CN114709003A - Main grid slurry containing silver-copper alloy powder and preparation method thereof - Google Patents
Main grid slurry containing silver-copper alloy powder and preparation method thereof Download PDFInfo
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- CN114709003A CN114709003A CN202210443201.3A CN202210443201A CN114709003A CN 114709003 A CN114709003 A CN 114709003A CN 202210443201 A CN202210443201 A CN 202210443201A CN 114709003 A CN114709003 A CN 114709003A
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- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 47
- 239000002002 slurry Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000011521 glass Substances 0.000 claims abstract description 43
- 229910052709 silver Inorganic materials 0.000 claims abstract description 40
- 239000004332 silver Substances 0.000 claims abstract description 40
- 239000002270 dispersing agent Substances 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 14
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- 229910002056 binary alloy Inorganic materials 0.000 claims abstract description 6
- 229910002058 ternary alloy Inorganic materials 0.000 claims abstract description 5
- 229910008332 Si-Ti Inorganic materials 0.000 claims abstract description 4
- 229910006749 Si—Ti Inorganic materials 0.000 claims abstract description 4
- 229910002059 quaternary alloy Inorganic materials 0.000 claims abstract description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 13
- 239000000956 alloy Substances 0.000 claims description 13
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
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- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 4
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 4
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- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 4
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- 229960002622 triacetin Drugs 0.000 claims description 4
- 239000003981 vehicle Substances 0.000 claims description 4
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
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- 239000004348 Glyceryl diacetate Substances 0.000 claims description 2
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- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
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- 150000001412 amines Chemical class 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- 229920006217 cellulose acetate butyrate Polymers 0.000 claims description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
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- 125000005456 glyceride group Chemical group 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- 235000019443 glyceryl diacetate Nutrition 0.000 claims description 2
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- 239000004645 polyester resin Substances 0.000 claims description 2
- 229940116411 terpineol Drugs 0.000 claims description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 2
- IFPMZBBHBZQTOV-UHFFFAOYSA-N 1,3,5-trinitro-2-(2,4,6-trinitrophenyl)-4-[2,4,6-trinitro-3-(2,4,6-trinitrophenyl)phenyl]benzene Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C(C=2C(=C(C=3C(=CC(=CC=3[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)C(=CC=2[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)=C1[N+]([O-])=O IFPMZBBHBZQTOV-UHFFFAOYSA-N 0.000 claims 1
- 238000003466 welding Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 5
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 4
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 description 4
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- -1 alcohol ester Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010344 co-firing Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003181 co-melting Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01L31/022441—Electrode arrangements specially adapted for back-contact solar cells
-
- 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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- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a main grid slurry containing silver-copper alloy powder and a preparation method thereof, wherein the main grid slurry comprises the following components in parts by weight: 75-90% of silver powder, 0.2-2% of glass powder, 0.1-20% of silver-copper alloy powder and 8-25% of organic carrier. The glass powder is one of Mn-Cu system glass and Pb-Si-Ti system glass; the silver-copper alloy powder is silver-copper binary, ternary or quaternary alloy powder, and the organic carrier comprises a solvent, a plasticizer, a thixotropic agent, a thickening agent and a dispersing agent. According to the invention, the silver-copper alloy powder is matched with the silver powder for use, so that the high-density main grid electrode is realized under the condition of low glass content, the resistivity of the main grid electrode body is reduced, the welding resistance of the main grid silver paste is improved, a high-electrical-property battery structure is further obtained, the glass content of the main grid paste is reduced, the battery open-circuit voltage is improved, and the photoelectric conversion efficiency of the battery is improved. Because the silver-copper alloy powder is used, the consumption of silver is reduced, the consumption of slurry is saved, and the cost is further reduced.
Description
Technical Field
The invention belongs to the technical field of crystalline silicon solar cells, and particularly relates to main grid slurry containing silver-copper alloy powder and a preparation method thereof.
Background
With the increasing quantity of photovoltaic loading machines, the silver consumption of photovoltaic cells is higher than that of industrial silver, and silver reduction or silver replacement of photovoltaic silver paste is more urgent. Traditional step-by-step printing main grid silver paste is used for meeting the requirements of electric conduction and welding by matching pure silver paste with specific glass in order to ensure better electric conductivity. Therefore, the silver occupation ratio of the main grid silver paste is high, the silver unit consumption in the printing process is high, and the cost is difficult to effectively control. In addition, in order to reduce the volume resistivity and improve the welding reliability, a certain amount of glass powder is used for the main grid silver paste to realize the reliability of the battery assembly. Inevitably, in the high-temperature process, the relatively excessive glass powder can corrode a silicon nitride layer on the surface of the silicon wafer, deteriorate passivation and reduce open voltage. In addition, the main grid and auxiliary grid glass are easy to interact in the sintering process, damage to a silicon wafer is worsened, open voltage is further reduced, and electrical property is influenced.
