CN116525175B - Electrode slurry, preparation method, electrode plate and photovoltaic cell - Google Patents
Electrode slurry, preparation method, electrode plate and photovoltaic cell Download PDFInfo
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- 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
-
- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/072—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
- H01L31/0745—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells
- H01L31/0747—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells comprising a heterojunction of crystalline and amorphous materials, e.g. heterojunction with intrinsic thin layer
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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
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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
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
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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
- H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
- H01L31/202—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials including only elements of Group IV of the Periodic Table
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Energy (AREA)
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Abstract
The invention discloses electrode paste, a preparation method thereof, an electrode plate and a battery, relates to the technical field of solar batteries, and aims to solve the problem that the existing electrode paste damages an amorphous silicon transparent conductive film layer on the surface of the battery due to overhigh sintering temperature. The electrode slurry comprises a modified silver-based conductive material and an organic carrier, wherein the modified silver-based conductive material comprises a silver-based conductive material and thermoplastic polyurethane wrapped on the surface of the silver-based conductive material, and the glass transition temperature of the thermoplastic polyurethane is 50-150 ℃. The preparation method is used for preparing the electrode slurry, the electrode slurry is used for the electrode plate, and the electrode plate is used for the battery. The electrode paste, the preparation method, the electrode plate and the battery provided by the invention are used for reducing damage to the amorphous silicon transparent conductive film layer in the battery manufacturing process.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to electrode slurry, a preparation method, an electrode plate and a photovoltaic cell.
Background
The theoretical efficiency of the heterojunction solar cell can reach 28%, which is far higher than that of the conventional PERC crystalline silicon solar cell, so that the heterojunction solar cell becomes one of the development directions of the next generation solar cell. At present, the surface of the heterojunction solar cell is mainly an amorphous silicon transparent conductive film layer, and the temperature resistance is lower than 250 ℃.
In the prior art, when an amorphous silicon transparent conductive film layer is produced, the main curing process is generally to sinter at 150-220 ℃ for 10-30 min to obtain the heterojunction solar cell. The high sintering temperature damages the conductive layer on the surface of the heterojunction battery, resulting in an increase in contact resistivity and a decrease in conversion efficiency. On the other hand, since the conventional conductive silver paste for heterojunction cells contains a certain amount of solvent, there is a certain risk of damage to the health of workers in the production site and the environment around the factory during the production process of solar cells.
Disclosure of Invention
The invention aims to provide electrode slurry, a preparation method, an electrode plate and a photovoltaic cell, and damage to an amorphous silicon transparent conductive film layer on the surface of the cell caused by overhigh sintering temperature in the process of manufacturing the cell is avoided.
In a first aspect, the invention provides an electrode slurry, which comprises a modified silver-based conductive material and an organic carrier, wherein the modified silver-based conductive material comprises a silver-based conductive material and thermoplastic polyurethane wrapped on the surface of the silver-based conductive material, and the glass transition temperature of the thermoplastic polyurethane is 50-150 ℃.
Compared with the prior art, the electrode slurry provided by the invention has the following advantages:
The electrode slurry provided by the invention comprises a modified silver-based conductive material and an organic carrier, wherein the modified silver-based conductive material comprises a silver-based conductive material and thermoplastic polyurethane wrapped on the surface of the silver-based conductive material. When the grid line is formed on the battery piece, the thermoplastic polyurethane is wrapped on the surface of the silver-based conductive material, so that the problem that normal printing cannot be performed due to aggregation of the silver-based conductive material can be avoided. Meanwhile, as the glass transition temperature of the thermoplastic polyurethane is 50-150 ℃, the silver-based conductive material modified by the thermoplastic polyurethane dispersed in the organic carrier can be solidified with the battery piece at 50-150 ℃, the solidification sintering temperature is reduced, and the problem that the amorphous silicon transparent conductive film layer of the heterojunction battery is damaged due to solidification of electrode slurry baked at high temperature during the production of the heterojunction battery is avoided. In addition, as the thermoplastic polyurethane is a flexible block polymer, ions of the amorphous silicon transparent conductive film layer can be complexed, the binding force of the silver grid line on the solar cell after solidification is improved, the contact resistivity is reduced, the conversion efficiency is improved, and the service life of the cell is prolonged.
In addition, the electrode paste can be cured without adding a solvent, and the damage to the health of workers and the damage to the environment can be reduced in the production process of the heterojunction solar cell.
Therefore, the electrode paste provided by the invention can reduce the sintering temperature and reduce the environmental pollution when the grid line is formed on the battery piece.
