, a layer of IrO is prepared on the surface by combining the characteristics of good corrosion resistance, strong binding force and the like of the micro-arc oxidation film layer 2 +Ta 2 O 5 The mixed oxide coating can obviously improve the current situations of poor binding force, short service life, insufficient electrocatalytic performance and the like of the existing electrolytic anode material coating. In view of the above, the present invention has been made.
Disclosure of Invention
Aiming at the technical problems in the related art, the invention provides a preparation method of an electrolytic anode based on a micro-arc oxidation technology, which can overcome the defects in the prior art.
In order to achieve the technical purpose, the technical scheme of the invention is realized as follows:
an electrolytic anode based on micro-arc oxidation technology;
the electrolytic anode based on the micro-arc oxidation technology comprises an insoluble valve metal or valve metal alloy matrix, a valve metal oxide intermediate layer and a noble metal oxide catalytic layer.
Further, the valve metal oxide intermediate layer comprises TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The thickness of the valve metal oxide intermediate layer is 0.1-1 mu m.
Further, the noble metal oxide catalyst layer comprises IrO 2 、Ta 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the The content of iridium in the noble metal oxide catalytic layer is 5-50g/m 2 。
Further, the insoluble valve metal or valve metal alloy substrate is titanium or titanium alloy.
According to another aspect of the invention, a method for preparing an electrolytic anode based on micro-arc oxidation technology is provided;
the preparation method of the electrolytic anode based on the micro-arc oxidation technology comprises the following steps:
s01: pretreatment of a substrate: firstly, degreasing a matrix, namely degreasing oil stains on the surface of an insoluble valve metal or valve metal alloy matrix, and then removing an oxide layer on the surface of the matrix by acid etching to increase the actual surface area of the matrix;
s02: intermediate layer preparation: adopting a micro-arc oxidation process, using different electric parameters, configuring different electrolytes, placing an insoluble valve metal or valve metal alloy matrix in an electrolytic cell as an anode, and forming a valve metal oxide intermediate layer on the surface of the matrix by in-situ growth;
s03: preparing a surface catalytic layer: noble metal solutions with different components and proportions are coated on the intermediate layer, high-temperature sintering is carried out at different temperatures, and catalytic layers with different contents and shapes are prepared by using a thermal decomposition method.
Further, the degreasing in S01 may be one or more processes selected from chemical degreasing, electrolytic degreasing, organic solvent degreasing, and the like.
Further, the acid etching in S01 may be one or more mixed acids selected from hydrofluoric acid, sulfuric acid, hydrochloric acid, oxalic acid, nitric acid, and the like.
Further, the electrical parameters described in S02 include current mode, current density, voltage, duty cycleRatio, pulse and frequency, wherein the current mode can be constant voltage method or constant current method, and the current density is 1-10A/dm 2 The voltage is 300-700V, the duty ratio is 0-20%, the pulse ratio is 1:1-5:1, and the frequency is 100-1000Hz.
Further, the different electrolytes described in S02 include one or more mixed electrolytes of silicate systems, sulfate systems, phosphate systems, aluminate systems, and the like.
Further, the preparation method of the catalytic layer in S03 comprises the steps of carrying out high-temperature sintering after each time of coating iridium and tantalum solution, wherein the total coating and sintering times are 5-30 times, the molar mass ratio of iridium to tantalum in each time of coating solution is consistent, and Ir is Ta=1:1-4:1; the high-temperature sintering temperature in S03 is set at 450-600 ℃ and the sintering time is 20min or more.