In the traditional auxiliary grid silver paste, Cu and Si are easy to form alloy, a composite center is formed in a battery structure, and the electrical property is deteriorated, so that copper elements are avoided or rarely contacted in the actual auxiliary grid silver paste. Therefore, even if the resistivity is close, in the actual sub-gate silver paste production, the use of copper and copper alloy powder is less mentioned. However, in the step printing process, the main grid is used as a bus bar collecting bus bar, and silicon nitride does not need to be burnt through to directly contact the silicon surface, so that the electrical property is not deteriorated even if copper and copper alloy powder are introduced. In the main grid paste formulas disclosed in patent CN111863309A and patent CN110648781A, silver powders with different particle sizes and ratio tables are generally used for mixing or designing and obtaining a main grid paste formula with low corrosion and high reliability aiming at various inorganic oxides, and there is only a few mention about the preparation of main grid paste by using low melting point alloy powder. The main grid silver paste has the advantages that certain reliability needs to be guaranteed, the glass quantity is relatively high or the corrosion of glass is relatively strong, the actual proportion of the paste is 0.6% -1.8%, the high glass content is not beneficial to the protection of a silicon nitride layer, the battery efficiency is deteriorated, and the output of terminal power is influenced.
Disclosure of Invention
Aiming at the problems, the invention provides the main grid paste containing the silver-copper alloy powder, which solves the technical problems that the cost is high due to the high silver occupation ratio in the traditional silver paste, and the battery performance is influenced due to the high glass content.
In order to achieve the purpose, the invention adopts the technical scheme that:
the main grid slurry containing silver-copper alloy powder comprises 75-90% of silver powder, 0.2-2% of glass powder, 0.1-20% of silver-copper alloy powder and 8-25% of organic carrier, wherein the mass sum of all the components is 100%.
The silver-copper alloy powder comprises alloy powder taking silver and copper such as but not limited to silver-copper binary alloy powder, ternary alloy powder and quaternary alloy powder as main phase, and can be one kind of alloy powder or the mixture of various kinds of alloy powder in slurry, not only the mixture of various binary alloy powders with different silver-copper ratios, but also the mixture of binary alloy powder and silver-copper such as ternary alloy powder as main phase; the size of the copper-silver alloy powder is 0.5-3.5 mu m, especially the D50 is about 1.5-2 mu m, and the main grid slurry has good printability and excellent electrical property and reliability; the specific surface area of the alloy powder is 0.3m2/g-4m2In g, preferably in the range of 0.4m2/g-0.8m2The better sintering activity can be obtained, and the excellent comprehensive performance can be obtained.
The silver-copper alloy powder can obtain better comprehensive performance of the main grid when the mass of the slurry accounts for 0.1-20%, and particularly in the range of 2-10%, the slurry can save silver unit consumption and can obtain excellent reliability and electrical performance.
The glass powder can be common Mn-Cu system glass and Pb-Si-Ti system glass, and particularly the main grid slurry in the Mn-Cu system can obtain excellent comprehensive performance and market performance; the content of the glass powder is 0.2-2%, particularly the performance of a Pb-Si-Ti system is extremely excellent in a slurry of 0.5-0.8%, and the performance of Mn-Cu system glass is extremely excellent in a slurry of 0.8-1.5%.
The silver powder D50 is between 0.5 and 2 mu m, especially the silver powder D50 is between 0.8 and 1.2 mu m, and the main grid slurry has better sintering activity and excellent electrical property; the silver powder can be a single silver powder with D50 of between 0.5 and 2 mu m, or a combination of multiple silver powders with D50 of between 0.5 and 2 mu m, particularly the silver powder with D50 of 0.8 to 1.1 mu m size is taken as a main body, and excellent performance can be obtained by using a small amount of submicron silver powder with D50 of 0.5 to 0.6 mu m and good dispersion.
The mass percentage of the silver powder in the slurry formula is 75-90%, particularly the mass percentage of the main body silver powder is 70-75%, 2-5% of the silver powder is added, and 2-10% of silver-copper alloy powder is matched to obtain excellent comprehensive performance.
