CN114934308B - High-temperature superconducting strip copper electroplating device and method based on insoluble anode - Google Patents
High-temperature superconducting strip copper electroplating device and method based on insoluble anode Download PDFInfo
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- CN114934308B CN114934308B CN202210761901.7A CN202210761901A CN114934308B CN 114934308 B CN114934308 B CN 114934308B CN 202210761901 A CN202210761901 A CN 202210761901A CN 114934308 B CN114934308 B CN 114934308B
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- superconducting tape
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- 239000010949 copper Substances 0.000 title claims abstract description 151
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 149
- 238000009713 electroplating Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000007747 plating Methods 0.000 claims abstract description 143
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000457 iridium oxide Inorganic materials 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000002161 passivation Methods 0.000 claims description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 238000007603 infrared drying Methods 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 21
- 239000003795 chemical substances by application Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000005282 brightening Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910021521 yttrium barium copper oxide Inorganic materials 0.000 description 3
- 229920002334 Spandex Polymers 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004759 spandex Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- BTGZYWWSOPEHMM-UHFFFAOYSA-N [O].[Cu].[Y].[Ba] Chemical compound [O].[Cu].[Y].[Ba] BTGZYWWSOPEHMM-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention belongs to the technical field of high-temperature superconducting strips, and particularly relates to a high-temperature superconducting strip copper electroplating device and method based on an insoluble anode, wherein the device comprises a plating solution tank, a copper plating pipe, an anode, a high-temperature superconducting strip and a conductive roller; the two ends of the copper plating pipe are obliquely arranged upwards and are communicated with the bottom of the plating solution tank through a pipeline; the anode is a titanium strip with the surface coated with iridium oxide; the conductive roller is used for conveying the high-temperature superconductive tape. The invention adopts the surface coating IrO 2 The titanium strip is used as an insoluble anode to replace a soluble anode, so that the cathode and anode area required in the copper plating process is fixed, the balance of the cathode and anode is ensured, the current edge effect is avoided, and the edge of the electroplated copper layer is consistent with the middle thickness; anode mud is not generated in the electroplating process, anode mud is prevented from shielding an anode, the purity of the plating copper is improved, the compactness and flexibility of the strip copper electroplating layer are enhanced, and the copper electroplating efficiency is improved.
Description
Technical Field
The invention belongs to the technical field of high-temperature superconducting strips, and particularly relates to a high-temperature superconducting strip copper electroplating device and method based on an insoluble anode.
Background
Two main applications of YBCO (yttrium barium copper oxide) high-temperature superconducting tapes are currently used: one is used as a magnet and the other is used as a cable; the requirements of domestic scientific research institutions and related enterprises on high-temperature superconducting tapes pay more attention to the mechanical properties of the tapes besides the current requirements of the superconducting tapes under a magnetic field; the mechanical properties of the high-temperature superconductive tape consist of a Harbour baseband, an isolation layer, a superconductive layer, a protective layer (Ag, 2 um) and a stabilizing layer (Cu, 5-25 um), wherein the stabilizing layer plays a role in preventing the silver layer from oxidizing and falling off for the superconductive tape, enhancing the mechanical strength of the superconductive tape, and leading out overload current and heat when in short circuit or quench, so that the quality of the copper plating layer plays an important role in the practical application of the superconductive tape.
At present, high-temperature superconducting tapes are required to be plated on a silver layer of a protective layer, the thickness of the copper plating layer is more than 5-25um, along with a 25um thin base band pushed by a United states Superpower, a 1mm-2mm narrow band, a 30um thin base band pushed by Russian SuperOx, a 2mm narrow band, and units such as domestic 585 place and 712 place are purchased to obtain the superconducting tape basically with the 2mm narrow band, so that a novel challenge is brought to the surface copper plating process of the superconducting tape, and the ultra-thin (25 um-65 um) and ultra-narrow (1 mm-2 mm) and ultra-soft characteristics of the YBCO high-temperature superconducting tape bring certain difficulty to copper plating of silver (Ag, 2 um) on the surface of the superconducting tape, and the conventional copper plating equipment and copper plating method cannot overcome the problem of 'yin-yang area matching' in electroplated copper, the power lines are denser at edge positions and sparse in middle positions, so that the phenomenon of thick and thin middle edges of the copper plating tape layer appears, and the market cannot be met.