In a second aspect, the present invention also provides a method for preparing an electrode slurry, comprising:
uniformly mixing a silver-based conductive material and thermoplastic polyurethane, and heating to prepare a modified silver-based conductive material;
And mixing an organic carrier with the modified silver conductive material to obtain electrode slurry, wherein the organic carrier comprises a vinyl compound, a sulfhydryl compound and a photoinitiator.
Compared with the prior art, the preparation method of the electrode slurry has the same beneficial effects as those of the electrode slurry in the first aspect, and the description is omitted here.
In a third aspect, the invention also provides an electrode sheet comprising the electrode slurry provided by the invention.
Compared with the prior art, the electrode plate provided by the invention comprises the electrode paste provided by the invention, so that the beneficial effects are the same as those of the electrode paste of the first aspect, and the description is omitted here.
In a fourth aspect, the invention also provides a photovoltaic cell comprising the electrode paste provided by the invention.
Compared with the prior art, the photovoltaic cell provided by the invention comprises the electrode paste provided by the invention, so that the beneficial effects are the same as those of the electrode paste of the first aspect, and the description is omitted here.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and do not constitute a limitation on the invention. In the drawings:
Fig. 1 is a schematic view of a battery according to an embodiment of the present invention;
fig. 2 is a flowchart of the preparation of an electrode paste according to an embodiment of the present invention.
Reference numerals:
100-battery, 101 a-positive electrode, 101 b-negative electrode, 102 a-first amorphous silicon transparent conductive film layer, 102 b-second amorphous silicon transparent conductive film layer, 103 a-first intrinsic amorphous silicon film, 103 b-second intrinsic amorphous silicon film, 104-P type amorphous silicon film, 105-N type amorphous silicon film.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise. The meaning of "a number" is one or more than one unless specifically defined otherwise.
The conventional crystalline silicon solar cell is formed by forming an N-type semiconductor on one side and a P-type semiconductor on the other side by using different doping processes on a complete silicon wafer, and PN junctions are formed in the regions near the interface of the two semiconductors. Heterojunction solar cells are all called intrinsic thin film Heterojunction cells (HJT, heterojunction WITH INTRINSIC THIN-layer), are a special PN junction formed by amorphous silicon and crystalline silicon materials, are amorphous silicon thin films deposited on crystalline silicon, and belong to one of N-type cells. The theoretical efficiency of the heterojunction cell can reach 28%, which is far higher than that of the conventional crystalline silicon solar cell, so the heterojunction cell becomes one of the development directions of the next generation solar cell.
Because the surface of the heterojunction solar cell is mainly an amorphous silicon transparent conductive film layer, the temperature resistance of the amorphous silicon transparent conductive film layer is lower than 250 ℃, and therefore, the surface of the heterojunction solar cell is printed with conductive silver paste with the solidification temperature below 220 ℃. However, the curing process of the conductive silver paste in the prior art is generally to sinter at 150-220 ℃ for 10-30 min, the curing temperature is higher, the surface amorphous silicon transparent conductive film layer of the heterojunction solar cell is at risk of damage, the sintering time is longer than that of the conventional crystalline silicon solar cell, and the production efficiency is not improved and the cost of the heterojunction solar cell is reduced.
In view of the above problems, embodiments of the present invention provide a heterojunction battery, which may include the electrode material of the embodiments of the present invention, so as to avoid damage to an amorphous silicon transparent conductive film layer on a battery surface caused by too high sintering temperature when sintering electrode slurry. It is understood that the heterojunction cell may include an electrode material, a substrate, an amorphous silicon transparent conductive thin film layer, a P-type amorphous silicon thin film, an intrinsic amorphous silicon thin film, and an N-type amorphous silicon thin film. Fig. 1 shows a schematic structural diagram of a battery according to an embodiment of the present invention, and as shown in fig. 1, a heterojunction battery 100 according to an embodiment of the present invention includes, from top to bottom, a positive electrode 101a, a first amorphous silicon transparent conductive film layer 102a, a P-type amorphous silicon film 104, a first intrinsic amorphous silicon film 103a, a substrate 106, a second intrinsic amorphous silicon film 103b, an N-type amorphous silicon film 105, a second amorphous silicon transparent conductive film layer 102b, and a negative electrode 101b.
The electrode paste provided by the embodiment of the invention can be applied to the battery. Comprising the following steps: the modified silver-based conductive material comprises a silver-based conductive material and thermoplastic polyurethane wrapped on the surface of the silver-based conductive material, wherein the glass transition temperature of the thermoplastic polyurethane is 50-150 ℃. It will be appreciated that the glass transition temperature of the thermoplastic polyurethane is preferably from 80℃to 120 ℃. The silver-based conductive material may be silver powder or silver alloy powder, which is not limited herein.
