CN117079860A - Low-temperature silver paste for low-consumption silver heterojunction solar cell, and preparation method and application thereof - Google Patents

Low-temperature silver paste for low-consumption silver heterojunction solar cell, and preparation method and application thereof Download PDF

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CN117079860A
CN117079860A CN202311320885.9A CN202311320885A CN117079860A CN 117079860 A CN117079860 A CN 117079860A CN 202311320885 A CN202311320885 A CN 202311320885A CN 117079860 A CN117079860 A CN 117079860A
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silver
low
powder
coated copper
organic solvent
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陈娜娜
张嘉宁
王林伟
陈小龙
冉红霞
冯如婷
刘洁
连军
胡西领
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Shanghai Yinjiang Technology 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
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    • 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
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    • 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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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention relates to the technical field of solar cells, in particular to low-temperature silver paste of a low-consumption silver heterojunction solar cell, a preparation method and application thereof, and the low-temperature silver paste comprises the following components in percentage by mass: 20-40% of micron-sized silver-coated copper ball powder, 30-60% of submicron-sized silver-coated copper ball powder, 3-10% of nano-sized flower-shaped spherical silver powder, 2-4% of epoxy resin, 1-2% of thermoplastic resin, 0.2-0.5% of curing agent, 0.1-0.5% of coupling agent, 0.1-0.3% of dispersing agent, 0.2-0.3% of antioxidant, 2-8% of first organic solvent and 1-5% of second organic solvent, wherein the boiling point of the first organic solvent is within 210-250 ℃, and the boiling point of the second organic solvent is within 140-200 ℃, and the silver paste provided by the invention has the advantages of low raw material cost, simple manufacturing process and excellent conductivity, and effectively solves the problems of small addition amount of silver-coated copper powder and easiness in cracking after silver paste curing.

Description

Low-temperature silver paste for low-consumption silver heterojunction solar cell, and preparation method and application thereof
Technical Field
The invention relates to the technical field of solar cells, in particular to low-temperature silver paste for a low-consumption silver heterojunction solar cell and a preparation method thereof.
Background
The heterojunction solar cell is a novel high-efficiency solar cell, and has a series of advantages of high conversion rate, low temperature coefficient, capability of realizing flaking and the like, so that the heterojunction solar cell becomes a novel technical trend of the solar industry. As a key material for realizing current collection and current discharge of the heterojunction battery, low-temperature conductive silver paste is also receiving wide attention, and according to analysis, the conductive silver paste market has a market scale of billions dollars each year, and has a promising prospect. The high performance and low cost are the necessary trend of slurry development while improving the competitiveness of the product.
In the prior art, in order to reduce the volume resistivity of the slurry, the silver powder is very high in proportion as a conductive phase, which is up to 90% -94%, so that the cost of the slurry is high. The silver-coated copper powder is used as a novel composite material, the conductivity can be regulated and controlled according to the compactness, thickness and silver content of the outer coating silver layer, and the silver-coated copper powder can replace a part of pure silver powder to reduce the cost of the slurry. However, the replacement amount of the silver-coated copper powder is only 30-50%, and if the addition amount of the silver-coated copper powder is excessive, the electrical property of the silver paste is reduced.
Disclosure of Invention
The invention aims to provide low-temperature silver paste for a low-consumption silver heterojunction solar cell, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides low-temperature silver paste of a low-consumption silver heterojunction solar cell, which comprises the following components in percentage by mass: 20-40% of micron-sized silver-coated copper ball powder, 30-60% of submicron-sized silver-coated copper ball powder, 3-10% of nano-sized flower-shaped spherical silver powder, 2-4% of epoxy resin, 1-2% of thermoplastic resin, 0.2-0.5% of curing agent, 0.1-0.5% of coupling agent, 0.1-0.3% of dispersing agent, 0.2-0.3% of antioxidant, 2-8% of first organic solvent and 1-5% of second organic solvent;
the boiling point of the first organic solvent is 210-250 ℃, and the boiling point of the second organic solvent is 140-200 ℃.
Preferably, the particle diameter D50 of the micron-sized silver-coated copper ball powder is 2-3 mu m, and the silver content is 10-20wt%; the particle size D50 of the submicron silver-coated copper ball powder is 1-1.5 mu m, and the silver content is 10-20wt%; the particle diameter D50 of the nano flower-shaped spherical silver powder is 0.3-0.5 mu m, and the specific surface area is 2.5-10 m 2 /g。
Preferably, the epoxy resin includes one or more of bisphenol a epoxy resin, hydrogenated bisphenol a epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, alicyclic epoxy resin, and hydantoin epoxy resin.
Preferably, the thermoplastic resin comprises one or more of polycaprolactone, polycarbonate, polyethylene oxide, polyimide siloxane, and polyetherimide.
Preferably, the curing agent comprises one or more of amine blocked hexafluoroantimonate, boron trifluoride-monoethylamine complex, 2-methylimidazole, dicyandiamide and modified fatty amines.
Preferably, the coupling agent comprises one or more of glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-aminopropyl triethoxysilane, and methacryloxypropyl trimethoxysilane.
