CN210048854U - Preparation system of titanium-based coating titanium anode - Google Patents
Preparation system of titanium-based coating titanium anode Download PDFInfo
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- CN210048854U CN210048854U CN201822259434.XU CN201822259434U CN210048854U CN 210048854 U CN210048854 U CN 210048854U CN 201822259434 U CN201822259434 U CN 201822259434U CN 210048854 U CN210048854 U CN 210048854U
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Abstract
The utility model belongs to the technical field of the preparation of electrochemistry industry titanium electrode, a preparation system of titanium base coating titanium anode is related to, specifically include following step: the pretreatment of the titanium substrate, namely degreasing → activation → laser etching → titanium chip removal → acid treatment → ultrasonic cleaning → drying → coating sintering → finished product. According to the preparation system, the coarsening treatment is carried out on the surface of the titanium substrate by using the laser etching system, the system is simple to use and pollution-free, oxide skin generated by the titanium substrate can be quickly treated, the acid solution is not needed to be treated for a long time, any regular coarsening arrangement can be obtained, the coating is easily filled into gaps of a grid, a uniform and compact structure is obtained, the working strength of large current can be borne, and the corrosion resistance is high.
Description
Technical Field
The utility model belongs to the technical field of the preparation of electrochemistry industry titanium electrode, a preparation system of titanium base coating titanium anode is related to.
Background
Titanium anodes are widely used in solution-related industries such as chlor-alkali industry, hypochlorite, persulfate, electrolytic water treatment, industrial water treatment, hydrometallurgy, aluminum foil and copper foil manufacturing, steel sheet galvanization, cathodic protection, seawater desalination, electroplating industry, and the like. The lifetime of a titanium anode is directly affected by the preparation process, the coating formulation, the thickness of the coating, and the preparation process and the coating formulation are different for each different anode. The coated titanium anode is prepared by using titanium as a substrate and performing certain surface treatment to obtain a canine-shaped and uneven pitted surface with a large specific surface area, so that the surface of the anode is roughened, and the adhesive force of the coating is enhanced.
In the traditional anode manufacturing process, the coating conditions of the coating can be achieved only through the processes of oil removal, acid etching, activation treatment and the like, the time is long, the labor amount is large, and the environment is affected. In addition, the substrate is susceptible to scratching and damage during handling and transport. The coarsening process is that through mechanical sand blasting, under certain pressure, direct injection or sand blasting at an angle of 30 degrees is carried out by selecting proper abrasive materials, the plate surface is easy to deform seriously in the sand blasting process, later-stage thermal sizing is needed, the process can cause the oxide skin to be too thick, the acid treatment is improper, and the treatment time is too long or too short, so that the roughness of the matrix can be influenced.
Some electrode experts in China have studied to obtain a roughened titanium-based surface by acid etching treatment. He considered the acid treated system to be 20% H
2SO
4Treating at a temperature of more than 95 ℃ for 2-3 h, or treating at a temperature of more than 30% HCl and 90 ℃ for 2-3 h; or at 10% H2C
2O
4And treating for 2-3 h under the condition of slight boiling. Go to another studyStudy directly by HF and HNO
3And H
2O
2And a corrosion inhibitor mixed solution, wherein a titanium plate with a smooth surface is immersed in the mixed solution, and the surface of a titanium substrate becomes rough and scratches within 5-10 min, but the operation of the process is dangerous. Therefore, for the matrix treatment of anode surface roughening, the consistency of the coating sintering process is difficult to achieve through sand blasting, because the sand grains have different sizes and different pit depths, the coating is difficult to avoid in the coating process, the adsorption amount of the coating is different, a cavity is easy to form in the pit depth during sintering, and the oxide film is easy to be punctured by large current in the electrifying process, so that the coating is quickly peeled off.
SUMMERY OF THE UTILITY MODEL
An object of the utility model is to overcome above-mentioned prior art's shortcoming, provide a titanium base coating titanium anode's preparation system, utilized laser sculpture to handle the titanium base member, reached and be net or honeycomb surface structure, made the coating active point be regular range on titanium base surface, realized the homogeneity.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation system of a titanium anode with a titanium-based coating comprises pretreatment units which are sequentially arranged and used for carrying out oil removal and degreasing treatment on a titanium substrate; the activation treatment unit is used for activating the titanium matrix subjected to oil removal and degreasing treatment; the laser etching unit is used for carrying out laser etching treatment on the activated titanium substrate; the titanium chip removing unit is used for removing titanium chips on the titanium substrate; the acid solution etching unit is used for carrying out acid etching treatment on the titanium substrate; the ultrasonic cleaning unit is used for cleaning the titanium substrate subjected to acid etching treatment; and the brushing sintering unit is used for brushing and sintering the dried titanium substrate to complete the preparation of the coated titanium anode.