The electrode slurry provided by the invention comprises a modified silver-based conductive material and an organic carrier, wherein the modified silver-based conductive material comprises a silver-based conductive material and thermoplastic polyurethane wrapped on the surface of the silver-based conductive material. When the grid line is formed on the battery piece, the thermoplastic polyurethane is wrapped on the surface of the silver-based conductive material, so that the problem that normal printing cannot be performed due to aggregation of the silver-based conductive material can be avoided. Meanwhile, as the glass transition temperature of the thermoplastic polyurethane is 50-150 ℃, the silver-based conductive material modified by the thermoplastic polyurethane dispersed in the organic carrier can be solidified with the battery piece at 50-150 ℃, so that the problem that the amorphous silicon transparent conductive film layer of the heterojunction battery is damaged due to solidification of electrode slurry baked at high temperature in the production of the heterojunction battery is avoided. In addition, as the thermoplastic polyurethane is a flexible block polymer, ions of the amorphous silicon transparent conductive film layer can be complexed, the binding force of the silver grid line on the solar cell after solidification is improved, the contact resistivity is reduced, the conversion efficiency is improved, and the service life of the cell is prolonged.
In addition, the electrode paste can be cured without adding a solvent, and the damage to the health of workers and the damage to the environment can be reduced in the production process of the heterojunction solar cell.
In one implementation manner, in the electrode slurry of the embodiment of the invention, the modified silver-based conductive material accounts for 75-95% of the mass of the electrode slurry, and the organic carrier accounts for 5-25% of the mass of the electrode slurry. Under the proportion, the modified silver conductive material can be fully dispersed in the organic carrier, and the glass transition temperature of thermoplastic polyurethane contained in the modified silver conductive material is 50-150 ℃, so that the modified silver conductive material and the organic carrier can be crosslinked and solidified at low temperature (50-150 ℃), the risk that the bonding force between the silver grid line and the battery piece on the surface of the heterojunction battery is easily broken at an excessively high baking temperature is reduced, the contact resistivity is reduced, and the conversion efficiency is improved.
In an alternative mode, the electrode slurry of the embodiment of the invention comprises, by mass, 1-10% of thermoplastic polyurethane and 90-99% of modified silver-based conductive material. That is, the electrode paste of the embodiment of the present invention can encapsulate the silver-based conductive material using a small amount of thermoplastic polyurethane.
For thermoplastic polyurethanes, it may be exemplified by polymers containing repeating urethane groups in the molecular structure, modified polymers containing repeating urethane groups in the molecular structure, or a combination of both. Preferably, the thermoplastic polyurethane may be a polymer having a glass transition temperature of 80 ℃ to 120 ℃ containing repeating urethane groups or a modified polymer thereof or a combination of both. The thermoplastic polyurethane may be selected from thermoplastic polyurethanes having a number average molecular weight between 10000Da and 500000 Da. The thermoplastic polyurethane of the embodiment of the invention is an elastic substance, and can greatly enhance the tensile resistance of the electrode plate, thereby improving the puncture resistance of the conductive film layer, reducing the probability of short circuit of the battery caused by puncture and improving the efficiency of the battery.
In an alternative manner, the organic carrier of the embodiment of the present invention includes a vinyl compound, a mercapto compound, and a photoinitiator, wherein the mass ratio of the vinyl compound, the mercapto compound, and the photoinitiator is (75 to 90): (5-25): (1-10).
Illustratively, the vinyl compound includes at least one of a modified epoxy resin, a modified polyurethane resin, and an acrylate compound. Wherein the acrylate compound includes at least one of methyl methacrylate, butyl methacrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate and pentaerythritol tetraacrylate. The mercapto compound includes at least one of 2-mercaptoethanol, 1, 6-hexanedithiol and N-acetylthiolactone. The photoinitiator comprises at least one of 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone and benzoin dimethyl ether.
The carbon-carbon double bond contained in the vinyl compound provided by the embodiment of the invention and the sulfhydryl compound undergo chain polymerization under the action of the photoinitiator to form a sulfhydryl-vinyl system, so that the vinyl compound is rapidly crosslinked and cured. The modified epoxy resin and the polyurethane resin have good toughness and low-temperature curing performance, so that the toughness and the low-temperature curing performance of the organic carrier can be enhanced, the low-temperature curing of the modified silver-based conductive material can be promoted, the electrode paste can be cured under the low-temperature condition, and the electrode formed by curing is strong in toughness and is not easy to crack.