Preferably, the dispersant comprises one or more of KD9 dispersant, KD13 dispersant, KD16 dispersant, BYK110 dispersant, BKY163 dispersant and BYK168 dispersant.
Preferably, the antioxidant comprises one or more of 2, 2-methylenebis (4-methyl-6-tert-butylphenol), 2, 6-di-tert-butyl-p-cresol, 1,3 tris (2-methyl-4 hydroxy-5-tert-butylphenyl) butane, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, N '-hexamethylenebis-3 (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide, 2' -methylenebis (4-methyl-6-tert-butylphenol), 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxyphenyl) isocyanate, 4-hydroxydodecanoyl anilide, tris (nonylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite and dioctadecyl pentaerythritol diphosphite.
Preferably, the first organic solvent comprises one or more of butyl carbitol, butyl carbitol acetate, terpineol, alcohol ester twelve, dipropylene glycol propyl ether and diethylene glycol butyl ether acetate.
Preferably, the second organic solvent comprises one or more of butanediol tertiary butyl ether, dipropylene glycol methyl ether, propylene glycol diacetate, ethylene glycol propyl ether and ethylene glycol butyl ether acetate.
The invention provides a preparation method of low-temperature silver paste, which comprises the following steps:
s1: mixing a first organic solvent and a second organic solvent to obtain a mixed solvent, and mixing an antioxidant, a dispersing agent and a coupling agent with the mixed solvent to obtain an organic carrier;
s2: mixing micron-sized silver-coated copper ball powder, submicron-sized silver-coated copper ball powder and nanometer-sized flower-shaped spherical silver powder with the organic carrier to obtain slurry;
s3: and mixing epoxy resin, thermoplastic resin and curing agent with the slurry to obtain the low-temperature silver slurry.
The invention provides the application of the low-temperature silver paste disclosed by the technical scheme or the low-temperature silver paste obtained by the preparation method disclosed by the technical scheme in the solar cell.
The beneficial effects of the invention are as follows: according to the invention, by adding the nano flower-shaped spherical silver powder, the characteristic of large specific surface area is fully utilized, and the addition amount of the powder in the silver paste can be reduced under the condition that the viscosity of the paste is ensured to be suitable for printing, so that the silver consumption is reduced, and the paste cost is reduced;
according to the invention, the nano flower-shaped spherical silver powder is added into the powder, and two solvents with different boiling points are selected, so that the content of the silver-coated copper powder can be increased on the basis of not affecting the electrical performance, and the silver consumption is reduced, and the basic principle is as follows: the nanometer flower-shaped spherical silver powder can be melted at the low temperature of 100-120 ℃ and is mutually bonded, two solvents with boiling point gradient are selected, petals of the nanometer flower-shaped spherical silver powder can be continuously melted along with disappearance of the solvents at different curing times, and due to proper shrinkage between epoxy resin and thermoplastic resin, silver-coated copper powder is continuously tensioned and bonded together, so that the silver paste has excellent electrical property after curing;
according to the invention, the thermoplastic resin is added into the epoxy resin system, so that on one hand, the shrinkage rate between the resins is increased, the powder can be tensioned, the electric performance is improved, and on the other hand, the thermoplastic resin has a toughening effect, the internal stress of the cured epoxy resin is reduced, and the phenomena of cracking and the like are not easy to occur after the silver paste is cured.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
Fig. 1 is an SEM image of a nano-scale flower-shaped spherical silver powder used for low-temperature silver paste of a low-consumption silver heterojunction solar cell in an embodiment of the invention.
Detailed Description
The invention provides low-temperature silver paste of a low-consumption silver heterojunction solar cell, which comprises the following components in percentage by mass: 20-40% of micron-sized silver-coated copper ball powder, 30-60% of submicron-sized silver-coated copper ball powder, 3-10% of nano-sized flower-shaped spherical silver powder, 2-4% of epoxy resin, 1-2% of thermoplastic resin, 0.2-0.5% of curing agent, 0.1-0.5% of coupling agent, 0.1-0.3% of dispersing agent, 0.2-0.3% of antioxidant, 2-8% of first organic solvent and 1-5% of second organic solvent;
the boiling point of the first organic solvent is 210-250 ℃, and the boiling point of the second organic solvent is 140-200 ℃.
The low-temperature silver paste for the low-consumption silver heterojunction solar cell provided by the invention comprises the following raw materials in percentage by mass: 20-40% of micron-sized silver-coated copper ball powder, preferably 30-40%, and more preferably 32-36%. In the invention, the silver content of the micron-sized silver-coated copper ball powder is 10-20wt%, preferably 10-15wt%, and more preferably 10-12wt%.
The low-temperature silver paste for the low-consumption silver heterojunction solar cell provided by the invention comprises the following raw materials in percentage by mass: 30-60% of submicron silver-coated copper ball powder, preferably 35-55%, and more preferably 40-50%. In the invention, the silver content of the submicron silver-coated copper ball powder is 10-20wt%, preferably 10-15wt%, and more preferably 10-12wt%.
