CN117613141A - Recovery method of defective solar cell and preparation method of solar cell - Google Patents
Recovery method of defective solar cell and preparation method of solar cell Download PDFInfo
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- CN117613141A CN117613141A CN202311578027.4A CN202311578027A CN117613141A CN 117613141 A CN117613141 A CN 117613141A CN 202311578027 A CN202311578027 A CN 202311578027A CN 117613141 A CN117613141 A CN 117613141A
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- 238000011084 recovery Methods 0.000 title claims abstract description 24
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Photovoltaic Devices (AREA)
Abstract
A recovery method of a defective solar cell and a preparation method of the solar cell belong to the technical field of solar cells. The recovery method of the defective solar cell comprises the following steps: soaking the solar cell with a first liquid medicine to remove tin grid lines and forming a first pretreatment sheet; soaking the first pretreatment piece by using a second liquid medicine to remove the copper grid line, so as to form a second pretreatment piece; and soaking the second pretreatment piece by using an organic solvent to remove carbon-containing residues, thereby obtaining the battery substrate. Wherein the first liquid formulation comprises an organic acid and the second liquid formulation comprises an oxidizing agent and a second acid. By utilizing the recycling method provided by the application example, the recycled battery substrate can be produced, and the solar battery obtained by reproduction has higher efficiency.
Description
Technical Field
The application relates to the technical field of solar cells, in particular to a recovery method of a defective solar cell and a preparation method of the solar cell.
Background
In some solar cell manufacturing processes, PVD sputtering is performed on the surface layer of the transparent conductive film to deposit a copper seed layer for electrical conduction. Then, a patterning process is performed on the copper seed layer, and then copper grid lines and tin grid lines are electroplated.
However, in the patterning process, the process of plating the gate line, and the like, poor patterning quality and poor quality of the plated gate line may occur, and a poor solar cell may be formed. Therefore, it is necessary to provide a method for recovering defective solar cells.
Disclosure of Invention
The present application aims to provide a recovery method of a defective solar cell and a preparation method of a solar cell, so as to partially or completely improve the recovery problem of the defective solar cell in the related art.
In a first aspect, an embodiment of the present application provides a method for recovering a defective solar cell, where the solar cell includes a cell substrate, a surface layer of the cell substrate is a transparent conductive film layer, and a copper grid line and a tin grid line located on a surface of the copper grid line are disposed on the transparent conductive film layer; the recovery method comprises the following steps: soaking the solar cell with a first liquid medicine to remove tin grid lines and forming a first pretreatment sheet; soaking the first pretreatment piece by using a second liquid medicine to remove the copper grid line, so as to form a second pretreatment piece; and soaking the second pretreatment piece by using an organic solvent to remove carbon-containing residues, thereby obtaining the battery substrate. Wherein the first liquid formulation comprises an organic acid and the second liquid formulation comprises an oxidizing agent and a second acid.
In the implementation process, the solar cell which is bad is soaked by using the first liquid medicine containing the organic acid, the organic acid in the first liquid medicine can react with the tin grid line quickly to remove the tin grid line, and the transparent conductive film is basically not damaged, so that the first pretreatment sheet is formed. Then, the first pretreatment sheet after the tin grid lines are removed is soaked by using a second liquid medicine containing a second acid and an oxidant, and the oxidant and the inorganic acid in the second liquid medicine oxidize the copper grid lines and remove the copper grid lines in an acidic environment to form a second pretreatment sheet. And then the second pretreatment piece is soaked by using an organic solvent, the carbon-containing residues remained on the transparent conductive film can be removed rapidly by using the organic solvent, the transparent conductive film is basically not damaged, and the recyclable battery substrate containing the transparent conductive film can be obtained.
In an alternative embodiment of the present application, in combination with the first aspect, the concentration of the second acid is 0.08 to 0.12mol/L.
In the implementation process, the oxidant is matched with the second acid with the concentration of 0.08-0.12mol/L, so that the damage degree of the second liquid medicine to the transparent conductive film can be reduced while the copper grid line is removed.
In an alternative embodiment of the present application, in combination with the first aspect, the organic acid is at least one selected from the group consisting of methanesulfonic acid, citric acid, and oxalic acid.
In the implementation process, organic acid such as methanesulfonic acid, citric acid or oxalic acid can react with the metal tin in the tin grid line quickly, and the tin grid line is removed.
