CN107591460B - Photovoltaic solder strip and preparation method thereof - Google Patents
Photovoltaic solder strip and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a photovoltaic solder strip and a preparation method thereof, wherein the photovoltaic solder strip comprises a base material and a tin-lead alloy solder coated on the base material, and the tin-lead alloy solder comprises 0.05-0.5% of copper, 0.1-1% of silver and 0.01-0.05% of phosphorus. The copper, silver and phosphorus elements added in the tin-lead alloy solder can improve the oxidation resistance, the wettability and the peeling strength of the photovoltaic solder strip, and simultaneously the resistivity of the photovoltaic solder strip is reduced by 9.8 percent, which is equivalent to improving the power of a photovoltaic module by about 0.8W and reducing the photoelectric conversion efficiency loss caused by resistance power loss. The copper, silver and phosphorus elements have higher intermiscibility, can inhibit the added copper and silver elements from being corroded by the tin liquid, and avoid the phenomenon of insufficient soldering of the battery piece. The surface layer of the photovoltaic solder strip disclosed by the invention is rich in phosphorus and tin alloy, and can play a role in reducing the local temperature of a solder joint during the welding of a battery piece, so that the welding is facilitated. The preparation method of the photovoltaic solder strip is simple, low in cost, easy to operate and implement, free of environmental pollution and convenient for industrial production and application.
Description
Technical Field
The invention relates to a solar photovoltaic welding strip and the processing technical field thereof, in particular to a photovoltaic welding strip and a preparation method thereof.
Background
The photovoltaic solder strip is an important raw material in the welding process of the photovoltaic module, the quality of the solder strip directly affects the current collection efficiency of the photovoltaic module, and the power of the photovoltaic module is greatly affected. At present, in a conventional photovoltaic module, different battery pieces are connected in series through an interconnection bar, and the purpose of module power output is achieved through a bus bar. The welding strip connects the battery pieces in a series connection mode, one end of the welding strip is welded on the front face of the battery, the other end of the welding strip is welded on the back face of the other battery, and the welding strip is packaged into the photovoltaic module. Sunlight enters the battery from the front side of the battery, the welding strip on the front side can shield a part of silicon wafer, and the light energy shielded on the part of the welding strip can not be converted into electric energy. One of the main functions of the solder strip is to conduct current, and from the viewpoint of resistivity analysis, the thinner the solder strip is, the smaller the conductive cross-sectional area is, and the greater the resistance loss is, so that the width of the solder strip is balanced between the light shielding area and the conductivity. How to reduce the resistivity of the photovoltaic solder strip under the condition of ensuring that the cross-sectional area of the solder strip is not changed, and further improve the photoelectric conversion efficiency of the photovoltaic module is a problem to be solved urgently.
In order to reduce the resistivity of the photovoltaic solder strip and improve the photoelectric conversion efficiency of the photovoltaic module, a plurality of solder strip manufacturers break through the aspects of reducing the shading area, increasing the reflectivity of light and the like. For example, holes are formed in the surface of the solder strip, so that the shading area and the use amount of the solder strip are reduced, but the production process of the solder strip needs to be increased, and the holes are greatly studied, so that the mechanical property of the solder strip cannot be reduced, and on the other hand, the subsequent processing procedure is inconvenient, the holes need to be bypassed to complete welding, and the method is a great challenge for series welding. In addition, the surface of the solder strip is provided with a reflective film to enhance the reflectivity of light, and consideration needs to be given to whether the bonding force between the reflective film material and the surface of the solder strip causes environmental pollution or not and whether the reflective film can last the service life of the photovoltaic module for 20-30 years or not.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a photovoltaic solder strip and a preparation method thereof, wherein the photovoltaic solder strip can reduce the resistivity, improve the photoelectric conversion efficiency, does not influence the basic performances of the photovoltaic solder strip such as yield strength, tensile strength and melting point, and can improve the oxidation resistance of the photovoltaic solder strip and prevent oxidative discoloration; the wettability and the peeling force are improved, and the welding of the photovoltaic welding strip is facilitated.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme.
The photovoltaic solder strip comprises a base material and a tin-lead alloy solder coated on the base material, wherein the tin-lead alloy solder contains copper, silver and phosphorus.
Preferably, on the basis of the weight of the tin-lead alloy solder, the copper accounts for 0.05-0.5 percent of the tin-lead alloy solder, the silver accounts for 0.1-1 percent of the tin-lead alloy solder, and the phosphorus accounts for 0.01-0.05 percent of the tin-lead alloy solder.
More preferably, on the basis of the weight of the tin-lead alloy solder, the copper accounts for 0.1-0.5% of the tin-lead alloy solder, the silver accounts for 0.5-1% of the tin-lead alloy solder, and the phosphorus accounts for 0.02-0.05% of the tin-lead alloy solder.
