CN114550969A - Glass powder, conductive silver paste, preparation method of conductive silver paste, front electrode and silicon solar cell - Google Patents
Glass powder, conductive silver paste, preparation method of conductive silver paste, front electrode and silicon solar cell Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 197
- 239000000843 powder Substances 0.000 title claims abstract description 144
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 49
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000010703 silicon Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 12
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 9
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 9
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 9
- 229910003069 TeO2 Inorganic materials 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000002562 thickening agent Substances 0.000 claims description 7
- 229910052745 lead Inorganic materials 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000007650 screen-printing Methods 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000002518 antifoaming agent Substances 0.000 claims description 5
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000007639 printing Methods 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- 229910052716 thallium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 210000004027 cell Anatomy 0.000 description 43
- 239000007788 liquid Substances 0.000 description 22
- 230000000694 effects Effects 0.000 description 19
- 239000013078 crystal Substances 0.000 description 16
- 229910052709 silver Inorganic materials 0.000 description 11
- 239000004332 silver Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 9
- 239000006060 molten glass Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 239000000395 magnesium oxide Substances 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 101100409194 Rattus norvegicus Ppargc1b gene Proteins 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910021418 black silicon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910003460 diamond Inorganic materials 0.000 description 3
- 239000010432 diamond Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 241000233805 Phoenix Species 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/122—Silica-free oxide glass compositions containing oxides of As, Sb, Bi, Mo, W, V, Te as glass formers
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Inorganic Chemistry (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses conductive silver paste for a front electrode of a silicon solar cell and glass powder thereof, wherein the glass powder comprises first-state glass powder and second-state glass powder, and the first-state glass powder mainly comprises at least one of W or Mo element oxides and TeO2MgO and Li2O, the second state glass powder mainly comprises SiO2、Bi2O3CuO and Li2And O. The invention also provides a preparation method of the conductive silver paste for the front electrode of the silicon solar cell, and the front electrode and the silicon solar cell containing the conductive silver paste. The silicon solar cell can be widely applied to silicon solar cells of different types, and has the advantages of high peeling strength of combination with the cells, long service life, low contact resistance and high photoelectric conversion efficiency.
Description
Technical Field
The invention relates to the field of silicon solar cells, in particular to glass powder for a front electrode of a silicon solar cell, conductive silver paste for the front electrode of the silicon solar cell, a preparation method of the conductive silver paste, the front electrode and the silicon solar cell.
Background
The problem of energy for human development is still one of the most important current problems, nuclear energy and solar energy are the two most important fossil energy substitution modes for replacing fossil energy, but the use of nuclear energy may bring potential safety hazards, so that the problem of environmental pollution caused by nuclear energy leakage cannot be solved by human beings so far, the use of nuclear energy by human beings is limited in decades or even hundreds of years in the future, and the fossil energy cannot be replaced by large-scale fossil energy as clean energy or novel energy, so that solar energy can be widely used as clean and pollution-free novel energy for replacing fossil energy most effectively.
Solar cells are the most effective way to convert solar energy into energy which is easy to use and store, and have been widely researched, and include silicon solar cells, perovskite structure solar cells, thin film solar cells, heterojunction solar cells and the like, among which the silicon solar cells are the most widely used and the technology is the most mature. The silicon solar cell is a device for converting photons of sunlight to generate electric energy by utilizing the photovoltaic effect of a p-n junction, and mainly comprises a front electrode, an antireflection film, a PN junction, a silicon substrate, a back electrode and the like, wherein the front electrode is formed by screen printing, drying and sintering conductive silver paste.
At present, with the development of technology, silicon solar cell technology also appears diversified, such as conventional polycrystal, polycrystalline black silicon, polycrystalline diamond wire, conventional single crystal cell, perc single crystal, Se-perc single crystal, N-type cell, etc., the cell variety is various, and the structure of the antireflection film related to materials such as silicon nitride, titanium oxide, aluminum oxide, silicon oxide, etc. is complex and various, which leads to that the conductive silver paste in the current market is difficult to consider various silicon solar cell technologies. The conductive silver paste of the silicon solar cell provided by the invention can be widely suitable for cells constructed by various processes and technologies, and has excellent grid line peeling strength and excellent photoelectric conversion efficiency.
Disclosure of Invention
The invention aims to provide glass powder of conductive silver paste of a front electrode of a silicon solar cell and the conductive silver paste containing the glass powder, which can be widely applied to the silicon solar cells with various process and technical structures, and have excellent grid line peeling strength and excellent photoelectric conversion efficiency.