In particular, copper plating process has difficulty in satisfying uniformity of copper layer and mechanical properties of strip, and then the key point of uniformity is that the superconducting tape is used as cathode to be matched with area proportion and shape of anode of titanium column filled with phosphor copper ball, and the matching of area proportion and shape of cathode and anode is difficult to stabilize due to thinness, softness, easy deformation and swing of strip.
Patent document CN110797148A discloses a superconducting tape suitable for an uninsulated coil, and a method for producing the same, wherein an electrochemical copper-plated superconducting tape is used, and a copper-plated layer on a transverse surface thereof has a bone-like structure with both ends larger than a middle portion. The subsequent application of the superconducting tape cannot be satisfied. Patent document CN113089060a discloses a roll-to-roll superconducting tape copper plating device and method, and patent document CN113089038A discloses a superconducting tape copper preplating method, copper plating method and copper plating device, and a copper plating scheme using phosphor copper balls in long titanium columns as anodes is still adopted, so that control of the ratio of the cathode to the anode in the electroplated copper and matching of the shape cannot be completed, and phenomena of oxidation, passivation, ash formation, abnormal loss and the like of the soluble phosphor copper balls affect the purity and compactness of a copper plating layer.
In the scheme, only the bone-shaped structure with two ends of the plating layer larger than the middle part is lightened, the thickness of the copper plating layer of the superconducting tape cannot be changed, the phenomenon that the middle part is thin and the two sides are thick is avoided, the copper plating process is complex, and copper plating equipment is expensive.
Disclosure of Invention
The invention aims to solve the problems and provides a high-temperature superconductive strip copper plating device and method based on an insoluble anode, which can realize controllable, excellent and stable copper plating effect, improve the quality of copper plating layers and reduce the copper plating cost of strips
According to the technical proposal of the invention, the high-temperature superconductive strip copper electroplating device based on the insoluble anode comprises,
a plating solution tank for storing a copper plating solution;
the two ends of the copper plating pipe are obliquely arranged upwards and are communicated with the bottom of the plating solution tank through a pipeline, and an acid-resistant pump is arranged on the pipeline; the middle part of the copper plating pipe extends into the plating solution tank and is provided with a liquid outlet;
an anode, the anode being surface coated with iridium oxide (IrO) 2 ) The anode is arranged in the copper plating pipe and is connected with the positive electrode of the power supply;
one end of the high-temperature superconducting tape is wound on the reel, and the other end of the high-temperature superconducting tape passes through the copper plating pipe;
the conductive roller is used for conveying the high-temperature superconducting tape, is arranged at two ends of the copper plating pipe and/or inside the copper plating pipe, and is connected with a power supply negative electrode.
The invention adopts the surface coating IrO 2 The titanium strip is used as an insoluble anode to replace a soluble anode, so that the cathode and anode area required in the copper plating process is fixed, the balance of the cathode and anode is ensured, the current edge effect is avoided, and the edge of the electroplated copper layer is consistent with the middle thickness;
no anode mud is generated in the electroplating process, anode shielding by the anode mud is avoided, the purity of the plating copper is improved, the compactness and flexibility of the strip copper electroplating layer are enhanced, and the copper electroplating efficiency is improved;
further, copper sulfate (CuSO) in the copper plating solution 4 ·5H 2 O) concentration of 180-220g/L, sulfuric acid concentration of 60-80g/L, cl – The concentration is 60-100mg/L, the concentration of the leveling agent is 3-15mL/L, and the concentration of the brightening agent is 1-4mL/L.
