CN114758849B - Superconducting tape, copper plating method for superconducting tape, method for producing superconducting tape, superconducting coil, and method for impregnating superconducting coil - Google Patents
Superconducting tape, copper plating method for superconducting tape, method for producing superconducting tape, superconducting coil, and method for impregnating superconducting coil Download PDFInfo
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- CN114758849B CN114758849B CN202210514162.1A CN202210514162A CN114758849B CN 114758849 B CN114758849 B CN 114758849B CN 202210514162 A CN202210514162 A CN 202210514162A CN 114758849 B CN114758849 B CN 114758849B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/22—Sheathing; Armouring; Screening; Applying other protective layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/005—Impregnating or encapsulating
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/04—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing coils
- H01F41/048—Superconductive coils
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F6/00—Superconducting magnets; Superconducting coils
- H01F6/06—Coils, e.g. winding, insulating, terminating or casing arrangements therefor
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- 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
Abstract
The invention provides a superconducting tape and a copper plating method thereof, a preparation method thereof, a superconducting coil and an impregnation method thereof, wherein the superconducting tape comprises the following components: integrally polishing the Hastelloy, and excessively polishing the edge part to ensure that the thickness of the Hastelloy edge part is smaller than that of the non-edge part; and sequentially plating a buffer layer, a superconducting layer and a copper layer on the polished Hastelloy to obtain the superconducting strip. The cross section of the superconducting strip finally obtained is in a shape that the thickness of the edge positions of two sides of a spindle shape is smaller than that of the middle position by carrying out electrochemical polishing on the Hastelloy, so that the defect that the bone-shaped cross section is obtained by copper plating of the superconducting strip is overcome.
Description
Technical Field
The invention relates to the field of superconducting materials, in particular to a superconducting tape and a copper plating and preparation method thereof, and a superconducting coil and an impregnation method thereof.
Background
Since the first discovery of superconducting phenomena in laboratories by professor dust Linang na of the university of Leiden (Leiden) in the netherlands in 1911, superconducting materials and applications thereof have been one of the most active leading-edge research fields of modern science and technology. During the last decades, the research on high-temperature superconducting power and magnet equipment represented by the second-generation high-temperature superconducting tape has been rapidly developed, and remarkable results are achieved in the fields of superconducting energy storage, superconducting motors, superconducting cables, superconducting current limiters, superconducting transformers, superconducting magnetic levitation, nuclear magnetic resonance and the like.
The second generation superconducting tapes made of REBCO (RE is a rare earth element) are also called as coated conductors, and have wider and better application prospects in various fields such as medical treatment, military, energy and the like because of higher current carrying capacity, higher magnetic field performance and lower material cost compared with bismuth-based tapes. Second generation superconducting tapes, which are also referred to as coated conductors, are generally produced by a process of applying a multilayer coating film on a nickel-based alloy substrate because REBCO, which is a superconducting current-carrying core, is inherently hard and brittle. The second generation superconducting tape generally consists of a base tape, a buffer layer (transition layer), a superconducting layer, and a protective layer. The function of the metal substrate is to provide the strip with excellent mechanical properties. The transition layer has the functions of preventing the mutual diffusion of elements between the superconducting layer and the metal substrate, and providing a good template for the epitaxial growth of the superconducting layer to improve the REBCO crystal grain arrangement quality. Coated conductors with excellent superconducting properties are produced, requiring a superconducting layer with a consistent biaxial texture. Biaxial texture means that the grains are nearly uniformly aligned in both the a/b axis and the c axis (the c axis is perpendicular to the a/b plane). The alignment degree (in-plane texture) of the REBCO film in the a/b axis direction is relatively difficult to realize, and the poor in-plane texture can seriously reduce the superconducting performance. It is therefore desirable to grow epitaxially a REBCO superconducting film on a transition layer that already has a biaxial texture and a matched lattice. Two main technical routes for realizing the biaxial texture are available in the preparation, one is a rolling auxiliary biaxial texture base band technology, and the other is an ion beam auxiliary deposition technology. The common techniques for preparing the REBCO superconducting layer are divided into various techniques, such as pulsed laser deposition, metal organic chemical vapor deposition, reactive co-evaporation and the like.
