CN114822909A - Crystalline silicon solar cell silver-aluminum paste for low-temperature sintering, preparation method and application - Google Patents
Crystalline silicon solar cell silver-aluminum paste for low-temperature sintering, preparation method and application Download PDFInfo
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- CN114822909A CN114822909A CN202210467240.7A CN202210467240A CN114822909A CN 114822909 A CN114822909 A CN 114822909A CN 202210467240 A CN202210467240 A CN 202210467240A CN 114822909 A CN114822909 A CN 114822909A
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- silver
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- crystalline silicon
- solar cell
- silicon solar
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- -1 silver-aluminum Chemical compound 0.000 title claims abstract description 96
- 229910021419 crystalline silicon Inorganic materials 0.000 title claims abstract description 89
- 238000009766 low-temperature sintering Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 127
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000011521 glass Substances 0.000 claims abstract description 45
- 239000002270 dispersing agent Substances 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 29
- 229910052709 silver Inorganic materials 0.000 claims abstract description 29
- 239000004332 silver Substances 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 8
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 6
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims description 4
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 4
- 239000001856 Ethyl cellulose Substances 0.000 claims description 4
- 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 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004359 castor oil Substances 0.000 claims description 4
- 235000019438 castor oil Nutrition 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 4
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 4
- 229920001249 ethyl cellulose Polymers 0.000 claims description 4
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- 229940116411 terpineol Drugs 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- IFPMZBBHBZQTOV-UHFFFAOYSA-N 1,3,5-trinitro-2-(2,4,6-trinitrophenyl)-4-[2,4,6-trinitro-3-(2,4,6-trinitrophenyl)phenyl]benzene Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C(C=2C(=C(C=3C(=CC(=CC=3[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)C(=CC=2[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)=C1[N+]([O-])=O IFPMZBBHBZQTOV-UHFFFAOYSA-N 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229920002396 Polyurea Polymers 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 3
- 229960001826 dimethylphthalate Drugs 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000005313 fatty acid group Chemical group 0.000 claims description 3
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 3
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 2
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 2
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- 239000012748 slip agent Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 abstract description 7
- 238000005275 alloying Methods 0.000 abstract description 6
- 230000001788 irregular Effects 0.000 abstract description 4
- 238000012163 sequencing technique Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 230000000694 effects Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920005591 polysilicon Polymers 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 1
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910003069 TeO2 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PZFKDUMHDHEBLD-UHFFFAOYSA-N oxo(oxonickeliooxy)nickel Chemical compound O=[Ni]O[Ni]=O PZFKDUMHDHEBLD-UHFFFAOYSA-N 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
Landscapes
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Sustainable Development (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Sustainable Energy (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Spectroscopy & Molecular Physics (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 a crystalline silicon solar cell silver-aluminum paste for low-temperature sintering, a preparation method and application thereof, wherein the crystalline silicon solar cell silver-aluminum paste comprises the following components: 84.0-90.0 parts of conductive silver powder, 0.7-5.0 parts of nano aluminum powder pre-dispersion, 2.0-8.0 parts of glass powder, 4.0-9.0 parts of organic solvent, 0.1-1.0 part of resin, 0.1-1.0 part of organic dispersant, 0.05-1.0 part of thixotropic agent and 0.1-1.0 part of slipping agent; the conductive silver powder is submicron or micron silver powder, and the particle size of the nano aluminum powder is 50-300 nm. 50-300 nm of nano aluminum powder is introduced into the silver-aluminum paste of the crystalline silicon solar cell, the temperature for fusing the nano aluminum powder and the conductive silver powder is reduced by utilizing the irregular atom sequencing characteristic of the surface of the nano aluminum powder, the sintering temperature of the original front silver-aluminum paste can be reduced from 760-780 ℃ to 720-750 ℃, and the sintering temperature is obviously reduced. Through the matching of the nano aluminum powder and the conductive silver powder, the alloying of silver and aluminum is formed, and the contact resistance between the silver layer and the crystalline silicon solar cell substrate is effectively reduced.
Description
Technical Field
The invention relates to the field of photovoltaic electronic paste, in particular to silver-aluminum paste for a crystalline silicon solar cell for low-temperature sintering, a preparation method and application.
Background
With the rapid development of photovoltaic technology, high-efficiency crystalline silicon solar cells gradually become the mainstream of the photovoltaic industry due to the characteristics of high conversion efficiency, long service life and the like, and conventional cells with relatively low efficiency gradually exit the market. At present, PERC high-efficiency crystalline silicon solar cells are the main technical route, and the n-type cell technology is also rapidly developed. According to prediction of photovoltaic market by ITRPV research institution in 2020, n-type cell accounts for about 10% of photovoltaic market in 2020, and 42% of market share after 2029.
