CN113571228A - Front conductive silver paste for crystalline silicon solar cell and preparation method thereof - Google Patents

Front conductive silver paste for crystalline silicon solar cell and preparation method thereof Download PDF

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Publication number
CN113571228A
CN113571228A CN202110748876.4A CN202110748876A CN113571228A CN 113571228 A CN113571228 A CN 113571228A CN 202110748876 A CN202110748876 A CN 202110748876A CN 113571228 A CN113571228 A CN 113571228A
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silver paste
conductive silver
crystalline silicon
silicon solar
solar cell
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CN202110748876.4A
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李宇
杨磊
赵德平
胡鹏
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Zhejiang Jingke New Material Co ltd
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Zhejiang Jingke New Material Co ltd
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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
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic 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
    • 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
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/05—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells
    • H01L31/0504—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells specially adapted for series or parallel connection of solar cells in a module
    • H01L31/0512—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells specially adapted for series or parallel connection of solar cells in a module made of a particular material or composition of materials
    • 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

Abstract

The invention discloses a front conductive silver paste for a crystalline silicon solar cell, which comprises the following raw materials: 72-90% of silver powder; glass powder: 4-10% of metal oxide, organic carrier: 5-20% of resin, dispersant, solvent and photo-curing material, wherein the resin accounts for 4-10%, the dispersant accounts for 2-8%, the solvent accounts for 75-85% and the photo-curing material accounts for 8-15%. The invention also provides a preparation method of the solar front conductive silver paste, and the organic carrier is added in the method, so that the conductive silver paste brings a high aspect ratio, and the electrical property of the paste is further improved. The conductive silver paste comprises silver powder, glass powder and an organic carrier, wherein the organic carrier comprises one or more photocuring materials, and the material can effectively improve the height-width ratio of the printed conductive silver paste, so that the solar energy conversion efficiency of the battery is improved.