The low-temperature silver paste for the low-consumption silver heterojunction solar cell provided by the invention comprises the following components in percentage by mass: 3-10% of nano-scale flower-shaped spherical silver powder, preferably 4-8%, and more preferably 5-6%. In the invention, the particle diameter D50 of the nano flower-shaped spherical silver powder is 0.3-0.5 mu m, and the specific surface area is 2.5-10 m 2 Preferably 2.5 to 7m 2 Preferably 2.5 to 4m 2 /g。
The low-temperature silver paste for the low-consumption silver heterojunction solar cell provided by the invention comprises the following components in percentage by mass: 2 to 4% of epoxy resin, preferably 2.5 to 3.5%, more preferably 3 to 3.5%. In the present invention, the epoxy resin includes one or more of bisphenol a epoxy resin, hydrogenated bisphenol a epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, alicyclic epoxy resin and hydantoin epoxy resin, preferably bisphenol a epoxy resin. When the epoxy resin is two or more of the above, the present invention is not particularly limited in the ratio of different types of epoxy resins, and may be adjusted according to actual needs.
The low-temperature silver paste for the low-consumption silver heterojunction solar cell provided by the invention comprises the following components in percentage by mass: 1 to 2% of a thermoplastic resin, preferably 1.2 to 1.7%, more preferably 1.4 to 1.6%. In the present invention, the thermoplastic resin includes one or more of polycaprolactone, polycarbonate, polyethylene oxide, polyimide siloxane, and polyetherimide, preferably polycaprolactone. When the thermoplastic resin is two or more of the above, the blending ratio of the thermoplastic resins of different types is not particularly limited, and may be adjusted according to actual needs.
The low-temperature silver paste for the low-consumption silver heterojunction solar cell provided by the invention comprises the following components in percentage by mass: 0.2 to 0.5% of a curing agent, preferably 0.2 to 0.4% of a curing agent, and more preferably 0.25 to 0.35%. In the present invention, the curing agent comprises one or more of amine-blocked hexafluoroantimonate, boron trifluoride-monoethylamine complex, 2-methylimidazole, dicyandiamide and modified aliphatic amine, preferably amine-blocked hexafluoroantimonate. When the number of the curing agents is two or more, the ratio of the curing agents of different types is not particularly limited, and the curing agents can be adjusted according to actual needs.
The low-temperature silver paste for the low-consumption silver heterojunction solar cell provided by the invention comprises the following components in percentage by mass: 0.1 to 0.5% of a coupling agent, preferably 0.2 to 0.5%, more preferably 0.4 to 0.5%. In the invention, the coupling agent comprises one or more of glycidoxypropyl trimethoxysilane, 3-glycidyl propyl trimethoxysilane, glycidyl ether oxypropyl trimethoxysilane, 3-aminopropyl triethoxysilane and methacryloxypropyl trimethoxysilane, preferably glycidoxypropyl trimethoxysilane. When the number of the coupling agents is two or more, the ratio of the coupling agents of different types is not particularly limited, and the coupling agents can be adjusted according to actual needs.
The low-temperature silver paste for the low-consumption silver heterojunction solar cell provided by the invention comprises the following components in percentage by mass: 0.1 to 0.3% of dispersant, preferably 0.15 to 0.25%, more preferably 0.2 to 0.25%. In the present invention, the dispersant includes one or more of KD9 dispersant, KD13 dispersant, KD16 dispersant, BYK110 dispersant, BKY163 dispersant and BYK168 dispersant, preferably BYK110 dispersant. When the number of the dispersant is two or more, the ratio of the dispersant of the present invention is not particularly limited, and the dispersant may be adjusted according to actual needs.
The low-temperature silver paste for the low-consumption silver heterojunction solar cell provided by the invention comprises the following components in percentage by mass: 0.2 to 0.3% of an antioxidant, preferably 0.2 to 0.25%. In the present invention, the antioxidant includes one or more of 2, 2-methylenebis (4-methyl-6-t-butylphenol), 2, 6-di-t-butyl-p-cresol, 1,3 tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene, N '-hexamethylenebis-3 (3, 5-di-t-butyl-4-hydroxyphenyl) propionamide, 2' -methylenebis (4-methyl-6-t-butylphenol), 1,3, 5-tris (3, 5-di-t-butyl-4-hydroxyphenyl) isocyanate, 4-hydroxydodecanoanilide, tris (2, 4-di-t-butylphenyl) phosphite and dioctadecyl pentaerythritol diphosphite, preferably 2, 6-di-t-butyl-p-cresol. When the antioxidant is two or more of the above, the proportion of the dispersant of the present invention is not particularly limited, and the dispersant may be adjusted according to actual needs.
The low-temperature silver paste for the low-consumption silver heterojunction solar cell provided by the invention comprises the following components in percentage by mass: 2 to 8% of a first organic solvent, preferably 3 to 7%, more preferably 5 to 7%. The boiling point of the first organic solvent is 210-250 ℃, preferably 220-250 ℃, and more preferably 240-250 ℃. In the present invention, the first organic solvent includes one or more of butyl carbitol (boiling point 230.6 ℃), butyl carbitol acetate (boiling point 247 ℃), terpineol (boiling point 217-218 ℃), alcohol ester twelve (boiling point 247 ℃), dipropylene glycol propyl ether (boiling point 222-232 ℃) and diethylene glycol butyl ether acetate (boiling point 246.4 ℃), preferably diethylene glycol butyl ether acetate. When the first organic solvent is two or more of the above, the ratio of the different types of the first organic solvents is not particularly limited, and may be adjusted according to actual needs.