Further, the plating solution tank can be arranged on the stainless steel frame and comprises a PP (polypropylene) tank body and stainless steel reinforcing ribs arranged outside the PP tank body.
Further, a micro groove is arranged in the plating solution groove and is used for dissolving copper oxide powder, supplementing copper ions in the plating solution groove and maintaining Cu in the plating solution groove 2+ Normal concentration of ions.
Furthermore, the inclination angle of the copper plating pipe is 25-45 degrees, preferably 30 degrees (an included angle with the horizontal plane), so that the copper plating solution can flow from the two ends of the copper plating pipe to the liquid outlet so as to flow back to the plating solution tank, the copper plating solution can form circulating flow, and the uniformity of the copper plating solution is ensured.
Further, a supporting piece for supporting the anode and the superconductive strip is arranged in the copper plating pipe; the shape of the supporting piece is suitable for stably supporting the anode and the high-temperature superconducting strip, and the section of the copper plating pipe is square, round, elliptic or other shapes.
Further, the copper plating tube is mounted on a rocking support.
Further, the copper plating pipe is U-shaped, the liquid outlet is arranged at the bottom of the U-shaped, and the liquid outlet is arranged at the liquid outlet pipe for drainage.
Further, the four groups of conductive rollers are respectively arranged outside openings at two ends of the copper plating pipe and at two corners of the U-shaped inside the copper plating pipe.
Further, the thickness of iridium oxide coated on the surface of the titanium strip is 2um-5um.
Further, the width of the anode is consistent with the width of the high-temperature superconducting tape.
Further, the device also comprises a cleaning tank, a passivation tank and an infrared drying device, and is used for post-treatment of the high-temperature superconductive strip after copper plating.
Furthermore, the other end of the high-temperature superconducting tape vertically passes through the copper plating pipe, so that the copper plating uniformity at two sides is ensured; anodes are arranged on two sides of the high-temperature superconducting tape and are parallel to the high-temperature superconducting tape.
Further, the conveying speed of the high-temperature superconducting tape is 0.8m/min-1.0m/min.
Specifically, the cleaning solution in the cleaning tank may be water (such as deionized water); the passivation solution of the passivation pool can be benzotriazole solution, and the concentration of the solution is 1.5-2.0 wt%; the drying temperature of the infrared drying device is 105-110 ℃.
In another aspect, the invention provides a method for electroplating copper on a high-temperature superconductive tape based on an insoluble anode, which adopts the device and comprises the following steps: copper plating solution is conveyed to two ends of a copper plating pipe along a pipeline under the action of an acid-resistant pump; and electrifying the conductive roller and the anode, and electroplating copper while the high-temperature superconductive strip moves along the inside of the copper plating pipe under the conveying action of the conductive roller.
Further, the temperature of the electroplating solution is 20-26 ℃, preferably 24-25 ℃, and the temperature of the electroplating solution can be regulated and controlled by a cold-hot circulation device.
Compared with the prior art, the technical scheme of the invention has the following advantages: the invention adopts the insoluble anode to electroplate copper on the high-temperature superconductive strip, has simple equipment structure, small volume and flexible use, ensures constant anode area in the production process, ensures uniform current distribution, does not need to stop the production line to clean and supplement anode materials, does not generate anode mud, ensures consistent surface color of a copper layer, does not have abnormal color visible to naked eyes, and has good flexibility of the strip; the electrode has long service life, can bear higher current density, has high production efficiency, ensures that the copper plating thickness of a single side of a high-temperature superconducting tape with the width of 2mm and the thickness of 25-65 um is 20um, the thickness of the double side is 40um, the uniformity of a copper plating layer is controlled within 3 percent, and has small middle gap and high stacking density when the tape is coiled for use without filling tin paste, thereby enhancing the superconducting performance of the superconductor and having good economic benefit.