Description

Front conductive silver paste for crystalline silicon solar cell and preparation method thereof
Technical Field
The invention belongs to the field of new materials for solar cells, and particularly relates to a front conductive silver paste for a crystalline silicon solar cell and a preparation method thereof.
Background
Energy is the basis of economic development and social development in the world, and solar energy as a novel clean energy is renewable energy and plays an important role in the future energy development process. The crystalline silicon solar cell is the main force of the existing solar cell, and the solar conductive silver paste is an important material required to be used in the process of preparing the crystalline silicon solar cell and has a crucial influence on the efficiency of a cell.
The conventional crystalline silicon solar cell prints conductive silver paste on the surface of a cell piece through a screen printing technology, an organic carrier mainly plays a role in wetting and dispersing inorganic components, the auxiliary slurry is used for printing smoothly through a screen printing plate, finger-shaped grid lines are formed on a silicon chip, and the silicon chip is dried and sintered, so that the organic components are volatilized and burnt out without residues. Silver powder is the conductive phase of conductive silver paste and is the main component of silver paste. The glass powder is a binding phase, and is sintered at high temperature to burn through an anti-reflection layer SiN of the cellXSo that the conductive phase silver electrode can be well contacted with silicon to form ohmic contact.
The invention patent CN 107919179 a proposes an organic carrier, which includes microgel particles and organic siloxane, and can better provide printing fluency of the slurry, and the aspect ratio of the printed grid line is improved to a certain extent, but the grid line still has a larger widening after sintering, and the widening of the grid line can increase the shading area on the surface of the battery piece, thereby reducing the short-circuit current and affecting the improvement of the efficiency.
Disclosure of Invention
In order to solve the technical problems, the invention provides a front conductive silver paste for a crystalline silicon solar cell and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
the front conductive silver paste for the crystalline silicon solar cell comprises the following raw materials in percentage by weight:
conductive metal: 72-90% of silver powder;
glass powder: 4-10% of metal oxide, and is used for etching the anti-reflection layer of the cell and enabling the electrode and the cell to form ohmic contact;
organic carrier: 5-20% of resin, 2-8% of dispersing agent, 75-85% of solvent and 8-15% of light-cured material.
Preferably, the raw materials of the material comprise the following components in percentage by weight: conductive metal: 80-90% of silver powder; glass powder: is metal oxide accounting for 4-8%; organic carrier: 6-14% of resin, 3-6% of dispersant, 75-80% of solvent and 10-12% of light-cured material.
Further, the light-curable material is an acrylic monomer or resin containing one or more multifunctional groups.
Further, the polyfunctional acrylic monomer is ethoxylated 1.6 hexanediol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, propoxylated (2) neopentyl glycol diacrylate, diethylene glycol diacrylate phthalate, tripropylene glycol diacrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, 1, 6-hexanediol diacrylate, ethoxylated 1.6 hexanediol diacrylate, 1, 4-butanediol diacrylate, ethoxylated (4) bisphenol A diacrylate, polyethylene glycol (200) diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated (3) glycerol triacrylate, One or more of pentaerythritol triacrylate, pentaerythritol tetraacrylate and dipentaerythritol pentaacrylate.
Furthermore, the multifunctional resin is one or more of epoxy acrylate, polyurethane acrylate, polyester acrylate, polyether acrylate, amino acrylate and acrylate.
Further, the organic carrier in the conductive silver paste at least comprises one or more than one monomer or resin containing 3 functional groups and more than one monomer or resin.
Further, the conductive silver powder comprises spherical silver powder, flake silver powder and nano silver powder, preferably the spherical silver powder, the particle diameter of the spherical silver powder is 2-6 mu m, and the tap density is more than 4 g/cm3。
Further, the metal oxide is at least one of lead oxide, zinc oxide, tellurium oxide, aluminum oxide and bismuth oxide.
Further, the resin comprises one or more of methyl cellulose, ethyl cellulose, cellulose acetate butyrate, nitrocellulose, rosin, modified rosin, polyvinyl alcohol, polyester resin and acrylic resin.
Further, the solvent in the organic carrier comprises one or more of terpineol, tributyl citrate, diethylene glycol butyl ether acetate, diethylene glycol dibutyl ether, diethylene glycol butyl ether, DBE, alcohol ester twelve, 2, 4-trimethyl-1, 3-pentanediol diisobutyrate, triethylene glycol and tripropylene glycol methyl ether;
further, the dispersing agent comprises one or more of lecithin, glyceryl monooleate, polyethylene glycol and polysorbate.
The invention also provides a preparation method of the front conductive silver paste for the crystalline silicon solar cell, which comprises the following steps:
1) according to the weight ratio of the materials, 4-10% of resin, 2-8% of dispersant, 75-85% of solvent and 8-15% of light-cured material are uniformly mixed by using a dispersing, emulsifying and stirring integrated machine, heated and dissolved uniformly at a constant temperature, cooled and filtered to obtain an organic carrier, wherein the heating and dissolving temperature is 60-70 ℃ at the constant temperature, and preferably 65 ℃;
2) adding the organic carrier, the glass powder and the silver powder obtained in the step 1) into a centrifuge or a planetary mixer according to the feeding proportion, uniformly mixing, and then grinding for 6-8 times by a three-roll grinder until the fineness of the slurry is less than 7 mu m to obtain the front conductive silver paste for the crystalline silicon solar cell.