With reference to the first aspect, in an alternative embodiment of the present application, the first lotion further includes a first surfactant.
Optionally, the first surfactant is selected from nonionic surfactants.
In the implementation process, the first surfactant such as the nonionic surfactant is added into the first liquid medicine, so that the product obtained after the reaction of the organic acid and the tin can be separated from the surface of the first pretreatment piece by utilizing the first surfactant, and the phenomenon that the product is attached to the surface of the first pretreatment piece to form impurities so as to influence the quality of the recovered battery substrate is avoided.
With reference to the first aspect, in an alternative embodiment of the present application, a method for removing tin grid lines by soaking a solar cell with a first liquid medicine includes: soaking the solar cell in the first liquid medicine at 45-50deg.C for 3-5min.
In the implementation process, when the first liquid medicine is used for soaking the solar cell to remove the tin grid line, the solar cell is soaked in the first liquid medicine at 45-50 ℃ for 3-5min, so that the reaction rate of the first liquid medicine and the tin grid line can be improved, the soaking time is shortened, the damage of the first liquid medicine to the transparent conductive film is reduced, and the quality of the recovered cell substrate is improved.
With reference to the first aspect, in an alternative embodiment of the present application, the second acid is selected from the group consisting of H 2 SO 4 、H 3 PO 4 、CH 3 At least one of COOH formic acid and acetic acid.
In the implementation process, 0.08-0.12mol/L H is utilized 2 SO 4 、H 3 PO 4 And CH (CH) 3 At least one of COOH, formic acid and acetic acid, can rapidly remove copper grid under the cooperation of the oxidizing agentThe wire does not damage the transparent conductive film basically, and the quality of the recovered battery substrate can be improved.
With reference to the first aspect, in an alternative embodiment of the present application, the oxidizing agent is selected from at least one of hydrogen peroxide or hydrogen persulfate.
Optionally, the concentration of the oxidizing agent is 14-22g/L.
In the implementation process, 14-22g/L of oxidant such as hydrogen peroxide or hydrogen persulfate can be utilized to rapidly catalyze the copper grid line reaction in an acidic environment, so that the soaking time of the first pretreatment piece is reduced, the damage of the second liquid medicine to the transparent conductive oxide is reduced, and the probability of introducing new impurity elements is also reduced.
With reference to the first aspect, in an alternative embodiment of the present application, a method for removing copper grid lines by soaking a first pretreatment sheet with a second liquid medicine includes: soaking the first pretreated sheet in the second medicinal liquid at 30-35deg.C for 3-5min.
In the implementation process, when the first pretreatment piece is soaked by the second liquid medicine to remove the copper grid line, the first pretreatment piece is soaked in the second liquid medicine at the temperature of 30-35 ℃ for 3-5min, so that the reaction rate of the second liquid medicine and the copper grid line can be improved, the soaking time is shortened, the damage of the second liquid medicine to the transparent conductive film is reduced, and the quality of the recovered battery substrate is improved.
With reference to the first aspect, in an alternative embodiment of the present application, at least one of dimethyl sulfoxide and tetramethylammonium hydroxide is included.
In the implementation process, the organic solvent containing dimethyl sulfoxide, methyl ammonium hydroxide and the like is used for soaking the second pretreatment piece, so that carbon-containing residues remained on the surface of the second pretreatment piece can be removed, and the quality of the recovered battery substrate is improved.
In an alternative embodiment of the present application, in combination with the first aspect, the organic solvent further comprises a second surfactant.
Optionally, the second surfactant is selected from anionic surfactants.
In the implementation process, the second surfactant such as the anionic surfactant is added into the organic solvent, so that the probability of adhesion of reaction residues on the surface of the battery substrate can be further reduced, and the quality of the recovered battery substrate is improved.
In a second aspect, an embodiment of the present application provides a method for manufacturing a solar cell, including:
according to the recycling method provided in the first aspect, a metal seed layer is sputtered on the surface of the battery substrate, photoresist is coated on the metal seed layer, a grid line groove is formed through exposure and development, and a grid line is electroplated in the grid line groove.