Further, the grid size of the laser etching is 0.02mm to 1.5 mm.
Further, the acid solution etching unit is formed by mixing a 10% oxalic acid solution and a 2-3% hydrochloric acid solution.
Further, the coating titanium anode is a titanium-based manganese dioxide electrode, a titanium-based lead dioxide electrode, a metal oxide coating chlorine/oxygen evolution electrode, a platinum and platinum-titanium electrode.
Further, the metal oxide chromatography chlorine/oxygen evolution electrode comprises a ruthenium-titanium electrode, a ruthenium-iridium-titanium electrode, an iridium-tantalum-cobalt electrode, an iridium-tantalum-platinum electrode and an iridium-tantalum-tin electrode.
Further, the ruthenium iridium titanium electrode coating comprises the following components: RuCl
3，Ti(RuO)
4HCl, n-butanol.
Further, the iridium tantalum titanium electrode coating component comprises: TaCl
5，IrCl
3，TiO
2HCl, n-butanol.
Compared with the prior art, the utility model provides a technical scheme includes following beneficial effect: the utility model discloses use laser etching's system to carry out alligatoring to titanium base body surface and handle, this system is simple to use, pollution-free, but the cinder that rapid processing titanium base body produced no longer needs the long-time processing of acid solution to can also obtain arbitrary regular alligatoring range, make the coating fill to the net gap easily, obtain even fine and close structure, can bear the working strength of heavy current simultaneously, corrosion resistance is strong.
Drawings
FIG. 1 is a schematic diagram of a laser etching process of a titanium substrate in a system for preparing a titanium-based coated titanium anode according to the present invention;
FIG. 2 is a surface grain morphology diagram of a titanium anode prepared when grid specifications of laser surface etching are respectively 0.5mm and 0.1mm when the coating titanium anode of the present invention is an iridium tantalum titanium electrode;
FIG. 3 is a view of the coating surface structure of FIG. 2 partially seen under SEM-EDS;
FIG. 4 is a surface grain morphology diagram of a titanium anode prepared when the grid specifications of laser surface etching are 1mm and 0.5mm respectively, when the coating titanium anode of the invention is a titanium platinized electrode.
Detailed Description
Reference will now be made in detail to the exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, like numbers in different drawings represent the same or similar elements unless otherwise indicated. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. Rather, they are merely examples of systems 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 present invention will be further described in detail with reference to the accompanying drawings and the embodiments.
Example 1:
a preparation system of a titanium anode with a titanium-based coating comprises pretreatment units which are sequentially arranged and used for carrying out oil removal and degreasing treatment on a titanium substrate; the activation treatment unit is used for activating the titanium matrix subjected to oil removal and degreasing treatment; the laser etching unit is used for carrying out laser etching treatment on the activated titanium substrate; the titanium chip removing unit is used for removing titanium chips on the titanium substrate; the acid solution etching unit is used for carrying out acid etching treatment on the titanium substrate; the ultrasonic cleaning unit is used for cleaning the titanium substrate subjected to acid etching treatment; and the brushing sintering unit is used for brushing and sintering the dried titanium substrate to complete the preparation of the coated titanium anode.
Further, the grid size of the laser etching is 0.02mm to 1.5 mm.
Further, the acid solution etching unit is formed by mixing a 10% oxalic acid solution and a 2-3% hydrochloric acid solution.
Further, the coating titanium anode is a titanium-based manganese dioxide electrode, a titanium-based lead dioxide electrode, a metal oxide coating chlorine/oxygen evolution electrode, a platinum and platinum-titanium electrode.
Further, the metal oxide chromatography chlorine/oxygen evolution electrode comprises a ruthenium-titanium electrode, a ruthenium-iridium-titanium electrode, an iridium-tantalum-cobalt electrode, an iridium-tantalum-platinum electrode and an iridium-tantalum-tin electrode.
Further, the ruthenium iridium titanium electrode coatingThe layer components include: RuCl
3，Ti(RuO)
4HCl, n-butanol.