The organic carrier comprises a solvent, a plasticizer, a thixotropic agent, a thickening agent, a dispersing agent and the like, and the actual mass ratio of the organic carrier in the slurry is 8-25%: the organic carrier comprises the following components in percentage by weight: 70-80% of solvent, 1-10% of plasticizer, 2-5% of thixotropic agent, 15-25% of thickening agent and 2-10% of dispersing agent.
The solvent is one or a combination of more of butyl carbitol acetate, alcohol ester twelve, terpineol, diethylene glycol dibutyl ether and diethylene glycol monobutyl ether.
The plasticizer is one or a combination of triacetin, diacetin, alcohol ester hexadecane, tributyl citrate, dibutyl phthalate and diethyl phthalate.
The thixotropic agent comprises one or more of polyamide wax, hydrogenated castor oil and fumed silica.
The thickening agent comprises one or more of methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose acetate butyrate, polyacrylic resin, rosin glyceride, polyvinyl butyral, epoxy resin and polyester resin.
The dispersant comprises one or more of organic acid dispersant, amine dispersant, acrylic dispersant and organic silicon dispersant.
The invention also provides a preparation method of the main grid slurry containing the silver-copper alloy powder, which comprises the following process steps of:
(1) preparation of organic vehicle: heating and dissolving 70-80% of solvent, 1-10% of plasticizer, 2-5% of thixotropic agent, 15-25% of thickening agent and 2-10% of dispersant in water bath according to a certain proportion to be uniform, and obtaining a uniform organic carrier;
(2) adding glass powder, silver powder and silver-copper alloy powder into the uniform organic carrier dissolved in the step (1) according to a specific proportion, and stirring and mixing uniformly;
(3) and (3) placing the uniformly mixed slurry obtained in the step (2) into a three-high mill for rolling for 4-6 times to obtain uniform silver paste with the fineness of less than 6 microns.
And printing the prepared uniform main grid silver paste on a single-crystal PERC blue diaphragm, then printing auxiliary grid paste, and co-firing at 770 ℃ to obtain the finished single-crystal PERC battery.
According to the invention, the low-melting point silver-copper alloy powder is introduced into the main grid slurry, so that on one hand, the silver-copper alloy has better wettability with the solder, the welding reliability of subsequent components is not influenced, and better reliability can be obtained; on the other hand, because the melting point of the silver-copper alloy powder is lower than that of pure silver powder, the silver-copper alloy powder has good wettability with the silver powder in the sintering process, and a compact main grid electrode can be obtained even under the condition of low glass content, so that the volume resistivity is further reduced. Meanwhile, due to the introduction of the silver-copper alloy powder, the system activity is improved, the content of silver paste glass can be further reduced, the deterioration of a passivation layer is weakened, and the battery efficiency is improved.
According to the invention, a certain amount of silver-copper alloy powder (silver-copper binary alloy powder with different proportions and other ternary and multicomponent alloys with the mass ratio of silver to copper exceeding 50%) is matched with silver powder for use, so that a high-density main grid electrode can be realized under the condition of low glass content, the resistivity of a main grid electrode body can be reduced, the density degree of welding PAD can be improved, the welding resistance of the main grid silver paste is improved, and a battery structure with high electrical performance and high reliability is obtained.
Because the silver-copper alloy powder has the characteristics of low melting point and high sintering activity, a certain amount of alloy powder is introduced into the formula, so that on one hand, the sintering activity of the electrode can be improved, the connection of the lap joint of the main grid and the auxiliary grid is improved, a compact electrode structure is obtained, the resistivity of the electrode body of the main grid is reduced, the conversion factor of the battery is improved, and the conversion efficiency of the battery is optimized; on the other hand, the high sintering activity of the alloy powder can further reduce the glass content of the main grid slurry, reduce the corrosion of glass to the silicon nitride surface, improve the open voltage of the battery and further improve the photoelectric conversion efficiency of the battery. In addition, due to the use of the silver-copper alloy powder, the consumption of noble metal silver is reduced, the cost of the slurry is saved, and the LCOE (leveling degree of electricity cost) is further reduced.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious 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.
