CN114892237B - Method for improving performance of titanium electrode by improving pretreatment process - Google Patents

Method for improving performance of titanium electrode by improving pretreatment process Download PDF

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CN114892237B
CN114892237B CN202210304172.2A CN202210304172A CN114892237B CN 114892237 B CN114892237 B CN 114892237B CN 202210304172 A CN202210304172 A CN 202210304172A CN 114892237 B CN114892237 B CN 114892237B
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titanium
sand
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titanium substrate
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CN114892237A (en
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冯庆
杨瑞锋
贾波
郝小军
任鹏
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Xian Taijin Xinneng Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
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    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F17/00—Multi-step processes for surface treatment of metallic material involving at least one process provided for in class C23 and at least one process covered by subclass C21D or C22F or class C25
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Abstract

The invention discloses a method for improving the performance of a titanium electrode by improving a pretreatment process, which specifically comprises the following steps: 1) Selecting a titanium substrate and processing and forming; 2) Mechanically blasting sand; 3) Performing thermal correction; 4) Acid etching; 5) Preparation of NH 4 F/H 2 SO 4 Mixing the solutions; 6) Anodic oxidation: 7) Preparing a noble metal solution; 8) And (5) coating and sintering. The method of the invention increases the anodic oxidation process based on the traditional sand blasting and oxalic acid etching, and sets reasonable parameters and conditions, and forms porous TiO on the surface of the titanium substrate through the synergistic effect of the two 2 The structure not only has obvious specific surface area of the titanium substrate, but also improves the binding force of the coating and the titanium substrate, effectively reduces the consumption of noble metal, prolongs the service life of the titanium electrode, and can greatly reduce the preparation cost of the titanium electrode under the same service life.

Description

Method for improving performance of titanium electrode by improving pretreatment process
Technical Field
The invention belongs to the technical field of titanium electrode material preparation, and particularly relates to a method for improving titanium electrode performance by improving a pretreatment process.
Background
Since 1786 l.galvani found an electrolytic process, human research and application of electrode materials for electrolytic processes has been for over 200 years. In the development history of electrode materials, a graphite electrode, a lead-based alloy electrode and a titanium-based active coating electrode form the development history of the electrode materials, and especially the continuous perfection of the titanium-based active coating electrode technology in recent 40 years drives the rapid development of the modern electrolytic industry technology.
It is well known that the working life of a titanium electrode is an extremely important indicator of its performance. In recent years, with the rapid development of the market, the requirements of the market on the electrode quality are higher and higher, however, the higher service life needs relatively more noble metal content, but with the annual rising of noble metal price, the preparation cost of the titanium electrode is greatly increased, which limits the development of the noble metal coated titanium electrode to a great extent. In addition, the influence factors on the working life of the titanium electrode are more, wherein the most critical is the pretreatment process of the titanium material, and the better pretreatment process can increase the binding force between the titanium substrate and the active coating, increase the service life of the titanium electrode and achieve the aim of reducing the cost. Therefore, how to find a method for reducing the manufacturing cost of the electrode under the same service life is a problem to be solved in the industry.
In view of the above, the present inventors have proposed a method for improving the performance of a titanium electrode by improving the pretreatment process, so as to overcome the drawbacks of the prior art.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for improving the performance of a titanium electrode by improving the pretreatment process, which increases the specific surface area of a titanium substrate obviously by the synergistic effect of two modes by adding an anodic oxidation process on the basis of traditional sand blasting and oxalic acid etching, so that porous TiO is formed 2 The structure improves the binding force between the coating and the titanium substrate, effectively reduces the consumption of noble metal, prolongs the service life of the titanium electrode, improves the performance of the titanium electrode and reduces the preparation cost of the titanium electrode.