Drawings
FIG. 1 is a schematic diagram of a high temperature superconducting tape copper electroplating apparatus based on an insoluble anode.
Fig. 2 is a schematic structural view of a copper plating tube.
Fig. 3 is a schematic cross-sectional view of a copper plating tube.
FIG. 4 is a lycra micrograph of the copper plated surface.
FIG. 5 is a graph of copper plating uniformity section analysis.
Reference numerals illustrate: 1-plating solution tank, 2-copper plating pipe, 3-pipeline, 4-acid-proof pump, 5-high temperature superconductive strip, 6-conductive roller, 7-anode, 8-drain pipe, 9-first support piece, 10-second support piece.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Example 1
As shown in FIGS. 1 to 3, the high temperature superconducting tape copper electroplating device based on the insoluble anode comprises a plating solution tank 1, a copper plating pipe 2, an anode 7, a superconducting tape 5 and a conductive roller 6.
Wherein the plating bath 1 has a length of 3.86m, a width of 0.8m and a height of 1.1m, and is used for storing copper plating solution therein. Copper sulfate (CuSO) in the copper plating solution 4 ·5H 2 O) concentration of 200g/L, sulfuric acid concentration of 70g/L, cl – The concentration is 80mg/L, the concentration of the leveling agent is 5mL/L, the concentration of the brightening agent is 2mL/L, and both the leveling agent and the brightening agent are commercial products. The working temperature of the copper plating solution is 24-26 ℃ and the current density (ASD) is 10-12. The bottom of the plating solution tank 1 is also provided with a cold and hot circulation device for adjusting the temperature.
A micro groove is arranged in the plating solution groove 1 and is used for dissolving copper oxide powder and supplementing copper ions in the plating solution groove 1. The mass of copper oxide powder added to the copper plating solution per minute was calculated from the mass of copper deposited on the surface of the strip (high temperature superconducting strip 5), i.e., copper oxide powder was added at CuO/cu=1.252.
The copper plating pipe 2 is U-shaped and forms an included angle of 30 degrees with the horizontal direction; the U-shaped bottom is positioned at a low position and is positioned in the plating solution tank 1; the U-shaped inlet and outlet are positioned at a high position and are positioned outside the plating solution tank 1; the U-shaped bottom is provided with a liquid outlet and a liquid outlet pipe 8. The U-shaped inlet and outlet are communicated with the bottom of the plating solution tank 1 through a pipeline 3, a 0.75W electric acid-resistant pump is arranged on the pipeline 3 to drive copper plating solution into the inlet and outlet, and then the copper plating solution flows out of the liquid outlet pipe 8 to form circulating flow, so that the uniformity of the copper plating solution is ensured.
The inside of the copper plating tube 2 is square, a plurality of groups of first supporting pieces 9 which are oppositely arranged are arranged on the left side wall and the right side wall of the copper plating tube, a plurality of groups of second supporting pieces 10 which are oppositely arranged are arranged on the upper side wall and the lower side wall of the copper plating tube, and the second supporting pieces 10 comprise supporting seats and arc-shaped supporting plates.
The copper plating pipe 2 is also provided with a cleaning tank, a passivation tank and an infrared lamp outside the outlet, deionized water is placed in the cleaning tank, 1.5wt% of benzotriazole solution is placed in the passivation tank, and the drying temperature of the infrared lamp is 105 ℃.
The anodes 7 are vertically arranged in U-shaped arms of the copper plating pipe 2 and are connected with a power supply anode, two anodes 7 are arranged in each U-shaped arm, and the anodes are supported between the inner end of the first supporting piece 9 and the outer end of the arc-shaped supporting plate of the second supporting piece 10. The anode 7 is a titanium strip coated with iridium oxide, the specific size of the titanium strip is 2mm according to the width of a plating piece (high-temperature superconducting strip 5) and the thickness of the titanium strip is 25-65 um, and the surface of the titanium strip is coated with 3um thick IrO 2 Is a 2mm by 3500mm titanium strip.