The N-type solar cell mainly comprises an HJT cell, an N-type Topcon crystalline silicon solar cell and an IBC cell, wherein except the HJT cell which uses low-temperature silver paste, the rest cells all use high-temperature silver aluminum paste/silver paste. The N-type Topcon crystalline silicon solar cell is firstly developed by a Fronofur solar research institute, combines new technologies such as thermal oxide film passivation and polycrystalline silicon film contact, has the characteristics of high open voltage, large current, high FF and the like, and becomes an important subject of research of large-scale photovoltaic cell companies/research institutions in China in two years. The N-TOPCon battery is a further upgrade of the N-PERT technology, and the current industrialized manufacturers mainly include China photovoltaic, forestry and ocean technology, crystallography energy, Tongwei solar energy, English and the like. Although the current problems are more and the process is more complex, the batch efficiency reaches about 24.0 percent. The highest efficiency of the large-size N-type polycrystalline i-TOPCon battery prepared by the solar energy in the celestial world is recorded to be 24.58%, and the N-type TOPCon battery has potential competitiveness.
However, the back surface of the N-type TOPCon crystalline silicon solar cell adopts the structural design of a 1-2 nm tunnel oxide layer, a 100nm polysilicon film and a passivation layer, and the corrosivity of the silver paste on the back surface is required to be lower; meanwhile, the doping concentration of the surface of the positive p + layer is low, good ohmic contact cannot be formed by pure positive silver paste, and good work function matching with p + can be formed by adopting positive silver-aluminum paste.
The existing silver-aluminum paste for the solar cell generally needs high-temperature sintering at 760-780 ℃, the sintering temperature is high, and the problem of burning through a back polysilicon film and a tunnel oxide layer easily occurs. Moreover, the pinning effect of the front silver-aluminum paste is more obvious, the metal induced recombination speed is obviously increased, and the characteristics of high open pressure and high conversion efficiency are not favorably realized. If the existing silver-aluminum paste formula is sintered at 720-750 ℃, the contact performance is poor, the contact resistivity is high, and the conversion efficiency is low. With the development of the N-type TOPCon crystalline silicon solar cell, the polycrystalline silicon film on the back surface of the N-type TOPCon crystalline silicon solar cell is thinner and thinner, and is more sensitive to the sintering temperature, and higher requirements are put forward on the matching performance of front silver-aluminum paste.
Disclosure of Invention
The invention aims to provide crystalline silicon solar cell silver-aluminum paste for low-temperature sintering, a preparation method and application thereof, and aims to solve the problems that in the prior art, the solar cell silver-aluminum paste is high in sintering temperature and is easy to burn through a back polysilicon film and a tunnel oxide layer.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a crystalline silicon solar cell silver-aluminum paste for low-temperature sintering, which comprises the following components in parts by weight:
the nano aluminum powder pre-dispersion comprises 0.2-2.0 parts of nano aluminum powder coating agent and 0.5-3.0 parts of nano aluminum powder; the nano aluminum powder coating agent is coated on the outer side of the nano aluminum powder; the conductive silver powder is submicron or micron silver powder, and the particle size of the nano aluminum powder is 50-300 nm.
In the crystalline silicon solar cell silver-aluminum paste for low-temperature sintering, the particle size of the conductive silver powder is 0.5-3.0 microns, the tap density of the conductive silver powder is 4.0-7.0 g/cm3, and the specific surface area of the conductive silver powder is 0.1-2.0 cm 2/g.
In the crystalline silicon solar cell silver-aluminum paste for low-temperature sintering, the nano aluminum powder coating agent comprises one or more of an organic silicon dispersing agent, an alkane dispersing agent and a siloxane dispersing agent.
In the crystalline silicon solar cell silver-aluminum paste for low-temperature sintering, the ratio of the nano aluminum powder coating agent to the nano aluminum powder is 1: 9-9: 1.
In the silver-aluminum paste for the low-temperature sintered crystalline silicon solar cell, the glass powder comprises the following components in parts by weight: 40-80 parts of PbO, 5-20 parts of B2O3, 0.2-10 parts of SiO2, 0.1-6 parts of Al2O3, 2-15 parts of ZnO and 0-10 parts of modified oxide;
the modified oxide comprises one or more of Li2O, Na2O, Sb2O3, V2O5, TeO2, Ga2O3, In2O3, GeO2, MgO, BaO, CaO, Ni2O3, Ag2O and Tl2O 3.
In the crystalline silicon solar cell silver-aluminum paste for low-temperature sintering, the slipping agent comprises one or more of silicone oil, oleamide and erucamide; the thixotropic agent comprises one or more combinations of hydrogenated castor oil, polyamide wax and polyurea.
In the silver-aluminum paste for the low-temperature sintered crystalline silicon solar cell, the resin comprises one or more of ethyl cellulose, polyvinyl butyral, acrylic resin and aldehyde ketone resin; the organic solvent comprises any two or more of diethylene glycol butyl ether acetate, alcohol ester dodeca, terpineol, diethylene glycol butyl ether acetate, dimethyl adipate, N-methyl pyrrolidone, dimethyl phthalate and dimethyl terephthalate; the organic dispersant includes one or more combinations of an amine functional group-containing dispersant and a fatty acid functional group-containing dispersant.