In the implementation process, the metal seed layer is prepared by using the battery substrate recovered and obtained in the first aspect, then the photoresist is coated on the metal seed layer, the grating groove is formed by exposure and development, and the grating line is electroplated in the grating groove, so that a new solar battery can be formed, and the reproduction of the recovered and obtained battery substrate is realized.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered limiting the scope, and that other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic cross-sectional view of a solar cell;
FIG. 2 is a schematic diagram of a recovery process of a defective solar cell;
FIG. 3 is a schematic cross-sectional view of a first pre-treatment sheet;
FIG. 4 is a schematic cross-sectional view of a second pretreatment sheet;
fig. 5 is a schematic diagram of a preparation flow of a solar cell provided by an example of the present application;
fig. 6 is an SEM image of a battery substrate provided in example 1 of the present application;
fig. 7 is a SEM image of a cross section of a battery substrate provided in example 1 of the present application.
Icon:
100-solar cell; 101-a transparent conductive film; 102-copper grid lines; 103-tin grid lines; 104-N type silicon chip; 105-an intrinsic amorphous silicon layer; a 106-N type doped layer; 107-P type doped layers; 110-a first pre-treatment sheet; 120-second pre-treatment sheet.
Detailed Description
As shown in fig. 1, the solar cell 100 includes: the surface layer of the battery substrate is a transparent conductive film 101, and a copper grid line 102 and a tin grid line 103 positioned on the surface of the copper grid line 102 are arranged on the transparent conductive film layer. The battery substrate further comprises an N-type silicon wafer 104, an intrinsic amorphous silicon layer 105 positioned on two sides of the N-type silicon wafer 104, and an N-type doped layer 106 and a P-type doped layer 107 respectively positioned on the surface of the intrinsic amorphous silicon layer 105.
Currently, in the process of manufacturing the solar cell 100, PVD sputtering is performed on the surface layer of the transparent conductive film 101 to deposit a copper seed layer for conductive. A patterning process is then performed on the copper seed layer, followed by electroplating of the copper gate line 102 and the tin gate line 103.
In the patterning process, the process of electroplating the gate line, etc., poor patterning quality and poor quality of the electroplated gate line may occur, and poor solar cell 100 may be formed.
For example, during the patterning process, transparent photoresist may remain at the bottom of the gate trench due to improper exposure and development parameters or operation discomfort of the photoresist. When the electroplating process is performed in the gate groove where the photoresist is remained, the copper gate line 102 is missing, falling off or increasing the internal resistance, so as to form a poor solar cell 100.
For example, during the electroplating process, a phenomenon such as winding plating may occur, which may cause thickening or thinning of the gate lines of the solar cell 100, and may cause uneven gate lines at different positions, thereby forming a defective solar cell 100.
In the process of manufacturing the solar cell 100, if the defective solar cells 100 are discarded, waste of resources is caused.
In the conventional process of recycling the solar cell 100, a pure silicon wafer containing only silicon element is generally obtained by a mechanical or chemical method, and then the silicon wafer is recycled.
However, the recovery processing of the solar cell 100 by the above method may damage other qualified layer structures in the solar cell 100, which may still result in waste of resources.
Therefore, the present application provides a recovery method of the defective solar cell 100, so that the recovery problem of the defective solar cell 100 can be improved to some extent. In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application.
Referring to fig. 2, the recovery method of the defective solar cell 100 includes:
s1, soaking the solar cell 100 with a first liquid medicine to remove the tin grid line 103, so as to form a first pretreatment sheet 110. Wherein the first liquid medicine comprises an organic acid. Referring to fig. 3, a schematic cross-sectional view of the first pre-processing sheet 110 is shown.
The solar cell 100 is immersed in the first liquid medicine containing the organic acid, the organic acid in the first liquid medicine can react with the tin grid line 103 quickly to remove the tin grid line 103, and the transparent conductive film 101 is not damaged basically, so that the first pretreatment sheet 110 is formed.
The specific type of organic acid is not limited in this application, and the relevant person may make a corresponding choice on the basis that the organic acid can react with tin quickly to remove the tin grid line 103 without substantially damaging the transparent conductive film 101.
In one possible embodiment, the organic acid is selected from at least one of methanesulfonic acid, citric acid, or oxalic acid.
The use of methanesulfonic acid, citric acid or oxalic acid can rapidly react with the tin gate line 103, and thus the soaking time can be reduced without substantially damaging the transparent conductive film 101.
Illustratively, the organic acid is selected from the group consisting of methylsulfonic acid.
Illustratively, the organic acid is selected from citric acid.
Illustratively, the organic acid is selected from oxalic acid.
