CN110415858B - Front silver paste for crystalline silicon solar cell in grading and preparation method thereof - Google Patents
Front silver paste for crystalline silicon solar cell in grading and preparation method thereof Download PDFInfo
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- CN110415858B CN110415858B CN201910567556.1A CN201910567556A CN110415858B CN 110415858 B CN110415858 B CN 110415858B CN 201910567556 A CN201910567556 A CN 201910567556A CN 110415858 B CN110415858 B CN 110415858B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 61
- 239000004332 silver Substances 0.000 title claims abstract description 61
- 229910021419 crystalline silicon Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000011521 glass Substances 0.000 claims abstract description 79
- 239000002002 slurry Substances 0.000 claims abstract description 69
- 239000000843 powder Substances 0.000 claims abstract description 64
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000007639 printing Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims description 27
- 239000000654 additive Substances 0.000 claims description 26
- 230000000996 additive effect Effects 0.000 claims description 26
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 21
- 239000002562 thickening agent Substances 0.000 claims description 20
- 239000013008 thixotropic agent Substances 0.000 claims description 18
- 239000006259 organic additive Substances 0.000 claims description 17
- 229910003069 TeO2 Inorganic materials 0.000 claims description 16
- 229910052681 coesite Inorganic materials 0.000 claims description 16
- 229910052906 cristobalite Inorganic materials 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 229910052682 stishovite Inorganic materials 0.000 claims description 16
- 229910052905 tridymite Inorganic materials 0.000 claims description 16
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 claims description 14
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 238000003723 Smelting Methods 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 6
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 6
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 6
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 6
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- 229940116411 terpineol Drugs 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 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 3
- 239000001856 Ethyl cellulose Substances 0.000 claims description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000012461 cellulose resin Substances 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 229920001249 ethyl cellulose Polymers 0.000 claims description 3
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 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 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 10
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 10
- 229910004205 SiNX Inorganic materials 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 5
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- XNRNVYYTHRPBDD-UHFFFAOYSA-N [Si][Ag] Chemical compound [Si][Ag] XNRNVYYTHRPBDD-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000003809 water extraction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 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
- 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
- H01L31/022433—Particular geometry of the grid contacts
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Photovoltaic Devices (AREA)
- Conductive Materials (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a front-side silver paste for crystalline silicon solar cells in a grading manner and a preparation method of the front-side silver paste, wherein the silver paste comprises a first paste and a second paste, the first paste is used for printing secondary grids of the cells, the second paste is used for printing primary grids of the cells, the first paste comprises spherical silver powder, first glass powder and a first organic carrier, and the second paste comprises silver-coated copper powder, spherical silver powder, flaky silver powder, second glass powder and a second organic carrier. According to the invention, through the mutual matching of the first slurry and the second slurry, the silver-coated copper powder, a small amount of spherical silver powder and flake silver powder are printed on the main grid in a multi-printing mode, and a large amount of spherical silver powder is printed on the auxiliary grid, so that the battery can keep good light receiving performance and electric conductivity, and the use amount of silver can be greatly reduced.
Description
Technical Field
The invention relates to the field of manufacturing of solar cells, in particular to front-side silver paste for grading of crystalline silicon solar cells and a preparation method thereof.
Background
The problems of traditional energy exhaustion and environmental pollution caused by the traditional energy exhaustion are more and more prominent, and the sustainable development of new energy and the environmental protection problem in the use process of the new energy are gradually concerned by people. Solar photovoltaic is an important new energy technology, and is favored by all countries in the world in recent years. The principle is based on the photovoltaic effect of a semiconductor PN junction, when light irradiates a P-N junction, photogenerated carriers are generated, and the carriers are led out of a battery through a metal conductor material, so that current generation is formed. The good metal conductor materials are front electrode silver paste, back electrode silver paste and back electrode aluminum paste, and are printed on the front surface and the back surface of the solar cell in a screen printing mode.