The invention has the beneficial effects that: the invention provides an electrolytic anode based on micro-arc oxidation technology and a preparation method thereof, which are compared with the prior common titanium-based IrO 2 -Ta 2 O 5 Compared with the mixed oxide anode (without an intermediate layer), the oxide intermediate layer prepared by the micro-arc oxidation technology grows on the surface of the base metal in situ, the surface of the oxide intermediate layer is honeycomb-shaped, has extremely strong binding force with the base and the catalytic layer, can effectively inhibit oxidation and passivation of the base and prevent the coating from falling off, and thus the service life of the electrode is prolonged. In addition, the middle layer with the special structure provides a framework for the catalytic layer, so that the number of catalytic active sites of the catalytic layer is obviously increased, the prepared electrode has low electrode potential, and the power consumption in the actual electrolysis process is reduced, thereby reducing the use cost of the anode. The electrolytic anode prepared by the process method has wide application prospect in the fields of electrolytic copper foil production, high-speed electrogalvanizing, electrolytic organic synthesis and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic view of an electrolytic anode based on micro-arc oxidation technology according to an embodiment of the present invention;
FIG. 2 is a surface SEM image of an oxide interlayer of example 5 of an electrolytic anode based on micro-arc oxidation techniques according to an embodiment of the present invention;
FIG. 3 is a cross-sectional SEM of an oxide interlayer of example 5 of an electrolytic anode based on micro-arc oxidation techniques according to an embodiment of the present invention;
FIG. 4 is a cross-sectional SEM of an electrolytic anode of example 5 of an electrolytic anode based on micro-arc oxidation technique according to an embodiment of the invention;
in the figure: 1. a titanium substrate; 2. an oxide interlayer; 3. IrO (IrO) 2 /TaO 5 A gradient catalytic layer.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
It should be understood that in the description of the embodiments of the present invention, the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings are merely for convenience in describing the embodiments of the present invention and to simplify the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the embodiments of the present invention. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more of the described features. In the description of embodiments of the invention, the meaning of "a number" is two or more, unless explicitly defined otherwise.
The invention aims to solve the problems of poor binding force, short service life, insufficient electrocatalytic performance and the like of the conventional titanium anode coating, and provides an electrolytic anode based on a micro-arc oxidation technology and a preparation method thereof. The anode consists of three parts: insoluble valve metal or valve metal alloy substrate, valve metal oxide intermediate layer, noble metal oxide catalytic layer. The anode plate after degreasing and acid etching is connected with the anode of a power supply by adopting a micro-arc oxidation process, the anode plate is placed in a prepared micro-arc oxidation electrolyte, electric parameters are set, the power supply is turned on, and a layer of oxide intermediate layer with a honeycomb structure is grown on the surface of a substrate in situ. The catalytic layer is coated on the intermediate layer by preparing solutions with different iridium and tantalum proportions, then sintered at high temperature, and a plurality of layers of uniform and complete catalytic layers are prepared by a thermal decomposition method repeatedly.
As shown in fig. 1-4, an electrolytic anode based on micro-arc oxidation technology according to an embodiment of the present invention includes an insoluble valve metal or valve metal alloy substrate, a valve metal oxide intermediate layer, and a noble metal oxide catalytic layer.
In some embodiments, the valve metal oxide interlayer comprises TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The thickness of the valve metal oxide intermediate layer is 0.1-1 mu m.
In some embodiments, the noble metal oxide catalyst layer comprises IrO 2 、Ta 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the The content of iridium in the noble metal oxide catalytic layer is 5-50g/m 2 。
In some embodiments, the insoluble valve metal or valve metal alloy substrate is titanium or a titanium alloy.
In addition, the preparation method of the electrolytic anode based on the micro-arc oxidation technology according to the embodiment of the invention comprises the following steps:
step S01, substrate pretreatment: firstly, degreasing a matrix, namely degreasing oil stains on the surface of an insoluble valve metal or valve metal alloy matrix, and then removing an oxide layer on the surface of the matrix by acid etching to increase the actual surface area of the matrix;
step S02, preparing an intermediate layer: adopting a micro-arc oxidation process, using different electric parameters, configuring different electrolytes, placing an insoluble valve metal or valve metal alloy matrix in an electrolytic cell as an anode, and forming a valve metal oxide intermediate layer on the surface of the matrix by in-situ growth;
step S03, preparing a surface catalytic layer: noble metal solutions with different components and proportions are coated on the intermediate layer, high-temperature sintering is carried out at different temperatures, and catalytic layers with different contents and shapes are prepared by using a thermal decomposition method.
In some specific preparation methods, the degreasing described in S01 may be one or more processes of chemical degreasing, electrolytic degreasing, organic solvent degreasing, and the like.