The low-temperature silver paste for the low-consumption silver heterojunction solar cell provided by the invention comprises the following components in percentage by mass: 1 to 5% of a second organic solvent, preferably 1 to 3%, more preferably 1 to 2%. The boiling point of the second organic solvent is 140-200 ℃, preferably 150-190 ℃, and more preferably 170-180 ℃. In the present invention, the second solvent includes one or more of butanediol t-butyl ether (boiling point 144 ℃), dipropylene glycol methyl ether (boiling point 190 ℃), propylene glycol diacetate (boiling point 191 ℃), ethylene glycol propyl ether (boiling point 151 ℃) and ethylene glycol butyl ether acetate (boiling point 192 ℃), preferably propylene glycol diacetate. When the second organic solvent is two or more of the above, the proportion of the second organic solvents of different types is not particularly limited, and the second organic solvents may be adjusted according to actual needs.
The invention provides a preparation method of low-temperature silver paste, which comprises the following steps:
s1: mixing a first organic solvent and a second organic solvent to obtain a mixed solvent, and mixing an antioxidant, a dispersing agent and a coupling agent with the mixed solvent to obtain an organic carrier;
s2: mixing micron-sized silver-coated copper ball powder, submicron-sized silver-coated copper ball powder and nanometer-sized flower-shaped spherical silver powder with the organic carrier to obtain slurry;
s3: mixing epoxy resin, thermoplastic resin and curing agent with the slurry, and grinding to obtain low-temperature silver slurry.
In the step S2, preferably, after the micron-sized silver-coated copper ball powder and the submicron-sized silver-coated copper ball powder are added to the organic carrier, stirring and dispersing are continued for 30min; adding the nano flower-shaped spherical silver powder, and continuing stirring and dispersing for 10min to obtain slurry.
In step S3, the epoxy resin, the thermoplastic resin, and the curing agent are preferably mixed with the slurry, followed by grinding, to finally obtain a low-temperature silver paste.
The grinding is not particularly limited, and may be performed according to a process well known in the art.
The invention provides low-temperature silver paste of the low-consumption silver heterojunction solar cell or application of the low-temperature silver paste obtained by the preparation method in the technical scheme in the solar cell. The method of application of the present invention is not particularly limited, and may be applied according to methods well known in the art.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
The reagents used in the examples below were all commercially available.
Example 1
The embodiment provides low-temperature silver paste of a low-consumption silver heterojunction solar cell, which comprises the following components in percentage by mass:
35% of micron-sized silver-coated copper ball powder (particle size D50: 2-3 μm, silver content: 10%);
submicron silver-coated copper ball powder (particle diameter D50: 1-1.5 μm, silver content 10%) 45%;
nanometer flower-shaped spherical silver powder (particle diameter D50: 0.3-0.5 μm, specific surface area: 2.7 m) 2 /g） 10%；
Epoxy resin: 3.5% of bisphenol A epoxy resin;
thermoplastic resin: polycaprolactone 1.5%;
curing agent: amine blocked hexafluoroantimonate 0.3%;
coupling agent: 0.5% of glycidoxypropyl trimethoxysilane;
dispersing agent: BYK110 dispersant 0.2%;
antioxidant: 2, 6-di-tert-butyl-p-cresol 0.2%;
a first organic solvent: diethylene glycol butyl ether acetate 2.3%;
a second organic solvent: propylene glycol diacetate 1.5%.
The preparation method adopted in the embodiment comprises the following steps:
s1: the preparation method comprises the steps of weighing diethylene glycol butyl ether acetate and propylene glycol diacetate in proportion, mixing to obtain a mixed solvent, adding the mixed solvent into a container, adding 2, 6-di-tert-butyl-p-cresol, BYK110 dispersant and glycidoxypropyl trimethoxy silane into the container, and uniformly stirring to obtain an organic carrier;
s2: weighing micron-sized silver-coated copper ball powder and submicron-sized silver-coated copper ball powder according to a proportion, adding the micron-sized silver-coated copper ball powder and submicron-sized silver-coated copper ball powder into the organic carrier, and stirring and dispersing for 30min; weighing the nano flower-shaped spherical silver powder with corresponding proportion, adding the nano flower-shaped spherical silver powder, and continuously stirring and dispersing for 10min to obtain uniform slurry;
s3: weighing bisphenol A epoxy resin, polycaprolactone and amine-blocked hexafluoroantimonate according to a proportion, adding the materials into the slurry, uniformly stirring, and grinding to obtain low-temperature silver paste.