The silver paste of the front electrode of the solar cell is one of the main raw materials affecting the electrical performance of the solar cell. The silver paste mainly comprises three components: the conductive phase, the glass powder and the organic carrier; the conductive phase is metal powder with conductive function, generally spherical silver powder with best conductive performance is adopted, and the content of the spherical silver powder is usually maintained at about 90%; the organic carrier mainly comprises an organic solvent, a plasticizer, a thixotropic agent, a flatting agent, a surfactant and the like, so that the slurry has rheological properties such as viscosity, thixotropy and the like suitable for screen printing; the glass powder mainly plays a role in burning through the anti-reflection layer and bonding. The cost of the silver paste accounts for a large part of the cost of the solar cell at present, and how to reduce the cost of the silver paste becomes an important problem of cost control of the solar cell at present.
Disclosure of Invention
The invention aims to solve the technical problem of providing the front silver paste for the crystalline silicon solar cell in a grading manner, which is low in cost and can ensure the photoelectric conversion efficiency of the cell.
The invention also provides a preparation method of the front silver paste for the fractional use of the crystalline silicon solar cell, which has the advantages of simple process, high production rate, rapid mass production and suitability for industrial mass production.
In order to solve the technical problem, the invention provides a front silver paste for a crystalline silicon solar cell in a grading mode, which comprises a first paste and a second paste, wherein the first paste is used for printing a secondary grid of the cell, the second paste is used for printing a main grid of the cell, the first paste comprises spherical silver powder, first glass powder and a first organic carrier, and the second paste comprises silver-coated copper powder, spherical silver powder, flaky silver powder, second glass powder and a second organic carrier.
As an improvement of the above scheme, the first slurry comprises the following components in percentage by mass: 85-95% of spherical silver powder, 1-3% of first glass powder and 4-13% of first organic carrier;
the second slurry comprises the following components in percentage by mass: 80-85% of silver-coated copper powder, 3-8% of spherical silver powder, 2-8% of flake silver powder, 2-4% of second glass powder and 5-17% of second organic carrier.
As an improvement of the above aspect, the first glass frit includes: PbO, Bi2O3、TeO2、SiO2And a first oxide additive;
the second glass frit comprises: na (Na)2O、TeO2、WO3、SiO2、Li2O and a second oxide additive.
As an improvement of the above scheme, the first glass frit comprises the following components in percentage by mass: 15-55% of PbO and Bi2O3 10～50％、TeO2 20～60％、SiO25-15% and 5-15% of a first oxide additive;
the second glass powder comprises the following components in percentage by mass: na (Na)2O10～20％、TeO2 15～35％、WO325～35％、SiO2 3～8％、Li2O2-6% and a second oxide additive 10-15%.
As a modification of the above, the first oxide additive comprises WO3、ZnO、CaO、MgO、Al2O3、Li2O、Na2O、Fe2O3、B2O3And BaO;
the second oxide additive comprises MgO and Al2O3、LaO、Bi2O3、Li2O、CaO、SnO2、Fe2O3、B2O3、BaO、ZrO2、K2O、CrO3And NiO.
As an improvement of the above scheme, the first glass frit comprises the following components in percentage by mass: 15-55% of PbO and Bi2O3 10～50％、TeO2 20～60％、SiO25-15% and 5-15% of a first oxide additive;
the second glass powder comprises the following components in percentage by mass: na (Na)2O10～20％、TeO2 15～35％、WO325～35％、SiO2 3～8％、Li2O2-6% and a second oxide additive 10-15%.
As a refinement of the above, the first organic vehicle includes a first thickener, a thixotropic agent, a first organic solvent, and an organic additive;
the first thickening agent is one or more of cellulose resin, acrylic resin, rosin resin and phenolic resin;
the first organic solvent is one or more of butyl carbitol, butyl carbitol acetate, terpineol and tributyl citrate;
the second organic vehicle comprises a second thickener, a thixotropic agent, a second organic solvent, and an organic additive;
the second thickening agent is one or more of ethyl cellulose, butyl cellulose, acrylic resin and phenolic resin;
the second organic solvent is one or more of butyl carbitol, butyl carbitol acetate and terpineol.
As an improvement of the above scheme, the first organic vehicle comprises the following components in percentage by mass: 30% of a first thickening agent, 30% of a thixotropic agent, 10% of a first organic solvent and 20% of an organic additive;
the second organic carrier comprises the following components in percentage by mass: 30% of a second thickening agent, 5-10% of a thixotropic agent, 40-45% of a second organic solvent and 20% of an organic additive.