(II) a preparation method of the photovoltaic solder strip, which comprises the following preparation steps:
step 1, adding copper, silver and phosphorus into tin-lead alloy solder, and heating and melting to obtain a photovoltaic solder strip coating;
and 2, coating the photovoltaic solder strip coating on the surface of the copper strip, cooling to room temperature, and collecting to obtain the photovoltaic solder strip.
Preferably, in step 1, the copper, silver and phosphorus are added to the tin-lead alloy solder in the form of copper-tin alloy, silver-tin alloy and phosphorus-tin alloy, respectively.
Preferably, in step 1, the copper and the silver are respectively added into the tin-lead alloy solder in the form of pure copper powder and pure silver powder.
Preferably, in step 1, the heating temperature is 225-235 ℃.
Preferably, in the step 2, the coating speed of the photovoltaic solder strip coating is 80-100 m/min.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, copper, silver and phosphorus elements are added into the tin-lead alloy solder of the photovoltaic solder strip, so that the resistivity of the photovoltaic solder strip can be reduced by 9.8%, which is equivalent to improving the power of a photovoltaic module by about 0.8W, the photoelectric conversion efficiency loss caused by resistance power loss is reduced, and the conductivity and the photoelectric conversion efficiency of the photovoltaic solder strip are improved.
(2) The photovoltaic solder strip can improve the oxidation resistance of the photovoltaic solder strip under the condition of reducing the resistivity, and prevent the oxidative discoloration of the matrix alloy in the photovoltaic solder strip.
(3) The wettability and the peeling force of the photovoltaic solder strip are improved, the wettability of the photovoltaic solder strip is improved, the welding of grid lines of the cell is facilitated, the peeling force is an important index for inspecting the performance of the cell, the peeling force is less than 1.5N, and the cell is a waste product.
(4) The photovoltaic solder strip provided by the invention can not influence the basic performances of yield strength, tensile strength, melting point and the like of the photovoltaic solder strip under the condition of reducing the resistivity.
(5) Because the copper, the silver and the phosphorus have higher intermiscibility, the corrosion of the tin liquid to the copper and the silver in the tin liquid can be inhibited, and the phenomenon of insufficient soldering of the battery piece is avoided.
(6) The surface layer of the photovoltaic solder strip disclosed by the invention is rich in phosphorus and tin alloy, and can play a role in reducing the local temperature of a welding spot during the welding of a cell, so that the welding is facilitated.
(7) The photovoltaic solder strip has reasonable contents of copper, silver and phosphorus, and the preparation method of the photovoltaic solder strip is simple, low in cost, easy to operate and implement, free of environmental pollution and convenient for industrial production and application.
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 photovoltaic solder strip comprises a copper substrate and a tin-lead alloy solder coated on the copper substrate, wherein the tin-lead alloy solder comprises 5.5% of copper-tin alloy, 11% of silver-tin alloy and 0.6% of phosphorus-tin alloy, the mass ratio of copper to tin in the copper-tin alloy is 5:95, the mass ratio of silver to tin in the silver-tin alloy is 5:95, and the mass ratio of phosphorus to tin in the tin alloy is 5: 95.
The preparation method of the photovoltaic solder strip comprises the following preparation steps:
step 1, adding copper-tin alloy, silver-tin alloy and phosphorus-tin alloy into tin-lead alloy solder, and heating and melting at 235 ℃ to obtain photovoltaic solder strip coating;
and 2, coating the photovoltaic solder strip coating on the surface of the copper strip at the speed of 80m/min, cooling to room temperature, and collecting to obtain the photovoltaic solder strip.
Example 2
A photovoltaic solder strip comprises a copper substrate and a tin-lead alloy solder coated on the copper substrate, wherein the tin-lead alloy solder comprises 5.5% of copper-tin alloy, 2% of silver-tin alloy and 0.2% of phosphorus-tin alloy, the mass ratio of copper to tin in the copper-tin alloy is 5:95, the mass ratio of silver to tin in the silver-tin alloy is 5:95, and the mass ratio of phosphorus to tin in the phosphorus-tin alloy is 5: 95.
The preparation method of the photovoltaic solder strip comprises the following preparation steps:
step 1, adding copper-tin alloy, silver-tin alloy and phosphorus-tin alloy into tin-lead alloy solder, and heating and melting at 230 ℃ to obtain photovoltaic solder strip coating;
and 2, coating the photovoltaic solder strip coating on the surface of the copper strip at the speed of 90m/min, cooling to room temperature, and collecting to obtain the photovoltaic solder strip.
Example 3
A photovoltaic solder strip comprises a copper base material and a tin-lead alloy solder coated on the copper base material, wherein the tin-lead alloy solder comprises 1% of copper-tin alloy, 20% of silver-tin alloy and 1% of phosphorus-tin alloy, the mass ratio of copper to tin in the copper-tin alloy is 5:95, the mass ratio of silver to tin in the silver-tin alloy is 5:95, and the mass ratio of phosphorus to tin in the phosphorus-tin alloy is 5: 95.