The invention also aims to provide a preparation method of the conductive silver paste, which has fewer implementation steps and is simple and practical.
Another object of the present invention is to provide a front electrode and a silicon solar cell including the glass frit or conductive silver paste, which can be widely applied to silicon solar cells with various processes and technical structures, and the silicon solar cells with different processes and technical structures all have excellent peeling strength of grid lines and excellent photoelectric conversion efficiency.
In order to achieve the above object, the present invention provides a glass frit combination suitable for conductive silver paste of a front electrode of a silicon solar cell, the glass frit combination comprises a first state glass frit and a second state glass frit, the first state glass frit mainly comprises TeO and at least one of W or Mo element oxides2MgO and Li2O, the second state glass powder mainly comprises SiO2、Bi2O3CuO and Li2O。
Further, the first-state glass powder also comprises a modified oxide, and the modified oxide is one or more of oxides formed by a first series of elements of Bi, Pb, Na, K, Al, Zn, Cu, Ca, Si, Ge, Tl, B, Ce, Ti, Fe, Sb, V, Sn, Pr, Sr and Ba or substances capable of decomposing to obtain the oxides formed by the first series of elements.
Further, based on the total mole number of the oxides contained in the first state glass powder as 100%, the mole percentages of the oxides in the first state glass powder are as follows:
further, the second-state glass powder also comprises an additive, and the additive is one or more of oxides formed by second series elements of Pb, Zn, W, Ge, B, Sb, Te and Fe or substances capable of decomposing to obtain the oxides formed by the second series elements.
Further, the total mole number of the oxides contained in the second state glass powder is 100%, and the mole percentages of the oxides in the second state glass powder are as follows:
further, the particle size of the glass powder is 0.2-10.0 μm, the softening point of the first state glass powder is 50-150 ℃ lower than that of the second state glass powder, and the mixing mass ratio of the first state glass powder to the second state glass powder is not less than 1: 3.
The invention also provides a conductive silver paste for the front electrode of the silicon solar cell, which comprises the following components in percentage by weight of 100 percent:
further, the silver powder is spherical silver powder, the particle size of the silver powder is 0.5-4.0 μm, and the D50 is 1.0-2.0 μm.
Further, the organic carrier comprises an organic solvent, an organic resin, a thickening agent, a defoaming agent and a curing agent, and the content of each component is as follows based on the total weight of the organic carrier as 100 percent:
the invention also provides a preparation method of the conductive silver paste of the front electrode of the silicon solar cell, which comprises the following steps: preparing first-state glass powder and second-state glass powder, wherein the first-state glass powder comprises TeO and at least one of W or Mo element oxides2MgO and Li2O, the second state glass powder comprises SiO2、Bi2O3CuO and Li2O, the first-state glass powder or the second-state glass powder is prepared by weighing raw materials according to the mass ratio, mixing, melting, quenching, drying and crushing, and the raw materials of the first-state glass powder and the second-state glass powder are oxides of corresponding elements or substances which can be decomposed by heating to obtain oxides of the corresponding elements; preparing an organic carrier, wherein the organic carrier comprises an organic solvent, organic resin, a thickening agent, a defoaming agent and a curing agent, and the organic carrier is prepared by mixing, heating in a water bath, centrifugally dispersing and cooling; and providing silver powder, and mixing, stirring, rolling and filtering the silver powder, the first state glass powder, the second state glass powder and the organic carrier to obtain the conductive silver paste.
The invention also provides a front electrode of the silicon solar cell, wherein the front electrode is prepared by printing conductive silver paste of the front electrode of the silicon solar cell on a crystalline silicon cell piece in a screen printing or spraying manner, and drying and sintering.
The invention also provides a silicon solar cell comprising a front electrode as described above.