As an improvement of the scheme, the thixotropic agent is polyamide wax, and the organic additive is one or more of a leveling agent, a dispersing agent and a surfactant.
Correspondingly, the invention also provides a preparation method of the front silver paste for the fractional use of the crystalline silicon solar cell, which comprises the following steps:
first, preparing a first slurry
a1, uniformly mixing and drying the components of the first glass powder to obtain a first mixture;
b1, smelting the first mixture obtained in the step (a1), and then extracting with water and drying;
c1, performing ball milling, drying and screening on the first mixture obtained in the step (b1) to obtain first glass powder;
d1, uniformly mixing the components of the first organic carrier, heating to 80-120 ℃, and continuously stirring for 60-90 minutes to obtain the first organic carrier;
e1, uniformly stirring the first glass powder obtained in the step (c1), the first organic carrier obtained in the step (d1) and the spherical silver powder at the temperature of 30-60 ℃ to form slurry, and rolling the stirred slurry to ensure that the fineness of the slurry is 10-15 microns and the viscosity is 50-500 Pascal seconds;
second, preparing a second slurry
a2, uniformly mixing and drying the components of the second glass powder to obtain a second mixture;
b2, smelting the second mixture obtained in the step (a2), and then extracting with water and drying;
c2, performing ball milling, drying and screening on the second mixture obtained in the step (b2) to obtain second glass powder;
d2, uniformly mixing the components of the second organic carrier, heating to 90-130 ℃, and continuously stirring for 80-100 minutes to obtain a second organic carrier;
e2, uniformly stirring the second glass powder obtained in the step (c2), the second organic carrier obtained in the step (d2) and the spherical silver powder at 40-60 ℃ to form slurry, and rolling the stirred slurry to ensure that the fineness of the slurry is 8-12 microns and the viscosity is 30-300 Pascal seconds.
The implementation of the invention has the following beneficial effects:
1. according to the invention, through the mutual matching of the first slurry and the second slurry, the silver-coated copper powder and a small amount of spherical silver powder and flake silver powder are printed on the main grid in a multi-printing mode, and a large amount of spherical silver powder is printed on the auxiliary grid, so that the battery can keep good light receiving performance and electric conductivity, and the use amount of silver can be greatly reduced.
2. The content of the spherical silver powder in the first paste is 85-95%, the content of the spherical silver powder is slightly higher than that of the conventional paste, the content of the glass powder is 1-3%, the content of the glass powder is slightly lower than that of the conventional paste, and compared with the existing paste, the grid line printed by the first paste is more compact, so that the loss of the fine grid in the current transmission process is reduced. The content of the silver-coated copper powder in the second slurry is 80-85%, wherein a large amount of silver-coated copper powder, a small amount of flaky silver powder and spherical silver powder in the second slurry form a conductive phase of the second slurry, so that the electrical property of the second slurry is ensured, and the cost of the slurry is reduced.
3. The first paste can burn through the SiNx antireflection layer of the cell to form good silver-silicon contact, the second paste cannot burn through the SiNx antireflection layer of the cell, current collected by the fine grid is mainly led out effectively, welding tension of the main grid is guaranteed, meanwhile, compounding of metal on the surface of the cell is reduced, and photoelectric conversion efficiency of the cell is improved effectively.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below.
The invention provides a front-side silver paste for crystalline silicon solar cells in a grading mode, which comprises a first paste and a second paste, wherein the first paste is used for printing secondary grids of the cells, the second paste is used for printing primary grids of the cells, the first paste comprises spherical silver powder, first glass powder and a first organic carrier, and the second paste comprises silver-coated copper powder, spherical silver powder, flaky silver powder, second glass powder and a second organic carrier.
At present, the front printing of the battery is divided into single printing and step-by-step printing, and the main grid paste and the auxiliary grid paste are printed together by the single printing, so that only one paste is available; the main grid slurry and the auxiliary grid slurry are printed step by step and are printed separately, the main grid slurry does not burn through the antireflection layer, the auxiliary grid slurry needs to burn through the antireflection layer to collect current, and therefore the two slurries have different components.