According to the front conductive silver paste for the crystalline silicon solar cell and the preparation method thereof, the performance of the conductive silver paste is improved by adding the photocuring material. After the conductive silver paste is printed on the silicon wafer, the conductive silver paste passes through the drying section, and because the photocuring material is cured, the grid line cannot collapse or widen, so that the molding of the grid line is ensured, and after the silicon wafer passes through the sintering section, the photocuring material can be basically burnt out and cannot be remained in the grid line. The light-cured material can avoid the condition that the common thermoplastic resin is softened in the drying section and collapses, and meanwhile, the light-cured material can avoid the problem that the conventional thermosetting resin is added into slurry to cause storage. After the paste is printed, the grid lines are not collapsed or widened in the sintering process, so that the height-width ratio of the grid lines is improved, and the photoelectric conversion efficiency of the solar cell can be improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that the terms "comprises" and "comprising," and any variations thereof, in the description and claims of this invention, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
Example 1
The preparation method of the front conductive silver paste for the crystalline silicon solar cell comprises the following steps:
1) according to parts by weight, 45 parts of oleyl alcohol, 10 parts of tributyl citrate, 10 parts of diethylene glycol butyl ether acetate, 10 parts of DBE, 2 parts of ethyl cellulose, 2 parts of rosin resin, 6 parts of lecithin, 6 parts of ethoxylated 1.6 hexanediol diacrylate, 4 parts of tripropylene glycol diacrylate and 5 parts of dipropylene glycol diacrylate are mixed and stirred uniformly, heated and stirred for 1h at the constant temperature of 65 ℃, cooled and filtered to prepare the organic carrier;
2) adding 8 parts by weight of organic carrier, 4 parts by weight of glass powder (zinc oxide) and 88 parts by weight of silver powder into a planetary mixer in sequence, uniformly mixing, and grinding for 8 times by a three-roll grinder until the fineness of the slurry is less than 7 mu m to obtain the front conductive silver paste for the solar cell.
Example 2
The preparation method of the front conductive silver paste for the crystalline silicon solar cell comprises the following steps:
1) mixing and stirring 40 parts by weight of diethylene glycol butyl ether, 10 parts by weight of DBE, 8 parts by weight of alcohol ester twelve, 12 parts by weight of 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate, 4 parts by weight of butyric acid fiber acetate, 4 parts by weight of modified rosin, 8 parts by weight of polysorbate, 4 parts by weight of ethylene glycol diacrylate, 3 parts by weight of triethylene glycol diacrylate, 4 parts by weight of tetraethylene glycol diacrylate and 3 parts by weight of 1, 6-hexanediol diacrylate uniformly, heating and stirring for 1h at the constant temperature of 70 ℃, cooling and filtering to prepare the organic carrier;
2) adding 12 parts by weight of organic carrier, 5 parts by weight of glass powder (bismuth oxide) and 83 parts by weight of silver powder into a planetary mixer in sequence, uniformly mixing, and grinding for 7 times by a three-roll grinder until the fineness of the slurry is less than 7 mu m to obtain the front conductive silver paste for the solar cell.
Example 3
The preparation method of the front conductive silver paste for the crystalline silicon solar cell comprises the following steps:
1) according to parts by weight, 50 parts of terpineol, 10 parts of 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate, 10 parts of triethylene glycol, 12 parts of tripropylene glycol methyl ether, 2 parts of polyester resin, 3 parts of acrylic resin, 3 parts of glycerol monooleate, 4 parts of epoxy acrylate, 3 parts of polyurethane acrylate and 3 parts of polyether acrylate are mixed and stirred uniformly, heated and stirred for 1 hour at the constant temperature of 65 ℃, cooled and filtered to prepare the organic carrier;
2) adding 15 parts by weight of organic carrier, 5 parts by weight of glass powder (bismuth oxide) and 80 parts by weight of silver powder into a planetary mixer in sequence, uniformly mixing, and grinding for 8 times by a three-roll grinder until the fineness of the slurry is less than 7 mu m to obtain the front conductive silver paste for the solar cell.
Example 4
The preparation method of the front conductive silver paste for the crystalline silicon solar cell comprises the following steps:
1) according to parts by weight, 45 parts of oleyl alcohol, 15 parts of tributyl citrate, 10 parts of diethylene glycol butyl ether acetate, 10 parts of DBE, 2 parts of ethyl cellulose, 2 parts of rosin resin, 6 parts of lecithin, 6 parts of glycerol monooleate and 4 parts of polyethylene glycol are mixed and stirred uniformly, heated and stirred for 1 hour at the constant temperature of 65 ℃, cooled and filtered to prepare the organic carrier;
2) adding 8 parts by weight of organic carrier, 4 parts by weight of glass powder (zinc oxide) and 88 parts by weight of silver powder into a planetary mixer in sequence, uniformly mixing, and grinding for 8 times by a three-roll grinder until the fineness of the slurry is less than 7 mu m to obtain the front conductive silver paste for the solar cell.
The relevant experimental data are characterized as shown in the following table:
characteristics of Example 1 Example 2 Example 3 Example 4
Efficiency (%) 22.68 22.69 22.70 22.63
Current (mA) 10.7530 10.7630 10.7653 10.7204
Voc（V） 0.6849 0.6850 0.6845 0.6847
Height (mum) 18.21 18.32 18.90 16.01
Width (mum) 35.22 35.65 35.87 40.02
Aspect ratio 0.517 0.513 0.527 0.40
The conductive silver pastes of example 1, example 2 and example 3 were added with the photo-curable material, while example 4 was not added, and it can be seen from the data that example 4 does not use the photo-curable material, the aspect ratio of the grid lines is lower, the current is significantly lower than the other three experiments, and the efficiency is also lower.