One end of the high-temperature superconducting tape 5 is wound on the reel, and the other end vertically penetrates through the copper plating pipe 2 and is supported between the arc-shaped supporting plates of the second supporting piece 10. The portion of the high temperature superconducting tape 5 passing through the copper plating tube 2 may also be provided with a tension member, such as a tension pulley, for adjusting the tension. Specifically, a lead can be welded at the other end of the high-temperature superconductive tape 5, the whole copper-plated pipe 2 is penetrated through the lead, the tension of the lead is adjusted, and then the superconductive tape 5 is guided to penetrate through the copper-plated pipe 2.
The conductive rollers 6 are connected with the power supply negative electrode, are four groups and are respectively arranged outside the inlet and outlet of the copper plating tube 2 and at two corners of the U-shaped inside the copper plating tube 2, and are used for uniformly distributing current to prevent the superconductive strip 5 from swinging in the copper plating tube 2 and affecting copper plating uniformity.
The copper plating tube 2 and the conductive roller 6 can also be arranged on a swinging bracket, and the swinging is driven by an eccentric wheel (other commercially available devices capable of realizing up-down, left-right and up-down reciprocating rotation) so as to fully exchange the solution.
Example 2
High-temperature superconducting strip copper electroplating method based on insoluble anode
(1) The plating solution is prepared by cleaning a plating solution tank, a micro tank for dissolving oxidized copper powder and related tools by deionized water according to the following proportion: h 2 O：200L，H 2 SO 4 ：35kg，(CuSO 4 ·5H 2 O): 100kg of HCl solution and 100mL of HCl solution are added into a plating solution tank according to the required sequence, then deionized water is used for replenishing the total amount of copper plating solution to 500L, a cold and hot circulation device is started, the temperature of the solution is ensured to be within the range of 20-26 ℃, after the copper plating solution has uniform components, 2.5L of leveling agent and 1L of brightening agent are added, and the plating solution is continuously circulated for 60 minutes.
(2) The superconducting tape (high-temperature superconducting tape) with the width of 2mm and silver plating is arranged on a unreeling disc, each wire joint in a copper plating groove is checked, each wire joint is guaranteed to be intact, a conductive roller runs freely, the lead tape and the silver plating superconducting tape are well spot-welded, the lead tape penetrates through a place where copper plating of the whole copper plating equipment is required to pass, the tension of the lead tape is regulated, and the driving wheel is guaranteed to act normally and the reel is guaranteed to be in a non-swinging state.
(3) The thickness of copper plated on one side is 20um, and the cathode current density ASD is 10.7A/dm 2 Setting the current output of the rectifier as 30A, setting the running speed as the tape feeding speed as 0.9m/min, setting the output current of the rectifier as 30A respectively, starting the conductive roller, and starting to perform copper electroplating on the high-temperature superconducting tape.
(4) And (3) after the copper plating belt is discharged from the copper plating solution, cleaning the copper plating belt by deionized water, then passivating the copper plating belt by a benzotriazole solution with the weight percent of 1.5-2.0%, cleaning the copper plating belt by deionized water, and then drying the copper plating belt by infrared lamp light (105-110 ℃), namely, winding the copper plating belt to finish the copper plating work of the superconducting belt.