The preparation method of the photovoltaic solder strip comprises the following preparation steps:
step 1, adding copper-tin alloy, silver-tin alloy and phosphorus-tin alloy into tin-lead alloy solder, and heating and melting at 230 ℃ to obtain photovoltaic solder strip coating;
and 2, coating the photovoltaic solder strip coating on the surface of the copper strip at the speed of 80m/min, cooling to room temperature, and collecting to obtain the photovoltaic solder strip.
Example 4
A photovoltaic solder strip comprises a copper base material and a tin-lead alloy solder coated on the copper base material, wherein the tin-lead alloy solder comprises 10% of copper-tin alloy, 2% of silver-tin alloy and 0.2% of phosphorus-tin alloy, the mass ratio of copper to tin in the copper-tin alloy is 5:95, the mass ratio of silver to tin in the silver-tin alloy is 5:95, and the mass ratio of phosphorus to tin in the phosphorus-tin alloy is 5: 95.
The preparation method of the photovoltaic solder strip comprises the following preparation steps:
step 1, adding copper-tin alloy, silver-tin alloy and phosphorus-tin alloy into tin-lead alloy solder, and heating and melting at 225 ℃ to obtain photovoltaic solder strip coating;
and 2, coating the photovoltaic solder strip coating on the surface of the copper strip at the speed of 100m/min, cooling to room temperature, and collecting to obtain the photovoltaic solder strip.
Example 5
A photovoltaic solder strip comprises a copper base material and a tin-lead alloy solder coated on the copper base material, wherein the tin-lead alloy solder comprises 1% of copper-tin alloy, 2% of silver-tin alloy and 1% of phosphorus-tin alloy, the mass ratio of copper to tin in the copper-tin alloy is 5:95, the mass ratio of silver to tin in the silver-tin alloy is 5:95, and the mass ratio of phosphorus to tin in the phosphorus-tin alloy is 5: 95.
The preparation method of the photovoltaic solder strip comprises the following preparation steps:
step 1, adding copper-tin alloy, silver-tin alloy and phosphorus-tin alloy into tin-lead alloy solder, and heating and melting at 235 ℃ to obtain photovoltaic solder strip coating;
and 2, coating the photovoltaic solder strip coating on the surface of the copper strip at the speed of 100m/min, cooling to room temperature, and collecting to obtain the photovoltaic solder strip.
Example 6
A photovoltaic solder strip comprises a copper base material and a tin-lead alloy solder coated on the copper base material, wherein the tin-lead alloy solder comprises 2% of copper-tin alloy, 10% of silver-tin alloy and 0.4% of phosphorus-tin alloy, the mass ratio of copper to tin in the copper-tin alloy is 5:95, the mass ratio of silver to tin in the silver-tin alloy is 5:95, and the mass ratio of phosphorus to tin in the phosphorus-tin alloy is 5: 95.
The preparation method of the photovoltaic solder strip comprises the following preparation steps:
step 1, adding copper-tin alloy, silver-tin alloy and phosphorus-tin alloy into tin-lead alloy solder, and heating and melting at 235 ℃ to obtain photovoltaic solder strip coating;
and 2, coating the photovoltaic solder strip coating on the surface of the copper strip at the speed of 100m/min, cooling to room temperature, and collecting to obtain the photovoltaic solder strip.
Example 7
A photovoltaic solder strip comprises a copper base material and a tin-lead alloy solder coated on the copper base material, wherein the tin-lead alloy solder comprises 6% of copper-tin alloy, 15% of silver-tin alloy and 0.7% of phosphorus-tin alloy, the mass ratio of copper to tin in the copper-tin alloy is 5:95, the mass ratio of silver to tin in the silver-tin alloy is 5:95, and the mass ratio of phosphorus to tin in the phosphorus-tin alloy is 5: 95.
The preparation method of the photovoltaic solder strip comprises the following preparation steps:
step 1, adding copper-tin alloy, silver-tin alloy and phosphorus-tin alloy into tin-lead alloy solder, and heating and melting at 230 ℃ to obtain photovoltaic solder strip coating;
and 2, coating the photovoltaic solder strip coating on the surface of the copper strip at the speed of 90m/min, cooling to room temperature, and collecting to obtain the photovoltaic solder strip.
Example 8
A photovoltaic solder strip comprises a copper base material and a tin-lead alloy solder coated on the copper base material, wherein the tin-lead alloy solder comprises 2% of copper-tin alloy, 15% of silver-tin alloy and 0.4% of phosphorus-tin alloy, the mass ratio of copper to tin in the copper-tin alloy is 5:95, the mass ratio of silver to tin in the silver-tin alloy is 5:95, and the mass ratio of phosphorus to tin in the phosphorus-tin alloy is 5: 95.
