CN102560561A - DSA (Dimensionally Stable Anode) electrode and manufacturing method thereof - Google Patents
DSA (Dimensionally Stable Anode) electrode and manufacturing method thereof Download PDFInfo
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- CN102560561A CN102560561A CN2010105833206A CN201010583320A CN102560561A CN 102560561 A CN102560561 A CN 102560561A CN 2010105833206 A CN2010105833206 A CN 2010105833206A CN 201010583320 A CN201010583320 A CN 201010583320A CN 102560561 A CN102560561 A CN 102560561A
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Abstract
The invention provides a DSA (Dimensionally Stable Anode) electrode and a manufacturing method thereof. The DSA electrode is formed by a metal matrix, a middle protective layer and a surface active coating. The metal matrix is selected from one of metal Ti, metal Ta or a metal composite of which the surface is coated with Ta; the middle protective layer is formed by a multiple compound consisting of a platinum group metal oxide and other metal oxides; and the surface active coating is formed by IrO2.Ta2O5. The manufacturing method of the DSA electrode comprises the steps of treatment of the matrix, preparation of the middle protective layer and preparation of the surface active coating. Compared with a conventional titanium-based platinum group metal oxide coating electrode, the DSA electrode manufactured by adopting the method provided by the invention has the advantages that the average service life is doubled and the oxygen evolution overpotential is reduced by about 5 percent. Particularly, due to the preparation of the middle protective layer, the diffusion of O2 generated inside the surface active coating toward the surface of the Ti matrix is stopped, the passivation effect on the Ti matrix is reduced, the middle protective layer is also tightly combined with the metal matrix and the surface active coating, and the service life of the electrode is greatly prolonged.
Description
Technical field
The present invention relates to electrolysis tech, relate in particular to DSA electrode of a kind of, Metal plating field concise, electrolytic copper foil industry and other electrolytic industry widespread uses and preparation method thereof at electrolytic etching of metal.
Background technology
Large-scale production on the electrolytic industry determines the key factor of its production cost to be the energy efficiency of electrolysis production.Produce under the electric current at fixed, do not consider the secondary reaction in the electrolyzer, its energy efficiency is simply represented with following formula:
η＝U
1/U
Wherein η is an energy efficiency, U
1Be theoretical decomposition voltage, U is actual bath voltage.
By on can know, reduce the actual bath voltage of electrolytic process, can improve electrolytic energy efficiency.Therefore, the overpotential of reduction electrode-solution interface is to improve the powerful measure of energy efficiency.
Compare with the Pb electrode with traditional Graphite Electrodes, DSA anode overpotential is lower, and the life-span is longer, has obtained excellent popularization in chlorine industry and electrolytic copper foil industry.Chlorine industry is mainly used and is analysed chlorine DSA electrode, and the electrolytic copper foil industry is mainly used and analysed oxygen DSA electrode.
In the electrolytic copper foil industry, the catalyst coatings of analysing oxygen DSA electrode adopts the oxide compound of expensive platinum group metal Ir, and cost is higher, and the combination between coating and the matrix is bad in addition, comes off easily and passivation.These factors become the major obstacle that limits its application.
Summary of the invention
The object of the invention, exactly for a kind of DSA electrode and preparation method thereof is provided, with solution DSA anodic matrix passivation and coating shedding problem, and the work-ing life of improving electrode.
In order to achieve the above object, the present invention has adopted following technical scheme: a kind of DSA electrode is made up of metallic matrix, intermediate protective layer and surface active coating; Metallic matrix is selected from metal Ti, metal Ta or surface and covers a kind of in the metal composite of Ta; The multi-element compounds that intermediate protective layer is made up of platinum group metal oxide and other MOX constitutes; Surface active coating is by IrO
2Ta
2O
5Constitute.
Described metallic matrix is a metal Ti, and described intermediate protective layer is by Ta
2O
5TiO
2Constitute.
The making method of above-mentioned DSA electrode may further comprise the steps:
The processing of A, matrix
With metallic matrix through pickling, sandblast, polish, obtain coarse, clean matrix surface;
The preparation of B, intermediate protective layer
With quantitative Ta (OC
4H
9)
5And Ti (OC
4H
9)
4Be dissolved in C
4H
9OH is mixed with Ta, Ti mixed organic solvents, and controls wherein that the concentration of Ta is 40-60g/L, and the mol ratio of Ta: Ti is 9～1: 1;
Above-mentioned Ta, Ti mixed organic solvents are uniformly coated on coarse, clean matrix surface, and the roasting conjunctiva so repeats coating-roasting majority then, forms and the compact Ta of matrix surface
2O
5TiO
2Intermediate protective layer;
The preparation of C, surface active coating
With quantitative IrCl
3And Ta (OC
4H
9)
5Be dissolved in C
4H
9OH is mixed with Ir, Ta mixed organic solvents, and controls wherein that the concentration of Ir is 50-100g/L, and the mol ratio of Ir: Ta is 9～1: 1～9;
Ir, Ta mixed organic solvents are uniformly coated on the surface of intermediate protective layer, roasting conjunctiva then, it is most so to repeat coating-roasting, forms and intermediate protective layer surface bonding IrO closely
2Ta
2O
5Surface active coating.