In an alternative mode, the particle size distribution D50 of the modified silver-based conductive material implemented by the invention is 0.1-5 mu m, the specific surface area of the modified silver-based conductive material is less than 3m 2/g, and the silver-based conductive material comprises spherical silver powder and/or flake silver powder. The spherical silver powder in the embodiment of the invention is contacted in a point-to-point manner, the contact area is relatively small, the flaky silver powder contains a large number of surface-to-surface contacts or surface-to-surface contacts, the contact area is relatively large, and when the particle size and the specific surface area of the modified silver-based conductive material are in the ranges, the modified silver-based conductive material has larger internal friction in relative displacement, so that the viscosity of the prepared slurry is high, and the curing time is shortened. Meanwhile, when the modified silver-based conductive material provided by the embodiment of the invention contains both spherical silver powder and flake silver powder, the spherical silver powder can fill gaps among the flake silver powder, so that the original non-contact adjacent flake silver powder contacts each other, a conductive path is increased, and the conductivity is improved.
Illustratively, the electrode paste of the embodiment of the invention has a fineness of 5 μm or less and a viscosity of 100 Pa.S to 300 Pa.S. When the fineness and viscosity of the electrode slurry are in the above ranges, the problem of stirring difficulty caused by overlarge viscosity of the slurry in the production and processing process can be avoided, so that good printing performance can be ensured, the problem of sedimentation of suspended particles caused by overlarge viscosity, which is unfavorable for slurry uniformity and stability, can be avoided, and the curing rate is improved.
Fig. 2 shows a flowchart of preparation of an electrode paste according to an embodiment of the present invention, and as shown in fig. 2, the present invention further provides a method for preparing the electrode paste, including:
Step 201: and uniformly mixing the silver-based conductive material with thermoplastic polyurethane, and heating to prepare the modified silver-based conductive material.
The thermoplastic polyurethane compound and the silver powder are mixed and stirred, the temperature is raised to 200 ℃, stirring is continued for 0.5 to h, and the mixture is cooled to room temperature, so that the modified silver-based conductive material is obtained. The silver-based conductive material uniformly wrapping the thermoplastic polyurethane compound can be obtained by mixing and stirring the polyurethane compound and the silver powder at 200 ℃.
Step 202: and mixing an organic carrier with the modified silver-based conductive material to obtain electrode slurry, wherein the organic carrier comprises a vinyl compound, a sulfhydryl compound and a photoinitiator.
For example: first, a vinyl compound, a mercapto compound, and a photoinitiator are mixed and stirred to obtain an organic vehicle. Then mixing the organic carrier with the modified silver-based conductive material, stirring, placing on a three-roller mill for grinding and rolling, further dispersing and homogenizing, and obtaining the electrode slurry when the scraper fineness of the three-roller mill is less than 5 mu m. Meanwhile, the viscosity at 10rmp rotational speed was measured at room temperature of 25℃using a Brookfield viscometer to be 100 Pa.S to 300 Pa.S.
The electrode slurry provided by the invention can uniformly disperse the silver conductive material in the organic carrier because the organic carrier is liquid, and the organic carrier comprises the vinyl compound, the sulfhydryl compound and the photoinitiator, and can absorb energy with a certain wavelength under the irradiation of ultraviolet light and then generate chemical change to generate free radicals or cations, so that the vinyl compound and the sulfhydryl compound contained in the organic carrier undergo linkage polymerization under the action of the free radicals or cations to form a sulfhydryl-vinyl system, thereby being rapidly crosslinked and cured. The glass transition temperature of the thermoplastic polyurethane contained in the modified silver conductive material is 50-150 ℃, so that the modified silver conductive material and the organic carrier can be crosslinked and solidified at a low temperature (50-150 ℃), the risk that the bonding force between the silver grid line and the battery piece on the surface of the heterojunction battery is easily broken at an excessively high baking temperature is reduced, the contact resistivity is reduced, and the conversion efficiency is improved. Meanwhile, in the ultraviolet light curing process of the mercapto-vinyl system, after the photoinitiator is decomposed into free radicals or cations, the free radicals or cations are easy to react with oxygen in the air to form peroxy free radicals with lower reactivity, and at the moment, the peroxy free radicals can abstract hydrogen atoms on mercapto groups to generate mercapto free radicals, so that the continuous proceeding of the polymerization reaction is ensured, the phenomenon of termination of the polymerization reaction caused by the existence of the peroxy free radicals is avoided, the curing rate is improved, and the curing time is shortened.