In some specific preparation methods, the acid etching described in S01 may be selected from one or more mixed acids of hydrofluoric acid, sulfuric acid, hydrochloric acid, oxalic acid, nitric acid, and the like.
In some specific preparation methods, the electrical parameters described in S02 include current mode, current density, voltage, duty cycle, pulse and frequency, wherein the current mode is selected from constant voltage method or constant current method, and the current density is 1-10A/dm 2 The voltage is 300-700V, the duty ratio is 0-20%, the pulse ratio is 1:1-5:1, and the frequency is 100-1000Hz.
In some specific methods of preparation, the different electrolytes described in S02 include one or more mixed electrolytes of silicate systems, sulfate systems, phosphate systems, aluminate systems, and the like.
In some specific preparation methods, the preparation method of the catalytic layer in S03 comprises the steps of carrying out high-temperature sintering after each time of coating iridium and tantalum solution, wherein the total coating and sintering times are 5-30 times, the molar mass ratio of iridium and tantalum in each time of coating solution is consistent, and Ir is ta=1:1-4:1; the high-temperature sintering temperature in S03 is set at 450-600 ℃ and the sintering time is 20min or more.
In order to make the technical purpose, technical scheme and beneficial effect of the present invention more clear, the present invention is further described below with reference to the accompanying drawings and examples. The scope of the invention is not limited to the following examples.
Example 1:
the embodiment provides an electrolytic anode based on a micro-arc oxidation technology and a preparation method thereof, and the electrolytic anode comprises a substrate 1, an intermediate layer 2 and a surface catalytic layer 3 as shown in figure 1. Wherein the middle layer 2 is grown on the outer surface of the substrate 1 in situ by using a micro-arc oxidation process, and the surface catalytic layer 3 is formed on the upper surface of the middle layer 2 by a coating and thermal decomposition method. The preparation process comprises the following steps:
pretreatment of a substrate: immersing industrial pure titanium plates (TA 1) with the specification of 200mm x 100mm x 8mm in a chemical degreasing agent for 1-2h, wherein the chemical degreasing agent comprises the following components: 15g/L sodium hydroxide, 35g/L trisodium phosphate, 10g/L sodium carbonate, 25ml/L OP-10. Soaking and boiling the mixture to be more than 95 ℃ and 20%wt of H after water washing 2 SO 4 And (3) acid etching for 1-2h, washing with water, and drying for later use.
Intermediate layer preparation: selecting a direct-current double-pulse micro-arc oxidation power supply, connecting a titanium substrate with the anode of the micro-arc oxidation power supply, and placing the titanium substrate in an electrolytic tank filled with a solution prepared in advance, wherein the components of the electrolyte are as follows: 5g/L sodium hexametaphosphate, 10g/L sodium silicate, 2g/L potassium titanium oxalate and 6g/L boric acid. The preparation is carried out by adopting a constant voltage method, the input voltage is set to be 600V, the duty ratio is set to be 6%, the positive and negative pulse ratio is set to be 1:1, the frequency is set to be 500Hz, and after the titanium substrate is electrified for 20min, as shown in figure 2, an off-white oxidation layer with the thickness of 500nm and a honeycomb-shaped microstructure is formed on the surface of the titanium substrate.
Preparing a surface catalytic layer: taking n-butanol-isopropanol (1:1) mixed solution as a solvent, adding H mixed in a certain proportion 2 IrCl 6 、TaCl 5 After full dissolution, coating liquid with the molar ratio of Ir and Ta of 7:3 is obtained, wherein the concentration of Ta in the coating liquid is 0.1mol/L. Uniformly coating the coating liquid on a titanium plate with an intermediate layer, and drying in an oven with the temperature of 90 ℃ after coatingDrying for 15min, and sintering in a furnace at 510 deg.C for 30-40min. Repeating the coating for 16 times to finally obtain the structure of Ti/TiO 2 /IrO 2 +Ta 2 O 5 Titanium anode (Iridium content 24 g/m) 2 Tantalum content of 8g/m 2 )。
Example 2:
the present embodiment provides an electrolytic anode based on micro-arc oxidation technology and its preparation method, which is basically the same as that in embodiment 1, except that a constant voltage method is selected for preparing the intermediate layer, and the input current ensures a current density of 3.5A/dm 2 。
Example 3:
this example provides an electrolytic anode based on micro-arc oxidation technology and a method for preparing the same, which is basically the same as in example 1, except that in preparing the intermediate layer: the duty cycle is 3%, the positive and negative pulse ratio is 3:1, and the frequency is 1000Hz.