The protective layer is mainly used for protecting the superconducting film layer, generally, a silver layer with the thickness of 0.5-5 μm is plated on the front surface and the back surface of the superconducting strip by magnetron sputtering or evaporation, in order to pursue lower material cost, the silver layer on the superconducting surface is generally set to be 1-2 μm, and the silver layer on the non-superconducting surface is generally set to be 0.5-1 μm. Is then cut into strips of 10-12 mm, depending on the width requirements of the particular application. And finally, carrying out copper plating or subsequent packaging reinforcement treatment. The thickness of the copper plating of the strip for subsequent packaging can be 1-10 mu m. The copper plating of the copper-plated reinforced strip material is performed with the thickness of copper plating on one surface of the copper-plated reinforced strip material being 10-30 mu m and the thickness of copper plating on the two surfaces of the copper-plated reinforced strip material being 20-60 mu m.
Superconducting tapes are used in many applications by being directly wound into a coil, as shown in fig. 1. The quality of the copper-plated protective layer directly affects the application of the superconducting tape. The superconducting tape material with electrochemical copper plating is adopted, and the copper plating layer of the cross section of the superconducting tape material has a bone-shaped structure with thicker edge parts than middle parts, as shown in figures 2 and 3. The sizes of various bones are different, and after some bone-shaped strips are wound into coils, a small amount of translational dislocation occurs between the strips, as shown in fig. 4. When the cake of the superconducting coil has axial sliding deviation, the whole coil is in a bamboo hat shape, as shown in fig. 5. This is the case, as the coils of this shape cannot be stacked, effectively cooling them and making subsequent use impossible. Therefore, the general deviation of the section thickness of the superconducting tape required by the product is within +/-5 μm, and even the general deviation of the section thickness of the tape required by some precise equipment is within +/-1 μm. But this is still very difficult with conventional copper electroplating. Because the ampere-turns of the coil are larger and larger, the original superconducting coil is in the grade of hundred turns, and the army is going to be developed towards the grade of thousand turns at present. Due to the cumulative effect, the ± 5 μm error, which is tolerable for the original copper plating, becomes intolerable as the coil increases. The requirement for the boneless type has become a difficult problem to do in the industry.
The material property of the superconducting conductor determines that the superconducting conductor is weak, and the superconducting conductor is easy to damage after the material is subjected to certain stress such as bending, stretching, twisting and the like, so that the critical current of the superconducting conductor is greatly reduced. When the superconducting coil normally works, the superconducting conductor is often subjected to large electromagnetic stress under the action of a magnetic field. In addition, external mechanical vibration applied to the superconducting coil is transmitted to the superconducting conductor. Especially in the application environment of superconducting motors and superconducting magnetic levitation, resonance and jitter are inevitable. Displacement occurs in each turn, and frictional heat generation occurs between the turns, which finally causes the conductor to quench. In addition, gaps are inevitably left between turns of the superconducting coil during the winding process, which also affects the cooling efficiency of the superconducting magnet.
The conventional superconducting coil is generally vacuum-impregnated with paraffin or epoxy resin at present, but a serious problem with this process is that the process itself may have a destructive effect on the conductor itself. As shown in fig. 1, the failure mechanism is that the paraffin or epoxy resin and the superconducting conductor are different in thermal expansion and contraction coefficient at low temperature, and the paraffin or epoxy resin on both sides of the superconducting conductor is very likely to apply peeling stress to the superconducting wire vertically along the peeling direction during cooling. In particular, yttrium-based superconducting conductors are a multi-layer coating material, and the performance of the conductors is greatly damaged when the interlayer bonding force is weaker than the peeling stress. Even if this problem does not occur after the initial vacuum impregnation, it will occur after a number of cold and hot cycles of application of the superconducting coil.
Epoxy impregnation has become the most difficult problem for the industry to overcome at present.
A number of ways are envisioned in the industry:
c Barth et al in Europe used quartz doped epoxy glue to adjust the thermal expansion and cold shrinkage of epoxy glue and superconducting tapes.
CN112143175A, epoxy resin composite material for superconducting magnets and a preparation method thereof, she Xinyu et al in China prepared a resin-based composite material with a thermal expansion coefficient, high thermal conductivity and high elastic modulus for impregnating coils.
Miyazaki et al, toshiba, japan, used a ribbon-segmented stress-controlling Method in the relaxation protocols of Different Types of REBCO-Coated Conductors and methods for Reducing Radial Thermal protocols of amplified REBCO Panel Coils to prevent cumulative stress tearing of the ribbon.