The electrode slurry provided by the invention comprises a modified silver-based conductive material and an organic carrier, wherein the modified silver-based conductive material comprises a silver-based conductive material and thermoplastic polyurethane wrapped on the surface of the silver-based conductive material. When the grid line is formed on the battery piece, the thermoplastic polyurethane is wrapped on the surface of the silver-based conductive material, so that the problem that normal printing cannot be performed due to aggregation of the silver-based conductive material can be avoided. Meanwhile, as the glass transition temperature of the thermoplastic polyurethane is 50-150 ℃, the silver-based conductive material modified by the thermoplastic polyurethane dispersed in the organic carrier can be solidified with the battery piece at 50-150 ℃, the solidification sintering temperature is reduced, and the problem that the amorphous silicon transparent conductive film layer of the heterojunction battery is damaged due to solidification of electrode slurry baked at high temperature during the production of the heterojunction battery is avoided.
In order to verify the effect of the electrode paste provided in the examples of the present invention, the examples of the present invention were demonstrated by comparing the examples with comparative examples.
Example 1
The electrode slurry provided by the embodiment of the invention comprises the following components in parts by mass: 85.5 parts by weight of spherical silver powder (model: GS753, manufactured by Zhejiang Guangda electronic technologies Co., ltd.), 4.5 parts by weight of polyurethane (model: 5778, manufactured by Lu Bo run Co.), 6 parts by weight of 1, 6-hexanediol diacrylate, 2 parts by weight of epoxy acrylate, 1 part by weight of 2-mercaptoethanol, 1 part by weight of 1-hydroxy-cyclohexyl-phenyl methanone.
The preparation method of the electrode slurry provided by the embodiment of the invention comprises the following steps:
firstly, preparing a modified silver-based conductive material: 85.5 parts by weight of commercial spherical silver powder (model: GS753, manufactured by Zhejiang Guangda electronic technology Co., ltd.) and 4.5 parts by weight of polyurethane compound (model: 5778, manufactured by Lu Bo run Co.) are mixed and stirred uniformly, the temperature is raised to 200 ℃, the heat preservation and stirring are continued for 45 minutes, and the polyurethane coated silver powder is obtained after cooling.
Second, organic carrier preparation: 1, 6-hexanediol diacrylate, epoxy acrylate (model: CN104NS, manufactured by Sadama Co.), 2-mercaptoethanol, and 1-hydroxy-cyclohexyl-phenyl ketone were mixed and stirred uniformly to obtain an organic carrier.
Thirdly, preparing electrode slurry: mixing the modified silver-based conductive material with the organic carrier mixture, stirring, and passing through a three-roller grinder to obtain the electrode slurry with the fineness of less than 5 mu m.
Example two
The electrode slurry provided by the embodiment of the invention comprises the following components in parts by mass: 80 parts by weight of spherical silver powder (model: GS753, manufactured by Zhejiang Guangda electronic technologies Co., ltd.), 10 parts by weight of polyurethane (model: 5778, manufactured by Lu Bo run Co.), 5 parts by weight of 1, 6-hexanediol diacrylate, 3 parts by weight of epoxy acrylate, 1 part by weight of 2-mercaptoethanol, 1 part by weight of 1-hydroxy-cyclohexyl-phenyl ketone.
The preparation method of the electrode slurry provided by the second embodiment of the invention comprises the following steps:
Firstly, preparing a modified silver-based conductive material: 80 parts by weight of commercial spherical silver powder (model: GS753, manufactured by Zhejiang Guangda electronic technology Co., ltd.) and 10 parts by weight of polyurethane compound (model: 5778, lu Bo run Co.) are mixed and stirred uniformly, the temperature is raised to 200 ℃, the heat preservation and stirring are continued for 45 minutes, and the polyurethane coated silver powder is obtained after cooling.
Second, organic carrier preparation: 1, 6-hexanediol diacrylate, epoxy acrylate (model: CN104NS, manufactured by Sadama Co.), 2-mercaptoethanol, and 1-hydroxy-cyclohexyl-phenyl ketone were mixed and stirred uniformly to obtain an organic carrier.
Thirdly, preparing electrode slurry: mixing the modified silver-based conductive material with the organic carrier mixture, stirring, and passing through a three-roller grinder to obtain the electrode slurry with the fineness of less than 5 mu m.