Example 4:
this example provides an electrolytic anode based on micro-arc oxidation technology and a method for preparing the same, which is basically the same as in example 1, except that in preparing the intermediate layer: the electrolyte comprises the following components: 13g/L sodium metavanadate, 20g/L sodium hydroxide and 2g/L ammonium metavanadate.
Example 5:
this example provides an electrolytic anode based on micro-arc oxidation technology and a method for preparing the same, which is basically the same as in example 1, except that in preparing the intermediate layer: the constant voltage method is adopted, and the input current ensures that the current density is 3.5A/dm 2 The duty cycle is 3%, the positive and negative pulse ratio is 3:1, and the frequency is 1000Hz.
Comparative example 1:
the present comparative example provides an electrolytic anode based on micro-arc oxidation technology and a method for preparing the same, which is basically the same as the method in example 1, except that the anode does not prepare an intermediate layer, and the surface catalytic layer is directly prepared after the substrate is pretreated, thus obtaining a junctionIs constructed as Ti/IrO 2 +Ta 2 O 5 Is a titanium anode.
Comparative example 2:
this comparative example provides an electrolytic anode based on micro-arc oxidation technology and a method for preparing the same, which is basically the same as that in example 1, except that the preparation method of the intermediate layer is different, and the preparation method of the surface catalytic layer is the same.
Intermediate layer preparation: tiCl having a Ti concentration of 0.1mol/L 4 The solution is uniformly coated on a titanium plate, dried in an oven at 90 ℃ for 15min after coating, and then placed in a furnace at 510 ℃ for thermal decomposition for 30-40min. Repeating the coating for 3 times to obtain TiO with the thickness of 500nm 2 Is a layer of the intermediate layer.
The electrodes prepared in examples 1 to 5 and comparative examples 1 to 2 were subjected to an electrode potential test, an accelerated lifetime test and a coating binding force test under the following conditions:
current density: 50A/m 2
Temperature: 25 DEG C
Electrolyte solution: 150g/L sulfuric acid solution
A reference electrode: mercurous sulfate
And (3) cathode: zr (Zr)
Polar distance: 1cm
Accelerated life test conditions were as follows:
current density: 500A/m 2
Electrolysis temperature: 60 DEG C
Electrolyte solution: 150g/L sulfuric acid solution
A counter electrode: zr (Zr)
Polar distance: 1cm
The film adhesive force test adopts an automatic scratch tester test, and the test conditions are as follows:
detection mode: acoustic emission mode
Load loading: 100N
The loading mode is as follows: unidirectional continuous loading
Scratch length: 6mm of
Loading rate: 60N/min
The accelerated life test uses an electrolytic voltage 1V higher than the initial voltage as the end of life, and the binding force test result is the critical load value at which the coating starts to break, and the result is shown in Table 1.
TABLE 1 comparison of the Properties of examples and comparative examples
Comparing examples 1-5 with comparative example 2, it is evident that the introduction of the micro-arc oxidation intermediate layer can significantly improve the binding force between the whole coating and the substrate, reduce the electrode potential, and significantly improve the working life. Comparing examples 2-4 with example 1, it can be seen that by adjusting the current mode, electrical parameters, and electrolyte composition in the middle layer preparation process, the adhesion of the coating is affected, thereby improving or reducing the service life. Comparing example 5 with example 1, it is clear that by selecting appropriate current mode and electrical parameters, the interlayer structure can be improved to a greater extent, thereby improving adhesion and prolonging service life.