Further, the iridium tantalum titanium electrode coating component comprises: TaCl
5，IrCl
3，TiO
2HCl, n-butanol.
Referring to fig. 1, the laser etching system used in the present invention is mainly arranged through regular grids to make the coating uniformly inlaid in the grids, and the main process flow is: the pretreatment of the titanium substrate, namely degreasing → activation → laser etching → titanium chip removal → acid treatment → ultrasonic cleaning → drying → coating sintering → finished product. Compared with the prior art, the process has the advantages that: firstly, the titanium substrate is always flat, and the shape correction treatment for sand blasting is not needed; secondly, the oxide skin content is low, the acid treatment concentration and time can be reduced, and the efficiency is improved; and thirdly, the laser etching process is pollution-free, so that not only can the grease oxide skin on the titanium substrate be rapidly treated, but also the metal etching can be carried out to ensure the roughness.
Example 2:
to prove the feasibility of the preparation system provided by the utility model, fig. 2 is a graph which is researched by a model of fig. 1 and is tested in the anode with oxygen evolution and hydrogen evolution, the coating system is an Ir-Ta system formula and a platinum anode, the sintering and spraying processes are repeatedly carried out, finally, the coating surface structure seen from a microscope can be clearly seen, the coating is regularly arranged, and SEM-EDS finds the IrO of the coating
2The active points are uniformly distributed, the coating has less cracks, and the requirement of the surface performance of the coating can be met.
When the coated titanium anode is a chlorine evolution electrode, for example, a ruthenium iridium titanium (RuIrani) anode sample with the size of 80mm multiplied by 50mm multiplied by 2mm is subjected to laser surface etching treatment, the grid specification of the laser surface etching treatment is 0.2mm multiplied by 0.2mm, and a single-side coated electrode is prepared by brushing. The coating comprises the following components in percentage by weight: RuCl
31-5g，Ti(RuO)
45-10ml, 1-5ml of HCl and 15-20ml of n-butanol; preparing TiO by thermal decomposition at the temperature of 600 ℃ under the temperature of 450-
2·IrO
2·RuO
2And coating the titanium electrode. After the preparation is finished, a reinforced service life test is carried out, and the test conditions are as follows: h with electrolyte concentration of 1mol/L
2SO
4Electric current ofThe density is 2A/cm
2The temperature is 50 ℃, and the service life of the obtained titanium electrode is 224 h.
When the coating titanium anode is an oxygen evolution electrode, for example, an iridium tantalum titanium (IrTaTi) electrode sample has the size of 60mm multiplied by 1mm, the laser surface etching treatment is carried out, the grid specification is 0.1mm multiplied by 0.1mm, and the double-sided coating electrode is prepared by brushing. The coating comprises the following components in percentage by weight: TaCl
515mg；IrCl
325mg；TiO
220 mg; 1-5ml of HCl and 1.9ml of n-butanol; thermal decomposing at 550 deg.C to obtain TiO
2·SnO
2·RuO
2And coating the titanium electrode. After the preparation is finished, a reinforced service life test is carried out, and the test conditions are as follows: h with electrolyte concentration of 1mol/L
2SO
4The current density is 2A/cm
2The temperature is 40-50 ℃, and the service life of the obtained titanium electrode is 580 h.
When the coated titanium anode is an oxygen evolving electrode, for example a titanium-based lead dioxide electrode (Ti/PbO)
2) An electrode sample with the size of 100mm multiplied by 2mm is brushed to prepare a double-sided coating electrode, the titanium-based lead-plated anode is etched on the surface of the electrode sample by laser, and the grid specification of the surface of the electrode sample is 0.5mm multiplied by 0.5 mm. The test conditions of the reinforced service life are as follows: h with electrolyte concentration of 1mol/L
2SO
4The current density is 2A/cm
2The temperature is 40-50 ℃, and the service life of the titanium electrode obtained by testing is 189 h.
When the coated titanium anode is a hydrogen evolution anode, for example, a titanium platinized (PtTi) anode sample with the size of 50mm multiplied by 40mm multiplied by 2mm is brushed to prepare a double-sided coated electrode, the laser surface is etched, the surface grid specification is 0.15mm multiplied by 0.02mm, and the formula of the electroplating solution is as follows: h
2PtCl
41.0-10.0 g/L; 0.5g/L of sulfamic acid, 0.3g/L of HCl1-2ml of additive and is electroplated to prepare the Ti/Pt coating titanium anode. After the preparation is finished, carrying out an enhanced life test under the following conditions: h with electrolyte concentration of 1mol/L
2SO
4Current density of 4A/cm
2The temperature is 40-50 ℃, and the service life of the titanium electrode obtained by testing is 168 h.