Further, the concentration of the organic acid in the first liquid medicine is not limited, and the related personnel can adjust the concentration according to the needs on the basis of improving the reaction rate with the tin grid line 103 and reducing the damage degree to the transparent conductive film 101.
Illustratively, the first lotion comprises 5% methylsulfonic acid.
Further, the present application is not limited to a specific time and soak temperature for immersing the solar cell 100 in the first medicinal liquid.
In one possible embodiment, solar cell 100 may be immersed in a first liquid formulation comprising 5% methylsulfonic acid at 45-50 ℃ for 3-5 minutes.
Illustratively, the soaking temperature at which the solar cell 100 is soaked in the first medicinal solution containing 5% methylsulfonic acid may be in a range between one or any two of 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃, or 50 ℃.
Illustratively, the soaking time of solar cell 100 in the first liquid medicine comprising 5% methylsulfonic acid at 45-50 ℃ may be in a range between one or any two of 3min, 3.5min, 4min, 4.5min, or 5min.
Further, in order to prevent the reaction products after the reaction of the tin wire 103 from remaining on the surface of the first pretreatment sheet 110, in one possible embodiment, a first surfactant may be added to the first liquid medicine.
Illustratively, the first surfactant may be selected from nonionic surfactants.
The nonionic surfactant may be exemplified by at least one selected from polyoxyethylene type, polyol type, alkanolamide type, polyether type, amine oxide type.
Illustratively, the first surfactant may be selected from alkylphenol ethoxylates.
The reactant obtained by reacting the organic acid with the tin grid line 103 can be separated from the first pretreatment sheet 110 by using the first surfactants such as polyoxyethylene type, polyol type, alkanolamide type, polyether type, amine oxide type and the like, and the cleanliness of the first pretreatment sheet 110 can be improved.
Alternatively, in another possible embodiment, the defective solar cell 100 may be immersed in the first liquid medicine in a flowing state, so that the reactant flows along with the first liquid medicine.
Illustratively, the treatment tank for containing the first chemical may have a double-tank structure of an inner tank and an outer tank, and the first chemical in the inner tank flows to the outer tank in an overflow manner. The defective solar cell 100 is immersed in the first liquid medicine in the inner tank, and the reactant overflows out of the inner tank, reducing the probability of the reactant adhering to the surface of the first pretreatment sheet 110.
In addition, the flowing first liquid medicine can also improve the contact uniformity of the first liquid medicine and the tin grid line, improve the reaction rate, further reduce the time for soaking the solar cell 100 in the first liquid medicine and reduce the influence of the first liquid medicine on the transparent conductive film 101.
Further, the solar cell 100 in the soaking state may be vibrated. For example, the first medicinal liquid may be ultrasonically vibrated to increase the reaction rate and reduce the impurity attachment rate.
With continued reference to fig. 2, the method for recovering a defective solar cell provided in the example of the present application further includes:
s2, soaking the first pretreatment piece 110 with a second liquid medicine to remove the copper grid line 102, so as to form a second pretreatment piece 120. Wherein the second liquid formulation comprises an oxidizing agent and a second acid. Referring to fig. 4, a schematic cross-sectional view of the second pre-treatment sheet 120 is shown.
Further, the concentration of the second acid may be 0.08 to 0.12mol/L.
The first pretreatment sheet 110 after the tin grid line 103 is removed by immersing in a second aqueous solution containing a second acid and an oxidizing agent, wherein the oxidizing agent in the second aqueous solution and the second acid having a concentration of 0.08 to 0.12mol/L are in contact with the copper grid line 102, copper in the copper grid line 102 is rapidly oxidized under the action of the oxidizing agent, and then the copper grid line 102 is removed by reacting with the second acid having a low concentration, and the second acid having a concentration of 0.08 to 0.12mol/L does not substantially damage the transparent conductive film 101, thereby forming the second pretreatment sheet 120.