Specifically, the first slurry comprises the following components in percentage by mass: 85-95% of spherical silver powder, 1-3% of first glass powder and 4-13% of first organic carrier; the second slurry comprises the following components in percentage by mass: 80-85% of silver-coated copper powder, 3-8% of spherical silver powder, 2-8% of flake silver powder, 2-4% of second glass powder and 5-17% of second organic carrier.
According to the invention, through the mutual matching of the first slurry and the second slurry, the silver-coated copper powder and a small amount of spherical silver powder and flake silver powder are printed on the main grid in a multi-printing mode, and a large amount of spherical silver powder is printed on the auxiliary grid, so that the battery can keep good light receiving performance and electric conductivity, and the use amount of silver can be greatly reduced.
Specifically, the content of the spherical silver powder in the first paste is 85-95%, which is slightly higher than that of the conventional paste, and the content of the glass powder is 1-3%, which is slightly lower than that of the conventional paste. The content of the silver-coated copper powder in the second slurry is 80-85%, wherein a large amount of silver-coated copper powder, a small amount of flaky silver powder and spherical silver powder in the second slurry form a conductive phase of the second slurry, so that the electrical property of the second slurry is ensured, and the cost of the slurry is reduced. The price of the copper powder is lower than that of the silver powder, and in addition, the flaky silver powder is filled in the middle of the spherical silver powder, so that the conductivity can be improved.
The granularity of the silver powder has influence in many aspects, the silver powder can not pass through a screen plate for screen printing if the granularity is too large, and the filling gaps among the silver powder are large, so that the conductivity is influenced to a certain extent; too small particle size can affect the dispersibility of the silver powder in the slurry, resulting in uneven distribution of the silver powder in the slurry, thereby affecting electrical properties; in addition, silver powders of different particle sizes also have some effect on the viscosity of the paste.
Preferably, the particle size of the spherical silver powder in the first slurry is 0.1-0.3 micrometer, the content of silver in the silver-coated copper powder in the second slurry is 20-50%, the particle size is 0.2-0.5 micrometer, the particle size of the spherical silver powder in the second slurry is 0.05-0.2 micrometer, and the particle size of the flaky silver powder is 0.1-0.3 micrometer.
Due to the structure of the silver-coated copper powder in the second slurry, the total content of silver in the silver paste can be reduced, the total content of silver in the light receiving layer after the silver paste is printed is greatly reduced, and therefore the production cost of the battery is reduced.
The first paste can burn through the SiNx antireflection layer of the cell to form good silver-silicon contact, the second paste cannot burn through the SiNx antireflection layer of the cell, current collected by the fine grid is mainly led out effectively, welding tension of the main grid is guaranteed, meanwhile, compounding of metal on the surface of the cell is reduced, and photoelectric conversion efficiency of the cell is improved effectively.
The first glass powder in the first paste and the second glass powder in the second paste have larger difference in components. Specifically, the first glass frit comprises: PbO, Bi2O3、TeO2、SiO2And a first oxide additive; the second glass frit comprises: na (Na)2O、TeO2、WO3、SiO2、Li2O and a second oxide additive.
The first glass powder in the first paste has a strong erosion effect on the SiNx antireflection layer, so that the paste has better silver-silicon contact while burning through the antireflection layer. The second glass powder in the second paste has a weak erosion effect on the SiNx antireflection layer, and mainly plays a role in effectively guiding out current collected by the fine grid, so that the welding tension is ensured, the composition of metal on the surface of the cell is reduced, the filling factor of the cell is ensured, and the photoelectric conversion efficiency of the cell is effectively improved.
Preferably, the first glass powder comprises the following components in percentage by mass: 15-55% of PbO and Bi2O3 10～50％、TeO2 20～60％、SiO25-15% and 5-15% of a first oxide additive; the second glass powder comprises the following components in percentage by mass: na (Na)2O10～20％、TeO2 15～35％、WO3 25～35％、SiO2 3～8％、Li2O2-6% and a second oxide additive 10-15%.