The silver-aluminum paste for the low-temperature sintered crystalline silicon solar cell further comprises 0-1.0 part of organic auxiliary agent, wherein the organic auxiliary agent comprises one or more of a flatting agent, an organic silicon defoaming agent, a silane coupling agent and a titanate coupling agent.
The invention also provides a preparation method of the crystalline silicon solar cell silver-aluminum paste for low-temperature sintering, which is used for the crystalline silicon solar cell silver-aluminum paste for low-temperature sintering and comprises the following steps:
preparing a nano aluminum powder pre-dispersion: mixing and stirring the nano aluminum powder and the nano aluminum powder coating agent according to the proportion to obtain a nano aluminum powder pre-dispersion;
preparing and mixing: weighing conductive silver powder, a nano aluminum powder pre-dispersion body, glass powder, an organic solvent, resin, an organic dispersant, a thixotropic agent, a slipping agent and an organic auxiliary agent according to the proportion, and mixing and stirring to obtain a semi-finished silver paste;
rolling: and grinding the semi-finished silver paste to obtain the crystalline silicon solar cell silver-aluminum paste for low-temperature sintering.
The invention also provides application of the silver-aluminum paste for the crystalline silicon solar cell for low-temperature sintering, and the crystalline silicon solar cell silver-aluminum paste for low-temperature sintering is used for preparing the TOPCon crystalline silicon solar cell, wherein the sintering temperature of the TOPCon crystalline silicon solar cell is 720-750 ℃.
One technical scheme in the invention can have the following beneficial effects:
the crystalline silicon solar cell silver-aluminum paste for low-temperature sintering is introduced with 50-300 nm of nano aluminum powder, the temperature for fusing the nano aluminum powder and the conductive silver powder is reduced by utilizing the irregular atom sequencing characteristic of the surface of the nano aluminum powder, silver-aluminum alloying is formed, the sintering temperature of the original front silver-aluminum paste can be reduced from 760-780 ℃ to 720-750 ℃, and the sintering temperature is obviously reduced. Through the matching of the nano aluminum powder and the conductive silver powder, the alloying of the silver and the aluminum is formed, the contact resistance between the silver layer and the crystalline silicon solar cell substrate is effectively reduced, and the metal induced recombination speed of the crystalline silicon solar cell substrate is reduced.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. In order to facilitate an understanding of the present invention, a more complete description of the present invention is provided below. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides a crystalline silicon solar cell silver-aluminum paste for low-temperature sintering, which comprises the following components in parts by weight:
the nano aluminum powder pre-dispersion comprises 0.2-2.0 parts of nano aluminum powder coating agent and 0.5-3.0 parts of nano aluminum powder; the nano aluminum powder coating agent is coated on the outer side of the nano aluminum powder; the conductive silver powder is submicron or micron silver powder, and the particle size of the nano aluminum powder is 50-300 nm.
According to the invention, 50-300 nm nanometer aluminum powder is introduced, the temperature for fusing the nanometer aluminum powder and the conductive silver powder is reduced by utilizing the irregular atom sequencing characteristic of the surface of the nanometer aluminum powder, the silver-aluminum alloying is formed, the sintering temperature of the original front silver-aluminum paste can be reduced from 760-780 ℃ to 720-750 ℃, and the sintering temperature is obviously reduced. Through the matching of the nano aluminum powder and the conductive silver powder, the alloying of the silver and the aluminum is formed, the contact resistance between the silver layer and the crystalline silicon solar cell substrate is effectively reduced, and the metal induced recombination speed of the crystalline silicon solar cell substrate is reduced.
In the specific application process, the thickness of a polycrystalline silicon film of the N-type TOPCon crystalline silicon solar cell and the infrared absorption effect of the back of the N-type TOPCon crystalline silicon solar cell can be reduced by matching with back silver paste suitable for low-temperature sintering at the temperature of 720-750 ℃, and the productivity and the conversion efficiency of the N-type TOPCon crystalline silicon solar cell are effectively improved.
The silver-aluminum paste contains a large amount of hydroxyl on the surface of aluminum powder, so that the silver-aluminum paste is easy to adsorb solvent and resin, the content of aluminum powder is too high, the viscosity is large, and the printability is poor. In addition, when the content of aluminum powder in the silver-aluminum paste is too high, the resistance of the silver-aluminum layer is high, the pinning effect is also high, and the open-circuit voltage is obviously reduced.