Since the oxidation resistance of the metallic tin in the tin grid line 103 is superior to that of metallic copper, the second liquid medicine does not substantially react with the tin grid line 103 if the defective solar cell 100 is directly soaked with the second liquid medicine. Further, the tin grid line 103 is generally disposed on the surface of the copper grid line 102, and the second liquid medicine does not substantially react with the copper grid line 102 due to the coating effect of the tin grid line 103. If the tin gate line 103 is disposed only on top of the copper gate line 102, the side of the copper gate line 102 is exposed, and the side area of the copper gate line 102 is small. At this time, even if the second liquid medicine contacts the side of the copper grid line 102, since the side of the copper grid line 102 is thin, the reaction rate of the second liquid medicine with the copper grid line 102 is low, and if the second liquid medicine is required to completely remove the copper grid line 102 from the surface of the transparent conductive film 101, the soaking time is required to be increased, and damage of the transparent conductive film 101 is increased. Therefore, in the recovery method of the defective solar cell 100 provided in the present example, the first liquid medicine is used to remove the tin grid line 103, and then the second liquid medicine is used to remove the copper grid line 102, so that the damage degree of the transparent conductive film 101 can be reduced in the recovery process.
The concentration of the second acid is not too high, and the high concentration of the second acid may damage the transparent conductive film 101. The specific concentration of the second acid is not limited in this application, and the relevant person may make corresponding selections within the above-described range as desired.
Illustratively, in the second medicinal liquid, the concentration of the second acid may be in a range between one or any two of 0.08mol/L, 0.09mol/L, 0.1mol/L, 0.11mol/L, and 0.12mol/L.
The present application is not limited to a particular type of second acid, in one possible embodiment, the second acid is selected from H 2 SO 4 、H 3 PO 4 、CH 3 At least one of COOH, formic acid and acetic acid.
Illustratively, the second acid is selected from H 2 SO 4 。
Further, the second acid is selected from the group consisting of hydrochloric acid, nitric acid, hydrofluoric acid, and the like, and even a low concentration of hydrochloric acid, nitric acid, hydrofluoric acid may increase the damage degree of the transparent conductive film 101.
The specific type of oxidizing agent is not limited in this application, and the relevant person may make a corresponding choice as required.
In one possible embodiment, the oxidizing agent is selected from at least one of hydrogen peroxide or hydrogen persulfate.
Illustratively, the oxidizing agent is selected from hydrogen peroxide.
Further, in the second liquid medicine, the concentration of the hydrogen peroxide can be 14-22g/L.
Illustratively, the concentration of hydrogen peroxide in the second medicant can be in a range between one or any two of 14g/L, 15g/L, 16g/L, 17g/L, 18g/L, 19g/L, 20g/L, 21g/L, or 22g/L.
Further, the specific time and temperature of soaking the first pre-treatment sheet 110 in the second medicinal liquid is not limited herein.
In one possible embodiment, the first pre-treatment sheet 110 may be immersed in a second aqueous solution comprising 0.08-0.12mol/L sulfuric acid and 14-22g/L hydrogen peroxide at 30-35℃ for 3-5 minutes.
Illustratively, the soaking temperature at which the first pre-treatment sheet 110 is soaked in the second medicinal liquid containing 0.08-0.12mol/L sulfuric acid and 14-22g/L hydrogen peroxide may be in a range between one or any two of 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃, or 35 ℃.
Illustratively, the soaking time of the first pre-treatment sheet 110 in the second medicinal liquid comprising 0.08-0.12mol/L sulfuric acid and 14-22g/L hydrogen peroxide at 30-35 ℃ may be in a range between one or any two of 3min, 3.5min, 4min, 4.5min, or 5min.
With continued reference to fig. 2, the method for recovering a defective solar cell provided in the example of the present application further includes:
and S3, soaking the second pretreatment piece 120 by using an organic solvent, and removing carbon-containing residues to obtain the battery substrate.
During the process of manufacturing the solar cell 100, photoresist may remain on the surface of the transparent conductive film 101, and these remaining photoresist may form carbon-containing residues under the action of the oxidizing agent in the second liquid medicine in step S2. The present example utilizes an organic solvent to soak the second pretreatment sheet 120, and these oxidized carbonaceous residues can be removed to obtain a battery substrate.
The application is not limited to the specific type of organic solvent, and the relevant person may make a corresponding choice as required.
In one possible embodiment, the organic solvent comprises at least one of dimethyl sulfoxide and tetramethylammonium hydroxide.
Illustratively, the organic solvent is selected from dimethyl sulfoxide and tetramethylammonium hydroxide.
Further, a second surfactant may be added to the organic solvent.
Illustratively, the second surfactant may be selected from anionic surfactants.
Illustratively, the anionic surfactant may be selected from one or more of sulfonates and sulfate salts.
Further, referring to fig. 5, the example of the present application further provides a method for manufacturing a solar cell 100, where the method for manufacturing a solar cell 100 includes:
s4, sputtering a metal seed layer on the surface of the battery substrate prepared in the step S3.