The invention aims at solving the problems by the following technical scheme:
a method for improving the performance of a titanium electrode by improving the pretreatment process, the method comprising in particular the steps of:
step one, selecting a titanium substrate and processing and forming
The titanium base material is TA1 titanium, and is cut and molded according to the required size;
step two, mechanical sand blasting
Performing sand blasting on the titanium base material processed and molded in the first step, wherein the surface of the titanium base material is required to be matte; wherein the pressure of sand blasting is more than or equal to 0.5MPa, and the distance between the nozzle of a sand blaster and the titanium substrate is less than or equal to 1.5cm;
step three, thermal calibration
The titanium base material after the sand blasting treatment in the second step is subjected to heavy pressure, and is naturally cooled to room temperature after being subjected to heat preservation for 3 hours at 550-600 ℃;
step four, acid etching
Soaking the titanium substrate subjected to the thermal correction treatment in hydrochloric acid solution with the concentration of 3-15% for 5-48 h, removing sand remained on the surface of the titanium substrate, washing cleanly, placing the titanium substrate in oxalic acid solution with the concentration of 5-15% for boiling, etching for 2-5 h, taking out, washing cleanly with tap water and deionized water respectively, and airing;
step five, preparing NH 4 F/H 2 SO 4 Mixed solution
NH concentration of 0.1mol/L 4 F and H with a concentration of 1mol/L 2 SO 4 Preparing with equal volume, and stirring to form NH 4 F/H 2 SO 4 Mixing the solutions, and sealing and preserving;
step six, anodic oxidation
Taking the titanium substrate subjected to the acid etching treatment in the step four as an anode, selecting a cathode electrode material, and preparing NH (NH) in the step five 4 F/H 2 SO 4 The solution is used as electrolyte, anodic oxidation is carried out under constant pressure, tap water is used for washing after oxidation, deionized water is used for ultrasonic washing, and the solution is dried;
step seven, preparing noble metal solution;
eighth step of coating and sintering
Uniformly coating the noble metal solution prepared in the seventh step on the surface of the titanium substrate subjected to the sixth step anodic oxidation treatment, placing the titanium substrate in a sintering furnace at 450 ℃ for 10min, taking out the titanium substrate after sintering, naturally cooling the titanium substrate to room temperature, and repeating the above processes until the ruthenium content in the coating is more than or equal to 0.6mg/cm 2 The iridium content is more than or equal to 0.3mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the And after the final brushing, preserving heat for 1h in a sintering furnace, taking out, and naturally cooling to room temperature to obtain the titanium electrode.
In the first step, the TA1 titanium material is selected from pure titanium plates or pure titanium coiled materials, and the thickness of the TA1 titanium material is more than or equal to 0.5mm.
Further, the sand mould subjected to sand blasting treatment in the second step is one or more of steel sand, brown corundum, white corundum, quartz sand, copper ore sand, silicon carbide and Hainan sand, and the size of the sand is 10-40 meshes.
Further, in the step six, when the anodic oxidation is performed, the oxidation voltage is set to be 5-30V, and the oxidation time is set to be 20-180 min.
Further, in the sixth step, the cathode electrode material is a titanium plate, a stainless steel plate, a nickel plate or a zirconium plate.
Further, the seven noble metal solution is mainly composed of RuCl 3 ·3H 2 O, butyl titanate, chloroiridium acid, hydrochloric acid and n-butyl alcohol, and the noble metal solution comprises the following ruthenium iridium titanium molar ratio: ru: ir: ti=3:1:6, the concentration range is 0.5-0.7 mol/L.
