CN111235522A - Method for producing photovoltaic solder strip by adopting evaporated tin-plated alloy - Google Patents
Method for producing photovoltaic solder strip by adopting evaporated tin-plated alloy Download PDFInfo
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- CN111235522A CN111235522A CN202010185803.4A CN202010185803A CN111235522A CN 111235522 A CN111235522 A CN 111235522A CN 202010185803 A CN202010185803 A CN 202010185803A CN 111235522 A CN111235522 A CN 111235522A
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- 229910000679 solder Inorganic materials 0.000 title claims abstract description 60
- 239000000956 alloy Substances 0.000 title claims abstract description 41
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 238000001704 evaporation Methods 0.000 claims abstract description 66
- 230000008020 evaporation Effects 0.000 claims abstract description 62
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 75
- 239000010949 copper Substances 0.000 claims description 69
- 229910052802 copper Inorganic materials 0.000 claims description 63
- 238000000576 coating method Methods 0.000 claims description 56
- 239000000463 material Substances 0.000 claims description 56
- 239000011248 coating agent Substances 0.000 claims description 53
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 48
- 238000005238 degreasing Methods 0.000 claims description 17
- 238000007747 plating Methods 0.000 claims description 14
- 238000004804 winding Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000013527 degreasing agent Substances 0.000 claims description 8
- 238000005237 degreasing agent Methods 0.000 claims description 8
- 238000005202 decontamination Methods 0.000 claims description 7
- 230000003588 decontaminative effect Effects 0.000 claims description 7
- 238000005476 soldering Methods 0.000 claims description 7
- 229910052580 B4C Inorganic materials 0.000 claims description 6
- 229910018082 Cu3Sn Inorganic materials 0.000 claims description 6
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000004907 flux Effects 0.000 claims description 6
- 229910000765 intermetallic Inorganic materials 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052745 lead Inorganic materials 0.000 description 10
- 238000001755 magnetron sputter deposition Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 238000003466 welding Methods 0.000 description 6
- 238000007738 vacuum evaporation Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000003618 dip coating Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000013077 target material Substances 0.000 description 3
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- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
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- 229910001174 tin-lead alloy Inorganic materials 0.000 description 2
- 229910020816 Sn Pb Inorganic materials 0.000 description 1
- 229910020922 Sn-Pb Inorganic materials 0.000 description 1
- 229910008783 Sn—Pb Inorganic materials 0.000 description 1
- QKAJPFXKNNXMIZ-UHFFFAOYSA-N [Bi].[Ag].[Sn] Chemical compound [Bi].[Ag].[Sn] QKAJPFXKNNXMIZ-UHFFFAOYSA-N 0.000 description 1
- KHZAWAWPXXNLGB-UHFFFAOYSA-N [Bi].[Pb].[Sn] Chemical compound [Bi].[Pb].[Sn] KHZAWAWPXXNLGB-UHFFFAOYSA-N 0.000 description 1
- PSYREZBZBZKHDF-UHFFFAOYSA-N [Sn].[Pb].CS(=O)(=O)O Chemical compound [Sn].[Pb].CS(=O)(=O)O PSYREZBZBZKHDF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
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- 229910052737 gold Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 238000006386 neutralization reaction Methods 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000009993 protective function Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
- C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention belongs to the technical field of photovoltaic solder strips, and discloses a method for producing a photovoltaic solder strip by adopting an evaporation tin-plated alloy, wherein the specified plastic elongation strength of the photovoltaic solder strip obtained by the method is reduced by 17.2-21.3%, the concentricity is improved by 19.82-61.90%, the process is simple, the cost is low, the production efficiency is high, no harmful substance is discharged in the whole production process, and the method is green and environment-friendly.
Description
Technical Field
The invention relates to the technical field of photovoltaic solder strips, in particular to a method for producing a photovoltaic solder strip by adopting an evaporation tinned alloy.