The preparation method of the photovoltaic solder strip comprises the following preparation steps:
step 1, adding copper-tin alloy, silver-tin alloy and phosphorus-tin alloy into tin-lead alloy solder, and heating and melting at 225 ℃ to obtain photovoltaic solder strip coating;
and 2, coating the photovoltaic solder strip coating on the surface of the copper strip at the speed of 80m/min, cooling to room temperature, and collecting to obtain the photovoltaic solder strip.
In the above examples 1 to 8, the ratio of the copper base material to the tin-lead alloy solder was: 20: 80, the tin-lead alloy solder comprises 40% Pb-60% Sn or 37% Pb-63% Sn.
The photovoltaic solder strip prepared by the embodiment has the following basic performance test analysis such as resistivity, oxidation resistance, wettability, melting point and mechanical property:
1. resistivity of
The specific resistance of the tin, lead, copper and silver metals are shown in the table 1, and the table 1 shows that the copper and silver have good electrical conductivity, and the silver addition amount in the tin-lead solder is very small, so that the photovoltaic solder strip is mainly used for enhancing the electrical conductivity and the thermal conductivity of the photovoltaic solder strip, the thermal fatigue resistance and the recrystallization temperature of the tin-lead alloy solder are improved, and the stripping force strength of the tin-lead alloy solder is improved. In addition, due to the existence of silver on the battery piece, the silver is added into the tin-lead alloy solder, so that the silver on the electrode can be prevented from diffusing into a solder strip, and the conductivity of the battery piece is influenced.
TABLE 1 resistivity of metals
| Composition (I) | Tin (Sn) | Lead (II) | Copper (Cu) | Silver (Ag) |
| Resistivity (omega mm)2/m) | 0.114 | 0.206 | 0.0169 | 0.0162 |
The addition of trace copper is beneficial to improving the bonding performance of the tin-lead alloy solder and a copper matrix and is also beneficial to improving the wettability of the photovoltaic solder strip. However, if the amount of copper added is too large, an intermetallic compound Sn is formed with Sn6Cu5The method can be used for solving the problems that the tin-lead alloy solder is agglomerated and scrapped, and the copper content in the tin liquor is used as a judgment basis for judging whether the tin liquor is usable or not in industrial production, so that the copper content needs to be controlled within a specific range.
The resistivity tests of the photovoltaic solder strips obtained in the examples were as follows:
1) the test method comprises the following steps: the resistivity was measured using a four-probe resistivity tester, and the average value was taken for 5 measurements of each group of samples, and the test results are shown in table 2.
Test 1: the photovoltaic solder strip obtained in example 1 was subjected to resistivity detection using a four-probe resistivity tester, and the test results are shown in table 2.
Comparative experiment 1: heating and melting the tin-lead alloy solder at 230 ℃, and then coating the tin-lead alloy solder on the surface of the copper strip to obtain a photovoltaic solder strip; the resistivity of the photovoltaic solder strip is detected by a four-probe resistivity tester, and the test result is shown in table 2. Comparative test 1 is different from test 1 in that copper, silver and phosphorus are not added to the tin-lead alloy solder of comparative test 1, and the test results are shown in table 2.
Comparative experiment 2: a photovoltaic solder strip comprises 5.5% of copper-tin alloy and 11% of silver-tin alloy which are added into tin-lead alloy solder, wherein the mass ratio of copper to tin in the copper-tin alloy is 5:95, and the mass ratio of silver to tin in the silver-tin alloy is 5: 95.
The preparation method of the photovoltaic solder strip comprises the following preparation steps:
step 1, adding copper-tin alloy and silver-tin alloy into tin-lead alloy solder, and heating and melting at 235 ℃ to obtain photovoltaic solder strip coating;
and 2, coating the photovoltaic solder strip coating on the surface of the copper strip at the speed of 80m/min, cooling to room temperature, and collecting to obtain the photovoltaic solder strip.
The difference between the comparative test 2 and the test 1 is that phosphorus is not added in the tin-lead alloy solder of the comparative test 1, a four-probe resistivity tester is used for detecting the resistivity of the obtained photovoltaic solder strip, and the test results are shown in table 2.
2) And (3) test results: the photovoltaic solder strip resistivity test results are shown in table 2.
TABLE 2 photovoltaic solder strip resistivity
| Sample number | Test 1 | Comparative experiment 1 | Comparative experiment 2 |
| Resistivity (omega mm)2/m) | 0.0202 | 0.0224 | 0.0214 |
As can be seen from Table 2, the resistivity of test 1 was reduced by 9.8% compared to comparative test 1, and the resistivity was reduced to 0.0202. omega. mm according to the conventional quad-grid module at present2And each cell module brings 0.8w of photoelectric conversion benefit, and the reduction of the resistivity is beneficial to the improvement of the photoelectric conversion efficiency of the photovoltaic module. The resistivity of the test 1 is lower than that of the comparative test 2, and the resistivity of the comparative test 1 is lower than that of the comparative test 2, which shows that the resistivity of the photovoltaic solder strip is reduced by adding copper and silver elements in the tin-lead alloy solder, and the resistivity of the photovoltaic solder strip can be further reduced by adding phosphorus elements in the tin-lead alloy solder.