Compared with the prior art, the invention has the following beneficial effects:
the method for improving the performance of the titanium electrode by improving the pretreatment process has the following advantages compared with the traditional process: (1) The anodic oxidation process is added on the basis of traditional sand blasting and oxalic acid etching, the specific surface of the titanium substrate is obviously increased through the synergistic effect of the two modes, and the anodic oxidation process is a relatively uniform process in solution, so that the phenomenon of uneven surface roughness of the titanium substrate caused by mechanical sand blasting is reduced to a certain extent; (2) The method does not limit the shape of the titanium base material, and compared with the traditional sand blasting, the surface of the titanium material treated by the process belongs to porous TiO 2 The specific surface area of the structure is increased, the binding force between the coating and the substrate is enhanced, the service life of the electrode is prolonged, and the preparation cost of the electrode can be reduced under the same service life; (3) The method has simple treatment process and easy operation, and is suitable for industrial mass production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate principles of the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to a person skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a flow chart of a method of improving the performance of a titanium electrode by improving the pretreatment process of the present invention;
FIG. 2 is a graph showing the microscopic morphology of a titanium substrate after the sandblasting+oxalic acid etching treatment in example 1 of the present invention;
FIG. 3 is a graph showing the microscopic morphology of the titanium substrate after the sand blasting, oxalic acid etching and anodic oxidation treatment in example 1 of the present invention.
Detailed Description
Reference will now be made in detail to exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, the same numbers in different drawings refer to the same or similar elements, unless otherwise indicated. The implementations described in the following exemplary examples do not represent all implementations consistent with the invention. Rather, they are merely examples of devices that are consistent with aspects of the invention that are set forth in the following claims.
The present invention will be described in further detail below with reference to the drawings and examples for better understanding of the technical solutions of the present invention to those skilled in the art.
Referring to fig. 1, the present invention provides a method for improving the performance of a titanium electrode by improving the pretreatment process, comprising the following specific steps:
step one, selecting a titanium substrate and processing and forming:
specifically, the titanium substrate is generally TA1 titanium, such as pure titanium plate or pure titanium coiled material, the thickness of which is more than or equal to 0.5mm, and is cut and molded according to the required size;
step two, mechanical sand blasting:
specifically, the titanium substrate after the processing and forming in the step one is subjected to sand blasting treatment, wherein a sand mold subjected to sand blasting treatment is one or more of steel sand, brown corundum, white corundum, quartz sand, copper ore sand, silicon carbide and Hainan sand, the size of the sand is 10-40 meshes, and the surface of the titanium substrate is required to be matte after sand blasting treatment; wherein the pressure of sand blasting is more than or equal to 0.5MPa, and the distance between the nozzle of a sand blaster and the titanium substrate is less than or equal to 1.5cm;
step three, thermal calibration
Specifically, the titanium base material subjected to sand blasting treatment in the second step is subjected to heavy pressure, the weight of the heavy material is 1-3 tons, the weight can be specifically determined according to the correction quantity and the flatness, and the titanium base material is naturally cooled to room temperature after heat preservation for 3 hours at 550-600 ℃;
step four, acid etching
Soaking the titanium substrate subjected to the thermal correction treatment in hydrochloric acid solution with the concentration of 3-15% for 5-48 hours (the soaking concentration and time are determined according to the residual quantity of sand grains on the surface, the sand grains are removed), removing the residual sand on the surface of the titanium substrate, washing the titanium substrate, placing the titanium substrate in oxalic acid solution with the concentration of 5-15% for boiling, etching the titanium substrate for 2-5 hours, taking out the titanium substrate (the oxalic acid concentration corresponds to the pickling time, the pickling time is long with small concentration and the pickling time is short with large concentration, and only the surface oxide skin is removed), washing the titanium substrate with tap water and deionized water, and airing the titanium substrate;
step five, preparing NH 4 F/H 2 SO 4 Mixed solution
Concentration of NH is 0.1mol/L 4 F and H with a concentration of 1mol/L 2 SO 4 Preparing with equal volume, and stirring to form NH 4 F/H 2 SO 4 Mixing the solutions, and sealing and preserving;
step six, anodic oxidation
Taking the titanium substrate subjected to the acid etching treatment in the step IV as an anode, additionally selecting a cathode electrode material, wherein the length and the width of the cathode electrode material are larger than those of the titanium substrate subjected to the acid treatment, such as a titanium plate, a stainless steel plate, a nickel plate, a zirconium plate or a platinized material, and the NH prepared in the step V 4 F/H 2 SO 4 The mixed solution is used as electrolyte to carry out anodic oxidation under constant pressure, the oxidation voltage is set to be 5-30V, the oxidation time is set to be 20-180 min, and the oxidation is carried outRespectively washing with tap water, ultrasonically washing with deionized water, and air drying;
step seven, preparing noble metal solution;
specifically, the noble metal solution is composed of RuCl 3 ·3H 2 O, butyl titanate, chloroiridic acid, hydrochloric acid and n-butyl alcohol, and the noble metal solution comprises ruthenium iridium titanium in a molar ratio of: ru: ir: ti=3:1:6, at a concentration of 0.6mol/L;
step eight, coating and sintering:
uniformly coating the noble metal solution prepared in the seventh step on the surface of the titanium substrate subjected to the sixth step anodic oxidation treatment, placing the titanium substrate in a sintering furnace at 450 ℃ for 10min, taking out the titanium substrate after sintering, naturally cooling the titanium substrate to room temperature, and repeating the above processes until the ruthenium content in the coating is more than or equal to 0.6mg/cm 2 The iridium content is more than or equal to 0.3mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the And after the final brushing, preserving heat for 1h in a sintering furnace, taking out, and naturally cooling to room temperature to obtain the titanium electrode.