Background
The photovoltaic solder strip is formed by uniformly coating a copper material with a tin alloy and then welding the tin alloy on a photovoltaic module cell to play a role in conducting and gathering electricity. The tin alloy which can be used for coating is divided into tin-lead, tin-lead-bismuth, tin-bismuth-silver and the like, wherein the tin-lead alloy is used in the largest amount and has the widest application range, and the tin-lead alloy is required to have uniform thickness, smooth surface, low specified plastic elongation strength, good concentricity and the like when being coated with a copper material.
In the prior art, the method for coating the surface of copper material with tin alloy mainly comprises three methods: hot dip plating, electroplating and magnetron sputtering. The hot dip coating method is characterized in that molten tin alloy liquid is adopted, copper materials are immersed and penetrated out at a high speed, and the tin liquid attached to the surface of the copper materials is uniformly expanded through surface tension, and then is solidified to form a coating after excessive tin liquid is scraped by an air knife or a mould. The thickness of the coating produced by the process is generally 15-25 microns, the tin consumption is large, tin slag and tin nodules are easily generated on the appearance, and the defects of uneven thickness, serious eccentricity and the like are easily generated.
The electroplating method is to electroplate tin, lead and other metal coatings on the surface of a copper material, but because the dispersion capacity of the coating solution is poor, the tip effect is large, thickening, burrs and filiform whiskers of the coating are easy to generate, meanwhile, the deposition speed of the coating is slow, the current efficiency is low, and secondly, the coating solution contains heavy metal and organic additives, so that the environmental pollution is serious.
Magnetron sputtering coating is a technology of bombarding the surface of a target by using charged particles in vacuum to deposit the bombarded particles on a substrate. But the working vacuum is lower than the evaporation coating by one order of magnitude, so the gas content of the film layer is higher than that of the evaporation coating; meanwhile, the utilization rate of the target material is not high, equipment is complex, the manufacturing cost is high, a high-pressure environment is required, and the requirement on an operator is high, so that the target material is not suitable for being used in a photovoltaic welding strip. In addition, the melting point of Sn-Pb alloy used for the solder strip is low, such as Sn60Pb40The melting point of the alloy is 190 ℃ in order to avoid Sn of the target material60Pb40Dissolution to form a karst cave and short circuit, and low power used during film coating to cause slow deposition rate; the magnetron sputtering coating power supply has poor protective function, cannot automatically stop working in time after being overloaded, and is not beneficial to mass production industrialization.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for producing a photovoltaic solder strip by adopting an evaporation tin-plated alloy, the specified plastic elongation strength of the photovoltaic solder strip obtained by the method is reduced by 17.2-21.3%, the concentricity is improved by 19.82-61.90%, the process is simple, the cost is low, the production efficiency is high, no harmful substance is discharged in the whole production process, and the method is green and environment-friendly.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme.
A method for producing a photovoltaic solder strip by adopting an evaporation tin-plated alloy comprises the following steps:
step 1, sequentially performing decontamination and degreasing, pre-drawing and straightening on the unreeled copper material, and applying voltage for softening to obtain a softened copper material;
step 2, activating and heating the softened copper material by using a soldering flux, and performing evaporation tin-plating alloy on the copper material by using an evaporation winding coating process to obtain the copper material with a tin alloy coating on the surface;
step 3, carrying out vacuum curing treatment on the copper material with the tin alloy coating on the surface to form Cu between the tin alloy coating and the copper base material6Sn5And Cu3Sn intermetallic compound.
Preferably, in the step 1, the copper material is a round or triangular section copper wire and a rectangular or trapezoidal section copper strip.
Preferably, in step 1, the degreasing and degreasing is performed by washing with water, degreasing with an alkaline degreasing agent, and washing with water again.
Preferably, in the step 1, the softening current is 15-40.6A, and the softening voltage is 16-43.3V.
Preferably, in the step 2, the heating temperature is 90-120 ℃.