The silver-aluminum paste of the crystalline silicon solar cell uses nano aluminum powder with the particle size of 50-300 nm. Compared with micron-sized aluminum powder, the nano-sized aluminum powder can be more effectively contacted with the conductive silver powder, so that the using amount of the aluminum powder can be reduced, and the effects of improving the printability of the balance silver-aluminum paste and reducing the contact resistivity are achieved. In the embodiment of the invention, the particle size of the nano aluminum powder is preferably 100-200 nm. When the particle size of the nano aluminum powder is larger than 300nm, the silver-aluminum paste cannot effectively realize the low-temperature sintering effect of 720-750 ℃. And when the particle size of the nano aluminum powder is less than 50nm, the specific surface area is large, the silver-aluminum-containing paste is easy to agglomerate, and the printability of the silver-aluminum paste is reduced.
The nano aluminum powder with the particle size of 50 nm-300 nm has strong activity, and can be rapidly oxidized in the naked air, even spontaneously combusted and exploded. The silver-aluminum paste of the crystalline silicon solar cell is prepared by modifying and coating the surface of the nano aluminum powder by the nano aluminum powder coating agent, so that the nano silver powder can be stored and used at normal temperature, and the prepared silver-aluminum paste can be used at normal temperature and has long quality guarantee period.
In the low-temperature sintering process at the temperature of 720-750 ℃, the nano aluminum powder coated with the nano aluminum powder coating agent is adsorbed on the surface of the conductive silver powder, and before the nano aluminum powder coating agent on the surface of the nano aluminum powder is volatilized, the nano aluminum powder and the conductive silver powder can be subjected to silver-aluminum alloying to form a silver-aluminum electrode, so that the ohmic contact between the silver-aluminum electrode and the p + layer substrate is realized. Meanwhile, the nano aluminum powder which is small in size and large in quantity and is wrapped by the nano aluminum powder wrapping agent can be uniformly distributed in a silver-aluminum paste system, so that more ohmic contact points are realized, the using amount of the aluminum powder is reduced, and the purpose of reducing the volume resistivity of the silver-aluminum electrode is achieved.
Specifically, the particle diameter of the conductive silver powder is 0.5-3.0 mu m, and the tap density of the conductive silver powder is 4.0-7.0 g/cm 3 The specific surface area of the conductive silver powder is 0.1-2.0 cm 2 /g。
By adopting the conductive silver powder, the silver-aluminum alloy of the conductive silver powder and the nano aluminum powder can be ensured to be realized at the temperature of 720-750 ℃, the contact resistance of the silver layer and the substrate is reduced, and the metal induced composition of the substrate is realized. In a preferred embodiment of the present invention, the conductive silver powder is spherical or quasi-spherical, the particle diameter of the conductive silver powder is 1.0 to 2.5 μm, and the tap density of the conductive silver powder is 4.5 to 6.0g/cm 3 The specific surface area of the conductive silver powder is 0.5-1.5 cm 2 /g。
Specifically, the nano aluminum powder coating agent comprises one or more of organic silicon dispersing agent, alkane dispersing agent and siloxane dispersing agent.
The preparation method of the nano aluminum powder comprises but is not limited to nitrogen atomization, electric explosion method and chemical reduction method. The organic silicon dispersing agent, the alkane dispersing agent and the siloxane dispersing agent belong to low-activity substances, do not react with the nano aluminum powder, and can volatilize at the temperature of 720-750 ℃. The nano aluminum powder coating agent is coated on the surface of the nano aluminum powder, the surface of the nano aluminum powder is modified and coated, and the nano aluminum powder is passivated at normal temperature, so that the nano aluminum powder is prevented from being rapidly oxidized in the air.
Specifically, the ratio of the nano aluminum powder coating agent to the nano aluminum powder is 1: 9-9: 1. By adopting the proportion, the nano aluminum powder coating agent fully coats the nano aluminum powder, so that the problem of rapid oxidation of the aluminum powder caused by exposure of the nano aluminum powder in the air is avoided.
Specifically, the glass powder comprises the following components in parts by weight: 40-80 parts of PbO and 5-20 parts of B 2 O 3 0.2 to 10 parts of SiO 2 0.1 to 6 parts of Al 2 O 3 2-15 parts of ZnO and 0-10 parts of modified oxide;
the modified oxide includes Li 2 O、Na 2 O、Sb 2 O 3 、V 2 O 5 、TeO 2 、Ga 2 O 3 、In 2 O 3 、GeO 2 、MgO、BaO、CaO、Ni 2 O 3 、Ag 2 O and Tl 2 O 3 One or more combinations thereof.
In the specific embodiment of the invention, the glass powder is prepared by a high-temperature smelting quenching method, and the specific steps comprise: proportioning according to the formula proportion of the glass powder, and uniformly mixing the raw materials by using a high-speed mixer; after mixing, putting the raw materials into a high-temperature-resistant crucible for smelting at 1000-1300 ℃, and keeping the temperature for 30-90 min; introducing the high-temperature molten glass liquid into cooling water or a cooling roller for quenching to obtain glass slag or glass sheets; crushing the mixture into glass powder by a water quenching ball milling method or a jet milling method, and then drying the glass powder. The average particle size of the glass powder is 0.5-5 μm, and in a preferred embodiment, the average particle size of the glass powder is 1-2 μm.