Specifically, the PbO in the first glass powder can reduce the melting point of the glass, improve the glass forming range of the glass and widen the process window. Meanwhile, PbO has good silver melting capability and etching capability to the passivation layer on the surface of the polysilicon battery piece. The Bi2O3The method is beneficial to reducing the melting point of glass and has better etching effect on the passivation layer on the surface of the polycrystalline silicon cell. Bi2O3Can be addedThe excessive corrosion of the glass material to the polycrystalline silicon battery plate can be improved by relatively reducing the dosage of PbO. The TeO2The method is beneficial to forming a glass network structure, improving the silver melting and silver precipitation capacity of the glass powder and reducing the corrosion of glass components to the surface of the polycrystalline silicon cell to a certain degree. The SiO2The network structure of the glass powder can be enhanced, and the stability is improved.
Na in the second glass frit2O and Li2O can help to reduce the melting point of the glass, and Li can also adjust the expansion coefficient of the glass layer, improve the strength of the glass powder and help the tensile property of the glass powder. The TeO2The method is beneficial to forming a glass network structure, improving the silver melting and silver precipitation capacity of the glass powder, improving the pulling force of the grid line and reducing the corrosion of glass components to the surface of the polycrystalline silicon cell to a certain degree. The SiO2The network structure of the glass powder can be enhanced, and the stability is improved.
The first oxide additive comprises WO3、ZnO、CaO、MgO、Al2O3、Li2O、Na2O、Fe2O3、B2O3And BaO, but not limited thereto. The second oxide additive comprises MgO and Al2O3、LaO、Bi2O3、Li2O、CaO、SnO2、Fe2O3、B2O3、BaO、ZrO2、K2O、CrO3And NiO, but not limited thereto. The second oxide additive may also include other compounds.
Preferably, the first oxide additive comprises the following components in percentage by mass: WO3 0.5～10％、ZnO 0.5～5％、CaO 0～2％、Li2O 0.5～3％、Na2O 0～2％、Fe2O3 0.5～2％、B2O30.5-2% and BaO 1-2%. The second oxide additive comprises the following components in percentage by mass: 1-2% of MgO and Al2O 0～2％、LaO 1～2％、BiO3 1～2％、Li2O 1～2％、CaO 1～2％、B2O3 1～2％、SnO2 1～2％、Fe2O3 1～2％、BaO 1～2％、ZrO2 0～2％、K2O 0～2％、CrO30-2% and NiO 0-2%.
Specifically, the first organic vehicle comprises a first thickener, a thixotropic agent, a first organic solvent and an organic additive; the first thickener is one or more of cellulose resin, acrylic resin, rosin resin and phenolic resin, and the first organic solvent is one or more of butyl carbitol, butyl carbitol acetate, terpineol and tributyl citrate. The second organic vehicle comprises a second thickener, a thixotropic agent, a second organic solvent, and an organic additive; the second thickener is one or more of ethyl cellulose, butyl cellulose, acrylic resin and phenolic resin, and the second organic solvent is one or more of butyl carbitol, butyl carbitol acetate and terpineol.
Preferably, the first organic carrier comprises the following components in percentage by mass: 30% of a first thickening agent, 30% of a thixotropic agent, 10% of a first organic solvent and 20% of an organic additive. The second organic carrier comprises the following components in percentage by mass: 30% of a second thickening agent, 5-10% of a thixotropic agent, 40-45% of a second organic solvent and 20% of an organic additive.
Preferably, the thixotropic agent is polyamide wax, and the organic additive is one or more of a leveling agent, a dispersing agent and a surfactant.
