CN117650184B - TOPCON solar cell metallization method using silver-coated copper paste and solar cell - Google Patents
TOPCON solar cell metallization method using silver-coated copper paste and solar cell Download PDFInfo
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 192
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 188
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 173
- 239000004332 silver Substances 0.000 title claims abstract description 173
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 160
- 239000010949 copper Substances 0.000 title claims abstract description 160
- 238000001465 metallisation Methods 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 64
- 238000005245 sintering Methods 0.000 claims abstract description 66
- 238000007650 screen-printing Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims description 57
- 239000002904 solvent Substances 0.000 claims description 33
- 238000009792 diffusion process Methods 0.000 claims description 32
- 229910045601 alloy Inorganic materials 0.000 claims description 29
- 239000000956 alloy Substances 0.000 claims description 29
- 239000003963 antioxidant agent Substances 0.000 claims description 29
- 230000003078 antioxidant effect Effects 0.000 claims description 29
- 239000011521 glass Substances 0.000 claims description 29
- 239000003112 inhibitor Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 20
- -1 nitrogen heterocyclic compounds Chemical class 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
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- 229910052796 boron Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 150000003983 crown ethers Chemical class 0.000 claims description 5
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
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- 150000004767 nitrides Chemical class 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
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- 150000002739 metals Chemical class 0.000 claims description 2
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- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910000676 Si alloy Inorganic materials 0.000 description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 3
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical compound O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
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- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 2
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- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- 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 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- 229910000789 Aluminium-silicon alloy Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 description 1
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 description 1
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical group [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 1
- VRUVRQYVUDCDMT-UHFFFAOYSA-N [Sn].[Ni].[Cu] Chemical compound [Sn].[Ni].[Cu] VRUVRQYVUDCDMT-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000004030 azacyclic compounds Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 150000004699 copper complex Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
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- 239000011777 magnesium Substances 0.000 description 1
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- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
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- 230000003595 spectral effect Effects 0.000 description 1
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- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Photovoltaic Devices (AREA)
Abstract
The invention belongs to the technical field of solar cells, and particularly relates to a TOPCON solar cell metallization method using silver-coated copper paste and a solar cell. The TOPCON solar cell metallization method comprises the following steps: screen printing silver-coated copper conductive paste on the surface of the TOPCON solar cell, drying, and sintering in air at 400-740 ℃ to obtain a first sintered cell; and performing laser enhanced sintering on the first sintered cell, and simultaneously applying a reverse deflection voltage to finish metallization of the TOPCON solar cell. According to the invention, low-cost silver-coated copper powder is adopted to replace silver powder for TOPCO solar cell metallization, so that the production cost is reduced, and the electrical performance of the TOPCO solar cell is improved by adopting a laser enhanced sintering process, and meanwhile, the requirements of TOPCO solar cell cost reduction and efficiency improvement are met.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a TOPCON solar cell metallization method using silver-coated copper paste and a solar cell.
Background
Tunneling oxide passivation contact solar cells (Tunnel Oxide Passivated Contact, TOPCon solar cells) are one type of solar cell that uses an ultra-thin oxide layer as the passivation layer structure. The TOPCO solar cell reduces metal contact recombination while improving metal contact, improves open-circuit voltage, short-circuit current and filling factor of the cell, and enables the TOPCO solar cell to have higher photoelectric conversion efficiency.
The traditional metallization process of the TOPCO solar cell comprises the steps of adopting silver-aluminum paste on the front side, adopting silver paste screen printing on the back side, drying and then sintering at high temperature. Because of high silver content in the silver-aluminum paste and the silver paste, the production cost of the silver-aluminum paste and the silver paste is high, and thus the production cost of the TOPCO solar cell is also directly determined.
The conductivity of the silver-coated copper powder is close to that of silver powder, and the use of the silver-coated copper powder can greatly reduce the use of silver, so that the silver-coated copper powder is regarded as an effective scheme for reducing the metallization cost of the solar cell. But at present, silver-coated copper paste is mainly used for low-temperature heterojunction solar cells.
Aiming at the cost reduction requirement of the TOPCO solar cell, the patent with publication number CN116543948A discloses silver aluminum paste for the N-type TOPCO solar cell, which comprises the following components in percentage by mass: 55-75% of silver powder, 10-30% of silver-coated copper powder, 1-4% of aluminum powder, 1-10% of glass powder, 3-10% of organic carrier I, 2-5% of organic carrier II, 0.2-3% of auxiliary agent and the balance of solvent. And sintering and light injection are carried out on the silver-aluminum paste prepared through screen printing in a sintering and annealing integrated furnace, so that the TOPCO solar cell is prepared. The cost can be reduced by only 10-24%, but the conversion efficiency is reduced by 0.071-0.174% compared with the conversion efficiency of a solar cell sintered with pure silver aluminum paste without silver-coated copper powder. This is far from meeting the requirements of TOPCon solar cell cost reduction and efficiency improvement.