Compared with the prior art, the first-state glass powder used in the invention is TeO2-MgO-Li2O main componentGlass powder, compared with the traditional TeO2-PbO-Li2O mainly constitutes glass powder, so that the lead content is greatly reduced, even lead is not contained, and the lead pollution is reduced, therefore, TeO2-MgO-Li2The O glass powder is more environment-friendly than the traditional glass powder; at the same time, TeO2-MgO-Li2The O glass powder uses high-melting-point magnesium oxide to replace a large amount of low-melting-point lead oxide, bismuth oxide, zinc oxide and other substances, so that the viscosity and the surface tension of the glass liquid are improved, the problem that the silver powder is insufficiently sintered due to over-high fluidity of the traditional glass powder at a low-temperature stage is well solved, the sintering-assisting effect of the glass liquid on the silver powder is improved, and in addition, the TeO glass powder disclosed by the invention has the advantages that2-MgO-Li2O glass powder using a large amount of WO3And MoO3To replace the conventional SiO2Tungsten and molybdenum elements can greatly reduce the high-temperature viscosity and the surface tension of the molten glass at the high-temperature stage of the molten glass, so that the problem that the viscosity of the molten glass is higher at the high-temperature stage due to high magnesium-containing elements is well solved, the molten glass can well flow and corrode an insulating layer on the surface of a battery at the high-temperature stage, and excellent ohmic contact is formed; thus, the TeO of the present invention was produced2-MgO-Li2The high-temperature glass liquid has high viscosity and high surface tension, and the high-temperature glass liquid has low viscosity and low surface tension, so that the sintering aid for the silver powder has a good sintering effect, the grid line stripping strength is high, the corrosion effect on a glass interface is good, the contact effect is good, and the electrical property is excellent.
The invention uses TeO as the first state glass powder2-MgO-Li2The glass powder mainly consists of O, and the second state SiO is also used2-Bi2O3-CuO-Li2O mainly forms glass powder, the sintering assisting effect of the silver powder and the contact effect of the silver paste are further improved, the second-state glass powder is also low-lead or lead-free glass powder, the second-state glass powder is high in silicon content and contains high bismuth oxide and copper oxide, so that the glass is high in softening point, the first-state glass powder and the second-state glass powder can be well fused when the mixing mass ratio of the first-state glass powder to the second-state glass powder is not less than 1:3, and the softening point of the second-state glass powder is higher than 50 ℃ DEG C.of the first-state glass powder150 ℃, the problem that the viscosity of the first-state glass powder is low in a high-temperature area is well solved, the glass liquid can better assist in sintering the silver layer at a high-temperature stage, meanwhile, the first-state glass liquid and the second-state glass liquid are gradually fused with each other near a highest sintering temperature area, so that a large amount of silicon elements in the second-state glass liquid enter the first-state glass liquid, the destructiveness of the first-state glass liquid on a PN junction layer is reduced, the voltage of a battery piece is increased, the silver elements fused in the first-state glass liquid are also promoted to be greatly separated out, a good contact effect is formed on a contact interface, the contact resistance is low, and the electrical property of the battery is improved.
The conductive silver paste provided by the invention comprises first-state glass powder and second-state glass powder, has excellent burning-assisting effect, greatly improves the peeling strength of grid lines, meets the requirement of using the peeling strength on various battery pieces, combines the characteristics of the first-state glass powder and the second-state glass powder, and realizes excellent contact effect and excellent electrical property on the battery pieces with different characteristics.
The conductive silver paste provided by the invention can be compatible with battery pieces of various processes, the process for manufacturing the conductive silver paste is simple, the cost is low, the prepared silicon solar battery and the front electrode thereof relate to various types of battery front electrodes and batteries such as conventional polycrystal, polycrystalline black silicon, polycrystalline diamond wire, conventional single crystal battery, perc single crystal, Se-perc single crystal and the like, and the practicability is wide.
Detailed Description
The "ranges" disclosed herein are in the form of lower and upper limits. There may be one or more lower limits, and one or more upper limits, respectively. The given range is defined by the selection of a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular range. All ranges that can be defined in this manner are inclusive and combinable, i.e., any lower limit can be combined with any upper limit to form a range. For example, ranges of 60-120 and 80-110 are listed for particular parameters, with the understanding that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present invention, all embodiments and preferred embodiments mentioned herein may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the technical features mentioned herein and preferred features may be combined with each other to form a new technical solution, if not specifically stated. In the present invention, all the steps mentioned herein may be performed sequentially or randomly, if not specifically stated, but preferably sequentially.