Correspondingly, the invention also provides a preparation method of the front silver paste for the crystalline silicon solar cell in the grading way, which is characterized by comprising the following steps:
first, preparing a first slurry
a1, uniformly mixing and drying the components of the first glass powder to obtain a first mixture;
b1, smelting the first mixture obtained in the step (a1), and then extracting with water and drying;
c1, performing ball milling, drying and screening on the first mixture obtained in the step (b1) to obtain first glass powder;
d1, uniformly mixing the components of the first organic carrier, heating to 80-120 ℃, and continuously stirring for 60-90 minutes to obtain the first organic carrier;
e1, uniformly stirring the first glass powder obtained in the step (c1), the first organic carrier obtained in the step (d1) and the spherical silver powder at the temperature of 30-60 ℃ to form slurry, and rolling the stirred slurry to ensure that the fineness of the slurry is 10-15 microns and the viscosity is 50-500 Pascal seconds;
second, preparing a second slurry
a2, uniformly mixing and drying the components of the second glass powder to obtain a second mixture;
b2, smelting the second mixture obtained in the step (a2), and then extracting with water and drying;
c2, performing ball milling, drying and screening on the second mixture obtained in the step (b2) to obtain second glass powder;
d2, uniformly mixing the components of the second organic carrier, heating to 90-130 ℃, and continuously stirring for 80-100 minutes to obtain a second organic carrier;
e2, uniformly stirring the second glass powder obtained in the step (c2), the second organic carrier obtained in the step (d2) and the spherical silver powder at 40-60 ℃ to form slurry, and rolling the stirred slurry to ensure that the fineness of the slurry is 8-12 microns and the viscosity is 30-300 Pascal seconds.
The invention will now be illustrated by the following specific examples
The front-side silver paste for the crystalline silicon solar cell in the grading mode comprises a first paste and a second paste, wherein the first paste is used for printing a secondary grid of the cell, and the second paste is used for printing a main grid of the cell;
the first slurry comprises the following components in percentage by mass: 90% of spherical silver powder, 2.5% of first glass powder and 7.5% of first organic carrier, wherein the particle size of the spherical silver powder is 2-3 microns;
the second slurry comprises the following components in percentage by mass: 82% of silver-coated copper powder, 6% of spherical silver powder, 2% of flake silver powder, 2% of second glass powder and 8% of second organic carrier, wherein the particle size of the silver-coated copper powder is 1-2 microns, and the particle size of the spherical silver powder is 2-3 microns;
the first glass powder comprises the following components in percentage by mass: PbO 25% and Bi2O3 30％、TeO2 25％、SiO210% and 10% of first oxide;
the first oxide additive comprises the following components in percentage by mass: WO3 3％、ZnO 2％，CaO 1％、Li2O1％、Na2O 0.5％、Fe2O3 0.5％、B2O30.3%, BaO 1%, and other compounds 0.7%;
the first organic carrier comprises the following components in percentage by mass: 30% of a first thickening agent, 30% of a thixotropic agent, 10% of a first organic solvent and 20% of an organic additive;
the second glass powder comprises the following components in percentage by mass: na (Na)2O 17％，TeO2 31.5％，WO3 28％，SiO2 6.5％，Li2O3% and a second oxide additive 14%.
The second oxide additive comprises the following components in percentage by mass: MgO 1.5%, Al2O 2％、LaO 1.5％、BiO3 1％、Li2O 1.7％、CaO 1.8％、B2O3 1％、SnO2 1％、Fe2O31%, BaO 1% and other compounds 0.5%;
the second organic carrier comprises the following components in percentage by mass: 30% of a second thickener, 6% of a thixotropic agent, 45% of a second organic solvent and 19% of an organic additive.
A preparation method of front silver paste for crystalline silicon solar cells in multiple use comprises the following steps:
first, preparing a first slurry
a1, uniformly mixing the components of the first glass powder in proportion, putting the mixture into a ceramic crucible, and drying to obtain a first mixture;
b1, putting the first mixture obtained in the step (a1) into a muffle furnace, smelting for about 1h, and drying after water extraction;
c1, grinding the first mixture obtained in the step (b1) by adopting a planetary ball mill, and carrying out ball milling, drying and sieving to obtain first glass powder;
d1, uniformly mixing the components of the first organic carrier in proportion, heating to 80-120 ℃, and continuously stirring for 90 minutes to obtain a transparent first organic carrier;
e1, adding the first glass powder obtained in the step (c1), the first organic carrier obtained in the step (d1) and the spherical silver powder into a stirrer in proportion, stirring uniformly at the temperature of 30-60 ℃ to form slurry, and rolling the stirred slurry for 5-10 times in a three-roll mill to ensure that the fineness of the slurry is 12 microns and the viscosity is 50-300 Pascal per second;
second, preparing a second slurry
a2, uniformly mixing the components of the second glass powder in proportion, and then putting the mixture into a ceramic crucible to be dried to obtain a second mixture;
b2, putting the second mixture obtained in the step (a2) into a muffle furnace, smelting for about 2 hours, and drying after water extraction;
c2, grinding the second mixture obtained in the step (b2) by adopting a planetary ball mill, and carrying out ball milling, drying and sieving to obtain second glass powder;
d2, uniformly mixing the components of the second organic carrier in proportion, heating to 80-120 ℃, and continuously stirring for 90 minutes to obtain a transparent second organic carrier;
e2, adding the second glass powder obtained in the step (c2), the second organic carrier obtained in the step (d2) and the spherical silver powder into a stirrer in proportion, stirring uniformly at 30-60 ℃ to form slurry, and rolling the stirred slurry for 5-10 times in a three-roll mill to ensure that the fineness of the slurry is 12 microns and the viscosity is 50-300 Pascal per second.