Example 2
The embodiment provides low-temperature silver paste of a low-consumption silver heterojunction solar cell, which comprises the following raw materials in percentage by mass:
35% of micron-sized silver-coated copper ball powder (particle size D50: 2-3 μm, silver content: 10%);
submicron silver-coated copper ball powder (particle diameter D50: 1-1.5 μm, silver content 10%) 45%;
nanometer flower-shaped spherical silver powder (particle diameter D50: 0.3-0.5 μm, specific surface area: 2.7 m) 2 /g） 8%；
Epoxy resin: 3.5% of bisphenol A epoxy resin;
thermoplastic resin: polycaprolactone 1.5%;
curing agent: amine blocked hexafluoroantimonate 0.3%;
coupling agent: 0.5% of glycidoxypropyl trimethoxysilane;
dispersing agent: BYK110 dispersant 0.2%;
antioxidant: 2, 6-di-tert-butyl-p-cresol 0.2%;
a first organic solvent: 4.3% of diethylene glycol butyl ether acetate;
a second organic solvent: propylene glycol diacetate 1.5%.
The preparation method adopted in the embodiment comprises the following steps:
s1: the preparation method comprises the steps of weighing diethylene glycol butyl ether acetate and propylene glycol diacetate in proportion, mixing to obtain a mixed solvent, adding the mixed solvent into a container, adding 2, 6-di-tert-butyl-p-cresol, BYK110 dispersant and glycidoxypropyl trimethoxy silane into the container, and uniformly stirring to obtain an organic carrier;
s2: weighing micron-sized silver-coated copper ball powder and submicron-sized silver-coated copper ball powder according to a proportion, adding the micron-sized silver-coated copper ball powder and submicron-sized silver-coated copper ball powder into the organic carrier, and stirring and dispersing for 30min; weighing the nano flower-shaped spherical silver powder with corresponding proportion, adding the nano flower-shaped spherical silver powder, and continuously stirring and dispersing for 10min to obtain uniform slurry;
s3: weighing bisphenol A epoxy resin, polycaprolactone and amine-blocked hexafluoroantimonate according to a proportion, adding the materials into the slurry, uniformly stirring, and grinding to obtain low-temperature silver paste.
Example 3
The embodiment provides low-temperature silver paste of a low-consumption silver heterojunction solar cell, which comprises the following raw materials in percentage by mass:
35% of micron-sized silver-coated copper ball powder (particle size D50: 2-3 μm, silver content: 10%);
submicron silver-coated copper ball powder (particle diameter D50: 1-1.5 μm, silver content 10%) 45%;
nanometer flower-shaped spherical silver powder (particle diameter D50: 0.3-0.5 μm, specific surface area: 2.7 m) 2 /g） 6%；
Epoxy resin: 3.5% of bisphenol A epoxy resin;
thermoplastic resin: polycaprolactone 1.5%;
curing agent: amine blocked hexafluoroantimonate 0.3%;
coupling agent: 0.5% of glycidoxypropyl trimethoxysilane;
dispersing agent: BYK110 dispersant 0.2%;
antioxidant: 0.2% of 2, 6-di-tert-butyl-p-cresol;
a first organic solvent: diethylene glycol butyl ether acetate 6.3%;
a second organic solvent: propylene glycol diacetate 1.5%.
The preparation method adopted in the embodiment comprises the following steps:
s1: the preparation method comprises the steps of weighing diethylene glycol butyl ether acetate and propylene glycol diacetate in proportion, mixing to obtain a mixed solvent, adding the mixed solvent into a container, adding 2, 6-di-tert-butyl-p-cresol, BYK110 dispersant and glycidoxypropyl trimethoxy silane into the container, and uniformly stirring to obtain an organic carrier;
s2: weighing micron-sized silver-coated copper ball powder and submicron-sized silver-coated copper ball powder according to a proportion, adding the micron-sized silver-coated copper ball powder and submicron-sized silver-coated copper ball powder into the organic carrier, and stirring and dispersing for 30min; weighing the nano flower-shaped spherical silver powder with corresponding proportion, adding the nano flower-shaped spherical silver powder, and continuously stirring and dispersing for 10min to obtain uniform slurry;
s3: weighing bisphenol A epoxy resin, polycaprolactone and amine-blocked hexafluoroantimonate according to a proportion, adding the materials into the slurry, uniformly stirring, and grinding to obtain low-temperature silver paste.
Example 4
The embodiment provides low-temperature silver paste of a low-consumption silver heterojunction solar cell, which comprises the following raw materials in percentage by mass:
35% of micron-sized silver-coated copper ball powder (particle size D50: 2-3 μm, silver content: 10%);
submicron silver-coated copper ball powder (particle diameter D50: 1-1.5 μm, silver content 10%) 45%;
nanometer flower-shaped spherical silver powder (particle diameter D50: 0.3-0.5 μm, specific surface area: 2.7 m) 2 /g） 4%；
Epoxy resin: 3.5% of bisphenol A epoxy resin;
thermoplastic resin: polycaprolactone 1.5%;
curing agent: amine blocked hexafluoroantimonate 0.3%;
coupling agent: 0.5% of glycidoxypropyl trimethoxysilane;
dispersing agent: BYK110 dispersant 0.2%;
antioxidant: 0.2% of 2, 6-di-tert-butyl-p-cresol;
a first organic solvent: 7.6% of diethylene glycol butyl ether acetate;
a second organic solvent: propylene glycol diacetate 3.2%.