Preferably, in the step 2, the vacuum degree of the evaporation winding coating is 4.5 × 10-4～7.5×10-4Pa, the current of the evaporation boat for the evaporation winding coating is 450-600A, the voltage is 4-7V, and the evaporation boat for the evaporation winding coating is made of boron carbide.
Preferably, in the step 2, the evaporation distance of the evaporation winding coating is 45-50 cm.
Preferably, in the step 2, the wire feeding amount of the evaporation winding coating film is 1.5-2.4 m/min, the diameter of the wire is phi 2mm, and the take-up speed of the evaporation winding coating film is 50-450 m/min.
Preferably, in the step 2, the thickness of the coating of the tin alloy is 3-5.5 microns.
Preferably, in step 3, the vacuum degree of the vacuum curing is 1 × 10-2～3×10-2Pa, the temperature of vacuum curing is 40-65 ℃, and the time of vacuum curing is 0.5-1.5 min.
Preferably, in step 3, the tin alloy is pure Sn or a Sn-based composite solder.
More preferably, the Sn-based composite solder is composed of Sn and one or more elements selected from Ag, Cu, Bi, Ni, Au, Pd, and Pb.
Compared with the prior art, the invention has the beneficial effects that:
1) the photovoltaic solder strip produced by the evaporation tinned alloy has the specified plastic elongation strength of 54.9228-57.143 Mpa, the elongation after fracture of 21.1338-24.5786%, the thickness of 3-5.5 mu m and the concentricity of 72-75.61%.
2) Compared with the prior art, the specified plastic elongation strength of the photovoltaic solder strip produced by the evaporation tin-plated alloy is reduced by 17.2-21.3%, and the concentricity of the solder strip is improved by 19.82-61.90%.
3) The method of the invention adopts evaporation plating to simplify the process flow, save the cost of an air knife or a die, reduce the specified plastic extension strength, improve the concentricity of the coating, optimize the surface quality of the welding strip and improve the production efficiency, and the whole production process has no discharge of harmful substances and is green and environment-friendly.
4) Compare with current high temperature curing, this application adopts vacuum curing to handle, can avoid the photovoltaic solder strip to be by oxidation, and the solidification required time is short, and production efficiency is high.
Drawings
FIG. 1 is an optical image of a section of a photovoltaic solder strip obtained in example 1;
FIG. 2 is an optical picture of a section of the photovoltaic solder strip obtained in comparative example 2;
FIG. 3 is an optical picture of a section of a photovoltaic solder ribbon obtained in comparative example 3;
in the figure, the inner ring is a copper base material, and the outer ring is a tin alloy coating.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
Example 1
A method for producing a photovoltaic solder strip by adopting an evaporation tin-plated alloy comprises the following steps:
step 1, pretreatment: after an oxygen-free copper wire with the size of phi 0.2mm is unreeled, decontamination and degreasing are sequentially carried out (firstly washing, then degreasing in an acid or alkali degreasing agent, then washing again, drying by compressed air), an alignment mechanism is adopted for pre-stretching alignment, and then the copper wire is placed between a front driving wheel and a rear driving wheel and is added with 15.1A/16.2V for softening and annealing, so as to obtain the softened copper material.
Step 2, evaporating the tin-plated alloy: the softened copper material is activated by using soldering flux (Hangzhou union cleaning-free type), and a vacuum chamber is vacuumized by 7 x 10-4Pa, heating the copper material to 120 ℃ by combining an evaporation boat and infrared, starting vacuum evaporation, wherein the voltage of the evaporation boat is 5V, the current is 500A, the evaporation distance is 45cm, the wire feeding speed is 2.2m/min, and the wire take-up speed is 50m/min, so as to obtain the copper material with the tin alloy coating on the surface; wherein the tin alloy is 60% Sn + 40% Pb, the evaporation boat is made of boron carbide, the tin alloy is 60% Sn + 40% Pb, and the average thickness of the coating of the tin alloy is 4.6 microns.