The embodiment provides a silicon solar cell, which mainly comprises a front electrode, an antireflection film, a PN junction, a silicon substrate, a back electrode and the like. The front electrode is prepared by printing conductive silver paste on a crystalline silicon battery piece in a screen printing or spraying mode, and drying and sintering. The embodiment provides a conductive silver paste, which comprises 79.00% -93.00% of silver powder, 0.30% -8.00% of first-state glass powder, 0.10% -3.00% of second-state glass powder and 5.00% -20.00% of an organic carrier, wherein the total weight of the conductive silver paste is 100%. Wherein the silver powder is spherical silver powder, the particle size of the silver powder is 0.5-4.0 μm, and the D50 is 1.0-2.0 μm. The organic carrier comprises 20.0-80.0 percent of organic solvent, 2.0-20 percent of organic resin, 1.0-20.0 percent of thickening agent, 0.1-5.0 percent of defoaming agent and 0.1-5.0 percent of curing agent by taking the total weight of the organic carrier as 100 percent.
The glass frit suitable for the conductive silver paste provided by the embodiment of the invention comprises a first state glass frit and a second state glass frit, wherein the first state glass frit comprises TeO and at least one of W or Mo element oxides2MgO and Li2And O. The first-state glass powder also comprises a modified oxide, wherein the modified oxide is an oxide formed by a first series of elements of Bi, Pb, Na, K, Al, Zn, Cu, Ca, Si, Ge, Tl, B, Ce, Ti, Fe, Sb, V, Sn, Pr, Sr and BaOr one or more of the substances that can decompose to give oxides of the first series of elements. Based on the total mole number of the oxides contained in the first state glass powder as 100%, the mole percentages of the oxides in the first state glass powder are as follows: TeO220.0-50.0 percent of MgO, 5.0-25.0 percent of Li210.0 to 30.0 percent of O, 2.0 to 15.0 percent of W or Mo element oxide and 0.1 to 30.0 percent of modified oxide.
The second state glass powder comprises SiO2、Bi2O3CuO and Li2And O. The second-state glass powder also comprises an additive, wherein the additive is one or more of oxides formed by Pb, Zn, W, Ge, B, Sb, Te and Fe second series elements or substances which can be decomposed to obtain the oxides formed by the second series elements. Based on the total mole number of the oxides contained in the second state glass powder as 100%, the corresponding mole percentages of the oxides in the second state glass powder are as follows: SiO 2215.0 to 60.0 percent of Bi2O31.0 to 10.0 percent of CuO, 2.0 to 15.0 percent of Li215.0 to 40.0 percent of O and 0.1 to 25.0 percent of additive.
The particle size of the glass powder is 0.2-10.0 μm, the softening point of the first state glass powder is 50-150 ℃ lower than that of the second state glass powder, and the mixing mass ratio of the first state glass powder to the second state glass powder is not less than 1: 3.
Preparing conductive silver paste:
preparing first-state glass powder and second-state glass powder, and calculating, weighing, mixing, melting, quenching, drying and crushing according to the designed formula of the first-state glass powder and the second-state glass powder to prepare the first-state glass powder and the second-state glass powder with proper particle sizes; the raw materials of the first state glass powder and the second state glass powder are oxides of corresponding elements or substances which can be decomposed by heating to obtain oxides of corresponding elements;
preparing an organic carrier, calculating, weighing, mixing, heating in a water bath, centrifugally dispersing and cooling according to a designed organic carrier formula to prepare the organic carrier;
and providing silver powder, and calculating, weighing, mixing, stirring, rolling and filtering the silver powder, the first state glass powder, the second state glass powder and the organic carrier according to the set mass proportion to obtain the conductive silver paste.
And printing the conductive silver paste on a crystalline silicon cell piece in a screen printing or spraying manner, and drying and sintering to obtain the front electrode containing the conductive silver paste.
The following is illustrated with reference to specific examples 1 to 10:
preparing first-state glass powder: the corrosion-resistant glass powder B1-B6 is prepared by sequentially calculating, weighing, mixing, melting, cold quenching, crushing and grading raw material oxides of the first-state glass powder or compounds capable of decomposing into the inorganic oxides, wherein the specific composition ratio of each glass powder is shown in Table 1.
Preparing second-state glass powder: and (3) calculating, weighing, mixing, melting, cold quenching, crushing and grading the raw material oxides of the second-state glass powder or the compounds or compounds capable of decomposing into the inorganic oxides in turn to prepare the corrosion-resistant glass powder C1-C4, wherein the specific composition ratio of each glass powder is shown in Table 2.
Preparation of organic vehicle: calculating, weighing, mixing and stirring organic solvent, organic resin, thickening agent, defoaming agent and curing agent raw materials for manufacturing the organic carrier according to mass percentage, heating in water bath to separate and disperse uniformly, and then cooling to obtain the organic carrier P1. Organic solvents, organic resins, thickeners, defoamers, and curing agents suitable for organic vehicles in the prior art are also suitable for use in the present invention and are not described herein in detail.