2. Oxidation resistance
1) The test method comprises the following steps: and (3) heating the sample to 230 ℃ at room temperature, keeping the temperature for 3 hours, cooling to room temperature, and measuring and calculating the weight gain of the sample before and after oxidation so as to represent the oxidation resistance of the sample, wherein the larger the oxidation weight gain is, the poorer the oxidation resistance is.
Test 1: the photovoltaic solder strip obtained in example 1 was tested according to the above oxidation resistance test method, and the test results are shown in table 3.
Comparative experiment 1: heating and melting the tin-lead alloy solder at 230 ℃, and then coating the tin-lead alloy solder on the surface of the copper strip at 90m/min to obtain a photovoltaic solder strip; the obtained photovoltaic solder strip is detected according to the oxidation resistance test method, and the test result is shown in table 3. Comparative test 1 is different from test 1 in that copper, silver and phosphorus are not added to the tin-lead alloy solder of comparative test 1, and the test results are shown in table 3.
Comparative experiment 2: a photovoltaic solder strip comprises 5.5% of copper-tin alloy and 11% of silver-tin alloy which are added into tin-lead alloy solder, wherein the mass ratio of copper to tin in the copper-tin alloy is 5:95, and the mass ratio of silver to tin in the silver-tin alloy is 5: 95.
The preparation method of the photovoltaic solder strip comprises the following preparation steps:
step 1, adding copper-tin alloy and silver-tin alloy into tin-lead alloy solder, and heating and melting at 235 ℃ to obtain photovoltaic solder strip coating;
and 2, coating the photovoltaic solder strip coating on the surface of the copper strip at the speed of 80m/min, cooling to room temperature, and collecting to obtain the photovoltaic solder strip.
The difference between the comparative test 2 and the test 1 is that no phosphorus element is added in the tin-lead alloy solder of the comparative test 1, the obtained photovoltaic solder strip is detected according to the oxidation resistance test method, and the test results are shown in table 3.
2) And (3) test results: the results of the oxidation resistance test are shown in Table 3
TABLE 3 Oxidation resistance
| Sample number | Test 1 | Comparative experiment 1 | Comparative experiment 2 |
| Oxidative weight gain (g) | 0.296 | 0.401 | 0.388 |
As can be seen from Table 3, the oxidation weight gain of test 1 is lower than that of comparative test 1 and comparative test 2, which shows that the oxidation resistance of the photovoltaic solder strip can be improved by adding copper, silver and phosphorus elements into the tin-lead alloy solder. The oxidation weight gain of the test 1 is lower than that of the comparative test 2, and the oxidation weight gain of the comparative test 2 is lower than that of the comparative test 1, which shows that the oxidation resistance of the photovoltaic solder strip can be only slightly improved by only adding copper and silver elements in the tin-lead alloy solder, and the oxidation resistance of the photovoltaic solder strip is greatly improved after the copper, silver and phosphorus elements are matched for use. The phosphorus element is mainly distributed on the surface of the tin-lead alloy solder, the combination capacity of the phosphorus and oxygen is strong, oxygen atoms are easy to be abstracted from the tin-lead alloy solder, and the phosphorus element is superior to other elements and is oxidized first, so that the base alloy in the tin-lead alloy solder is protected from being oxidized, and the oxidation resistance of the photovoltaic solder strip is improved.
3. Wettability
1) The test method comprises the following steps: polishing the annealed red copper sheet by using sand paper to remove an oxide layer, wiping the annealed red copper sheet by using ethanol, placing 10g of sample on the red copper sheet, covering the sample by using rosin or other scaling powder, heating to 230 ℃, keeping the temperature for 60s, then taking out, cooling to room temperature to measure the spreading area, calculating the area of the spreading area by using a photographing method and using Imge-Pro plus software, respectively performing 3 groups of wetting property tests of the sample, measuring and calculating the average value of the spreading area, converting the wetting relative area of the sample by taking the wetting area of the photovoltaic welding strip without element addition as 100%, representing the wetting property by using the spreading area of the sample on the oxygen-free red copper surface, wherein the larger the spreading relative area is, the better the wetting property is, and the test results are shown in a table 4.
Test 1: the photovoltaic solder ribbons obtained in example 1 were tested by the wettability test method described above, and the test results are shown in table 4.