The preparation method adopted in the embodiment comprises the following steps:
s1: the preparation method comprises the steps of weighing diethylene glycol butyl ether acetate and propylene glycol diacetate in proportion, mixing to obtain a mixed solvent, adding the mixed solvent into a container, adding 2, 6-di-tert-butyl-p-cresol, BYK110 dispersant and glycidoxypropyl trimethoxy silane into the container, and uniformly stirring to obtain an organic carrier;
s2: weighing micron-sized silver-coated copper ball powder and submicron-sized silver-coated copper ball powder according to a proportion, adding the micron-sized silver-coated copper ball powder and submicron-sized silver-coated copper ball powder into the organic carrier, and stirring and dispersing for 30min; weighing the nano flower-shaped spherical silver powder with corresponding proportion, adding the nano flower-shaped spherical silver powder, and continuously stirring and dispersing for 10min to obtain uniform slurry;
s3: weighing bisphenol A epoxy resin, polycaprolactone and amine-blocked hexafluoroantimonate according to a proportion, adding the materials into the slurry, uniformly stirring, and grinding to obtain low-temperature silver paste.
Example 5
The embodiment provides low-temperature silver paste of a low-consumption silver heterojunction solar cell, which comprises the following raw materials in percentage by mass:
35% of micron-sized silver-coated copper ball powder (particle size D50: 2-3 μm, silver content: 10%);
submicron silver-coated copper ball powder (particle diameter D50: 1-1.5 μm, silver content 10%) 45%;
nanometer flower-shaped spherical silver powder (particle diameter D50: 0.3-0.5 μm, specific surface area: 2.7 m) 2 /g） 6%；
Epoxy resin: 3.5% of hydrogenated bisphenol A epoxy resin;
thermoplastic resin: polycaprolactone 1.5%;
curing agent: amine blocked hexafluoroantimonate 0.3%;
coupling agent: 0.5% of glycidoxypropyl trimethoxysilane;
dispersing agent: BYK110 dispersant 0.2%;
antioxidant: 0.2% of 2, 6-di-tert-butyl-p-cresol;
a first organic solvent: diethylene glycol butyl ether acetate 6.3%;
a second organic solvent: propylene glycol diacetate 1.5%.
The preparation method adopted in the embodiment comprises the following steps:
s1: the preparation method comprises the steps of weighing diethylene glycol butyl ether acetate and propylene glycol diacetate in proportion, mixing to obtain a mixed solvent, adding the mixed solvent into a container, adding 2, 6-di-tert-butyl-p-cresol, BYK110 dispersant and glycidoxypropyl trimethoxy silane into the container, and uniformly stirring to obtain an organic carrier;
s2: weighing micron-sized silver-coated copper ball powder and submicron-sized silver-coated copper ball powder according to a proportion, adding the micron-sized silver-coated copper ball powder and submicron-sized silver-coated copper ball powder into the organic carrier, and stirring and dispersing for 30min; weighing the nano flower-shaped spherical silver powder with corresponding proportion, adding the nano flower-shaped spherical silver powder, and continuously stirring and dispersing for 10min to obtain uniform slurry;
s3: weighing bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin and amine-blocked hexafluoroantimonate according to a proportion, adding the materials into the slurry, uniformly stirring, and grinding to obtain low-temperature silver paste.
Example 6
The embodiment provides low-temperature silver paste of a low-consumption silver heterojunction solar cell, which comprises the following raw materials in percentage by mass:
35% of micron-sized silver-coated copper ball powder (particle size D50: 2-3 μm, silver content: 10%);
submicron silver-coated copper ball powder (particle diameter D50: 1-1.5 μm, silver content 10%) 45%;
nanometer flower-shaped spherical silver powder (particle diameter D50: 0.3-0.5 μm, specific surface area: 2.7 m) 2 /g） 6%；
Epoxy resin: 3.5% of bisphenol F epoxy resin;
thermoplastic resin: polycaprolactone 1.5%;
curing agent: amine blocked hexafluoroantimonate 0.3%;
coupling agent: 0.5% of glycidoxypropyl trimethoxysilane;
dispersing agent: BYK110 dispersant 0.2%;
antioxidant: 0.2% of 2, 6-di-tert-butyl-p-cresol;
a first organic solvent: diethylene glycol butyl ether acetate 6.3%;
a second organic solvent: propylene glycol diacetate 1.5%.
The preparation method adopted in the embodiment comprises the following steps:
s1: the preparation method comprises the steps of weighing diethylene glycol butyl ether acetate and propylene glycol diacetate in proportion, mixing to obtain a mixed solvent, adding the mixed solvent into a container, adding 2, 6-di-tert-butyl-p-cresol, BYK110 dispersant and glycidoxypropyl trimethoxy silane into the container, and uniformly stirring to obtain an organic carrier;
s2: weighing micron-sized silver-coated copper ball powder and submicron-sized silver-coated copper ball powder according to a proportion, adding the micron-sized silver-coated copper ball powder and submicron-sized silver-coated copper ball powder into the organic carrier, and stirring and dispersing for 30min; weighing the nano flower-shaped spherical silver powder with corresponding proportion, adding the nano flower-shaped spherical silver powder, and continuously stirring and dispersing for 10min to obtain uniform slurry;
s3: weighing bisphenol A epoxy resin, bisphenol F epoxy resin and amine-blocked hexafluoroantimonate according to a proportion, adding the materials into the slurry, uniformly stirring, and grinding to obtain the low-temperature silver paste.