In the sintering process, the glass powder can effectively melt silicon nitride, an ultrathin glass layer is formed on the interface of the silicon substrate, and a large number of nano silver microcrystals are formed in the glass layer, so that the resistivity of the glass layer body can be effectively reduced.
Specifically, the slipping agent comprises one or more of silicone oil, oleamide and erucamide; the thixotropic agent comprises one or more combinations of hydrogenated castor oil, polyamide wax and polyurea.
The slipping agent can reduce the frictional resistance between the silver-aluminum paste and the screen printing plate, improve the screen passing characteristic of the paste and avoid the screen blocking after long-time printing. The thixotropic agent can ensure the low viscosity characteristic of the silver-aluminum paste under high shearing force, improve the surface leveling characteristic of the paste after passing through the net and ensure good flat line shape.
Specifically, the resin comprises one or more of ethyl cellulose, polyvinyl butyral, acrylic resin and aldehyde ketone resin; the organic solvent comprises any two or more of diethylene glycol butyl ether acetate, alcohol ester dodeca, terpineol, diethylene glycol butyl ether acetate, dimethyl adipate, N-methyl pyrrolidone, dimethyl phthalate and dimethyl terephthalate; the organic dispersant includes one or more combinations of an amine functional group-containing dispersant and a fatty acid functional group-containing dispersant.
By adopting the resin, the printing effect of the paste can be effectively improved, the good height-width ratio is ensured, and the short-circuit current density of the solar cell is improved. The solvent has the functions of dissolving resin, reducing the viscosity of the paste, improving the printability and promoting the leveling of the paste.
The organic dispersing agent can effectively enhance the wetting effect on the conductive silver powder and the nano aluminum powder, adjust the viscosity difference of the silver-aluminum paste in high and low rotating speeds, more effectively contact the nano aluminum powder with the conductive silver powder and reduce the volume resistivity characteristic. In a specific embodiment of the present invention, the organic dispersant may be a BYK110 organic dispersant, or a Tego655 organic dispersant.
Optionally, the crystalline silicon solar cell silver-aluminum paste for low-temperature sintering further comprises 0-1.0 part of organic auxiliary agent, wherein the organic auxiliary agent comprises one or more of a leveling agent, an organic silicon defoaming agent, a silane coupling agent and a titanate coupling agent.
The organic auxiliary agent can be added according to the actual production requirement, and the leveling agent can effectively reduce the surface tension of the silver-aluminum paste and improve the leveling property and uniformity of the silver-aluminum paste; the organic silicon defoaming agent can reduce the surface tension of the silver-aluminum paste and prevent the formation of foam; the silane coupling agent and the titanate coupling agent play a role in improving the dispersion degree of the conductive silver powder and the nano aluminum powder.
The invention also provides a preparation method of the crystalline silicon solar cell silver-aluminum paste for low-temperature sintering, which is used for preparing the crystalline silicon solar cell silver-aluminum paste for low-temperature sintering and comprises the following steps:
preparing a nano aluminum powder pre-dispersion: mixing and stirring the nano aluminum powder and the nano aluminum powder coating agent according to the proportion to obtain a nano aluminum powder pre-dispersion;
preparing and mixing: weighing conductive silver powder, a nano aluminum powder pre-dispersion body, glass powder, an organic solvent, resin, an organic dispersant, a thixotropic agent, a slipping agent and an organic auxiliary agent according to the proportion, and mixing and stirring to obtain a semi-finished silver paste;
rolling: and grinding the semi-finished silver paste to obtain the crystalline silicon solar cell silver-aluminum paste for low-temperature sintering.
In the step of preparing the nano aluminum powder pre-dispersion, the nano aluminum powder soft aggregate is fully opened and uniformly distributed in the nano aluminum powder coating agent, so that the surface of the nano aluminum powder is prevented from being excessively oxidized. And then, fully mixing the conductive silver powder, the nano aluminum powder pre-dispersion body, the glass powder, the organic solvent, the resin, the organic dispersing agent, the thixotropic agent, the slipping agent and the organic auxiliary agent through the steps of material mixing and mixing, so that the conductive silver powder and the nano aluminum powder pre-dispersion body are wetted by the resin and the organic solvent. In the rolling process, parameters such as different roller gaps, grinding speed, grinding times and the like can be adjusted according to actual requirements, so that the semi-finished silver paste is ground to the fineness of below 10 mu m, and the crystalline silicon solar cell silver-aluminum paste for low-temperature sintering is obtained.
The invention also provides application of the silver-aluminum paste for the crystalline silicon solar cell for low-temperature sintering, and the crystalline silicon solar cell silver-aluminum paste for low-temperature sintering is used for preparing the TOPCon crystalline silicon solar cell, wherein the sintering temperature of the TOPCon crystalline silicon solar cell is 720-750 ℃.