Step 3, vacuum curing: placing the copper material with tin alloy coating on the surface in a vacuum degree of 1 × 10-2Continuously solidifying for 1min in a vacuum exchange chamber with Pa and a temperature of 55 ℃, facilitating the wire take-up after the reciprocating solidification of a mechanical device, and forming Cu between the tin alloy coating and the copper base material6Sn5And Cu3Sn intermetallic compound to obtain the photovoltaic solder strip, wherein the optical picture of the section of the photovoltaic solder strip is shown in figure 1.
Example 2
A method for producing a photovoltaic solder strip by adopting an evaporation tin-plated alloy comprises the following steps:
step 1, pretreatment: after an oxygen-free copper wire (a copper wire with an equilateral triangle section with the side length of 0.5 mm) is unreeled, decontamination and degreasing (washing first, degreasing in an alkali degreasing agent, washing again, drying by compressed air) are sequentially carried out, straightening is carried out by adopting a straightening mechanism in a pre-stretched mode, and then the copper material is placed between a front driving wheel and a rear driving wheel and is softened and annealed by adding 20A/20V to obtain the softened copper material.
Step 2, evaporating the tin-plated alloy: the softened copper material is activated by using soldering flux (Hangzhou union cleaning-free type), and a vacuum chamber is vacuumized by 4.5 multiplied by 10-4Pa, heating the copper material to 110 ℃ by combining an evaporation boat and infrared, starting vacuum evaporation, and obtaining the copper material with a tin alloy coating on the surface, wherein the voltage of the evaporation boat is 4V, the current is 450A, the evaporation distance is 50cm, the wire feeding speed is 2.4m/min, and the wire take-up speed is 150 m/min; wherein the tin alloy is 60% Sn + 40% Pb, the evaporation boat is made of boron carbide, the tin alloy is 60% Sn + 40% Pb, and the average thickness of the coating of the tin alloy is 3 microns.
Step 3, vacuum curing: putting the copper material with the tin alloy coating on the surface into a vacuum degree of 2 multiplied by 10-2Continuously solidifying for 1min in a vacuum exchange chamber with Pa and 40 ℃, facilitating the wire take-up after the reciprocating solidification of a mechanical device, and forming Cu between the tin alloy coating and the copper base material6Sn5And Cu3Sn intermetallic compound, namely the photovoltaic solder strip with the average concentricity of 72 percent.
Example 3
A method for producing a photovoltaic solder strip by adopting an evaporation tin-plated alloy comprises the following steps:
step 1, pretreatment: after an oxygen-free copper strip (a copper strip with an equilateral rectangular section with the side length of 0.5 mm) is unreeled, decontamination degreasing (firstly washing, then degreasing in an alkali degreasing agent, washing again, drying by compressed air) is carried out in sequence, straightening is carried out in a pre-tensioning manner by adopting a straightening mechanism, and then the copper strip is placed between a front driving wheel and a rear driving wheel and is softened and annealed by adding 30A/30V to obtain the softened copper material.
Step 2, evaporating the tin-plated alloy: the softened copper material is activated by using soldering flux (Hangzhou union cleaning-free type), and a vacuum chamber is vacuumized by 6 multiplied by 10-4Pa, heating the copper material to 90 ℃ by combining an evaporation boat and infrared raysStarting vacuum evaporation, wherein the voltage of an evaporation boat is 7V, the current is 600A, the evaporation distance is 47cm, the wire feeding speed is 1.5m/min, and the wire take-up speed is 350m/min, so as to obtain copper material with a tin alloy coating on the surface; wherein the tin alloy is 60% Sn + 40% Pb, the evaporation boat is made of boron carbide, the tin alloy is 60% Sn + 40% Ag, and the average thickness of the coating of the tin alloy is 5.5 microns.