Disclosure of Invention
In order to simultaneously meet the requirements of TOPCO solar cell on cost reduction and efficiency improvement, the invention provides a TOPCO solar cell metallization method using silver-coated copper paste and a solar cell.
In a first aspect, the present invention provides a method for metallizing a TOPCon solar cell using silver-coated copper paste, which is implemented by adopting the following technical scheme:
a method for metallizing a TOPCon solar cell with silver-coated copper paste, comprising the steps of:
screen printing silver-coated copper conductive paste on the surface of the TOPCON solar cell, drying, and sintering in air at 400-740 ℃ to obtain a first sintered cell;
performing laser enhanced sintering on the first sintered cell, and simultaneously applying reverse deflection voltage to finish metallization of the TOPCON solar cell;
the silver-coated copper conductive paste comprises, by mass, 5-95% of silver-coated copper powder, 0-75% of silver powder, 0-2% of alloy powder, 1-6% of glass powder, 0.1-3% of organic resin, 0.1-1% of dispersing agent, 0-5% of copper diffusion inhibitor, 0-5% of antioxidant and the balance of solvent.
According to the invention, low-cost silver-coated copper powder is adopted to replace silver powder for TOPCO solar cell metallization, so that the production cost is reduced, and the electrical performance of the TOPCO solar cell is improved by adopting a laser enhanced sintering process, and meanwhile, the requirements of TOPCO solar cell cost reduction and efficiency improvement are met.
Preferably, the sintering temperature in the air is 450-700 ℃.
More preferably, the temperature of sintering in air is 500-650 ℃.
Most preferably, the temperature of sintering in air is 600 ℃.
Preferably, the copper diffusion inhibitor is contained in an amount of 0.1 to 5wt%.
More preferably, the copper diffusion inhibitor is contained in an amount of 0.1 to 0.4wt%.
Preferably, the copper diffusion inhibitor is selected from one or more of silicon or silicon-containing alloy powder, organic matter containing adsorption chelating group, silicate or aluminate with copper ion adsorption function, glass powder reacted with copper oxide, metal or metal alloy powder and nitride.
The copper diffusion inhibitor is added into the silver-coated copper conductive paste, so that the composite loss caused by copper diffusion into the silicon body at high temperature is avoided, and the negative influence of silver-coated copper paste high-temperature sintering on the electrical performance of the TOPCO solar cell is avoided.
In the present application, the silicon-containing alloy powder in the silicon or silicon-containing alloy powder includes, but is not limited to, one or more of boron silicon alloy powder, magnesium silicon alloy powder, or aluminum silicon alloy powder.
Preferably, the organic matter containing the adsorption chelating group is a small molecule, a surfactant or a macromolecular resin containing one or more groups of carboxylic acid, phosphoric acid or sulfonic acid, or a mixture containing one or more of crown ether, EDTA and organic matter containing EDTA groups, wherein the crown ether is complexed with copper.
In this application, the silicate or aluminate having copper ion adsorption includes, but is not limited to, one or more of molecular sieves, zeolites, bentonite or montmorillonite.
In the present application, the metal in the metal or metal alloy powder includes, but is not limited to, one or more of gold, nickel, aluminum, chromium or tantalum; the metal or metal alloy powder in the metal alloy powder includes but is not limited to nickel copper tin alloy powder.
In this application, the nitride includes, but is not limited to, one or more of titanium nitride, tantalum nitride, or tungsten nitride.
More preferably, the copper diffusion inhibitor is a copper complex containing crown ether.
In this application, the crown ethers containing copper complexes include, but are not limited to, dicyclohexyl-18-crown-6.
Preferably, the antioxidant is present in an amount of 0.1 to 4wt%.
More preferably, the antioxidant is present in an amount of 0.1 to 0.4wt%.
Preferably, the antioxidant is selected from one or more of carbon materials, nitrogen heterocyclic compounds, phosphoric acid and phosphite compounds, compounds with reducibility, metals which are more noble than copper, boron powder and germanium powder.