A method of a felt-tip test was developed by HyungSeop Shin et al, korea, in the "propagation of transition content and stress of crystalline current and propagation noise in GdBCO coated conductor tapes by negative stress test" to characterize the delamination stress resistance of a superconducting tape.
Ibrahim Kesgin et al, USA, in the Influence of superconductor film composition on adhesion stress of coated conductors, used a splitting method to characterize the delamination stress of a strip.
In Dai Kaihang, china, et al, improved the laser-driven electroplated copper pillars of superconducting tapes to increase the Delamination stress of tapes in the improvement of the improved said tapes.
A method for increasing the roughness of a buffer layer to increase the delamination stress of a strip material is developed in CN107103957A, namely a processing method for improving the interlayer bonding force of a second-generation high-temperature superconducting strip material by Zhao Yue and the like in China.
Chinese Zhu Jiamin et al in CN107275471A, a superconducting tape packaging device, developed a method for increasing the delamination stress of tapes by adding a packaging layer.
China Qu Timing et al, CN106373772A, "method for manufacturing high temperature superconducting coil and high temperature superconducting coil", developed a way of impregnating paraffin in the middle of coil and wrapping epoxy on the outer side. The paraffin is broken after being impregnated, and the damage phenomenon occurs after a long time.
A coil epoxy impregnation method was developed in CN113085071a "a superconducting coil impregnation die and method of use thereof", hu Lei et al, china.
Chinese li liang et al in CN110111969a "an insulation reinforcing method for superconducting coils" used water to freeze into ice at low temperature instead of epoxy impregnated coils. Such use is effective but disposable.
However, no solution has been provided to solve this problem. This problem still hinders the advancement of the industry.
The coil can be used only for a short time if it is not impregnated with epoxy, and is certainly used for a long time. However, if the coil is impregnated, the wound coil cannot be detached once the epoxy shrinkage transversely tears the superconducting tape. The superconducting tape is usually hundreds of meters short and several kilometers long. If the epoxy is not selected well or details are not made in place. Possibly tens of coils are wound down, with no exception of failure. Such failures are not accepted at all in light of the current price of superconducting tapes in 400 yuan/meter renminbi. This problem is not solved, and the application of superconducting is still in advance, which is a significant bottleneck restricting the further development of superconducting application.
The methods of the foregoing invention, while theoretically all beneficial for coil dipping, may be beneficial to the extent that the success rate of tens of dipped coils is increased by only 5-10%, or very little. Therefore, the current industry is very cautious to the problem of superconducting impregnation, and dare not to impregnate and dare not to completely impregnate. The compromises include partial epoxy impregnation, impregnation of the tape turns with paraffin or no or incomplete impregnation, followed by epoxy coating of the surface of the superconducting coils, i.e. the end faces of the tape. Thus, the influence of epoxy impregnation on strip delamination is not touched, the coil is solidified to a certain degree, and the problems of cold conduction and stress are partially solved.
However, in the use of the coil, the epoxy glue brushed on the end part of the superconducting tape can be separated from the surface of the superconducting coil after a plurality of cold and hot cycles because the epoxy glue can not be completely dipped on the surface of the superconducting tape when partial dipping is carried out or the paraffin wax on the surface of the tape is dipped in epoxy at the end part. This can lead to failure of the dip cure, again leading to failure of the superconducting application.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a superconducting tape and copper plating thereof, a preparation method, a superconducting coil and a dipping method thereof.
The preparation method of the superconducting tape provided by the invention comprises the following steps:
integrally polishing the Hastelloy, and excessively polishing the edge part to ensure that the thickness of the Hastelloy edge part is smaller than that of the non-edge part;
and plating a buffer layer and a superconducting layer on the polished Hastelloy in sequence to obtain the superconducting strip.
Preferably, the thickness of the edge part of the superconducting tape is 50% -85% of the thickness of the non-edge part, the thickness of the electrochemically polished edge part of the hastelloy is 50% -85% of the thickness of the non-edge part, and the width of the region with the thickness change of the edge part on one side after electrochemical polishing accounts for 5% -25%.
Preferably, the polishing comprises:
the Hastelloy is subjected to front washing, the purpose that the thickness of the edge part is smaller than that of the non-edge part is achieved through large-current electrochemical polishing, then the roughness of the Hastelloy is controlled within a preset range through small-current electrochemical polishing, and the Hastelloy is subjected to rear washing and drying.