The crystalline silicon solar cell silver-aluminum paste for low-temperature sintering can be used as the front silver-aluminum paste of the TOPCon crystalline silicon solar cell and used for preparing the TOPCon crystalline silicon solar cell. The silver-aluminum paste of the crystalline silicon solar cell utilizes the irregular atom sequencing characteristic of the surface of the aluminum powder with the nanometer size to reduce the fusion temperature of the nanometer aluminum powder and the conductive silver powder, so that the sintering temperature of the TOPCon crystalline silicon solar cell is reduced to 720-750 ℃, and the requirement of low-temperature sintering of the TOPCon crystalline silicon solar cell is met.
Example group A
Preparing glass powder: batching according to the formula of the glass powder raw materials in the weight parts in the table 1; smelting the glass for 60min at 1200 ℃ by using a high-temperature smelting furnace, and after the glass is fully molten, rapidly cooling the glass liquid by using a water quenching method to obtain glass slag; rapidly ball-milling the glass slag by using a planetary ball mill filled with zirconium beads to ensure that the particle size of the glass powder is 2.5-3.0 um, and filtering the glass liquid by using a 250-mesh screen plate; and drying the glass liquid by using an oven to obtain the glass powder.
TABLE 1 glass powder raw material weight part formulation
Example group B
The preparation method of the silver-aluminum paste for the crystalline silicon solar cell comprises the following steps:
preparing a nano aluminum powder pre-dispersion: mixing and stirring the nano aluminum powder and the nano aluminum powder coating agent according to the proportion shown in the table 2 to obtain a nano aluminum powder pre-dispersion;
preparing and mixing: weighing conductive silver powder, a nano aluminum powder pre-dispersion body, glass powder, an organic solvent, resin, an organic dispersant, a thixotropic agent, a slipping agent and an organic auxiliary agent according to the proportion in the table 2, and mixing and stirring to obtain a semi-finished silver paste;
rolling: and grinding the semi-finished silver paste by using a three-roll grinder, and evaluating the fineness by using a scraper fineness meter, wherein the grinding fineness of the slurry is below 10 mu m, so that the silver-aluminum paste for the crystalline silicon solar cell for low-temperature sintering is obtained.
TABLE 2 silver aluminium paste composition
Wherein the particle diameter of the conductive silver powder in Table 2 is 1.0-2.5 μm, and the tap density of the conductive silver powder is 4.5-6.0 g/cm 3 The specific surface area of the conductive silver powder is 0.5-1.5 cm 2 (ii) in terms of/g. The glass frit used in example 4 was the glass frit used in example 1, the glass frit used in example 2 was the glass frit used in examples 5 and 7 to 9, and the glass frit used in example 3 was the glass frit used in example 6.
In examples 4 to 6, the average particle size of the nano aluminum powder is 50 to 60nm, the nano aluminum powder coating agent is an organic silicon dispersant, the slipping agent is silicone oil, the thixotropic agent is hydrogenated castor oil, the resin is ethyl cellulose, the organic solvent is a mixture of diethylene glycol butyl ether acetate and alcohol ester twelve, and the organic dispersant is BYK110 in a commercial model.
In examples 7 to 9, the average particle size of the nano aluminum powder is 80 to 100nm, the nano aluminum powder coating agent is a siloxane dispersant, the slipping agent is erucamide, the thixotropic agent is polyamide wax, the resin is aldehyde ketone resin, the organic solvent is terpineol mixed with dimethyl adipate, the organic dispersant is Tego655, and the organic auxiliary agent is an organic silicon defoamer.
Comparative example 1
The preparation method of the comparative example 1 is consistent with that of the example 1, and the difference is that the components of the comparative example 1 comprise 83 parts of conductive silver powder, 7 parts of glass powder described in the example 1, 1 part of aluminum powder with the average particle size of 1.5-2.0 um, and the rest of other components are consistent with those of the example 1.
Comparative example 2
The preparation method of the comparative example 1 is consistent with that of the example 1, and the difference is that the components of the comparative example 2 comprise 83 parts of conductive silver powder, 5 parts of glass powder described in the example 2, 2 parts of aluminum powder with the average particle size of 2.0-3.0 um, and the rest of the components are consistent with those of the example 1.
Comparative example 3
The preparation method of the comparative example 1 is consistent with that of the example 1, and the difference is that the components of the comparative example 3 comprise 84 parts of conductive silver powder, 3 parts of glass powder described in the example 3, 3 parts of aluminum powder with the average particle size of 3.0-4.0 um, and the rest of other components are consistent with those of the example 1.