The thickness of the metallic matrix described in the steps A is 25-45mm, and the geomery of geomery and electroplating device is suitable.
Pickling described in the steps A is that metallic matrix is put into oxalic acid solution digestion 2-4 hour that concentration expressed in percentage by weight is 7-15%.
Roasting described in step B and the step C is the matrix after the coating to be placed slowly be heated to 500-550 ℃ in the electric furnace, then at 500-550 ℃ of following roasting 10-20min.
Coating described in the step B-roasting number of times is 2～10 times, and each glue spread is 80ml/m
2
Coating described in the step C-roasting number of times is 8～15 times, and each glue spread is 20～80ml/m
2
DSA electrode of the present invention and preparation method thereof makes it compared with prior art owing to adopted above technical scheme, has following advantage and characteristics:
1, the existence of intermediate protective layer separates activated coating and matrix, avoids infiltrating acidic solution and the O in the crackle of top layer
2Diffusion loses good electrical conductivity with the matrix oxidation.
2, advanced person's the intermediate protective layer and the preparation technology of surface active coating make middle layer and surface layer grain size even, moderate crystal grain size, and the metallic element of bonding interface both sides has carried out good diffusion, has avoided local excessive concentration gradient, has both stoped O
2To the diffusion of matrix, guaranteed the bonding strength at interface again, also guaranteed the thin intermediate good electrical conductivity simultaneously.
3, advanced intermediate protective layer preparation technology and middle layer prescription combine, and make the middle layer combine closely difficult drop-off with substrate.
4, owing to the existence of intermediate protective layer, under the prerequisite that does not influence work-ing life and catalytic activity, the thickness of surface active coating can significantly reduce, thereby the consumption of precious metal Ir is reduced, and has greatly reduced the production cost of electrode.
Description of drawings
Fig. 1 is the sectional structure synoptic diagram of the DSA electrode among the present invention.
Embodiment
Referring to Fig. 1, DSA electrode of the present invention is made up of metallic matrix 1, intermediate protective layer 2 and surface active coating 3.Metallic matrix wherein is selected from metal Ti, metal Ta or surface and covers a kind of in the metal composite of Ta; The multi-element compounds that intermediate protective layer is made up of platinum group metal oxide and other MOX constitutes; Surface active coating is by IrO
2Ta
2O
5Constitute.
The preferable formation of DSA electrode of the present invention is, is matrix with the metal Ti, with Ta
2O
5TiO
2Make intermediate protective layer, with IrO
2Ta
2O
5Make surperficial activated coating.
The making method of DSA electrode of the present invention is given birth to the paper tinsel machine with the preparation electrolytic copper foil and is used the DSA electrode to be example, and step is following:
Select the long 1575mm of titanium plate for use, wide 1000mm, thick 40mm is processed into the arc that radius is 1000mm.
After the polishing of titanium matrix surface, carry out sandblasting, make the solid-state spot and the rusty stain wearing and tearing on surface.Then, use detergent wash, remove greasy dirt, obtain the matrix 1 of surface irregularity, cleaning.
The titanium matrix of handling well was put into 10% oxalic acid solution digestion 2 hours, make titanium matrix surface roughening.Then, with zero(ppm) water cleaning, drying repeatedly.
Configuration Ta, Ti compound organic solution.With Ta (OC
4H
9)
5And Ti (OC
4H
9)
4, be to be dissolved in C at 4: 1 with the mol ratio of Ta: Ti
4H
9OH forms solution, and wherein the concentration of Ta is about 50g/L.
Above-mentioned solution is uniformly coated on matrix surface, and glue spread is about 80ml/m
2, coated Ti plate placed slowly be heated to 500-550 ℃ in the electric furnace, then roasting 10-20min.
Repeat coating-roasting about 4-6 time, make intermediate protective layer 2.
Configuration Ir, Ta mixed organic solvents.With IrCl
3And Ta (OC
4H
9)
5, be to be dissolved in C at 4: 1 with the mol ratio of Ir: Ta
4H
9OH forms mixing solutions, and wherein the concentration of Ir is about 50-100g/L.
Above-mentioned solution is uniformly coated on matrix surface, and glue spread is about 40ml/m
2, coated Ti plate placed slowly be heated to 500-550 ℃ in the electric furnace, then roasting 10-20min.
Repeat coating-roasting about 10-15 time, make surface active coating 3.
Accomplish the making of DSA electrode.
Claims (8)
1. a DSA electrode is characterized in that: be made up of metallic matrix, intermediate protective layer and surface active coating; Metallic matrix is selected from metal Ti, metal Ta or surface and covers a kind of in the metal composite of Ta; The multi-element compounds that intermediate protective layer is made up of platinum group metal oxide and other MOX constitutes; Surface active coating is by IrO
2Ta
2O
5Constitute.