Preferably, the electrochemical polishing employs an electropolishing solution comprising: 10-30% of sulfuric acid, 70-90% of phosphoric acid, 0.5-3% of citric acid and 0.5-3% of glycerol, wherein the electrochemical polishing temperature is 30-80 ℃;
a shielding plate is arranged between the anode and the cathode of the electrochemical polishing, the cathode is hastelloy, and the exposed area ratio of the cathode to the anode after shielding is 1:1-3:1, the shielding plate is arranged in parallel with the cathode and the anode in the vertical projection range of the hastelloy, and the distance between the cathode and the anode and the shielding plate is 0-20mm.
The copper plating method for the superconducting strip provided by the invention comprises the following steps:
s1: sequentially carrying out primary cleaning treatment, bright copper plating treatment and sand copper plating treatment on the superconducting strip obtained by the method of claim 1 and then carrying out secondary cleaning treatment;
s2: and passivating and drying the superconducting strip subjected to the secondary cleaning treatment.
Preferably, in step S1, a pre-copper plating process is performed before the bright copper plating process, the pre-copper plating process employs a first current electroplating process, the bright copper plating process employs a third current electroplating process, and the sand copper plating process employs a second current electroplating process.
Preferably, the first current has a current density of 6-20A/dm 2 The current density adopted by the third current is 0.5-3.5A/dm 2 The current density adopted by the second current is 3-8A/dm 2 。
Preferably, the amount of the plating solution added to the plating solution for copper pre-plating is allowed to be 6 to 20A/dm 2 The pre-plating acid copper additive for current density work comprises the following pre-plating copper electroplating solution by weight:
200-240 parts of copper sulfate;
50-70 parts of sulfuric acid;
0.08 to 0.1 portion of chloride ion;
the addition allowance of 0.5-3.5A/dm in the bright copper plating electroplating solution adopted in the bright copper plating treatment 2 The bright copper acid copper additive for current density work comprises the following components in parts by weight:
60-100 parts of copper sulfate;
170-200 parts of sulfuric acid;
0.06-0.09 part of chloride ion;
the sand copper electroplating solution used for the sand copper plating treatment is added with a permissible range of 3-8A/dm 2 The sand copper plating solution additive with current density working comprises the following components in parts by weight:
180-220 parts of copper sulfate;
50-80 parts of sulfuric acid;
0.06 to 0.13 portion of chloride ion.
Preferably, a shielding plate is arranged between the anode and the cathode plated with copper, the cathode is a superconducting tape, the shielding plate is arranged between the superconducting tape and the anode, is arranged in parallel with the cathode and the anode and shields the edge part of the superconducting tape, and the distance between the cathode and the shielding plate and the distance between the anode and the shielding plate are 0-20mm;
the shielding plate is provided with a plurality of through holes, and the copper plating uniformity is improved by shielding a part of current curve through the shielding plate.
According to the superconducting tape provided by the invention, the superconducting tape is prepared by adopting the copper plating method, and the section of the superconducting tape is rectangular or in a spindle shape, wherein the thickness of the edge part is smaller than that of the non-edge part.
According to the dipping method of the superconducting coil provided by the invention, the method is implemented by adopting the superconducting strip material and comprises the following steps:
winding a superconducting strip to obtain a lead coil body, wherein turn-to-turn gaps are formed between turns of the lead coil body, and paraffin is not filled or filled between turns;
and carrying out epoxy treatment on the wire coil body to fill epoxy between turns of the wire coil body, forming an encapsulation structure on the wire coil body to obtain the superconducting coil, and filling the epoxy in the turn-to-turn gap at the edge part of the superconducting strip.
According to the superconducting coil provided by the invention, the superconducting coil is prepared by adopting the dipping method of the superconducting coil.
Preferably, the epoxy has a thickness of 0.1mm to 5mm in the outer coating layer of the superconducting coil.
Compared with the prior art, the invention has the following beneficial effects:
1. the cross section of the superconducting strip finally obtained is in a shape that the thickness of the edge positions of two sides of a spindle shape is smaller than that of the middle position by carrying out electrochemical polishing on the hastelloy, so that the defect that the bone-shaped cross section is obtained by copper plating of the superconducting strip is overcome.