Step 3, vacuum curing: placing the copper material with tin alloy coating on the surface in a vacuum degree of 3 multiplied by 10-2Continuously solidifying for 1.5min in a vacuum exchange chamber with Pa and a temperature of 65 ℃, facilitating the wire take-up after the reciprocating solidification of a mechanical device, and forming Cu between the tin alloy coating and the copper base material6Sn5And Cu3Sn intermetallic compound, namely the photovoltaic solder strip with the average concentricity of 73.4 percent.
Example 4
A method for producing a photovoltaic solder strip by adopting an evaporation tin-plated alloy comprises the following steps:
step 1, pretreatment: after an oxygen-free copper wire with the size of phi 0.375mm is unreeled, decontamination and degreasing are sequentially carried out (firstly washing, then degreasing in an alkali degreasing agent, secondly washing, drying by compressed air), an alignment mechanism is adopted for pre-stretching and aligning, and then the copper wire is placed between a front driving wheel and a rear driving wheel and is added with 40A/40V for softening and annealing, so as to obtain the softened copper material.
Step 2, evaporating the tin-plated alloy: the softened copper material is activated by using soldering flux (Hangzhou union cleaning-free type), and a vacuum chamber is vacuumized by 7.5 multiplied by 10-4Pa, heating the copper material to 105 ℃ by combining an evaporation boat and infrared, starting vacuum evaporation, wherein the voltage of the evaporation boat is 4V, the current is 450A, the evaporation distance is 50cm, the wire feeding speed is 1.5m/min, and the wire take-up speed is 220m/min, so as to obtain the copper material with the tin alloy coating on the surface; wherein the tin alloy is pure Sn, the evaporation boat is made of boron carbide, the tin alloy is 60% Sn + 40% Pb, and the average thickness of the coating of the tin alloy is 4.3 microns.
Step 3, vacuum curing: placing the copper material with tin alloy coating on the surface in a vacuum degree of 7.5 multiplied by 10-4Continuously solidifying for 1min in a vacuum exchange chamber with Pa and a temperature of 57 ℃, facilitating the wire take-up after the reciprocating solidification of a mechanical device, and forming Cu between the tin alloy coating and the copper base material6Sn5And Cu3Sn intermetallic compound, namely the photovoltaic solder strip with average concentricity of 73.67 percent.
In the above examples, the alkaline degreasing agent used was a commercially available alkaline degreasing agent.
Comparative example 1
A method for producing a solar photovoltaic welding strip by adopting magnetron sputtering tinned alloy comprises the following steps:
step 1, pretreatment: after an oxygen-free copper wire with the size of phi 0.375mm is unreeled, sequentially carrying out decontamination, degreasing, pre-drawing and straightening, and then placing between a front driving wheel and a rear driving wheel to carry out softening annealing by adding 23.5A/22.9V;
step 2, magnetron sputtering of tin-plated alloy: vacuum chamber is vacuumized by 4 x 10-3Pa, heating the copper material to 200 ℃ by adopting infrared, introducing argon, starting vacuum evaporation, controlling the cathode voltage to be 300V, controlling the current to be 9A, sputtering and vacuum plating to be 0.13-1.3 Pa, controlling the sputtering time to be 10min and controlling the take-up speed to be 50m/min, wherein the tin alloy is 60% Sn + 40% Pb;
and 3, curing the copper material subjected to magnetron sputtering of the tin-plated alloy at a high temperature of 150-180 ℃ for 15-20 min to obtain the copper material.
Comparative example 2
A method for producing a photovoltaic solder strip by adopting an electroplated tin alloy comprises the following steps:
step 1, pretreatment: after an oxygen-free copper wire with the size of phi 0.375mm is unreeled, the oxygen-free copper wire is sequentially decontaminated, degreased and pre-stretched and aligned, then is placed between a front driving wheel and a rear driving wheel, is added with 23.5A/22.9V for softening and annealing, and is then placed in an acidic sulfonate solution for etching, so that a pre-treated copper material is obtained.