Example 7
The embodiment provides low-temperature silver paste of a low-consumption silver heterojunction solar cell, which comprises the following raw materials in percentage by mass:
35% of micron-sized silver-coated copper ball powder (particle size D50: 2-3 μm, silver content: 10%);
submicron silver-coated copper ball powder (particle diameter D50: 1-1.5 μm, silver content 10%) 45%;
nanometer flower-shaped spherical silver powder (particle diameter D50: 0.3-0.5 μm, specific surface area: 2.7 m) 2 /g） 6%；
Epoxy resin: 3.5% of bisphenol A epoxy resin;
thermoplastic resin: 1.5% of polycarbonate;
curing agent: amine blocked hexafluoroantimonate 0.3%;
coupling agent: 0.5% of glycidoxypropyl trimethoxysilane;
dispersing agent: BYK110 dispersant 0.2%;
antioxidant: 0.2% of 2, 6-di-tert-butyl-p-cresol;
a first organic solvent: diethylene glycol butyl ether acetate 6.3%;
a second organic solvent: propylene glycol diacetate 1.5%.
The preparation method adopted in the embodiment comprises the following steps:
s1: the preparation method comprises the steps of weighing diethylene glycol butyl ether acetate and propylene glycol diacetate in proportion, mixing to obtain a mixed solvent, adding the mixed solvent into a container, adding 2, 6-di-tert-butyl-p-cresol, BYK110 dispersant and glycidoxypropyl trimethoxy silane into the container, and uniformly stirring to obtain an organic carrier;
s2: weighing micron-sized silver-coated copper ball powder and submicron-sized silver-coated copper ball powder according to a proportion, adding the micron-sized silver-coated copper ball powder and submicron-sized silver-coated copper ball powder into the organic carrier, and stirring and dispersing for 30min; weighing the nano flower-shaped spherical silver powder with corresponding proportion, adding the nano flower-shaped spherical silver powder, and continuously stirring and dispersing for 10min to obtain uniform slurry;
s3: weighing bisphenol A epoxy resin, polycarbonate and amine-blocked hexafluoroantimonate according to a proportion, adding the materials into the slurry, uniformly stirring, and grinding to obtain low-temperature silver paste.
Comparative example 1
The difference from example 3 is that: the procedure of example 3 was repeated except that the nano-scale flower-like spherical silver powder was replaced with nano-scale spherical silver powder (D50:0.3 to 0.5 μm).
Comparative example 2
The difference from example 3 is that: the thermoplastic resin was removed and the amount of bisphenol A epoxy resin added was changed to 5%, with the remainder being the same as in example 3.
Comparative example 3
The difference from example 3 is that: the second organic solvent was removed and the amount of the first organic solvent added was changed to 7.8%, with the remainder being the same as in example 3.
Performance testing
The low-temperature conductive silver pastes prepared in examples 1 to 7 and comparative examples 1 to 3 are used as samples, and each sample is printed on the same heterojunction cell substrate for performing relevant property test, wherein the test process is as follows:
1. resistivity test: the resistance at both ends of the electrode was tested using a four-probe ohmmeter.
2. Viscosity test: the viscosity test is to test the viscosity value at stirring for 4min with a Bowler-Nordheim viscometer at 10 revolutions per minute.
3. Contact resistance: printing a specific pattern on the heterojunction battery piece by the low-temperature silver paste, and then drying and curing; cutting out a battery piece with a printed pattern area of a preset size by using a laser slicer; the contact resistance is measured using a contact resistance device.
The test results are shown in Table 1 below.
Table 1 resistivity, viscosity and contact battery test results of the silver pastes prepared in examples 1 to 7 and comparative examples 1 to 3
As can be seen from Table 1, in examples 1 to 4, the contents of the nano-scale flower-like spherical silver powder were 10%, 8%, 6% and 4%, respectively, and the test results showed that the low-temperature silver paste prepared in example 3, that is, the powder content was 14%, was moderate in viscosity and excellent in resistivity and contact resistance.
Compared with the embodiment 3, the comparative example 1 replaces the nano-scale flower-shaped spherical silver powder with the nano-scale spherical silver powder, the viscosity is changed, the electrical property is relatively poor, and the nano-scale flower-shaped spherical silver powder has good activity when being solidified due to the fact that the common nano-scale spherical silver powder is not as high as the flower-shaped nano-scale spherical silver powder, and the petal diameters of the nano-scale flower-shaped spherical silver powder are about 5-10 nm; compared with example 3, the comparative example 2 is not added with thermoplastic resin, so that the powder is not well tensioned in the curing process, and the electrical performance is poor; compared with example 3, the second solvent is not added, so that the solvent is not volatilized in a gradient manner during curing, the activity of the nano-scale flower-shaped spherical silver powder is not exerted, and the electric performance is poor.