2. The superconducting coil is prepared by the superconducting tape, and epoxy can better enter a gap formed in a spindle-shaped structure in epoxy curing, so that epoxy colloid can not fall off.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a schematic view of a superconducting coil;
FIG. 2 is a schematic view showing a bone shape formed at the end portion after the plating of the superconducting tape;
FIG. 3 is a schematic view showing a bone shape formed at the end portion after the plating of the superconducting tape;
FIG. 4 is a schematic view showing displacement in a width direction of the tape caused by stacking of the superconducting tapes of the tape frame type of FIG. 3;
FIG. 5 is a schematic diagram of a superconducting coil in cross-section in a bamboo hat shape;
FIG. 6 is a schematic cross-section of a partially epoxy-impregnated superconducting coil for a coreless tape wound coil;
FIG. 7 is a schematic view of a portion of the epoxy dip being disconnected from the superconducting body after a cold-hot cycle;
FIG. 8 is a schematic cross-sectional view of a superconducting spindle tape of the present invention;
FIG. 9 is a schematic cross-sectional view of a ready-to-cure superconducting coil of the present invention;
FIG. 10 is an applied cross-sectional view of the tape shield configuration during electropolishing;
fig. 11 is an applied cross-sectional view of the tape shield structure during electroplating.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the invention.
Example 1
The present embodiment provides a method for manufacturing a superconducting tape, including:
step 1: and polishing the whole Hastelloy, and performing transition polishing on the edge part to ensure that the thickness of the Hastelloy edge part is smaller than that of the non-edge part.
Step 2: and sequentially plating a buffer layer and a superconducting layer on the polished Hastelloy, and plating a copper layer to obtain the superconducting strip shown in FIG. 8, wherein the section of the superconducting strip is in a spindle shape with small thickness at the edge position but not large thickness at the edge position due to the shape relationship of the Hastelloy.
The polishing mode can adopt electrochemical polishing: the Hastelloy is subjected to pre-washing, the forming purpose is achieved by large-current (200-300A) electrochemical polishing, and then the roughness of the Hastelloy is controlled within a preset range by small-current (90-150A) electrochemical polishing. The electro-polishing solution used for the electrochemical polishing comprises: 10-30% of sulfuric acid, 70-90% of phosphoric acid, 0.5-3% of citric acid and 0.5-3% of glycerol, wherein the electrochemical polishing temperature is 30-80 ℃. As shown in fig. 10, a shielding plate is disposed between the anode and the cathode of the electrochemical polishing, the cathode is hastelloy, and the exposed area ratio of the cathode to the anode after shielding is 1:1-3:1, the shielding plate is arranged in parallel with the cathode and the anode in the vertical projection range of the hastelloy, and the distance between the cathode and the anode and the shielding plate is 0-20mm. And finally, carrying out post-washing and drying on the hastelloy, wherein the drying temperature is 100-500 ℃, pure water is adopted for both the front washing and the post-washing, the front washing is subdivided into immersion washing and spraying, and the post-washing is subdivided into spraying and immersion washing.
The thickness of the edge part of the Hastelloy after electrochemical polishing is 50% -85% of the thickness of the non-edge part, the width of the area with the thickness change of the edge part at one side after electrochemical polishing is 5% -25%, and similarly, the thickness of the edge part of the superconducting strip is 50% -85% of the thickness of the non-edge part.
The efficiency of the copper electroplating process is also sought, however, the higher the current density applied. The ends or sharp points of the ribbon cross-section tend to produce a more intense electric field concentration effect, resulting in a bone-like shape of the ribbon cross-section. In addition, the superconducting tape may undergo a cooling-heating cycle during use. When the superconducting tape is returned to the temperature, a large amount of water is inevitably formed on the surface of the superconducting tape. Water reacts directly with the superconducting material, causing the properties of the superconducting material to be destroyed.
As shown in FIG. 11, a shielding plate is arranged between the anode and the cathode plated with copper, the cathode is a superconducting tape, the shielding plate is shielded between the edge part of the superconducting tape and the anode, and is arranged parallel to the cathode and the anode, the edge part of the superconducting tape is shielded, the distance between the cathode and the shielding plate and the anode is 0-20mm, the shielding plate is preferably made of PP material, a plurality of through holes are arranged on the shielding plate, the size of the through holes is 3-8mm, and the uniformity of copper plating is improved by shielding a part of current curve through the shielding plate.
The copper plating method comprises the following steps:
s1: and sequentially carrying out primary cleaning treatment, bright copper plating treatment and sand copper plating treatment on the obtained superconducting strip, and then carrying out secondary cleaning treatment.