The silver-aluminum paste for the crystalline silicon solar cell for low-temperature sintering, prepared in the embodiments 2-7 and the comparative examples 1-3, is applied to a TOPCon crystalline silicon solar cell, and the specific cell preparation comprises the following steps:
carrying out front cleaning, texturing and rear cleaning on the N-type crystal silicon wafer, then forming a front p + layer through a high-temperature diffusion or plasma doping process, forming a tunnel oxide layer on the back through an oxidation process, and depositing by LPCVD or APCVD equipment to form a back polycrystalline silicon film. And forming a front and back passivation dielectric film by LPCVD, ALD or the like. And printing silver-aluminum paste of the crystalline silicon solar cell on the front surface of the TOPCon semi-finished blue membrane in a screen printing or ink-jet printing mode, and printing silver paste on the back surface of the TOPCon semi-finished blue membrane in the same way. After the drying and sintering process, the silver-aluminum paste of the crystalline silicon solar cell and the silver paste on the back surface are volatilized organically, the glass powder is softened, and the silver powder, the aluminum powder or other inorganic powder is wetted. The glass powder of the silver-aluminum paste of the crystalline silicon solar cell is melted at high temperature, and the front surface dielectric film and a small amount of p + layer substrate are melted, and meanwhile, the conductive silver powder is alloyed with the nano-aluminum powder, so that the silver-aluminum alloy and the substrate are promoted to form good ohmic contact, and the ultrathin glass film and the substrate are promoted to form good ohmic contact. The back silver paste also melts the dielectric film such as back silicon nitride, and forms good ohmic contact with the back polysilicon film. After the process, a complete TOPCon crystalline silicon solar cell is formed.
The contact resistivity of the silver layer to the substrate was evaluated by using the conventional four-probe method (TLM), and the bulk resistivity of the silver layer was evaluated by using an ohmic resistance tester. The conversion efficiency of the solar cell was evaluated using a current-voltage electrical tester (IV tester) commonly used for solar cells, and the test results are shown in table 3.
TABLE 3-TOPCon crystalline silicon solar cell Electrical Properties and contact resistivities
The sintering temperature is 750 ℃, in the electrical property, Voc is open-circuit voltage, Isc is short-circuit current, FF is a filling factor, Rs is series resistance, Rsh is parallel resistance, Eta is conversion efficiency, and Irev2 is saturated leakage current.
The nano-scale aluminum powder is introduced into the silver-aluminum paste of the crystalline silicon solar cell, so that the deep pinning effect of the micro-scale aluminum powder or aluminum-silicon alloy powder on the silicon substrate can be reduced, the destructive effect of active aluminum on a p-n junction is reduced, the effective contact area of a silver-aluminum layer electrode and the silicon substrate is increased under the condition of the same aluminum content, and the contact resistance of the silver electrode and the substrate is reduced. According to the test results shown in table 3, the design of the comparative examples 1 to 3 with the micron aluminum powder is adopted, and along with the increase of the content of the micron aluminum powder, the content of aluminum actually participating in the contact of the silicon substrate is increased, the contact resistivity is sharply reduced, and the series resistance is smaller and smaller. In contrast, in comparative examples 4 to 6 and examples 7 to 9, the contact resistivity decreased with the increase in the content of the nano-aluminum powder in the content range of the nano-aluminum powder. As can be seen from the embodiment group B and the comparative examples 1-3, the introduction of the nano aluminum powder can effectively balance the relationship between the open-circuit voltage and the contact resistance, and the filling factor is improved, so that the conversion efficiency of the TOPCon crystalline silicon solar cell is improved, and the micron-sized aluminum powder cannot achieve the effect.
The crystalline silicon solar cell silver-aluminum paste prepared in example 8 and comparative example 2 was sintered at 730 ℃ and 750 ℃ to prepare TOPCon crystalline silicon solar cells, and the prepared TOPCon crystalline silicon solar cells were subjected to electrical property data and contact resistivity tests, and the test results are shown in table 4.
TABLE 4 TOPCon crystalline silicon solar cell and contact resistivity at different sintering temperatures
As can be seen from table 4, comparative example 2 using the micron aluminum powder resulted in a significant increase in series resistance, a significant decrease in the filled silver FF, and a large fluctuation in conversion efficiency with a decrease in sintering temperature. While low temperature sintering had little effect on example 8 using nano-aluminum powder. Therefore, when the crystalline silicon solar cell silver-aluminum paste is applied to preparation of the TOPCon crystalline silicon solar cell, the sintering temperature can be effectively reduced, higher conversion efficiency is ensured, and the development requirement of low-temperature sintering of the TOPCon crystalline silicon solar cell can be met.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be taken in any way as limiting the scope of the invention. Other embodiments of the invention will occur to those skilled in the art without the exercise of inventive faculty based on the explanations herein, and such equivalent modifications or substitutions are intended to be included within the scope of the present invention as defined in the appended claims.
Claims (10)
1. The silver-aluminum paste for the crystalline silicon solar cell for low-temperature sintering is characterized by comprising the following components in parts by weight:
the nano aluminum powder pre-dispersion comprises 0.2-2.0 parts of nano aluminum powder coating agent and 0.5-3.0 parts of nano aluminum powder; the nano aluminum powder coating agent is coated on the outer side of the nano aluminum powder; the conductive silver powder is submicron or micron silver powder, and the particle size of the nano aluminum powder is 50-300 nm.