Comparative experiment 1: heating and melting the tin-lead alloy solder at 230 ℃, and then coating the tin-lead alloy solder on the surface of the copper strip at 90m/min to obtain a photovoltaic solder strip; the obtained photovoltaic solder strip is detected according to the wettability test method, and the test result is shown in table 4. Comparative test 1 is different from test 1 in that copper, silver and phosphorus are not added to the tin-lead alloy solder of comparative test 1, and the test results are shown in table 4.
Comparative experiment 2: a photovoltaic solder strip comprises 5.5% of copper-tin alloy and 11% of silver-tin alloy which are added into tin-lead alloy solder, wherein the mass ratio of copper to tin in the copper-tin alloy is 5:95, and the mass ratio of silver to tin in the silver-tin alloy is 5: 95.
The preparation method of the photovoltaic solder strip comprises the following preparation steps:
step 1, adding copper-tin alloy and silver-tin alloy into tin-lead alloy solder, and heating and melting at 235 ℃ to obtain photovoltaic solder strip coating;
and 2, coating the photovoltaic solder strip coating on the surface of the copper strip at the speed of 80m/min, cooling to room temperature, and collecting to obtain the photovoltaic solder strip.
The difference between the comparative test 2 and the test 1 is that no phosphorus element is added to the tin-lead alloy solder in the comparative test 1, and the obtained photovoltaic solder strip is detected according to the wettability test method, and the test results are shown in table 4.
2) And (3) test results: the results of the wettability test are shown in Table 4
TABLE 4 wettability
| Sample number | Test 1 | Comparative experiment 1 | Comparative experiment 2 |
| Relative area of spread (%) | 119 | 100 | 116 |
As can be seen from table 4, the spreading relative area of the test 1 is higher than that of the comparative test 1, which indicates that the wettability of the photovoltaic solder strip of the test 1 is better, and the wettability of the photovoltaic solder strip can be improved by adding copper, silver and phosphorus elements into tin-lead solder of the photovoltaic solder strip, because the copper and silver elements have good wettability, the improvement of the wettability of the photovoltaic solder strip is beneficial to the welding of the grid line of the cell. The relative spreading area of the test 1 is slightly larger than that of the comparative test 2, and the relative spreading area of the comparative test 2 is larger than that of the comparative test 1, so that the wettability of the photovoltaic solder strip can be obviously improved by adding copper and silver elements in tin-lead solder of the photovoltaic solder strip, and the integral wettability of the photovoltaic solder strip can be slightly improved by adding phosphorus elements.
4. Melting Point
1) The test method comprises the following steps: melting points were measured using a Differential Scanning Calorimeter (DSC).
Test 1: the melting point of the photovoltaic solder strip obtained in example 1 was measured by DSC, and the test results are shown in table 5.
Comparative experiment 1: heating and melting the tin-lead alloy solder at 230 ℃, and then coating the tin-lead alloy solder on the surface of the copper strip at 90m/min to obtain a photovoltaic solder strip; the melting point of the obtained photovoltaic solder strip is detected by DSC, and the test result is shown in Table 5. Comparative test 1 is different from test 1 in that copper, silver and phosphorus are not added to the tin-lead alloy solder of comparative test 1, and the test results are shown in table 5.
Comparative experiment 2: a photovoltaic solder strip comprises 5.5% of copper-tin alloy and 11% of silver-tin alloy which are added into tin-lead alloy solder, wherein the mass ratio of copper to tin in the copper-tin alloy is 5:95, and the mass ratio of silver to tin in the silver-tin alloy is 5: 95.
The preparation method of the photovoltaic solder strip comprises the following preparation steps:
step 1, adding copper-tin alloy and silver-tin alloy into tin-lead alloy solder, and heating and melting at 235 ℃ to obtain photovoltaic solder strip coating;
and 2, coating the photovoltaic solder strip coating on the surface of the copper strip at the speed of 80m/min, cooling to room temperature, and collecting to obtain the photovoltaic solder strip.
The difference between the comparative test 2 and the test 1 is that no phosphorus element is added to the tin-lead alloy solder in the comparative test 1, and the melting point of the obtained photovoltaic solder strip is detected by DSC, and the test results are shown in table 5.
2) And (3) test results: the melting point test results are shown in Table 5
TABLE 5 melting Point
| Sample number | Test 1 | Comparative experiment 1 | Comparative experiment 2 |
| Melting Point (. degree.C.) | 196 | 183 | 196 |
As can be seen from table 5, the melting point of test 1 is the same as the melting point of comparative test 2, and both are higher than the melting point of comparative test 1, the melting point of test 1 is increased by 7% to 196 ℃ compared with comparative test 1, the melting point of the tin liquid is increased, but for the current photovoltaic module, the melting point is 196 ℃, which does not affect the welding performance of the subsequent cell; meanwhile, the phosphorus element added in the tin-lead alloy solder has little influence on the melting point of the photovoltaic solder strip.