S2: and passivating and drying the superconducting strip subjected to the secondary cleaning treatment.
In the step S1, a pre-copper plating treatment is carried out before a bright copper plating treatment, the first current electroplating treatment is adopted in the pre-copper plating treatment, the third current electroplating treatment is adopted in the bright copper plating treatment, and the second current electroplating treatment is adopted in the sand copper plating treatment. The first current adopts a current density of 6-20A/dm 2 The current density of the third current is 0.5-3.5A/dm 2 The current density adopted by the second current is 3-8A/dm 2 。
The allowance of the addition of the plating solution of 6 to 20A/dm to the plating solution of the pre-plating copper for the pre-plating copper treatment 2 The pre-plating acid copper additive for current density work comprises the following pre-plating copper electroplating solution by weight:
200-240 parts of copper sulfate;
50-70 parts of sulfuric acid;
0.08 to 0.1 portion of chloride ion;
adding the plating solution of 0.5-3.5A/dm into the plating solution of bright copper for bright copper plating treatment 2 The bright copper sulfate additive for current density operation comprises the following components in parts by weight:
60-100 parts of copper sulfate;
170-200 parts of sulfuric acid;
0.06-0.09 part of chloride ion;
adding allowable 3-8A/dm into sand copper electroplating solution for treating sand copper 2 The additive of the sand copper acid working at current density comprises the following components in parts by weight:
180-220 parts of copper sulfate;
50-80 parts of sulfuric acid;
0.06 to 0.13 portion of chloride ion.
In the electroplating process, the pre-copper plating operation is firstly carried out through the preset current so that the copper quickly coats the surface of the strip, the influence of liquid on the performance of the strip due to the fact that the liquid contacts the strip through the holes in the silver plating surface can be effectively prevented, the problem that the liquid corrodes a superconducting layer is solved, a copper plating layer forms a complete sheath, and the quality of the strip is greatly improved. The shielding structure is arranged in the copper plating operation process, the power lines are uniform and not concentrated, the bone type structure in the prior art can be effectively avoided, the bone type of the cross section is small, the total deviation of the thickness of the cross section of the strip material reaches +/-1 mu m, and the quality of the superconducting strip material is ensured. The electroplating solution of the invention can also increase the effect and speed of preplating to a certain extent.
Example 2
The present embodiment provides a dipping method of a superconducting coil, which uses the superconducting tape prepared in embodiment 1, and performs the steps including:
the superconducting tape is wound as shown in fig. 1 to obtain a superconducting coil body, the cross section is shown in fig. 9, turn-to-turn gaps are formed between turns of the superconducting coil body, and the turns can be filled with paraffin or not filled with paraffin. Since the edge thickness of the superconducting tape is smaller than that of the waste edge, the inter-turn gap at the edge position is larger, and the epoxy is simultaneously filled in the inter-turn gap at the edge portion of the superconducting tape.
And fixing the superconducting coil body in a pouring mold, and carrying out epoxy treatment on the superconducting coil body to fill epoxy between turns of the superconducting coil body, so as to form an encapsulation structure on the superconducting coil body and obtain the superconducting coil. The specific operation mode comprises the following steps: the superconducting coil body is fixed and then immersed in a pouring mold with epoxy materials. Meanwhile, verified tension can be applied to the two ends of the superconducting coil body, and the curing effect is guaranteed. And after the superconducting coil body is fully immersed, taking out the superconducting coil body for cooling, so that the epoxy is effectively filled in gaps among turns of the spindle-shaped strip.
In the description of the present application, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience in describing the present application and simplifying the description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present application.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (13)
1. A method for producing a superconducting tape, comprising:
integrally polishing the Hastelloy, and excessively polishing the edge part to ensure that the thickness of the edge part of the Hastelloy is 50-85% of the thickness of the non-edge part;
and sequentially plating a buffer layer, a superconducting layer and a copper layer on the polished Hastelloy to obtain the superconducting strip.
2. The method of manufacturing a superconducting tape according to claim 1, wherein the thickness of the edge portion of the superconducting tape is 50 to 85% of the thickness of the non-edge portion, and the thickness variation region of the edge portion after the overpolishing accounts for 5 to 25% of the width of the hastelloy.