2. The silver-aluminum paste for the crystalline silicon solar cell for low-temperature sintering as claimed in claim 1, wherein the particle size of the conductive silver powder is 0.5-3.0 μm, and the tap density of the conductive silver powder is 4.0-7.0 g/cm 3 The specific surface area of the conductive silver powder is 0.1-2.0 cm 2 /g。
3. The silver-aluminum paste for the crystalline silicon solar cell for low-temperature sintering as claimed in claim 1, wherein the nano aluminum powder coating agent comprises one or more of organosilicon dispersant, alkane dispersant and siloxane dispersant.
4. The silver-aluminum paste for the low-temperature sintered crystalline silicon solar cell of claim 1, wherein the ratio of the nano aluminum powder coating agent to the nano aluminum powder is 1: 9-9: 1.
5. The silver-aluminum paste for the low-temperature sintered crystalline silicon solar cell of claim 1, wherein the glass powder comprises the following components in parts by weight: 40-80 parts of PbO and 5-20 parts of B 2 O 3 0.2 to 10 parts of SiO 2 0.1-6 parts of Al 2 O 3 2-15 parts of ZnO and 0-10 parts of modified oxide;
the modified oxide includes Li 2 O、Na 2 O、Sb 2 O 3 、V 2 O 5 、TeO 2 、Ga 2 O 3 、In 2 O 3 、GeO 2 、MgO、BaO、CaO、Ni 2 O 3 、Ag 2 O and Tl 2 O 3 One or more of the above.
6. The silver-aluminum paste for the low-temperature sintered crystalline silicon solar cell of claim 1, wherein the slip agent comprises one or more of silicone oil, oleamide and erucamide; the thixotropic agent comprises one or more combinations of hydrogenated castor oil, polyamide wax and polyurea.
7. The silver-aluminum paste for the low-temperature sintered crystalline silicon solar cell as claimed in claim 1, wherein the resin comprises one or more of ethyl cellulose, polyvinyl butyral, acrylic resin and aldehyde ketone resin; the organic solvent comprises any two or more of diethylene glycol butyl ether acetate, alcohol ester dodeca, terpineol, diethylene glycol butyl ether acetate, dimethyl adipate, N-methyl pyrrolidone, dimethyl phthalate and dimethyl terephthalate; the organic dispersant includes one or more combinations of an amine functional group-containing dispersant and a fatty acid functional group-containing dispersant.
8. The silver-aluminum paste for the crystalline silicon solar cell sintered at the low temperature of claim 1, further comprising 0-1.0 part of an organic assistant, wherein the organic assistant comprises one or more of a leveling agent, an organic silicon defoamer, a silane coupling agent and a titanate coupling agent.
9. A preparation method of crystalline silicon solar cell silver-aluminum paste for low-temperature sintering is used for preparing the crystalline silicon solar cell silver-aluminum paste for low-temperature sintering as claimed in any one of claims 1-8, and is characterized by comprising the following steps:
preparing a nano aluminum powder pre-dispersion: mixing and stirring the nano aluminum powder and the nano aluminum powder coating agent according to the proportion to obtain a nano aluminum powder pre-dispersion;
preparing and mixing: weighing conductive silver powder, a nano aluminum powder pre-dispersion body, glass powder, an organic solvent, resin, an organic dispersant, a thixotropic agent, a slipping agent and an organic auxiliary agent according to the proportion, and mixing and stirring to obtain a semi-finished silver paste;
rolling: and grinding the semi-finished silver paste to obtain the crystalline silicon solar cell silver-aluminum paste for low-temperature sintering.
10. Use of the crystalline silicon solar cell silver-aluminum paste for low-temperature sintering for preparing TOPCon crystalline silicon solar cells, which is prepared by using the crystalline silicon solar cell silver-aluminum paste for low-temperature sintering of any one of claims 1-8, wherein the sintering temperature of the TOPCon crystalline silicon solar cells is 720-750 ℃.
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| CN115881338A (en) * | 2022-12-28 | 2023-03-31 | 广东南海启明光大科技有限公司 | Front-side silver-aluminum paste of high-reliability TOPCon crystalline silicon solar cell, preparation and application |
| WO2023124495A1 (en) * | 2021-12-31 | 2023-07-06 | 广东南海启明光大科技有限公司 | Glass powder for thick film silver paste adapting to crystalline silicon p+ layer contact and preparation method therefor |
| WO2024050767A1 (en) * | 2022-09-08 | 2024-03-14 | 深圳市首骋新材料科技有限公司 | Frit and preparation method therefor, conductive paste and preparation method therefor, and solar cell |
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| CN115881338A (en) * | 2022-12-28 | 2023-03-31 | 广东南海启明光大科技有限公司 | Front-side silver-aluminum paste of high-reliability TOPCon crystalline silicon solar cell, preparation and application |
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| CN114822909B (en) | 2024-03-26 |
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