Example III
The electrode slurry provided by the embodiment of the invention comprises the following components in parts by mass: 82 parts by weight of spherical silver powder (model: GS753, manufactured by Zhejiang Guangda electronic technologies Co., ltd.), 8 parts by weight of polyurethane (model: 5778, manufactured by Lu Bo run Co.), 3 parts by weight of 1, 6-hexanediol diacrylate, 5 parts by weight of epoxy acrylate, 1 part by weight of 2-mercaptoethanol, 1 part by weight of 1-hydroxy-cyclohexyl-phenyl ketone.
The preparation method of the electrode slurry provided by the third embodiment of the invention comprises the following steps:
firstly, preparing a modified silver-based conductive material: 82 parts by weight of commercial spherical silver powder (model: GS753, manufactured by Zhejiang Guangda electronic technology Co., ltd.) and 8 parts by weight of polyurethane compound (model: 5778, lu Bo run Co.) are mixed and stirred uniformly, the temperature is raised to 200 ℃, the heat preservation and stirring are continued for 45 minutes, and the polyurethane coated silver powder is obtained after cooling.
Second, organic carrier preparation: 1, 6-hexanediol diacrylate, epoxy acrylate (model: CN104NS, manufactured by Sadama Co.), 2-mercaptoethanol, and 1-hydroxy-cyclohexyl-phenyl ketone were mixed and stirred uniformly to obtain an organic carrier.
Thirdly, preparing electrode slurry: mixing the modified silver-based conductive material with the organic carrier mixture, stirring, and passing through a three-roller grinder to obtain the electrode slurry with the fineness of less than 5 mu m.
Example IV
The electrode slurry provided by the embodiment of the invention comprises the following components in parts by mass: 60 parts by weight of spherical silver powder, 23 parts by weight of plate-like silver powder, 7 parts by weight of a polyurethane compound, 6 parts by weight of methyl methacrylate, 2 parts by weight of epoxy acrylate, 1 part by weight of 1, 6-hexanedithiol and 1 part by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone.
The preparation method of the electrode slurry provided by the fourth embodiment of the invention comprises the following steps:
Firstly, preparing a modified silver-based conductive material: 60 parts by weight of spherical silver powder, 23 parts by weight of flake silver powder, 7 parts by weight of polyurethane compound, 6 parts by weight of methyl methacrylate, 2 parts by weight of epoxy acrylate, 1 part by weight of 1, 6-hexamethylene dithiol and 1 part by weight of 2-hydroxy-2-methyl-1-phenyl-1-acetone are mixed and stirred uniformly, the temperature is raised to 200 ℃, the heat preservation and stirring are continued for 45 minutes, and the polyurethane coated silver powder is obtained after cooling.
Second, organic carrier preparation: methyl methacrylate, epoxy acrylate, 1, 6-hexamethylene dithiol and 1 part by weight of 2-hydroxy-2-methyl-1-phenyl-1-acetone are mixed and stirred uniformly to obtain an organic carrier.
Thirdly, preparing electrode slurry: and adding the modified silver-based conductive material into the organic carrier, fully and uniformly stirring, and putting the mixed electrode slurry on a three-roller mill for dispersion grinding to prepare the electrode slurry.
Example five
The electrode slurry provided by the embodiment of the invention comprises the following components in parts by mass: 65 parts by weight of spherical silver powder, 15 parts by weight of plate-like silver powder, 10 parts by weight of a polyurethane compound, 6 parts by weight of butyl methacrylate, 2 parts by weight of epoxy acrylate, 1 part by weight of 1, 6-hexanedithiol and 1 part by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone.
The preparation method of the electrode slurry provided by the fifth embodiment of the invention comprises the following steps:
firstly, preparing a modified silver-based conductive material: mixing and stirring 65 parts by weight of spherical silver powder, 15 parts by weight of flake silver powder, 10 parts by weight of polyurethane compound, 6 parts by weight of butyl methacrylate, 2 parts by weight of epoxy acrylate, 1 part by weight of 1, 6-hexamethylene dithiol and 1 part by weight of 2-hydroxy-2-methyl-1-phenyl-1-acetone uniformly, heating to 200 ℃, continuing to keep the temperature and stirring for 45 minutes, and cooling to obtain polyurethane coated silver powder, namely the modified silver-based conductive material.
Second, organic carrier preparation: butyl methacrylate, epoxy acrylate, 1, 6-hexamethylene dithiol and 1 part by weight of 2-hydroxy-2-methyl-1-phenyl-1-acetone are mixed and stirred uniformly to obtain an organic carrier.