The formulation of the specific different embodiments and reference examples is as follows:
| example one | Example two | EXAMPLE III | Example four | Reference example | |
| Silver powder 1 | 80.00％ | 75.00％ | 80.00％ | 75.00％ | 80.00％ |
| Silver powder II | 5.00％ | 5.00％ | |||
| Glass powder | 0.60％ | 0.40％ | 0.40％ | 0.80％ | 1.20％ |
| Silver-copper alloy powder one | 5.00％ | 5.00％ | 3.00％ | 3.00％ | |
| Silver-copper alloy powder II | 2.00％ | 2.00％ | |||
| Organic vehicle | 14.40％ | 14.60％ | 14.60％ | 19.40％ | 13.80％ |
The silver powder D50 used in the above examples was 0.9 to 1.1 μm, and the specific surface area SSA was 0.45 to 0.6m2(g, TD in the range of 5-6 g/cm)3Silver powder with a double D50 particle size of 0.4-0.7 μm and SSA of 0.9-1.5m2(g) TD of 3-4.5g/cm3；
The glass powder used in the above examples is the same formulation of glass powder, and is composed of 5% -25% MnO by mass2、4％～10％CuO、10％～35％PbO、2％～25％Bi2O3、20％～30％SiO2、2％～12％TiO2、0％～5％TeO2、0％～5％ZnO、0％～2％MgO、2％～12％B2O3、0％～2％Li2Co-melting glass powder with an oxide of O;
the silver-copper alloy powder used in the above examples was a metal powder of silver 20 copper 80, D50 in the range of 0.8 to 1.5 μm, and SSA in the range of 0.4 to 0.8m2The second silver-copper alloy powder is AgCu26Zn4 ternary alloy powder, D50 is 0.8-1.5 mu m, and SSA is 0.4-0.8m2/g；
The organic carrier is prepared by dissolving 15% of ethyl cellulose, 4% of polyvinyl butyral, 2% of polyacrylate, 2% of polyamide wax, 5% of organic acid dispersant, 25% of butyl carbitol acetate, 12% of diethylene glycol monobutyl ether, 15% of diethylene glycol dibutyl ether, 5% of triacetin and 15% of alcohol ester in twelve weight percent.
The production process of the silver paste in the above embodiment and the reference example is as follows:
step one, heating and dissolving ethyl cellulose, polyvinyl butyral, polyacrylic acid, an organic acid dispersant, polyamide wax powder, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, triacetin and alcohol ester in a water bath according to a certain proportion to be uniform to obtain a uniform carrier;
step two, adding glass powder, silver powder and silver-copper alloy powder into the uniform carrier dissolved in the step one according to a specific proportion, and stirring and mixing uniformly;
step three, placing the uniformly mixed slurry into a three-high mill for rolling for 4-6 times to obtain uniform silver slurry with the fineness of less than 6 microns;
step four, printing uniform main grid silver paste on the single crystal PERC blue diaphragm, then printing auxiliary grid paste, and co-firing at 770 ℃ to obtain a finished product single crystal PERC battery, and testing efficiency and tensile force;
the examples were tested for electrical properties and tensile force as follows:
comparing examples with reference examples, examples obtained reliable tensile force and more outstanding electrical properties with less glass content and low silver powder content, reference examples had disadvantages compared to the invention examples in both open press and FF;
comparing the first embodiment with the third embodiment, the third embodiment adopts two alloy powders to mix to obtain better open pressure and more outstanding tension, the third embodiment has certain advantages of both open pressure and series resistance, and the photoelectric efficiency is higher than that of the first embodiment, which is derived from the compounding of two different alloy powders, so that the sintering activity can be effectively improved, the glass usage amount is reduced, and the damage of slurry to a battery passivation layer is weakened;
comparing the fourth embodiment with the reference embodiment, the fourth embodiment obtains the photoelectric conversion efficiency close to that of the reference embodiment under the condition of low silver content, and the actual pull-off force is not obviously reduced, so that the silver unit consumption can be effectively reduced;
comparing the first embodiment with the second embodiment, the use of the compound silver powder and the alloy powder I can be observed, the glass content can be further reduced, the slurry corrosion can be improved, and the battery conversion efficiency can be optimized;
from the comparison between the embodiment and the reference example, the silver-copper alloy powder is added into the main grid slurry, so that the use amount of glass can be reduced, the damage of the slurry to a silicon nitride passivation layer can be weakened, the open voltage can be improved, and the photoelectric efficiency can be improved; meanwhile, the silver-copper alloy powder has a lower melting point and better wettability with silver powder, so that the compactness of a silver layer can be improved, and the welding reliability is improved. Furthermore, due to the fact that certain silver-copper alloy powder is used, unit consumption of a battery piece can be effectively reduced, the cost of manufacturing silver paste of the battery is reduced, the power consumption cost of the battery is reduced, and the competitiveness of photovoltaic energy and other traditional fossil energy is improved.
Claims (10)
1. The main grid slurry containing the silver-copper alloy powder is characterized by comprising the following components in percentage by weight: 75-90% of silver powder, 0.2-2% of glass powder, 0.1-20% of silver-copper alloy powder and 8-25% of organic carrier, wherein the silver powder is single silver powder or a mixture of silver powders with different particle sizes, and the organic carrier comprises a solvent, a plasticizer, a thixotropic agent, a thickening agent and a dispersing agent.