To further verify the effect of the preparation method of the present invention, the inventors have carried out the following specific implementation
Example 1
1) Selecting a TA1 pure titanium plate with the length of 1.0mm, and mechanically cutting into three titanium substrates with the length and width of 100mm respectively, namely, the dimensions of the titanium substrates are 100 x 1.0mm;
2) Performing sand blasting treatment on the titanium base material processed and molded in the step 1), wherein 15-mesh white corundum is selected as a sand mold, the sand blasting pressure is 0.6MPa, the minimum distance between a nozzle of a sand blaster and the titanium base material is 1cm, and the surface of the titanium base material after the sand blasting treatment is required to be matte;
3) Pressing the titanium substrate subjected to the sand blasting treatment in the step 2) under the condition of stainless steel with the weight of about 2t, preserving heat for 3 hours at 570 ℃, and naturally cooling to room temperature;
4) Soaking the titanium material subjected to the thermal correction treatment in the step 3) in hydrochloric acid solution with the concentration of 10% for 15 hours, removing sand remained on the surface of the titanium substrate, and washing the titanium substrate with tap water; placing the glass in oxalic acid solution with the concentration of 10% for boiling, etching for 2.5 hours, taking out, washing with high-pressure tap water, removing floating ash, washing with deionized water, airing, wherein the average roughness of the surface is Ra=5.3 mu m, and observing the microstructure as shown in figure 2;
5) NH concentration of 0.1mol/L 4 F and H with a concentration of 1mol/L 2 SO 4 Preparing with equal volume, and stirring to form NH 4 F/H 2 SO 4 Mixing the solutions, and sealing and preserving;
6) Taking the titanium substrate subjected to the acid etching treatment in the step 4) as an anode, alternatively taking a pure titanium plate (the length and the width are larger than those of the titanium substrate subjected to the acid treatment) as a cathode material, and taking NH prepared in the step 5) 4 F/H 2 SO 4 The solution is used as electrolyte, anodic oxidation is carried out under constant pressure, the oxidation voltage is set to 15V, and the oxidation time is set to 60min; after the oxidation is finished, washing with tap water, washing with deionized water in an ultrasonic manner, and airing, wherein the average roughness Ra=6.3 mu m of the surface is shown in the figure 3; the method comprises the steps of carrying out a first treatment on the surface of the
7) Preparing a metal solution by using ruthenium trichloride, butyl titanate, chloroiridium acid, hydrochloric acid and n-butanol, wherein Ru: ir: ti=3:1:6 (molar ratio), and the concentration of the prepared noble metal coating liquid is 0.6mol/L for standby;
8) Uniformly coating the noble metal coating solution prepared in the step 7) on the titanium substrate subjected to acid treatment by utilizing a wool brush, naturally airing for 2min to uniformly diffuse the coating solution, then placing the coating solution in a baking oven at 120 ℃ to completely volatilize the solvent, then placing the coating solution in a sintering furnace at 450 ℃ for sintering for 10min, taking out, and naturally cooling to room temperature. Repeating the steps of brushing, sintering and the like until the ruthenium content in the coating is more than or equal to 0.6mg/cm 2 The iridium content is more than or equal to 0.3mg/cm 2 And finally, carrying out heat preservation for 1h in a sintering furnace after the coating, and taking out the titanium electrode, and naturally cooling the titanium electrode to room temperature to obtain the titanium electrode.