Thirdly, preparing electrode slurry: and adding the modified silver-based conductive material into the organic carrier, fully and uniformly stirring, and putting the mixed electrode slurry on a three-roller mill for dispersion grinding to prepare the electrode slurry.
Example six
The electrode slurry provided by the embodiment of the invention comprises the following components in parts by mass: 70 parts by weight of spherical silver powder, 20 parts by weight of plate-like silver powder, 5 parts by weight of a polyurethane compound, 2 parts by weight of trimethylolpropane triacrylate, 1 part by weight of methyl methacrylate, 1 part by weight of N-acetylthiolactone and 1 part by weight of benzoin dimethyl ether.
The preparation method of the electrode slurry provided by the sixth embodiment of the invention comprises the following steps:
Firstly, preparing a modified silver-based conductive material: 70 parts by weight of spherical silver powder, 20 parts by weight of flake silver powder, 5 parts by weight of polyurethane compound, 2 parts by weight of trimethylolpropane triacrylate, 1 part by weight of methyl methacrylate, 1 part by weight of N-acetylthiolactone and 1 part by weight of benzoin dimethyl ether are mixed and stirred uniformly, the temperature is raised to 200 ℃, the heat preservation and stirring are continued for 45 minutes, and the polyurethane coated silver powder is obtained after cooling, namely the modified silver-based conductive material.
Second, organic carrier preparation: trimethylolpropane triacrylate, methyl methacrylate, N-acetylthiolactone and 1 part by weight of benzoin dimethyl ether are mixed and stirred uniformly to obtain the organic carrier.
Thirdly, preparing electrode slurry: and adding the modified silver-based conductive material into the organic carrier, fully and uniformly stirring, and putting the mixed electrode slurry on a three-roller mill for dispersion grinding to prepare the electrode slurry.
Comparative example one
The electrode paste of the comparative example of the present application does not contain the modified silver-based conductive material of the present application.
The preparation method of the electrode slurry provided by the comparative example comprises the following steps:
First, preparing an organic carrier: 3 parts by weight of 1, 6-hexanediol diacrylate, 5 parts by weight of epoxy acrylate (model: CN104NS, manufactured by the company Sadoma), 1 part by weight of 2-mercaptoethanol, 1 part by weight of 1-hydroxy-cyclohexyl-phenyl ketone were mixed and stirred uniformly to obtain an organic carrier.
Secondly, preparing electrode slurry: 90 parts by weight of spherical silver powder (model: GS753, manufactured by Zhejiang Guangda electronic technology Co., ltd.) was added to the above-mentioned organic vehicle and stirred well, and the mixed electrode paste was put on a three-roll mill to be dispersed and ground, to prepare an electrode paste.
Comparative example two
The electrode paste of the second comparative example of the present application does not contain the modified silver-based conductive material of the present application.
The preparation method of the electrode slurry provided by the second comparative example comprises the following steps:
First, preparing an organic carrier: 7 parts by weight of hydrogenated epoxy resin (model: HE2025, manufacturer: shanghai complex advanced Material Co., ltd.), 1 part by weight of dicyandiamide, 2 parts by weight of diethylene glycol butyl ether acetate were mixed and stirred uniformly to obtain an organic carrier.
Secondly, preparing electrode slurry: 90 parts by weight of spherical silver powder (average particle diameter d50=1.5 μm, specific surface area 0.2m 2/g) was added to the above-mentioned organic carrier and sufficiently stirred uniformly, and the mixed electrode slurry was put on a three-roll mill to be dispersed and ground, to prepare an electrode slurry.
The preparation process of the heterojunction battery formed by the electrode slurry provided by the embodiment of the invention comprises the following steps:
and firstly, cleaning and texturing the silicon wafer.
Second, amorphous silicon deposition: the intrinsic amorphous silicon film and the P-type amorphous silicon film are prepared by adopting an amorphous silicon front PECVD method, and the intrinsic amorphous silicon film and the N-type amorphous silicon film are prepared by adopting a back PECVD method.
And thirdly, depositing a transparent conductive film, and depositing transparent conductive oxide films on two sides by a sputtering method.
Fourth, screen printing the low-temperature cured electrode slurry.
And fifthly, irradiating the electrode slurry for not more than 1min by using a mercury lamp with the power of 60W/cm to obtain the heterojunction battery.
The low temperature curing conductive silver paste of examples 1-3 and comparative examples 1-2 was subjected to a related performance test in this example; specific results are shown in table 1, specific tests include:
1. Viscosity test
The viscosity test is a viscosity value at 2 minutes using a Brookfield viscometer, a rotational speed of 10 revolutions per minute.