In summary, by means of the technical scheme of the invention, the electrolytic anode based on the micro-arc oxidation technology and the preparation method thereof provided by the invention are compared with the titanium-based IrO commonly used at present 2 -Ta 2 O 5 Compared with the mixed oxide anode (without an intermediate layer), the oxide intermediate layer prepared by the micro-arc oxidation technology grows on the surface of the base metal in situ, the surface of the oxide intermediate layer is honeycomb-shaped, has extremely strong binding force with the base and the catalytic layer, can effectively inhibit oxidation and passivation of the base and prevent the coating from falling off, and thus the service life of the electrode is prolonged. In addition, the middle layer with the special structure provides a framework for the catalytic layer, so that the number of catalytic active sites of the catalytic layer is obviously increased, the prepared electrode has low electrode potential, and the power consumption in the actual electrolysis process is reduced, thereby reducing the use cost of the anode. The electrolytic anode prepared by the process method has wide application prospect in the fields of electrolytic copper foil production, high-speed electrogalvanizing, electrolytic organic synthesis and the like.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. An electrolytic anode based on micro-arc oxidation technology is characterized by comprising an insoluble valve metal or valve metal alloy matrix, a valve metal oxide intermediate layer and a noble metal oxide catalytic layer.
2. The electrolytic anode based on micro-arc oxidation technology according to claim 1, wherein the valve metal oxide intermediate layer comprises TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The thickness of the valve metal oxide intermediate layer is 0.1-1 mu m.
3. The micro-arc oxidation technology-based electrolytic anode according to claim 1, wherein the noble metal oxide catalyst layer is composed of IrO 2 、Ta 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the The content of iridium in the noble metal oxide catalytic layer is 5-50g/m 2 。
4. The electrolytic anode based on micro-arc oxidation technology according to claim 1, wherein the insoluble valve metal or valve metal alloy substrate is titanium or titanium alloy.
5. A method for preparing an electrolytic anode based on micro-arc oxidation technology according to any one of claims 1-4, characterized in that it comprises the following steps:
s01: pretreatment of a substrate: firstly, degreasing a matrix, namely degreasing oil stains on the surface of an insoluble valve metal or valve metal alloy matrix, and then removing an oxide layer on the surface of the matrix by acid etching to increase the actual surface area of the matrix;
s02: intermediate layer preparation: adopting a micro-arc oxidation process, using different electric parameters, configuring different electrolytes, placing an insoluble valve metal or valve metal alloy matrix in an electrolytic cell as an anode, and forming a valve metal oxide intermediate layer on the surface of the matrix by in-situ growth;
s03: preparing a surface catalytic layer: noble metal solutions with different components and proportions are coated on the intermediate layer, high-temperature sintering is carried out at different temperatures, and catalytic layers with different contents and shapes are prepared by using a thermal decomposition method.
6. The method for preparing an electrolytic anode based on micro-arc oxidation technology according to claim 5, wherein the degreasing in S01 is one or more of chemical degreasing, electrolytic degreasing, organic solvent degreasing, and the like.
7. The method for preparing an electrolytic anode based on micro-arc oxidation technology according to claim 5, wherein the acid etching in S01 is selected from one or more mixed acids of hydrofluoric acid, sulfuric acid, hydrochloric acid, oxalic acid, nitric acid, etc.
8. The method of claim 5, wherein the electrical parameters in S02 include current mode, current density, voltage, duty cycle, pulse ratio and frequency, wherein the current mode is selected from constant voltage method or constant current method, and the current density is 1-10A/dm 2 The voltage is 300-700V, the duty cycle is 0-20%, the pulse ratio is 1:1-5:1, and the frequency is 100-1000Hz.
9. The method according to claim 5, wherein the different electrolytes in S02 include one or more mixed electrolytes of silicate system, sulfate system, phosphate system, aluminate system, etc.
10. The method for preparing the electrolytic anode based on the micro-arc oxidation technology according to claim 5, wherein the preparation method of the catalytic layer in S03 is to perform high-temperature sintering after each application of iridium and tantalum solution, the total application and sintering times are 5-30 times, the molar mass ratio of iridium and tantalum in each application solution is consistent, and Ir: ta=1:1-4:1; the high-temperature sintering temperature in S03 is set at 450-600 ℃ and the sintering time is 20min or more.
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