Example 2
1) Selecting a TA1 pure titanium plate with the length of 1.5mm, and mechanically cutting into three titanium base materials with the length and the width of 80mm respectively, namely, the titanium base materials with the size of 80 x 1.5mm;
2) Carrying out sand blasting on the titanium base material processed and molded in the step 1), wherein a sand mould adopts 40-mesh steel sand, the sand blasting pressure is 0.8MPa, the minimum distance between a nozzle of a sand blaster and the titanium base material is 1.2cm, and the surface of the titanium base material after sand blasting is required to be matte;
3) Pressing the titanium substrate subjected to the sand blasting treatment in the step 2) under stainless steel with the weight of about 3t, preserving heat for 3 hours at 600 ℃, and naturally cooling to room temperature;
4) Soaking the titanium material subjected to the thermal correction treatment in the step 3) in a hydrochloric acid solution with the concentration of 15% for 5 hours, removing sand remained on the surface of the titanium substrate, and washing the titanium substrate with tap water; boiling in 5% oxalic acid solution, etching for 5 hr, taking out, washing with high pressure tap water to remove floating ash, washing with deionized water, and air drying to obtain surface with average roughness of Ra=5.8 μm;
5) NH concentration of 0.1mol/L 4 F and H with a concentration of 1mol/L 2 SO 4 Preparing with equal volume, and stirring to form NH 4 F/H 2 SO 4 Mixing the solutions, and sealing and preserving;
6) Taking the titanium substrate subjected to the acid etching treatment in the step 4) as an anode, additionally selecting a stainless steel plate (the length and the width are larger than those of the titanium substrate subjected to the acid treatment) as a cathode material, and taking the NH prepared in the step 5) 4 F/H 2 SO 4 The solution is used as electrolyte, anodic oxidation is carried out under constant pressure, the oxidation voltage is set to be 5V, and the oxidation time is set to be 180min; after the oxidation is finished, washing with tap water, ultrasonic washing with deionized water, and airing, wherein the average surface roughness Ra=7.2 mu m;
7) Preparing a metal solution by using ruthenium trichloride, butyl titanate, chloroiridium acid, hydrochloric acid and n-butanol, wherein Ru: ir: ti=3:1:6 (molar ratio), and the concentration of the prepared noble metal coating liquid is 0.7mol/L for standby;
8) Uniformly coating the noble metal coating solution prepared in the step 7) on the titanium substrate subjected to acid treatment by utilizing a wool brush, naturally airing for 2min to uniformly diffuse the coating solution, then placing the coating solution in a baking oven at 120 ℃ to completely volatilize the solvent, then placing the coating solution in a sintering furnace at 450 ℃ for sintering for 10min, taking out, and naturally cooling to room temperature. Repeating the steps of brushing, sintering and the like until the ruthenium content in the coating is more than or equal to 0.6mg/cm 2 The iridium content is more than or equal to 0.3mg/cm 2 And finally, carrying out heat preservation for 1h in a sintering furnace after the coating, and taking out the titanium electrode, and naturally cooling the titanium electrode to room temperature to obtain the titanium electrode.