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
Claims (8)
1. The front-side silver paste for the crystalline silicon solar cell in the grading mode is characterized by comprising a first paste and a second paste, wherein the first paste is used for printing a cell secondary grid, and the second paste is used for printing a cell main grid;
the first slurry comprises the following components in percentage by mass: 85-95% of spherical silver powder, 1-3% of first glass powder and 4-13% of first organic carrier;
the second slurry comprises the following components in percentage by mass: 80-85% of silver-coated copper powder, 3-8% of spherical silver powder, 2-8% of flake silver powder, 2-4% of second glass powder and 5-17% of second organic carrier;
the first glass powder comprises the following components in percentage by mass: 15-55% of PbO and Bi2O3 10～50％、TeO2 20～60％、SiO25-15% and 5-15% of a first oxide additive;
the second glass powder comprises the following components in percentage by mass: na (Na)2O10～20％、TeO2 15～35％、WO3 25～35％、SiO2 3～8％、Li22-6% of O2 and 10-15% of a second oxide additive;
the first oxide additive comprises WO3、ZnO、CaO、MgO、Al2O3、Na2O、Fe2O3And BaO;
the second oxide additive comprises MgO and Al2O3、Bi2O3、CaO、SnO2、Fe2O3、B2O3、BaO、ZrO2、K2O、CrO3And NiO.
2. The graded front-side silver paste of the crystalline silicon solar cell as claimed in claim 1, wherein the spherical silver powder in the first paste has a particle size of 0.1-0.3 μm.
3. The graded front-side silver paste of the crystalline silicon solar cell of claim 1, wherein the silver paste is a silver paste,
in the second slurry, the particle size of the spherical silver powder is 0.05-0.2 microns, and the particle size of the flaky silver powder is 0.1-0.3 microns.
4. The graded front-side silver paste for the crystalline silicon solar cell according to claim 1, wherein the first oxide additive comprises the following components in percentage by mass: WO3 0.5～10％、ZnO0.5～5％、CaO 0～2％、Na2O 0～2％、Fe2O30.5-2% and 1-2% of BaO;
the second oxide additive comprises the following components in percentage by mass: 1-2% of MgO and Al2O30～2％、Bi2O3 1～2％、CaO 1～2％、B2O3 1～2％、SnO2 1～2％、Fe2O3 1～2％、BaO 1～2％、ZrO2 0～2％、K2O 0～2％、CrO30-2% and NiO 0-2%.
5. The graded front-side silver paste of the crystalline silicon solar cell of claim 1, wherein the first organic vehicle comprises a first thickener, a thixotropic agent, a first organic solvent and an organic additive;
the second organic vehicle comprises a second thickener, a thixotropic agent, a second organic solvent, and an organic additive;
the first thickening agent is one or more of cellulose resin, acrylic resin, rosin resin and phenolic resin;
the first organic solvent is one or more of butyl carbitol, butyl carbitol acetate, terpineol and tributyl citrate;
the second thickening agent is one or more of ethyl cellulose, butyl cellulose, acrylic resin and phenolic resin;
the second organic solvent is one or more of butyl carbitol, butyl carbitol acetate and terpineol.