The superconducting tape after copper plating was tested, wherein the morphology of the copper plating layer surface (lycra microscope) was as shown in fig. 4, and the copper plating layer uniformity analysis (slicing) was as shown in fig. 5, and the uniformity was (20.5-20)/(20.5=2.439%.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. A high-temperature superconductive strip copper electroplating device based on an insoluble anode is characterized by comprising,
a plating solution tank (1), wherein the plating solution tank (1) is used for storing copper plating solution;
the copper plating pipe (2) is U-shaped, two ends of the copper plating pipe (2) are obliquely arranged upwards and are communicated with the bottom of the plating solution tank (1) through a pipeline (3), and an acid-resistant pump (4) is arranged on the pipeline (3); the middle part of the copper plating pipe (2) extends into the plating solution tank (1) and is provided with a liquid outlet;
the anode (7) is a titanium strip with the surface coated with iridium oxide, and the anode (7) is arranged in the copper plating tube (2) and is connected with the positive electrode of a power supply;
the copper plating device comprises a high-temperature superconducting tape (5), wherein one end of the high-temperature superconducting tape (5) is wound on a reel, the other end of the high-temperature superconducting tape passes through the copper plating pipe (2), anodes (7) are arranged on two sides of the high-temperature superconducting tape (5), and the anodes (7) are arranged parallel to the high-temperature superconducting tape (5);
the conductive roller (6), conductive roller (6) are used for conveying high temperature superconducting tape (5), and conductive roller (6) set up in copper pipe (2) both ends and/or copper pipe (2) inside to connect the power negative pole.
2. The high-temperature superconducting tape copper electroplating device based on the insoluble anode, as claimed in claim 1, wherein a micro-groove is arranged in the plating solution groove (1) and is used for dissolving copper oxide powder and supplementing copper ions in the plating solution groove (1).
3. The insoluble anode based high temperature superconducting tape copper electroplating apparatus according to claim 1, wherein the copper plating tube (2) is inclined at an angle of 25 ° -45 °.
4. The insoluble anode-based high temperature superconducting tape copper electroplating device according to claim 1, wherein a support member for supporting the anode (7) and the superconducting tape (5) is provided in the copper plating tube (2).
5. The insoluble anode-based high temperature superconducting tape copper electroplating apparatus according to claim 1, wherein the copper plating tube (2) is mounted on a rocking support.
6. The high-temperature superconducting tape copper electroplating device based on the insoluble anode according to claim 1, wherein the four groups of conductive rollers (6) are respectively arranged outside the openings at two ends of the copper plating tube (2) and at two corners of the U-shape inside the copper plating tube (2).
7. The insoluble anode based high temperature superconducting tape copper electroplating apparatus according to claim 1, wherein the iridium oxide coated on the surface of the titanium strip has a thickness of 2 μm to 5 μm.
8. The insoluble anode based high temperature superconducting tape copper electroplating apparatus of claim 1, further comprising a cleaning bath, a passivation bath and an infrared drying device.
9. A method for electroplating copper on a high temperature superconducting tape based on an insoluble anode, characterized in that the apparatus according to any one of claims 1 to 8 is used, comprising the steps of: the copper plating solution is conveyed to two ends of a copper plating pipe (2) along a pipeline (3) under the action of an acid-resistant pump (4); electrifying the conductive roller (6) and the anode (7), and electroplating copper while the superconductive tape (5) moves along the inner part of the copper plating tube (2) under the conveying action of the conductive roller (6).
10. The method for electroplating copper on a non-soluble anode-based high temperature superconducting tape according to claim 9, wherein the copper plating solution has a temperature of 20 ℃ to 25 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210761901.7A CN114934308B (en) | 2022-06-30 | 2022-06-30 | High-temperature superconducting strip copper electroplating device and method based on insoluble anode |
Applications Claiming Priority (1)
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| JPH07211950A (en) * | 1994-01-19 | 1995-08-11 | Nippon Telegr & Teleph Corp <Ntt> | Superconductor electrode |
| CN102409298A (en) * | 2011-11-18 | 2012-04-11 | 上海超导科技股份有限公司 | Continuous rapid laser coating method of superconducting layer in second-generation high-temperature superconducting strip |
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| CN107723766A (en) * | 2016-08-10 | 2018-02-23 | 凯基有限公司 | The two-sided electrolytic copper plating device of volume to volume and its copper electroplating method for flexible circuit board |
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| JPH07211950A (en) * | 1994-01-19 | 1995-08-11 | Nippon Telegr & Teleph Corp <Ntt> | Superconductor electrode |
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