Example 3
1) Selecting a TA1 pure titanium plate with the length of 0.8mm, and mechanically cutting into three titanium base materials with the length and width of 100mm respectively, namely, the dimension of 100 x 0.8mm;
2) Performing sand blasting treatment on the titanium base material processed and molded in the step 1), wherein a sand mold adopts 10-mesh quartz sand, the sand blasting pressure is 0.5MPa, the minimum distance between a nozzle of a sand blaster and the titanium base material is 1.5cm, and the surface of the titanium base material after the sand blasting treatment is required to be matte;
3) Pressing the titanium substrate subjected to the sand blasting treatment in the step 2) under stainless steel with the weight of about 1t, preserving heat for 3 hours at 550 ℃, and naturally cooling to room temperature;
4) Soaking the titanium material subjected to the thermal correction treatment in the step 3) in hydrochloric acid solution with the concentration of 3% for 48 hours, removing sand remained on the surface of the titanium substrate, and washing the titanium substrate with tap water; boiling in 15% oxalic acid solution, etching for 2 hr, taking out, washing with high pressure tap water to remove floating ash, washing with deionized water, and air drying to obtain surface with average roughness of Ra=5.2 μm;
5) NH concentration of 0.1mol/L 4 F and H with a concentration of 1mol/L 2 SO 4 Preparing with equal volume, and stirring to form NH 4 F/H 2 SO 4 Mixing the solutions, and sealing and preserving;
6) Taking the titanium substrate subjected to the acid etching treatment in the step 4) as an anode, additionally selecting a nickel plate zirconium plate (the length and the width are larger than those of the titanium substrate subjected to the acid treatment) as a cathode material, and taking the NH prepared in the step 5) 4 F/H 2 SO 4 The solution is used as electrolyte, anodic oxidation is carried out under constant pressure, the oxidation voltage is set to be 30V, and the oxidation time is set to be 20min; after the oxidation is finished, washing with tap water, ultrasonic washing with deionized water, and airing, wherein the average surface roughness Ra=6.6 mu m;
7) Preparing a metal solution by using ruthenium trichloride, butyl titanate, chloroiridium acid, hydrochloric acid and n-butanol, wherein Ru: ir: ti=3:1:6 (molar ratio), and the concentration of the prepared noble metal coating liquid is 0.7mol/L for standby;
8) Uniformly coating the noble metal coating solution prepared in the step 7) on the titanium substrate subjected to acid treatment by using a wool brushNaturally airing for 2min to uniformly diffuse the coating liquid, then placing in a baking oven at 120 ℃ to completely volatilize the solvent, then placing in a sintering furnace at 450 ℃ to sinter for 10min, taking out, and naturally cooling to room temperature. Repeating the steps of brushing, sintering and the like until the ruthenium content in the coating is more than or equal to 0.6mg/cm 2 The iridium content is more than or equal to 0.3mg/cm 2 And finally, carrying out heat preservation for 1h in a sintering furnace after the coating, and taking out the titanium electrode, and naturally cooling the titanium electrode to room temperature to obtain the titanium electrode.
The description is as follows: in the above 3 examples, one titanium substrate was completed according to all the above steps, respectively, as an experimental group; the other titanium substrate is not subjected to the relevant steps of oxidation treatment, and the other conditions are the same, namely the titanium electrode pretreatment is subjected to sand blasting and acid etching treatment, so that a control group 1 is formed; the remaining 1 piece of titanium substrate was not subjected to the steps related to the blast + acid etching treatment, and the remaining conditions were the same, i.e., the titanium electrode pretreatment was subjected to the oxidation treatment, as a control group 2, and the roughness after the oxidation treatment of the three examples were respectively 3.7 μm, 3.5 μm and 3.8 μm.
In order to verify the effect of the titanium electrode prepared by the invention, the following tests were carried out on the service lives of each implementation and control group respectively, the test conditions of which are referred to GB/T22839-2010, in particular to the electrolyte: h of 1mol/L 2 SO 4 The method comprises the steps of carrying out a first treatment on the surface of the Electrolyte temperature: 40 ℃ +/-2 ℃; anode current density: 20000A/m 2 The test results are shown in the following table:
Figure BDA0003564174440000121
in conclusion, the invention combines oxidation treatment based on the traditional pretreatment process (sand blasting and acid etching), and forms porous TiO on the surface of the titanium material by the synergistic effect of the two modes 2 The structure remarkably obtains the titanium substrate with larger specific surface area, improves the binding force between the titanium electrode coating and the titanium substrate, and effectively reduces the consumption of noble metal, thereby reducing the preparation cost of the electrode and meeting the market demand better.