6. The graded front-side silver paste of the crystalline silicon solar cell of claim 5, wherein the first organic carrier comprises the following components in percentage by mass: 30% of a first thickening agent, 30% of a thixotropic agent, 10% of a first organic solvent and 20% of an organic additive;
the second organic carrier comprises the following components in percentage by mass: 30% of a second thickening agent, 5-10% of a thixotropic agent, 40-45% of a second organic solvent and 20% of an organic additive.
7. The front-side silver paste for fractional use of a crystalline silicon solar cell according to claim 5, wherein the thixotropic agent is polyamide wax, and the organic additive is one or more of a leveling agent, a dispersing agent and a surfactant.
8. The preparation method of the front-side silver paste for the fractional use of the crystalline silicon solar cell according to any one of claims 1 to 7, is characterized by comprising the following steps:
first, preparing a first slurry
a1, uniformly mixing and drying the components of the first glass powder to obtain a first mixture;
b1, smelting the first mixture obtained in the step (a1), and then extracting with water and drying;
c1, performing ball milling, drying and screening on the first mixture obtained in the step (b1) to obtain first glass powder;
d1, uniformly mixing the components of the first organic carrier, heating to 80-120 ℃, and continuously stirring for 60-90 minutes to obtain the first organic carrier;
e1, uniformly stirring the first glass powder obtained in the step (c1), the first organic carrier obtained in the step (d1) and the spherical silver powder at the temperature of 30-60 ℃ to form slurry, and rolling the stirred slurry to ensure that the fineness of the slurry is 10-15 microns and the viscosity is 50-500 Pascal seconds;
second, preparing a second slurry
a2, uniformly mixing and drying the components of the second glass powder to obtain a second mixture;
b2, smelting the second mixture obtained in the step (a2), and then extracting with water and drying;
c2, performing ball milling, drying and screening on the second mixture obtained in the step (b2) to obtain second glass powder;
d2, uniformly mixing the components of the second organic carrier, heating to 90-130 ℃, and continuously stirring for 80-100 minutes to obtain a second organic carrier;
e2, uniformly stirring the second glass powder obtained in the step (c2), the second organic carrier obtained in the step (d2) and the spherical silver powder at 40-60 ℃ to form slurry, and rolling the stirred slurry to ensure that the fineness of the slurry is 8-12 microns and the viscosity is 30-300 Pascal seconds.
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| CN111106206A (en) * | 2019-12-12 | 2020-05-05 | 浙江爱旭太阳能科技有限公司 | Manufacturing method of single crystal silicon SE-PERC solar cell |
| CN110957387A (en) * | 2019-12-24 | 2020-04-03 | 广东爱旭科技有限公司 | Electrode structure of high-efficiency solar cell suitable for step-by-step printing |
| CN111146297A (en) * | 2019-12-24 | 2020-05-12 | 广东爱旭科技有限公司 | Electrode step-by-step printing method of efficient solar cell |
| CN114530508A (en) * | 2020-11-02 | 2022-05-24 | 苏州阿特斯阳光电力科技有限公司 | PERC battery and photovoltaic module |
| CN113380904A (en) * | 2021-01-12 | 2021-09-10 | 宣城睿晖宣晟企业管理中心合伙企业(有限合伙) | Electrode of silicon heterojunction solar cell, preparation method thereof and cell |
| CN115945825A (en) * | 2023-01-30 | 2023-04-11 | 昆山百柔新材料技术有限公司 | Slurry, preparation method thereof and packaging method of chip heat dissipation structure |
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Effective date of registration: 20220119 Address after: 300403 No. 73, Gaoxin Avenue, Science Park, Tianjin Beichen economic and Technological Development Zone, Beichen District, Tianjin Patentee after: Tianjin Aixu Solar Energy Technology Co.,Ltd. Patentee after: ZHEJIANG AIKO SOLAR ENERGY TECHNOLOGY Co.,Ltd. Patentee after: Guangdong aixu Technology Co.,Ltd. Patentee after: Zhuhai Fushan aixu Solar Energy Technology Co.,Ltd. Address before: 300403 northeast of the intersection of Gaoxin Avenue and Jingtong Road, Science Park, Tianjin Beichen economic and Technological Development Zone, Beichen District, Tianjin Patentee before: Tianjin Aixu Solar Energy Technology Co.,Ltd. |