Therefore, the utility model provides a titanium base coating titanium anode's preparation system carries out the alligatoring to titanium base body surface through the system that uses laser etching and handles, and this system is simple to use, pollution-free, and the oxide skin that can handle titanium base body production fast no longer needs the long-time processing of acid solution to can also obtain arbitrary regular alligatoring range, make the coating fill up to the net gap easily, obtain even fine and close structure, can bear the working strength of heavy current simultaneously, corrosion resistance is strong.
The above description is only exemplary of the invention, and is intended to enable those skilled in the art to understand and implement 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 is to be understood that the present invention is not limited to the above, and various modifications and changes may be made without departing from the scope thereof. The scope of the present invention is limited only by the appended claims.
Claims (4)
1. The preparation system of the titanium anode with the titanium-based coating is characterized by comprising pretreatment units which are sequentially arranged and used for carrying out oil removal and degreasing treatment on a titanium substrate; the activation treatment unit is used for activating the titanium matrix subjected to oil removal and degreasing treatment; the laser etching unit is used for carrying out laser etching treatment on the activated titanium substrate; the titanium chip removing unit is used for removing titanium chips on the titanium substrate; the acid solution etching unit is used for carrying out acid etching treatment on the titanium substrate; the ultrasonic cleaning unit is used for cleaning the titanium substrate subjected to acid etching treatment; and the brushing sintering unit is used for brushing and sintering the dried titanium substrate to complete the preparation of the coated titanium anode.
2. The system for preparing titanium-based coated titanium anode of claim 1, wherein said laser etching unit, laser etching grid size is 0.02mm-1.5 mm.
3. The system of claim 1, wherein the titanium-based coated titanium anode is a titanium-based manganese dioxide electrode or a titanium-based lead dioxide electrode or a metal oxide coated chlorine/oxygen evolution electrode or a platinum and platinum titanium electrode.
4. The system for preparing the titanium-based coating titanium anode according to claim 3, wherein the metal oxide chromatographic chlorine/oxygen evolution electrode is a ruthenium-titanium electrode or a ruthenium-iridium-titanium electrode or an iridium-tantalum-cobalt electrode or an iridium-tantalum-platinum electrode or an iridium-tantalum-tin electrode.
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| CN201822259434.XU CN210048854U (en) | 2018-12-29 | 2018-12-29 | Preparation system of titanium-based coating titanium anode |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112663124A (en) * | 2020-12-18 | 2021-04-16 | 西安泰金工业电化学技术有限公司 | Preparation method of precious metal anode for horizontal electroplating of PCB |
| CN114990531A (en) * | 2022-06-28 | 2022-09-02 | 西安泰金工业电化学技术有限公司 | Method for cleaning and regenerating and repairing titanium anode for electrolytic copper foil |
-
2018
- 2018-12-29 CN CN201822259434.XU patent/CN210048854U/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112663124A (en) * | 2020-12-18 | 2021-04-16 | 西安泰金工业电化学技术有限公司 | Preparation method of precious metal anode for horizontal electroplating of PCB |
| CN114990531A (en) * | 2022-06-28 | 2022-09-02 | 西安泰金工业电化学技术有限公司 | Method for cleaning and regenerating and repairing titanium anode for electrolytic copper foil |
| CN114990531B (en) * | 2022-06-28 | 2022-12-13 | 西安泰金工业电化学技术有限公司 | Method for cleaning and regenerating and repairing titanium anode for electrolytic copper foil |
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Address after: 710299 No. 15, west section of Xijin Road, Jingwei Industrial Park, Xi'an Economic and Technological Development Zone, Xi'an City, Shaanxi Province Patentee after: Xi'an Taijin Xinneng Technology Co.,Ltd. Address before: 710201 No. 15 West Jin Road, Jingwei Industrial Park, Xi'an economic and Technological Development Zone, Shaanxi Patentee before: XI'AN TAIJIN INDUSTRIAL ELECTROCHEMICAL TECHNOLOGY Co.,Ltd. |
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