A copper seed layer is deposited on the transparent conductive film 101 on the front and back surfaces to facilitate the subsequent electroplating of the gate line on the metal seed layer.
Illustratively, a yellow patch is obtained by depositing a copper seed layer having a thickness of 150-250nm on the ITO thin film using a PVD method.
Further, in order to improve the quality of the subsequent electroplated gate line, the preparation method of the solar cell may further include:
s5, edge wrapping.
And (3) edge wrapping is carried out on four edges and side edges of the yellow diaphragm obtained in the step (S4), so that the copper seed layer at the edge of the yellow diaphragm is prevented from being contacted with electroplating liquid in electroplating operation, and the quality of the grid line is prevented from being influenced.
Illustratively, with encapsulation, a concave-shaped border is formed at the edge of Huang Mopian, the border having a thickness of 8-14 μm.
S6, coating photoresist
And coating photoresist on the copper seed layers on the front and back surfaces to cover the copper seed layers.
Illustratively, the surface of the copper seed layer exposed after edging is covered entirely with a photoresist layer having a thickness of 10-14 μm.
S7, printing and developing
And printing a predetermined pattern on the photoresist film by laser according to the pre-designed grid line pattern. The photoresist is denatured and distinguished from the unexposed portion of the photoresist. And then removing the denatured photoresist by using a developing solution to form a grid line groove with a preset shape.
Illustratively, the photoresist is cleaned with an alkaline sodium nitrate solution to remove the photoresist from the exposed portion and form the gate trench.
S8, electroplating
A copper gate line 102 is formed by electroplating in the gate groove, and then a tin gate line 103 is formed by electroplating on the surface of the copper gate line 102.
Further, in order to improve the efficiency of the solar cell 100, the cell after S8 plating may be subjected to light injection.
The recovery method of the defective solar cell 100 provided in the examples of the present application and the preparation method of the solar cell 100 are described in further detail below with reference to examples.
Example 1
Embodiment 1 provides a method for recovering a defective solar cell, comprising:
(1) The defective solar cell 100 was immersed in the first medicinal liquid at 45 ℃ for 5min to obtain a first pretreatment sheet 110. Wherein the first liquid medicine comprises: 5% of methylsulfonic acid and 10% of nonionic surfactant.
(2) And (3) immersing the first pretreatment sheet 110 obtained in the step (1) in a second liquid medicine at 35 ℃ for 3min to obtain a second pretreatment sheet 120. Wherein the second liquid medicine comprises 8g/L H 2 SO 4 And 14g/L H 2 O 2 . The second pretreatment sheet 120 was subjected to microscopic elemental analysis, and the analysis results are shown in table 1. As can be seen from table 1, the surface of the second pretreatment sheet 120 contains carbon elements.
(3) And (3) immersing the second pretreatment sheet 120 obtained in the step (2) in an organic solvent for 3min to obtain a battery substrate. Wherein the organic solvent comprises dimethyl sulfoxide, tetramethylammonium hydroxide and an anionic surfactant.
TABLE 1
| Element number | Element symbol | Element name | Atomic content | Weight content |
| 6 | C | Carbon (C) | 15.194 | 6.294 |
| 8 | O | Oxygen gas | 9.776 | 5.395 |
| 13 | Al | Aluminum (Al) | 0.000 | 0.000 |
| 14 | Si | Silicon (Si) | 69.809 | 67.632 |
| 49 | In | Indium (indium) | 5.221 | 20.679 |
Example 2
Example 2 provides a method for recovering a solar cell, which is different from example 1 in that: in the step (1), the first liquid medicine does not contain a first surfactant.
Example 3
Embodiment 3 provides a method for manufacturing a solar cell, including:
(4) And (3) performing PVD (physical vapor deposition) on the upper surface and the lower surface of the battery substrate obtained in the step (3) of the example 1 to form a copper seed layer with the thickness of about 40-50nm, thereby obtaining a yellow membrane.
(5) And (3) edge covering is carried out on the yellow membrane in the step (4), then photoresist is coated, exposure and development are carried out, a grid line groove is formed, a copper grid line 102 is formed in the grid line groove in an electroplating mode, and a tin grid line 103 is formed on the surface of the copper grid line 102 in an electroplating mode, so that the solar cell 100 is manufactured. Wherein, the technological parameters of copper electroplating are 460S, 4ASD; the technological parameters of the electrotinning are 80S,4ASD. The width of the grid line is 16-18 mu m, and the height of the grid line is 8-10 mu m.