3. A method for manufacturing a superconducting tape according to claim 1, wherein the polishing is performed by:
the Hastelloy is subjected to pre-washing, the purpose that the thickness of the edge part is smaller than that of the non-edge part is achieved through large-current electrochemical polishing, then the roughness of the Hastelloy is controlled within a preset range through small-current electrochemical polishing, and the Hastelloy is subjected to post-washing and drying.
4. A method for producing a superconducting tape according to claim 3, wherein the electropolishing solution used for the electrochemical polishing comprises: 10-30% of sulfuric acid, 70-90% of phosphoric acid, 0.5-3% of citric acid and 0.5-3% of glycerol, wherein the electrochemical polishing temperature is 30-80 ℃;
a shielding plate is arranged between the anode and the cathode of the electrochemical polishing, the cathode is hastelloy, and the exposed area ratio of the cathode to the anode after shielding is 1:1-3:1, the shielding plate is arranged in parallel with the cathode and the anode within the vertical projection range of the hastelloy, and the distance between the cathode and the anode and the shielding plate is 0-20mm.
5. The method of manufacturing a superconducting tape according to claim 1, wherein the copper plating layer comprises the steps of:
s1: sequentially carrying out primary cleaning treatment, bright copper plating treatment and sand copper plating treatment on the hastelloy before copper plating, and then carrying out secondary cleaning treatment;
s2: and passivating and drying the hastelloy subjected to the secondary cleaning treatment.
6. The method of manufacturing a superconducting tape according to claim 5, wherein a pre-copper plating treatment is performed before the bright copper plating treatment in step S1, the pre-copper plating treatment is a first current plating treatment, the bright copper plating treatment is a third current plating treatment, and the matte copper plating treatment is a second current plating treatment.
7. The method for producing a superconducting tape according to claim 6, wherein the first current has a current density of 6 to 20A/dm 2 The current density adopted by the third current is 0.5-3.5A/dm 2 The current density adopted by the second current is 3-8A/dm 2 。
8. The method for producing a superconducting tape according to claim 7, wherein the copper pre-plating solution is added to the copper pre-plating solution to be used in the copper pre-plating treatment in an amount of 6 to 20A/dm 2 The acid copper pre-plating additive for current density work comprises the following pre-plating copper electroplating solution in parts by weight:
200-240 parts of copper sulfate;
50-70 parts of sulfuric acid;
0.08 to 0.1 portion of chloride ion;
the addition allowance of 0.5-3.5A/dm in the bright copper plating electroplating solution adopted in the bright copper plating treatment 2 The bright copper acid copper additive for current density work comprises the following components in parts by weight:
60-100 parts of copper sulfate;
170-200 parts of sulfuric acid;
0.06-0.09 part of chloride ion;
the sand copper electroplating solution adopted by the sand copper plating treatment is added with a permissible amount of 3-8A/dm 2 The sand copper plating solution additive with current density working comprises the following components in parts by weight:
180-220 parts of copper sulfate;
50-80 parts of sulfuric acid;
0.06 to 0.13 portion of chloride ion.
9. A method for manufacturing a superconducting tape according to claim 5, wherein a shielding plate is provided between the anode and the cathode plated with copper, the cathode is the superconducting tape, the shielding plate is provided between the superconducting tape and the anode, and is provided in parallel with the cathode and the anode to shield an edge portion of the superconducting tape, and the distance between the cathode and the shielding plate and the distance between the anode and the shielding plate are 0 to 20mm;
the shielding plate is provided with a plurality of through holes, and the copper plating uniformity is improved by shielding a part of current curve through the shielding plate.
10. A superconducting tape produced by the method for producing a superconducting tape according to any one of claims 5 to 9, which has a rectangular cross section or a spindle shape having a thickness in an edge portion smaller than that in a non-edge portion.
11. A method of dipping a superconducting coil, characterized in that the method, using the superconducting tape of claim 10, is performed by:
winding a superconducting strip to obtain a lead coil body, wherein turn-to-turn gaps are formed between turns of the lead coil body, and paraffin is not filled or filled between turns;
and carrying out epoxy treatment on the wire coil body to fill epoxy between turns of the wire coil body, forming an encapsulation structure on the wire coil body to obtain the superconducting coil, and filling the epoxy in the turn-to-turn gap at the edge part of the superconducting strip.
12. A superconducting coil produced by the dipping method for a superconducting coil according to claim 11.
13. The superconducting coil of claim 12, wherein the epoxy has a thickness of 0.1mm to 5mm in an outer coating layer of the superconducting coil.
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