Claims (10)

1. The front conductive silver paste for the crystalline silicon solar cell is characterized by comprising the following raw materials in percentage by weight:
conductive metal: 72-90% of silver powder;
glass powder: 4-10% of metal oxide, and is used for etching the anti-reflection layer of the cell and enabling the electrode and the cell to form ohmic contact;
organic carrier: 5-20% of resin, 2-8% of dispersing agent, 75-85% of solvent and 8-15% of light-cured material.
2. The front conductive silver paste for the crystalline silicon solar cell according to claim 1, wherein the raw materials comprise the following components in percentage by weight:
conductive metal: 80-90% of silver powder;
glass powder: is metal oxide accounting for 4-8%;
organic carrier: 6-14% of resin, 3-6% of dispersant, 75-80% of solvent and 10-12% of light-cured material.
3. The front conductive silver paste for the crystalline silicon solar cell of claim 1, wherein the light-curable material is an acrylic monomer or resin containing one or more multifunctional groups.
4. The front conductive silver paste for crystalline silicon solar cells as recited in claim 3, wherein the multifunctional acrylic monomer is ethoxylated 1.6 hexanediol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, propoxylated (2) neopentyl glycol diacrylate, diethylene glycol diacrylate phthalate, tripropylene glycol diacrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, 1, 6-hexanediol diacrylate, ethoxylated 1.6 hexanediol diacrylate, 1, 4-butanediol diacrylate, ethoxylated (4) bisphenol A diacrylate, polyethylene glycol (200) diacrylate, trimethylolpropane triacrylate, One or more of ethoxylated trimethylolpropane triacrylate, propoxylated (3) glycerol triacrylate, pentaerythritol tetraacrylate and dipentaerythritol pentaacrylate.
5. The front conductive silver paste for the crystalline silicon solar cell as recited in claim 3, wherein the multifunctional resin is one or more of epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, amino acrylate and acrylate.
6. The front conductive silver paste for the crystalline silicon solar cell according to claim 3 or 4, wherein the organic vehicle in the conductive silver paste at least comprises one or more monomers or resins containing 3 functional groups and more.
7. The front-side conductive silver paste for crystalline silicon solar cells according to claim 1, wherein the conductive silver metal powder comprises spherical silver powder, flake silver powder and nano silver powder, preferably spherical silver powderThe powder has particle diameter of 2-6 μm and tap density of more than 4 g/cm3The metal oxide is at least one of lead oxide, zinc oxide, tellurium oxide, aluminum oxide and bismuth oxide.
8. The front conductive silver paste for the crystalline silicon solar cell as recited in claim 1, wherein the resin comprises one or more of methyl cellulose, ethyl cellulose, cellulose acetate butyrate, nitrocellulose, rosin, modified rosin, polyvinyl alcohol, polyester resin and acrylic resin.
9. The front conductive silver paste for the crystalline silicon solar cell as recited in claim 1, wherein the solvent in the organic vehicle comprises one or more of terpineol, tributyl citrate, diethylene glycol butyl ether acetate, diethylene glycol dibutyl ether, diethylene glycol butyl ether, DBE, alcohol ester twelve, 2, 4-trimethyl-1, 3-pentanediol diisobutyrate, triethylene glycol, tripropylene glycol methyl ether, and the dispersant comprises one or more of lecithin, glycerol monooleate, polyethylene glycol, and polysorbate.
10. The preparation method of the front conductive silver paste for the crystalline silicon solar cell according to any one of claims 1 to 9, characterized by comprising the following steps:
1) according to the weight ratio of the materials, 4-10% of resin, 2-8% of dispersant, 75-85% of solvent and 8-15% of light-cured material are uniformly mixed by using a dispersing, emulsifying and stirring integrated machine, heated and dissolved uniformly at a constant temperature, cooled and filtered to obtain an organic carrier, wherein the heating and dissolving temperature is 60-70 ℃, and preferably 65 ℃;
2) adding the organic carrier, the glass powder and the silver powder obtained in the step 1) into a centrifuge or a planetary mixer according to the feeding proportion, uniformly mixing, and then grinding for 6-8 times by a three-roll grinder until the fineness of the slurry is less than 7 mu m to obtain the front conductive silver paste for the crystalline silicon solar cell.
CN202110748876.4A 2021-07-02 2021-07-02 Front conductive silver paste for crystalline silicon solar cell and preparation method thereof Pending CN113571228A (en)

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CN116206800A (en) * 2023-04-28 2023-06-02 乾宇微纳技术(深圳)有限公司 Medium slurry and preparation method thereof
CN116543947A (en) * 2023-06-26 2023-08-04 浙江晶科新材料有限公司 Additive of silver-aluminum paste of N-type solar cell, preparation method of additive and silver-aluminum paste

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CN114582544A (en) * 2022-02-18 2022-06-03 南通俊丰新材料科技有限公司 Conductive paste, preparation method and application thereof
CN116206800A (en) * 2023-04-28 2023-06-02 乾宇微纳技术(深圳)有限公司 Medium slurry and preparation method thereof
CN116206800B (en) * 2023-04-28 2023-07-21 乾宇微纳技术(深圳)有限公司 Medium slurry and preparation method thereof
CN116543947A (en) * 2023-06-26 2023-08-04 浙江晶科新材料有限公司 Additive of silver-aluminum paste of N-type solar cell, preparation method of additive and silver-aluminum paste
CN116543947B (en) * 2023-06-26 2023-10-31 浙江晶科新材料有限公司 Additive of silver-aluminum paste of N-type solar cell, preparation method of additive and silver-aluminum paste

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