5. Mechanical properties
5.1 yield Strength and tensile Strength
1) The test method comprises the following steps: the samples were tested for yield strength and tensile strength using a universal tensile tester (YTM2503), and each sample was tested five times and the average was taken as the test result.
Test 1: the photovoltaic solder strip obtained in example 1 was tested for yield strength and tensile strength using a universal tensile testing machine, and the test results are shown in table 4.
Comparative experiment 1: heating and melting the tin-lead alloy solder at 230 ℃, and then coating the tin-lead alloy solder on the surface of the copper strip at 90m/min to obtain a photovoltaic solder strip; the yield strength and tensile strength of the obtained photovoltaic solder strip are detected by a universal tensile testing machine, and the test results are shown in table 4. Comparative test 1 is different from test 1 in that copper, silver and phosphorus are not added to the tin-lead alloy solder of comparative test 1, and the test results are shown in table 4.
Comparative experiment 2: a photovoltaic solder strip comprises 5.5% of copper-tin alloy and 11% of silver-tin alloy which are added into tin-lead alloy solder, wherein the mass ratio of copper to tin in the copper-tin alloy is 5:95, and the mass ratio of silver to tin in the silver-tin alloy is 5: 95.
The preparation method of the photovoltaic solder strip comprises the following preparation steps:
step 1, adding copper-tin alloy and silver-tin alloy into tin-lead alloy solder, and heating and melting at 235 ℃ to obtain photovoltaic solder strip coating;
and 2, coating the photovoltaic solder strip coating on the surface of the copper strip at the speed of 80m/min, cooling to room temperature, and collecting to obtain the photovoltaic solder strip.
The difference between the comparative test 2 and the test 1 is that phosphorus is not added in the tin-lead alloy solder of the comparative test 1, a universal tensile testing machine is adopted to detect the yield strength and the tensile strength of the obtained photovoltaic solder strip, and the test results are shown in table 4.
2) And (3) test results: the results of the yield strength and tensile strength tests are shown in table 4.
5.2 Peel force
1) The test method comprises the following steps: and (3) welding the photovoltaic solder strip after soaking the soldering flux in the battery piece, measuring the stripping force of the photovoltaic solder strip by using a universal tensile testing machine, wherein the direction of the applied force is 180 degrees with the solder strip, and carrying out the stripping force test.
Test 1: the photovoltaic solder strip obtained in example 1 was tested for peel strength using a universal tensile testing machine, and the test results are shown in table 6.
Comparative experiment 1: heating and melting the tin-lead alloy solder at 230 ℃, and then coating the tin-lead alloy solder on the surface of the copper strip at 90m/min to obtain a photovoltaic solder strip; the obtained photovoltaic solder strip was tested for peel strength using a universal tensile testing machine, and the test results are shown in table 6. Comparative test 1 is different from test 1 in that copper, silver and phosphorus are not added to the tin-lead alloy solder of comparative test 1, and the test results are shown in table 6.
Comparative experiment 2: a photovoltaic solder strip comprises 5.5% of copper-tin alloy and 11% of silver-tin alloy which are added into tin-lead alloy solder, wherein the mass ratio of copper to tin in the copper-tin alloy is 5:95, and the mass ratio of silver to tin in the silver-tin alloy is 5: 95.
The preparation method of the photovoltaic solder strip comprises the following preparation steps:
step 1, adding copper-tin alloy and silver-tin alloy into tin-lead alloy solder, and heating and melting at 235 ℃ to obtain photovoltaic solder strip coating;
and 2, coating the photovoltaic solder strip coating on the surface of the copper strip at the speed of 80m/min, cooling to room temperature, and collecting to obtain the photovoltaic solder strip.
The difference between the comparative test 2 and the test 1 is that the tin-lead alloy solder in the comparative test 1 is not added with phosphorus, a universal tensile testing machine is used for detecting the peeling force of the obtained photovoltaic solder strip, and the test results are shown in table 6.
2) And (3) test results: the peel force test results are shown in table 6.
TABLE 6 mechanical Property test results
| Sample number | Test 1 | Comparative experiment 1 | Comparative experiment 2 |
| Yield strength (MPa) | 67 | 65 | 67 |
| Tensile strength (MPa) | 188 | 190 | 188 |
| Peel force (N) | 2.45 | 1.97 | 2.22 |
As can be seen from table 6, the yield strength and tensile strength of test 1 are not much different from those of comparative tests 1 and 2, which indicates that the addition of copper, silver and phosphorus elements in the tin-lead alloy solder does not affect the mechanical properties such as yield strength and tensile strength of the photovoltaic solder strip.