2. Contact resistivity test
And testing the contact resistivity between the grid line and the battery piece after curing by adopting a four-probe ohmmeter.
3. Adhesion test
The 3M6100 adhesive tape is attached to the grid line in the direction of 90 degrees, and is repeatedly pressed for 3 times by an index finger, the adhesive tape is pulled at a uniform speed in the direction of 180 degrees, and the falling-off condition of the grid line is observed.
4. Electrical performance testing
Solar simulator, M1.5 spectrum, 1.000KW/M 2 at 25 ℃.
The test results of the electrode pastes provided in examples 1 to 3 and comparative examples 1 to 2 of the present invention are shown in the following table:
As can be seen from the above table, the heterojunction cells prepared from the electrode pastes of examples one to three had much lower contact resistivity than those of comparative examples one to two, which did not contain the modified silver-based conductive material, and had higher conversion efficiency than those of comparative examples one to two. Meanwhile, the grid lines formed by sintering the electrode slurry are not easy to fall off. That is, the grid line formed by sintering the click slurry is greatly improved in bonding force with the solar cell after solidification, greatly reduced in contact resistivity, better in conversion efficiency and beneficial to prolonging the service life of the cell.
The foregoing is merely a specific embodiment of the invention, and it will be apparent that various modifications and combinations thereof can be made without departing from the spirit and scope of the invention. Accordingly, the specification and drawings are merely exemplary illustrations of the present invention as defined in the appended claims and are considered to cover any and all modifications, variations, combinations, or equivalents that fall within the scope of the invention. It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. Any person skilled in the art can easily think of changes or substitutions within the technical scope of the present disclosure, and the present disclosure is intended to be covered by the present disclosure. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A method for preparing an electrode slurry, comprising:
Uniformly mixing a silver-based conductive material and thermoplastic polyurethane, and heating to prepare a modified silver-based conductive material, wherein the glass transition temperature of the thermoplastic polyurethane is 50-150 ℃, the thermoplastic polyurethane accounts for 1-10% of the modified silver-based conductive material in percentage by mass, the silver-based conductive material accounts for 90-99% of the modified silver-based conductive material in percentage by mass, and the thermoplastic polyurethane has a number average molecular weight of 10000-500000 Da;
And mixing an organic carrier with the modified silver-based conductive material to obtain electrode slurry, wherein the organic carrier comprises a vinyl compound, a sulfhydryl compound and a photoinitiator.
2. An electrode paste prepared by the preparation method of the electrode paste according to claim 1, which is characterized by comprising a modified silver-based conductive material and an organic carrier, wherein the modified silver-based conductive material comprises a silver-based conductive material and thermoplastic polyurethane coated on the surface of the silver-based conductive material, and the glass transition temperature of the thermoplastic polyurethane is 50-150 ℃.
3. The electrode paste according to claim 2, wherein the modified silver-based conductive material accounts for 75-95% of the mass of the electrode paste, and the organic carrier accounts for 5-25% of the mass of the electrode paste.
4. The electrode paste according to claim 2, wherein the thermoplastic polyurethane accounts for 1-10% by mass of the modified silver-based conductive material, and the silver-based conductive material accounts for 90-99% by mass of the modified silver-based conductive material.
5. The electrode paste according to claim 2, wherein the thermoplastic polyurethane comprises a polymer having a repeating urethane group in a molecular structure and/or a modified polymer having a repeating urethane group in a molecular structure.
6. The electrode paste according to claim 2, wherein the organic vehicle comprises a vinyl compound, a mercapto compound, and a photoinitiator, the mass ratio of the vinyl compound, the mercapto compound, and the photoinitiator being (75 to 90): (5-25): (1-10).
7. The electrode paste according to claim 6, wherein the vinyl compound comprises at least one of a modified epoxy resin, a modified polyurethane resin, and an acrylate compound;
the sulfhydryl compound comprises at least one of 2-mercaptoethanol, 1, 6-hexanedithiol and N-acetylthiolactone;
The photoinitiator comprises at least one of 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone and benzoin dimethyl ether.
8. The electrode paste according to any one of claims 2 to 7, wherein the modified silver-based conductive material has a particle size distribution D50 of 0.1 μm to 5 μm, and the modified silver-based conductive material has a specific surface area of less than 3m 2/g;
The silver-based conductive material comprises spherical silver powder and/or flake silver powder.
9. An electrode sheet, characterized in that the electrode sheet comprises the electrode slurry according to any one of claims 2 to 8.
10. A photovoltaic cell comprising the electrode sheet of claim 9.
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