Step 2, electroplating tin alloy: immersing the pretreated copper wire into an electroplating bath solution at the speed of 10m/min and the current density of 40A/dm2 at the temperature of 25 ℃ for 100-180 s, wherein the bath solution comprises the following components: the tin-lead methane sulfonic acid system, wherein the molar concentration ratio of tin to lead is 30:20, and the copper material after electrolytic tin alloy plating is obtained.
And 3, placing the copper material plated with the tin alloy in a sodium phosphate solution for neutralization to obtain a finished photovoltaic solder strip with the tin alloy of 60% Sn + 40% Pb, wherein an optical picture of a section of the photovoltaic solder strip obtained by the electroplating method is shown in FIG. 2.
Comparative example 3
A method for producing photovoltaic solder strips by using hot dip tinned alloy comprises the following steps:
step 1, pretreatment: after an oxygen-free copper wire with the size of phi 0.375mm is unreeled, the oxygen-free copper wire is sequentially decontaminated, degreased, pre-stretched and straightened, and then placed between a front driving wheel and a rear driving wheel to be softened by adding 23.5A/22.9V, so as to obtain the softened copper material.
Step 2, hot-dip tinning alloy: hot-dip coating the softened copper material with a tin alloy material for 0.15 second at 240 ℃, wherein the take-up speed is 50m/min, so as to obtain a photovoltaic solder strip, and an optical picture of a section of the photovoltaic solder strip obtained by the hot-dip coating method is shown in fig. 3; wherein the tin alloy is 60% Sn + 40% Pb.
Test of
Test 1
1) The test method comprises the following steps: the photovoltaic solder strip produced by the evaporation tin-plated alloy in example 1 was sampled 20 times, the maximum force (Fm), the tensile strength (Rm), the specified plastic elongation (Rp), and the elongation after fracture (a) of the photovoltaic solder strip were measured, and the average of the 20 measurement results was obtained, and the specific test method was referred to GB/T228.1-2010 "part 1 of the metal material tensile test: room temperature test methods.
2) And (3) test results: as shown in table 1.
Table 1 mechanical property test results of photovoltaic solder strips of example 1
The lower the Rp value and the higher the A value, the better the welding performance of the welding strip. As can be seen from Table 1, the photovoltaic solder strip produced by using the evaporated tin-plated alloy has better soldering performance.
Test 2
1) Test method
Photovoltaic solder strip obtained in example 1 and photovoltaic solder produced by adopting electroplated tin alloy in comparative example 1Tapes, comparative example 2 photovoltaic solder tapes produced from hot dip tinned alloy, comparative example 3 solar photovoltaic solder tapes produced from magnetron sputtering tinned alloy, specified plastic elongation (Rp), elongation after break (a), maximum thickness (δ)max) Minimum thickness (delta)min) And concentricity of&) And (6) carrying out testing. The specified plastic elongation (Rp) and the elongation after fracture (a) of the photovoltaic solder strip obtained in example 1 are the average values of test 1, and 2 significant figures are retained.
Concentricity of&＝(1-(δmax－δmin)/δmin)×100
In the formula (I), the compound is shown in the specification,&representing the evaluation value of concentricity, δmaxAnd deltaminThe maximum value and the minimum value are measured on a single side of the coating respectively. When in use&When the concentricity is 100, the concentricity of the plating layer is optimal; while&And when the maximum value is 0, the maximum value of one side of the coating of the product is 2 times of the minimum value.
2) And (3) test results: the test results are shown in table 2.
TABLE 2 product Performance test results of example 1 and comparative examples 1 to 3
As can be seen from Table 2, the specified plastic elongation strength of the photovoltaic solder ribbon produced by the evaporation tin-plated alloy of the present application is significantly lower than that of the photovoltaic solder ribbons obtained in comparative examples 1 to 3 in terms of the specified plastic elongation strength Rp, and is reduced by 17.2% in comparison with the magnetron sputtering plating of comparative example 1, 21.2% in comparison with the plating of comparative example 2, and 21.3% in comparison with the hot dip plating of comparative example 3.