The peeling force of the test 1 is obviously higher than that of the comparative test 1, the peeling force of the test 1 is improved by 24 percent compared with that of the comparative test 1, and the improvement of the peeling force indicates that the better the peeling resistance of the photovoltaic solder strip is. The stripping force of the test 1 is higher than that of the comparative test 2, and the stripping force of the comparative test 2 is higher than that of the comparative test 1, which shows that the stripping force of the photovoltaic solder strip can be improved by adding copper and silver elements in the tin-lead alloy solder, and the stripping force of the photovoltaic solder strip can be further improved by adding phosphorus element. The structure improves the bonding force of the tin-lead alloy solder and a copper matrix and obviously improves the stripping force of subsequent battery pieces. The stripping force is an important index for inspecting the performance of the battery piece, the stripping force is less than 1.5N, and the battery piece is a waste product.
The electrical resistivity, oxidation resistance, wettability, melting point and mechanical property effects of the photovoltaic solder strips obtained in examples 2-8 are the same as those of example 1.
The content of copper, silver and phosphorus added in the tin-lead alloy solder of the photovoltaic solder strip is reasonable, the obtained photovoltaic solder strip can improve the oxidation resistance, wettability and stripping force of the photovoltaic solder strip under the condition of reducing the resistivity, and simultaneously, the basic performances of the photovoltaic solder strip, such as melting point, yield strength, tensile strength and the like, are not influenced.
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 (8)
1. A photovoltaic solder strip comprises a base material and a tin-lead alloy solder coated on the base material, and is characterized in that the tin-lead alloy solder consists of a tin-lead alloy, copper, silver and phosphorus; based on the weight of the tin-lead alloy solder, the copper accounts for 0.05 to 0.5 percent of the tin-lead alloy solder, the silver accounts for 0.1 to 1 percent of the tin-lead alloy solder, and the phosphorus accounts for 0.01 to 0.05 percent of the tin-lead alloy solder; the tin-lead alloy is 40% Pb-60% Sn or 37% Pb-63% Sn.
2. The photovoltaic solder strip of claim 1, wherein the copper comprises 0.1-0.5% of the tin-lead alloy solder, the silver comprises 0.5-1% of the tin-lead alloy solder, and the phosphorus comprises 0.02-0.05% of the tin-lead alloy solder, on a weight basis of the tin-lead alloy solder.
3. The photovoltaic solder ribbon of any one of claims 1-2, wherein the substrate is copper.
4. A preparation method of a photovoltaic solder strip is characterized in that the photovoltaic solder strip based on claim 1 comprises the following preparation steps:
step 1, adding copper, silver and phosphorus into tin-lead alloy solder, and heating and melting to obtain a photovoltaic solder strip coating;
and 2, coating the photovoltaic solder strip coating on the surface of the copper strip, cooling to room temperature, and collecting to obtain the photovoltaic solder strip.
5. The method for preparing the photovoltaic solder strip according to claim 4, wherein in the step 1, the copper, the silver and the phosphorus are respectively added into the tin-lead alloy solder in the form of copper-tin alloy, silver-tin alloy and phosphorus-tin alloy.
6. The method for preparing the photovoltaic solder strip according to claim 4, wherein in the step 1, the copper and the silver are respectively added into the tin-lead alloy solder in the form of pure copper powder and pure silver powder.
7. The method for preparing a photovoltaic solder strip as claimed in claim 4, wherein the heating temperature in step 1 is 225-235 ℃.
8. The method for preparing the photovoltaic solder strip according to claim 4, wherein in the step 2, the coating speed of the photovoltaic solder strip is 80-100 m/min.
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| CN85108518A (en) * | 1985-10-19 | 1987-04-22 | 郴州电光源焊料厂 | Rare earth-tin-lead solder and preparation method |
| JP2010016320A (en) * | 2008-04-15 | 2010-01-21 | Hitachi Cable Ltd | Solar cell lead, method of manufacturing the same, and solar cell using the same |
| US9279176B2 (en) * | 2008-11-27 | 2016-03-08 | Hitachi Metals, Ltd. | Lead wire for solar cell, manufacturing method and storage method thereof, and solar cell |
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| CN105870238B (en) * | 2015-01-23 | 2018-05-08 | 比亚迪股份有限公司 | A kind of photovoltaic welding belt and a kind of photovoltaic module |
| CN104889592B (en) * | 2015-04-28 | 2018-01-16 | 太仓巨仁光伏材料有限公司 | A kind of solder on the mutual latticing of solar cell module |
| CN106159018B (en) * | 2016-08-19 | 2018-07-17 | 徐九生 | A kind of photovoltaic welding belt and its apply process of tin |
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Denomination of invention: The invention relates to a photovoltaic welding belt and a preparation method thereof Effective date of registration: 20220218 Granted publication date: 20200609 Pledgee: Agricultural Bank of China Limited Shaanxi pilot Free Trade Zone Xi'an high tech branch Pledgor: XI'AN TELISON NEW MATERIALS CO.,LTD. Registration number: Y2022610000037 |