Preparing conductive silver paste: 2 commercially available glass powders were used as comparative examples, and were numbered A1 and a2, A1 glass powder was obtained from E066 front silver glass powder produced by korean bass, and a2 glass powder was obtained from a105 front silver glass powder produced by korean phoenix. And calculating and weighing the prepared silver powder, glass powder and organic carrier according to the mass percentage of the conductive silver paste, uniformly stirring the silver powder, the glass powder and the organic carrier by using a stirrer, finally rolling the silver powder by using a three-roll machine, and performing suction filtration to obtain the conductive silver paste D1-D10, which is shown in Table 3.
The prepared conductive silver paste is printed on the surface of the cell by silk screen printing on cell pieces with different processes, and then is dried, sintered and cooled to obtain the silicon solar cell containing the printed silver grid line electrode, the efficiency test and the grid line peel strength test are carried out on the obtained silicon solar cell, and the test results are shown in table 4.
Table 1 molar composition table (mol%) of first state glass frit examples
Table 2 second state glass frit examples molar composition table (mol%)
| Name (R) | C1 | C2 | C3 | C4 |
| SiO2 | 59.9 | 15.2 | 45.0 | 36.4 |
| Bi2O3 | 4.1 | 9.6 | 5.8 | 6.0 |
| CuO | 6.4 | 14.7 | 8.5 | 2.1 |
| Li2CO3 | 15.5 | 39.5 | 22.7 | 30.7 |
| PbO | 3.8 | 3.2 | 2.1 | |
| ZnO | 8.0 | 1.5 | 14.1 | |
| WO3 | 9.2 | 1.8 | 5.4 | |
| GeO2 | 3.3 | 3.0 | 0.7 | |
| B2O3 | 2.0 | 1.0 | 0.5 | |
| TiO2 | 1.0 | |||
| TeO2 | 1.3 | 1.0 | ||
| MgO | 2.5 | 7.5 | 2.0 | |
| Na2CO3 | 1.5 | 0.5 | ||
| Sb2O3 | 1.0 |
Table 3 example silver paste composition table (%)
| Name (R) | Content of silver powder% | First state glass powder/content% | Second state glass powder/content% | Content of organic vehicle% |
| D1 | 89.6 | A1/2.2 | P1/8.2 | |
| D2 | 89.6 | A2/2.2 | P1/8.2 | |
| D3 | 89.6 | B1/2.0 | C1/0.2 | P1/8.2 |
| D4 | 89.6 | B2/1.8 | C4/0.4 | P1/8.2 |
| D5 | 92.7 | B3/0.6 | C4/1.5 | P1/5.2 |
| D6 | 88.2 | B4/1.3 | C3/0.7 | P1/9.8 |
| D7 | 86.3 | B5/1.5 | C1/1.5 | P1/10.7 |
| D8 | 81.7 | B6/5.7 | C2/0.3 | P1/12.3 |
| D9 | 79.2 | B1/1.4 | C2/2.7 | P1/16.7 |
| D10 | 90.4 | B6/1.7 | C4/0.4 | P1/7.5 |
As can be seen from table 4, in the silicon solar cell prepared by the conductive silver paste provided in the embodiment of the present invention, the photoelectric conversion efficiency of the conductive silver paste D3-D10 is higher than that of the comparative examples D1 and D2 in the polycrystalline cell, the conventional single-crystal cell, the Perc-single crystal and the Se-Perc-single crystal, the peeling strength of the grid lines on different cell sheets is obvious, the peeling tensile force is higher than that of the comparative examples, the silver paste difference between D1 and D2 on the polycrystalline and conventional single-crystal sheets is smaller than that of the embodiment of the present invention, but the difference between the Perc-single-crystal and Se-Perc-single-crystal sheets is obvious, the EL problems of different degrees occur in D1 and D2, and the efficiency is obvious, therefore, the conductive silver paste provided in the present invention can be compatible with the cell sheets of various processes, can be widely used for the polycrystalline cell sheets, the conventional single-crystal cell, the single-Perc sheet, the Se-Perc-single-crystal sheet, and the grid lines are high in peeling strength, the photoelectric conversion efficiency is high.