The concentricity of the photovoltaic solder ribbon produced by the evaporation tin-plated alloy is obviously higher than that of the photovoltaic solder ribbons obtained by the comparative examples 1-3, and the evaporation plating is improved by 31.06 percent compared with the magnetron sputtering plating of the comparative example 1, is improved by 19.82 percent compared with the electroplating of the comparative example 2, and is improved by 61.90 percent compared with the hot dip plating of the comparative example 3. And as can be seen from fig. 1 to 3, the concentricity of the photovoltaic solder strip obtained in the present application is significantly better than that of the photovoltaic solder strips obtained in comparative examples 2 to 3.
In conclusion, compared with the prior art, the method has the advantages that the Rp is reduced by 17.2-21.3%, and the concentricity of the plating layer is improved by 19.82-61.90%.
Although the present invention has been described in detail in this specification with reference to specific embodiments and illustrative embodiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto based on the present invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (9)
1. A method for producing a photovoltaic solder strip by adopting an evaporation tin-plated alloy is characterized by comprising the following steps:
step 1, sequentially performing decontamination and degreasing, pre-drawing and straightening on the unreeled copper material, and applying voltage for softening to obtain a softened copper material;
step 2, activating and heating the softened copper material by using a soldering flux, and performing evaporation tin-plating alloy on the copper material by using an evaporation winding coating process to obtain the copper material with a tin alloy coating on the surface;
step 3, carrying out vacuum curing treatment on the copper material with the tin alloy coating on the surface to form Cu between the tin alloy coating and the copper base material6Sn5And Cu3Sn intermetallic compound.
2. The method for producing photovoltaic solder strips by using evaporated tin-plated alloy according to claim 1, wherein in step 1, the copper materials are round or triangular cross-section copper wires and rectangular or trapezoidal cross-section copper strips.
3. The method for producing photovoltaic solder strips by using evaporated tin-plated alloy according to claim 1, wherein in the step 1, the degreasing and degreasing is water washing, degreasing in an alkaline degreasing agent and water washing again.
4. The method for producing the photovoltaic solder strip by using the evaporation tin-plated alloy according to claim 1, wherein in the step 1, the softening current is 15-40.6A, and the softening voltage is 16-43.3V.
5. The method for producing the photovoltaic solder strip by using the evaporation tin-plated alloy as recited in claim 1, wherein the heating temperature in the step 2 is 90-120 ℃.
6. The method for producing photovoltaic solder ribbon by using evaporation tin-plated alloy according to claim 1, wherein in the step 2, the degree of vacuum of the evaporation coil coating is 4.5 x 10-4～7.5×10-4Pa, the current of the evaporation boat for the evaporation winding coating is 450-600A, the voltage is 4-7V, and the evaporation boat for the evaporation winding coating is made of boron carbide.
7. The method for producing the photovoltaic solder strip by adopting the evaporation tin-plated alloy according to claim 1, wherein in the step 2, the evaporation distance of the evaporation winding coating is 45-50 cm, the wire feeding amount of the evaporation winding coating is 1.5-2.4 m/min, the diameter of the wire is phi 2mm, and the take-up speed of the evaporation winding coating is 50-450 m/min.
8. The method for producing the photovoltaic solder strip by using the evaporation tin-plated alloy according to claim 1, wherein in the step 2, the thickness of the coating of the tin alloy is 3-5.5 microns.
9. The method for producing photovoltaic solder ribbon by using evaporation tin-plated alloy as recited in claim 1, wherein in step 3, the degree of vacuum solidification is 1 x 10-2～3×10-2Pa, the temperature of vacuum curing is 40-65 ℃, and the time of vacuum curing is 0.5-1.5 min.
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