2. The main grid slurry containing the silver-copper alloy powder according to claim 1, wherein the organic vehicle comprises the following components in percentage by weight: 70-80% of solvent, 1-10% of plasticizer, 2-5% of thixotropic agent, 15-25% of thickening agent and 2-10% of dispersing agent.
3. The primary grid paste comprising silver-copper alloy powder according to claim 1, wherein said silver powder is one of the following: a single silver powder with D50 between 0.5 and 2 mu m, and a plurality of silver powders with D50 between 0.5 and 2 mu m.
4. The primary grid paste of claim 2, wherein the silver powders include a bulk silver powder having a D50 of 0.8-1.1 μm and a submicron partner silver powder having a D50 of 0.5-0.6 μm.
5. The main grid paste containing silver-copper alloy powder according to claim 1, wherein the glass powder is at least one of Mn-Cu system glass and Pb-Si-Ti system glass.
6. The main grid paste containing the silver-copper alloy powder as claimed in claim 1, wherein the silver-copper alloy powder is at least one of silver-copper binary alloy powder, silver-copper ternary alloy powder and silver-copper quaternary alloy powder which mainly contain silver and copper.
7. The main grid paste containing silver-copper alloy powder according to claim 5, wherein the particle size of the silver-copper alloy powder is 0.5 to 3.5 μm, and the specific surface area is 0.3m2/g-4m2/g。
8. The primary grid paste of claim 1, wherein the solvent is one or more of butyl carbitol acetate, alcohol ester dodeca, terpineol, diethylene glycol dibutyl ether, and diethylene glycol monobutyl ether; the plasticizer is one or a combination of triacetin, diacetin, alcohol ester hexadecane, tributyl citrate, dibutyl phthalate and diethyl phthalate; the thixotropic agent comprises one or more of polyamide wax, hydrogenated castor oil and fumed silica; the thickening agent comprises one or more of methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose acetate butyrate, polyacrylic resin, rosin glyceride, polyvinyl butyral, epoxy resin and polyester resin; the dispersant comprises one or more of organic acid dispersant, amine dispersant, acrylic dispersant and organic silicon dispersant.
9. The main grid paste containing the silver-copper alloy powder according to claim 1, which comprises the following components in percentage by weight: 75-90% of silver powder, 0.8-1.5% of glass powder, 2-10% of silver-copper alloy powder and 8-25% of organic carrier, wherein D50 of the silver-copper alloy powder is 1.5-2 mu m, and the specific surface area is 0.4-0.8m2(ii)/g; the glass powder is Mn-Cu system glass, and the silver powder is submicron silver powder with D50 of 0.8-1.1 mu m and D50 of 0.5-0.6 mu m.
10. A method for preparing a main grid paste containing silver-copper alloy powder according to any one of claims 1 to 9, comprising the steps of:
(1) preparation of organic vehicle: heating and dissolving 70-80% of solvent, 1-10% of plasticizer, 2-5% of thixotropic agent, 15-25% of thickening agent and 2-10% of dispersant in water bath according to a certain proportion to be uniform, and obtaining a uniform organic carrier;
(2) adding glass powder, silver powder and alloy powder into the uniform organic carrier dissolved in the step (1) according to a specific proportion, and stirring and mixing uniformly;
(3) and (3) placing the uniformly mixed slurry obtained in the step (2) into a three-high mill for rolling for 4-6 times to obtain uniform silver paste with the fineness of less than 6 microns.
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| CN103545015A (en) * | 2013-10-21 | 2014-01-29 | 深圳首创光伏有限公司 | Crystalline silicon solar cell front electrode electrocondution slurry and preparation method thereof |
| CN104867535A (en) * | 2014-02-26 | 2015-08-26 | 赫劳斯贵金属北美康舍霍肯有限责任公司 | Glass comprising tungsten and lead in a solar cell paste |
| CN109801735A (en) * | 2018-12-24 | 2019-05-24 | 上海银浆科技有限公司 | A kind of hetero-junction solar cell low temperature silver paste and preparation method |
| CN111863309A (en) * | 2020-08-26 | 2020-10-30 | 南通天盛新能源股份有限公司 | High-tension main grid silver paste applied to N-type solar cell and preparation method thereof |
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| CN103545015A (en) * | 2013-10-21 | 2014-01-29 | 深圳首创光伏有限公司 | Crystalline silicon solar cell front electrode electrocondution slurry and preparation method thereof |
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