2. DSA electrode as claimed in claim 1 is characterized in that: described metallic matrix is a metal Ti, and described intermediate protective layer is by Ta
2O
5TiO
2Constitute.
3. the making method of DSA electrode as claimed in claim 1 is characterized in that: may further comprise the steps:
The processing of A, matrix
With metallic matrix through pickling, sandblast, polish, obtain coarse, clean matrix surface;
The preparation of B, intermediate protective layer
With quantitative Ta (OC
4H
9)
5And Ti (OC
4H
9)
4Be dissolved in C
4H
9OH is mixed with Ta, Ti mixed organic solvents, and controls wherein that the concentration of Ta is 40-60g/L, and the mol ratio of Ta: Ti is 9～1: 1;
Above-mentioned Ta, Ti mixed organic solvents are uniformly coated on coarse, clean matrix surface, and the roasting conjunctiva so repeats coating-roasting majority then, forms and the compact Ta of matrix surface
2O
5TiO
2Intermediate protective layer;
The preparation of C, surface active coating
With quantitative IrCl
3And Ta (OC
4H
9)
5Be dissolved in C
4H
9OH is mixed with Ir, Ta mixed organic solvents, and controls wherein that the concentration of Ir is 50-100g/L, and the mol ratio of Ir: Ta is 9～1: 1～9;
Ir, Ta mixed organic solvents are uniformly coated on the surface of intermediate protective layer, roasting conjunctiva then, it is most so to repeat coating-roasting, forms and intermediate protective layer surface bonding IrO closely
2Ta
2O
5Surface active coating.
4. the making method of DSA electrode as claimed in claim 3 is characterized in that: the thickness of the metallic matrix described in the steps A is 25-45mm, and the geomery of geomery and electroplating device is suitable.
5. the making method of DSA electrode as claimed in claim 3 is characterized in that: the pickling described in the steps A is that metallic matrix is put into oxalic acid solution digestion 2-4 hour that concentration expressed in percentage by weight is 7-15%.
6. the making method of DSA electrode as claimed in claim 3 is characterized in that: the roasting described in step B and the step C is the matrix after the coating to be placed slowly be heated to 500-550 ℃ in the electric furnace, then at 500-550 ℃ of following roasting 10-20min.
7. the making method of DSA electrode as claimed in claim 3 is characterized in that: the coating described in the step B-roasting number of times is 2～10 times, and each glue spread is 80ml/m
2
8. the making method of DSA electrode as claimed in claim 3 is characterized in that: the coating described in the step C-roasting number of times is 8～15 times, and each glue spread is 20～80ml/m
2
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|---|---|---|---|
| CN2010105833206A CN102560561A (en) | 2010-12-10 | 2010-12-10 | DSA (Dimensionally Stable Anode) electrode and manufacturing method thereof |
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|---|---|---|---|
| CN2010105833206A CN102560561A (en) | 2010-12-10 | 2010-12-10 | DSA (Dimensionally Stable Anode) electrode and manufacturing method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108660488A (en) * | 2018-05-29 | 2018-10-16 | 江阴安诺电极有限公司 | The preparation method of electrolytic copper foil anode plate |
| CN110342565A (en) * | 2019-08-15 | 2019-10-18 | 安徽绿洲危险废物综合利用有限公司 | A kind of Kocide SD of acidic etching liquid and preparation method thereof |
| CN114182307A (en) * | 2021-11-23 | 2022-03-15 | 西安泰金工业电化学技术有限公司 | Preparation method of noble metal anode for electrolytic copper foil |
| CN115537883A (en) * | 2022-09-20 | 2022-12-30 | 江苏铭丰电子材料科技有限公司 | Iro for electrolytic copper foil production 2 -Ta 2 O 5 Method for reducing oxygen evolution potential of/Ti electrode |
| WO2023203231A1 (en) * | 2022-04-21 | 2023-10-26 | Magneto Special Anodes B.V. | Anode with metallic interlayer for electrodeposition |
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2010
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108660488A (en) * | 2018-05-29 | 2018-10-16 | 江阴安诺电极有限公司 | The preparation method of electrolytic copper foil anode plate |
| CN110342565A (en) * | 2019-08-15 | 2019-10-18 | 安徽绿洲危险废物综合利用有限公司 | A kind of Kocide SD of acidic etching liquid and preparation method thereof |
| CN114182307A (en) * | 2021-11-23 | 2022-03-15 | 西安泰金工业电化学技术有限公司 | Preparation method of noble metal anode for electrolytic copper foil |
| WO2023203231A1 (en) * | 2022-04-21 | 2023-10-26 | Magneto Special Anodes B.V. | Anode with metallic interlayer for electrodeposition |
| CN115537883A (en) * | 2022-09-20 | 2022-12-30 | 江苏铭丰电子材料科技有限公司 | Iro for electrolytic copper foil production 2 -Ta 2 O 5 Method for reducing oxygen evolution potential of/Ti electrode |
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Application publication date: 20120711 |