Compared with the prior art, the first-state glass powder used in the invention is TeO2-MgO-Li2O mainly comprises glass powder, compared with the traditional TeO2-PbO-Li2O mainly constitutes glass powder, so that the lead content is greatly reduced, even lead is not contained, and the lead pollution is reduced, therefore, TeO2-MgO-Li2The O glass powder is more environment-friendly than the traditional glass powder; at the same time, TeO2-MgO-Li2The O glass powder uses high-melting-point magnesium oxide to replace a large amount of low-melting-point lead oxide, bismuth oxide, zinc oxide and other substances, so that the viscosity and the surface tension of the glass liquid are improved, the problem that the silver powder is insufficiently sintered due to over-high fluidity of the traditional glass powder at a low-temperature stage is well solved, the sintering-assisting effect of the glass liquid on the silver powder is improved, and in addition, the TeO glass powder disclosed by the invention has the advantages that2-MgO-Li2O glass powder using a large amount of WO3And MoO3To replace the conventional SiO2Tungsten and molybdenum elements can greatly reduce the high-temperature viscosity and the surface tension of the molten glass at the high-temperature stage of the molten glass, so that the problem that the viscosity of the molten glass is higher at the high-temperature stage due to high magnesium-containing elements is well solved, the molten glass can well flow and corrode an insulating layer on the surface of a battery at the high-temperature stage, and excellent ohmic contact is formed; thus, the TeO of the present invention was produced2-MgO-Li2The high-temperature glass liquid has high viscosity and high surface tension, and the high-temperature glass liquid has low viscosity and low surface tension, so that the sintering aid for the silver powder has a good sintering effect, the grid line stripping strength is high, the corrosion effect on a glass interface is good, the contact effect is good, and the electrical property is excellent.
The invention uses TeO as the first state glass powder2-MgO-Li2The glass powder mainly consists of O, and the second state SiO is also used2-Bi2O3-CuO-Li2O mainly forms glass powder, the sintering assisting effect of the silver powder and the contact effect of the silver powder and the silver paste are further improved, the second-state glass powder is also low-lead or lead-free glass powder, the silicon content of the second-state glass powder is high, and the second-state glass powder contains higher bismuth oxide and copper oxide, so that the glass is softThe melting point is higher, the first state glass powder and the second state glass powder can be well fused when the mixing mass ratio of the first state glass powder to the second state glass powder is not less than 1:3, the softening point of the second state glass powder is higher than that of the first state glass powder by 50-150 ℃, the problem of low viscosity of the first-state glass powder in a high-temperature area is well solved, the silver layer is well sintered by the glass liquid in a high-temperature stage, and simultaneously, the first state glass liquid and the second state glass liquid are gradually fused with each other near the highest temperature zone of sintering, therefore, a large amount of silicon elements in the second-state glass liquid enter the first-state glass liquid, the destructiveness of the first-state glass liquid on the PN junction layer is reduced, the open pressure of the battery piece is improved, a large amount of silver elements melted in the first-state glass liquid are promoted to be separated out, and a better contact effect and lower contact resistance are formed on a contact interface, and the electrical property of the battery is improved.
The conductive silver paste provided by the invention comprises first-state glass powder and second-state glass powder, has excellent burning-assisting effect, greatly improves the peeling strength of grid lines, meets the requirement of using the peeling strength on various battery pieces, combines the characteristics of the first-state glass powder and the second-state glass powder, and realizes excellent contact effect and excellent electrical property on the battery pieces with different characteristics.
The conductive silver paste provided by the invention can be compatible with battery pieces of various processes, the process for manufacturing the conductive silver paste is simple, the cost is low, the prepared silicon solar battery and the front electrode thereof relate to various types of battery front electrodes and batteries such as conventional polycrystal, polycrystalline black silicon, polycrystalline diamond wire, conventional single crystal battery, perc single crystal, Se-perc single crystal and the like, and the practicability is wide.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the scope of the present invention, therefore, the present invention is not limited by the appended claims.
Claims (12)
1. The glass powder suitable for conductive silver paste of the front electrode of the silicon solar cell is characterized by comprising first-state glass powder and second-state glass powder, wherein the first-state glass powder mainly comprises at least one of W or Mo element oxides, TeO2MgO and Li2O, the second state glass powder mainly comprises SiO2、Bi2O3CuO and Li2O。
2. The glass frit according to claim 1, wherein: the first-state glass powder also comprises a modified oxide, wherein the modified oxide is one or more of oxides formed by a first series of elements of Bi, Pb, Na, K, Al, Zn, Cu, Ca, Si, Ge, Tl, B, Ce, Ti, Fe, Sb, V, Sn, Pr, Sr and Ba or substances capable of decomposing to obtain the oxides formed by the first series of elements.