Test example 1
The battery substrate obtained in example 1 was subjected to morphological analysis, and the analysis results of example 1 are shown in fig. 6 and 7.
Analysis of results: as can be seen from a comparison of fig. 6 and 7, the embodiment provides a battery substrate in which the surface of the transparent conductive film 101 is substantially free from impurities, the thickness of the transparent conductive film 101 is substantially undamaged, and the thickness is about 69.05nm.
Test example 2
The solar cell 100 prepared in example 3 and the control group were subjected to performance test using the conventional solar cell 100 as the control group, and the test results are shown in table 2. The conventional solar cell 100 is provided by the recycling method of the cell substrate in example 1.
| Type(s) | Count | Eta/％ | Uoc/V | Isc/A | FF/％ | Rser/mΩ |
| Example 3 | 150 | 24.43 | 0.7477 | 8.709 | 82.72 | 2.261 |
| Control group | 150 | 24.58 | 0.7481 | 8.761 | 82.69 | 2.521 |
| Type(s) | Rshunt/Ω | IRev2/V | Eta std | Eta-MAX | Eta＜23％ | Yield/% |
| Example 3 | 1846 | 0.0017 | 0.146 | 24.64 | 0 | 80％ |
| Control group | 2441 | 0.0034 | 0.094 | 24.72 | 0 | 91％ |
As can be seen from table 1, the efficiency of the solar cell obtained by the recovery method provided by the example of the present application is not greatly different from that of the existing solar cell, and the recovered battery substrate can be used for reproduction, and the high yield can still be maintained after reproduction.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the same, but rather, various modifications and variations may be made by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.
Claims (10)
1. The recovery method of the bad solar cell comprises a cell substrate, wherein the surface layer of the cell substrate is a transparent conductive film layer, and a copper grid line and a tin grid line positioned on the surface of the copper grid line are arranged on the transparent conductive film layer; the recycling method is characterized by comprising the following steps:
soaking the solar cell by using a first liquid medicine to remove the tin grid line, so as to form a first pretreatment sheet; soaking the first pretreatment piece by using a second liquid medicine to remove the copper grid line, so as to form a second pretreatment piece; soaking the second pretreatment sheet by using an organic solvent to remove carbon-containing residues, thereby obtaining the battery substrate; wherein the first liquid formulation includes an organic acid and the second liquid formulation includes an oxidizing agent and a second acid.
2. The recovery process of claim 1, wherein the concentration of the second acid is from 0.08 to 0.12mol/L.
3. The recovery method according to claim 1, wherein the organic acid is selected from at least one of methylsulfonic acid, citric acid, or oxalic acid;
optionally, the first lotion further comprises a first surfactant;
optionally, the first surfactant is selected from nonionic surfactants.
4. The method of claim 3, wherein the immersing the solar cell with the first liquid medicine to remove tin grid lines comprises: soaking the solar cell in the first liquid medicine at 45-50 ℃ for 3-5min.
5. The recovery process of claim 1, wherein the second acid is selected from the group consisting of H 2 SO 4 、H 3 PO 4 、CH 3 At least one of COOH, formic acid and acetic acid.
6. The recovery method according to claim 5, wherein the oxidizing agent is selected from at least one of hydrogen peroxide or hydrogen persulfate;
optionally, the concentration of the oxidant is 14-22g/L.
7. The recycling method according to claim 6, wherein the method of immersing the first pretreatment sheet with a second liquid medicine to remove the copper grid line comprises: soaking the first pretreated sheet in the second medicinal liquid at 30-35deg.C for 3-5min.
8. The recovery method according to any one of claims 1 to 7, wherein the organic solvent comprises at least one of dimethyl sulfoxide and tetramethylammonium hydroxide.
9. The recovery method according to claim 8, wherein the organic solvent further comprises a second surfactant;
optionally, the second surfactant is selected from anionic surfactants.
10. A method of manufacturing a solar cell, comprising:
the battery substrate manufactured by the recycling method according to any one of claims 1-9, a metal seed layer is sputtered on the surface of the battery substrate, photoresist is coated on the metal seed layer, a grid line groove is formed by exposure and development, and a grid line is electroplated in the grid line groove.
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