The foregoing is only a specific embodiment of the invention to enable those skilled in the art to understand or practice the 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 will be understood that the 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 (3)

1. A method for improving the performance of a titanium electrode by improving the pretreatment process, characterized in that it comprises in particular the following steps:
step one, selecting a titanium substrate and processing and forming
The titanium base material is TA1 titanium, and is cut and molded according to the required size;
step two, mechanical sand blasting
Performing sand blasting on the titanium base material processed and molded in the first step, wherein the surface of the titanium base material is required to be matte; wherein the pressure of sand blasting is more than or equal to 0.5MPa, the distance between the nozzle of a sand blasting machine and a titanium substrate is less than or equal to 1.5cm, the sand mould subjected to sand blasting is one or more of steel sand, brown corundum, white corundum, quartz sand, copper ore sand, silicon carbide and Hainan sand, and the size of the sand is 10-40 meshes;
step three, thermal calibration
The titanium base material after the sand blasting treatment in the second step is subjected to heavy pressure, and is naturally cooled to room temperature after being subjected to heat preservation for 3 hours at 550-600 ℃;
step four, acid etching
Soaking the titanium substrate subjected to the thermal correction treatment in hydrochloric acid solution with the concentration of 3-15% for 5-48 h, removing sand remained on the surface of the titanium substrate, washing cleanly, placing the titanium substrate in oxalic acid solution with the concentration of 5-15% for boiling, etching for 2-5 h, taking out, washing cleanly with tap water and deionized water respectively, and airing;
step five, preparing NH 4 F/H 2 SO 4 Mixed solution
NH concentration of 0.1mol/L 4 F and H with a concentration of 1mol/L 2 SO 4 Preparing with equal volume, and stirring to form NH 4 F/H 2 SO 4 Mixing the solutions, and sealing and preserving;
step six, anodic oxidation
Taking the titanium base material subjected to the acid etching treatment in the step four as an anode, additionally selecting a titanium plate, a stainless steel plate, a nickel plate or a zirconium plate as a cathode electrode material, and taking NH prepared in the step five as a cathode electrode material 4 F/H 2 SO 4 Taking the solution as electrolyte, performing anodic oxidation for 20-180 min at constant pressure of 5-30V, respectively washing with tap water after oxidation, ultrasonically washing with deionized water, and airing;
step seven, preparing noble metal solution;
eighth step of coating and sintering
Uniformly coating the noble metal solution prepared in the seventh step on the surface of the titanium substrate subjected to the sixth step anodic oxidation treatment, placing the titanium substrate in a sintering furnace at 450 ℃ for 10min, taking out the titanium substrate after sintering, naturally cooling the titanium substrate to room temperature, and repeating the above processes until the ruthenium content in the coating is more than or equal to 0.6mg/cm 2 The iridium content is more than or equal to 0.3mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the And after the final brushing, preserving heat for 1h in a sintering furnace, taking out, and naturally cooling to room temperature to obtain the titanium electrode.
2. The method for improving the performance of a titanium electrode by improving the pretreatment process according to claim 1, wherein in the first step, the TA1 titanium material is selected from pure titanium plate material or pure titanium coiled material, and the thickness of the pure titanium plate material or the pure titanium coiled material is more than or equal to 0.5mm.
3. The method for improving the performance of a titanium electrode by improving the pretreatment process according to claim 1, wherein the step of the seven noble metal solution is mainly composed of RuCl 3 ·3H 2 O, butyl titanate, chloroiridium acid, hydrochloric acid and n-butyl alcohol, and the noble metal solution comprises the following ruthenium iridium titanium molar ratio: ru: ir: ti=3:1:6, the concentration range is 0.5-0.7 mol/L.
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