It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (10)

1. The low-temperature silver paste for the low-consumption silver heterojunction solar cell is characterized by comprising the following components in percentage by mass: 20-40% of micron-sized silver-coated copper ball powder, 30-60% of submicron-sized silver-coated copper ball powder, 3-10% of nano-sized flower-shaped spherical silver powder, 2-4% of epoxy resin, 1-2% of thermoplastic resin, 0.2-0.5% of curing agent, 0.1-0.5% of coupling agent, 0.1-0.3% of dispersing agent, 0.2-0.3% of antioxidant, 2-8% of first organic solvent and 1-5% of second organic solvent;
the boiling point of the first organic solvent is 210-250 ℃, and the boiling point of the second organic solvent is 140-200 ℃;
the particle diameter D50 of the nano flower-shaped spherical silver powder is 0.3-0.5 mu m, and the specific surface area is 2.5-10 m 2 /g；
The first organic solvent comprises one or more of butyl carbitol, terpineol, alcohol ester twelve, dipropylene glycol propyl ether and diethylene glycol butyl ether acetate;
the second organic solvent comprises one or more of butanediol tertiary butyl ether, dipropylene glycol methyl ether, propylene glycol diacetate, ethylene glycol propyl ether and ethylene glycol butyl ether acetate.
2. The low-temperature silver paste for the low-consumption silver heterojunction solar cell, which is characterized in that the particle size D50 of the micron-sized silver-coated copper ball powder is 2-3 mu m, and the silver content is 10-20wt%; the submicron silver-coated copper ball powder has a particle size D50 of 1-1.5 mu m and silver content of 10-20wt%.
3. The low-loss silver heterojunction solar cell low-temperature silver paste of claim 1, wherein the epoxy resin comprises one or more of bisphenol a epoxy resin, hydrogenated bisphenol a epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, alicyclic epoxy resin, and hydantoin epoxy resin.
4. The low-loss silver heterojunction solar cell low-temperature silver paste of claim 1, wherein the thermoplastic resin comprises one or more of polycaprolactone, polycarbonate, polyethylene oxide, polyimide siloxane, and polyetherimide.
5. The low-temperature silver paste for low-consumption silver heterojunction solar cells of claim 1, wherein the curing agent comprises one or more of amine-blocked hexafluoroantimonate, boron trifluoride-monoethylamine complex, 2-methylimidazole, dicyandiamide and modified fatty amines.
6. The low-temperature silver paste for low-consumption silver heterojunction solar cells of claim 1, wherein the coupling agent comprises one or more of glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-aminopropyl triethoxysilane, and methacryloxypropyl trimethoxysilane.
7. The low-consumption silver heterojunction solar cell low-temperature silver paste of claim 1, wherein the dispersant comprises one or more of KD9 dispersant, KD13 dispersant, KD16 dispersant, BYK110 dispersant, BKY163 dispersant, and BYK168 dispersant.
8. The low-temperature silver paste of claim 1, wherein the antioxidant comprises one or more of 2, 2-methylenebis (4-methyl-6-tert-butylphenol), 2, 6-di-tert-butyl-p-cresol, 1,3 tris (2-methyl-4 hydroxy-5-tert-butylphenyl) butane, 1,3, 5-trimethyl 2,4,6 tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, N '-hexamethylenebis-3 (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide, 2' -methylenebis (4-methyl-6-tert-butylphenol), 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxyphenyl) isocyanate, 4-hydroxydodecanoic acid anilide, tris (nonylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, and dioctadecyl pentaerythritol diphosphite.
9. The method for preparing the low-temperature silver paste for the low-consumption silver heterojunction solar cell according to any one of claims 1 to 8, which is characterized by comprising the following steps:
s1: mixing a first organic solvent and a second organic solvent to obtain a mixed solvent, and mixing an antioxidant, a dispersing agent and a coupling agent with the mixed solvent to obtain an organic carrier;
s2: mixing micron-sized silver-coated copper ball powder, submicron-sized silver-coated copper ball powder and nanometer-sized flower-shaped spherical silver powder with the organic carrier to obtain slurry;
s3: and mixing epoxy resin, thermoplastic resin and curing agent with the slurry to obtain the low-temperature silver slurry.
10. The low-temperature silver paste for a low-consumption silver heterojunction solar cell according to any one of claims 1-8 or the application of the low-temperature silver paste obtained by the preparation method according to claim 9 in the solar cell.
CN202311320885.9A 2023-10-12 2023-10-12 Low-temperature silver paste for low-consumption silver heterojunction solar cell, and preparation method and application thereof Pending CN117079860A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117650184A (en) * 2024-01-30 2024-03-05 晶澜光电科技(江苏)有限公司 TOPCON solar cell metallization method using silver-coated copper paste and solar cell

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117650184A (en) * 2024-01-30 2024-03-05 晶澜光电科技(江苏)有限公司 TOPCON solar cell metallization method using silver-coated copper paste and solar cell
CN117650184B (en) * 2024-01-30 2024-04-05 晶澜光电科技(江苏)有限公司 TOPCON solar cell metallization method using silver-coated copper paste and solar cell

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