3. The glass frit according to claim 2, wherein: based on the total mole number of the oxides contained in the first state glass powder as 100%, the mole percentages of the oxides in the first state glass powder are as follows:
4. the glass frit according to claim 1, wherein the second state glass frit further comprises an additive, and the additive is one or more of an oxide formed by a second series element of Pb, Zn, W, Ge, B, Sb, Te, and Fe, or a substance which can be decomposed to obtain an oxide formed by the second series element.
5. The glass frit according to claim 4, wherein the second state glass frit comprises the following oxides in terms of mole percentage, based on the total mole number of the oxides of the second state glass frit being 100%:
6. the glass frit according to claim 1, wherein the glass frit has a particle size of 0.2 to 10.0 μm, the softening point of the first state glass frit is 50 to 150 ℃ lower than that of the second state glass frit, and the mixing mass ratio of the first state glass frit and the second state glass frit is not less than 1: 3.
7. The conductive silver paste suitable for the front electrode of the silicon solar cell is characterized in that the conductive silver paste comprises the following components in percentage by total weight of 100 percent:
79.00% -93.00% of silver powder;
0.50 to 6.00% of the first glass frit according to any of claims 1 to 6;
0.10 to 3.00% of a second state glass frit according to any of claims 1 to 6;
5.00 to 17.00 percent of organic carrier.
8. The conductive silver paste of claim 7, wherein the silver powder is spherical silver powder, the particle size of the silver powder is 0.5 to 4.0 μm, and the D50 is 1.0 to 2.0 μm.
9. The conductive silver paste of claim 7, wherein the organic vehicle comprises an organic solvent, an organic resin, a thickener, a defoamer and a curing agent, and the content of each component is as follows, based on 100% of the total weight of the organic vehicle:
10. a preparation method of conductive silver paste of a front electrode of a silicon solar cell is characterized by comprising the following steps:
preparing first-state glass powder and second-state glass powder, wherein the first-state glass powder comprises TeO and at least one of W or Mo element oxides2MgO and Li2O, the second state glass powder comprises SiO2、Bi2O3CuO and Li2O, the first-state glass powder or the second-state glass powder is prepared by mixing, melting, quenching, drying and crushing, and the raw materials of the first-state glass powder and the second-state glass powder are oxides of corresponding elements or substances capable of being decomposed by heating to obtain the oxides of the corresponding elements;
preparing an organic carrier, wherein the organic carrier comprises an organic solvent, organic resin, a thickening agent, a defoaming agent and a curing agent, and the organic carrier is prepared by mixing, heating in a water bath, centrifugally dispersing and cooling; and
providing silver powder, and mixing, stirring, rolling and filtering the silver powder, the first state glass powder, the second state glass powder and the organic carrier to obtain the conductive silver paste.
11. The front electrode of the silicon solar cell is characterized in that the front electrode is prepared by printing conductive silver paste of the front electrode of the silicon solar cell in any one of claims 7 to 9 on a crystalline silicon cell sheet in a screen printing or spraying manner, and drying and sintering the crystalline silicon cell sheet.
12. A silicon solar cell, characterized in that it comprises a front electrode as claimed in claim 11.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116453738A (en) * | 2023-03-27 | 2023-07-18 | 上海银浆科技有限公司 | Main grid silver paste, preparation method, electrode and silicon solar cell |
| CN116759133A (en) * | 2023-04-28 | 2023-09-15 | 上海银浆科技有限公司 | Conductive silver-aluminum paste, preparation method, electrode and N-type Topcon battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116453738A (en) * | 2023-03-27 | 2023-07-18 | 上海银浆科技有限公司 | Main grid silver paste, preparation method, electrode and silicon solar cell |
| CN116759133A (en) * | 2023-04-28 | 2023-09-15 | 上海银浆科技有限公司 | Conductive silver-aluminum paste, preparation method, electrode and N-type Topcon battery |
| CN116759133B (en) * | 2023-04-28 | 2024-04-30 | 上海银浆科技有限公司 | Conductive silver-aluminum paste, preparation method, electrode and N-type Topcon battery |
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