The antioxidant is added into the silver-coated copper conductive paste, so that the oxidation resistance of copper is improved, the resistance loss caused by copper oxidation at high temperature is avoided, and the negative influence of high-temperature sintering of the silver-coated copper paste on the electrical performance of the TOPCO solar cell is avoided.
In this application, the carbon material includes, but is not limited to, one or more of graphite, graphene, carbon nanotubes, carbon fibers, or fullerenes. The carbon material may prevent oxidation of copper.
In the present application, the azacyclic compound includes, but is not limited to, one or more of benzotriazole, benzimidazole, 2-mercaptobenzimidazole, benzothiazole, mercaptobenzothiazole, 2-mercaptopyridine, or 2-hydroxypyridine.
In this application, the reducing compounds include, but are not limited to, hydrazine hydrate and/or sodium borohydride.
In this application, the copper-specific metal includes, but is not limited to, one or more of magnesium, aluminum, zinc, or nickel.
More preferably, the antioxidant is germanium powder.
Preferably, the silver content of the silver-coated copper powder is 10-90wt%.
Preferably, the composition of the silver-coated copper conductive paste for the P region metallization comprises, in mass percent, 5-95% of silver-coated copper powder, 0-75% of silver powder, 0-2% of aluminum powder, 0-2% of alloy powder, 1-6% of glass powder, 0.1-3% of organic resin, 0.1-1% of dispersing agent, 0-5% of copper diffusion inhibitor, 0-5% of antioxidant and the balance of solvent.
Preferably, the composition of the glass powder for P region metallization of the silver-coated copper conductive paste comprises, in mass percent, 30-90% of PbO and Bi 2 O 3 0-20%、SiO 2 0-35%、Li 2 O 0-7%、Na 2 O 0-10%、ZnO 0-15%、Al 2 O 3 0-35%、B 2 O 3 5-60%, baO 0-50% and TiO 2 0-30%。
Preferably, the composition of the glass powder for P-zone metallization of the silver-coated copper conductive paste further comprises one or more of the following elements or compounds containing the elements: te, se, sn, ag, ce, cs, cu, fe, K, rb, W, ge, ga, in, ni, ca, mg, sr, mo, Y, as, la, nd, co, pr, gd, sm, dy, eu, ho, yb, lu, ta, V, hf, cr, cd, sb, F, zr, mn, ru, re, P and Nb.
Preferably, the composition of the alloy powder for P-zone metallization of the silver-coated copper conductive paste contains one or more of Al, si, B, mg, ti, ni and Fe.
In a preferred embodiment, the silver-coated copper conductive paste has a content of 0.01 to 2wt% of alloy powder for P-zone metallization.
In a preferred embodiment, the silver-coated copper conductive paste has an aluminum content for P-zone metallization of 0.1-2wt%.
In a preferred embodiment, the silver-coated copper conductive paste has a copper diffusion inhibitor content of 0.1 to 5wt% for P-zone metallization.
More preferably, the silver-coated copper conductive paste has a copper diffusion inhibitor content of 0.1 to 0.4wt% for P-region metallization.
In a preferred embodiment, the silver-coated copper conductive paste has an antioxidant content of 0.1 to 4wt% for the P-zone metallization.
More preferably, the silver-coated copper conductive paste has an antioxidant content of 0.1 to 0.4wt% for the P-zone metallization.
Preferably, the composition of the silver-coated copper conductive paste for N-zone metallization comprises, in mass percent, 5-95% of silver-coated copper powder, 0-75% of silver powder, 0-2% of alloy powder, 1-6% of glass powder, 0.1-3% of organic resin, 0.1-1% of dispersing agent, 0-5% of copper diffusion inhibitor, 0-5% of antioxidant and the balance of solvent.
Preferably, the composition of the glass powder for N-region metallization comprises, in mass percent, teO 0-80%, pbO 0-50%, bi 2 O 3 0-50%、SiO 2 0-50% and Li 2 O0-50%; the contents of TeO and PbO cannot be 0% at the same time.
Preferably, the composition of the glass frit for N-region metallization further comprises one or more of the following elements or compounds containing the elements: zn, B, sn, ti, ag, al, ce, cs, cu, fe, K, na, rb, W, ge, ga, in, ni, ca, mg, sr, ba, se, mo, Y, as, la, nd, co, pr, gd, sm, dy, eu, ho, yb, lu, ta, V, hf, cr, cd, sb, F, zr, mn, P, ru, re and Nb.
Preferably, the composition of the alloy powder for N-zone metallization contains one or more of P, sb and Bi.
In a preferred embodiment, the silver-coated copper conductive paste has a content of 0.01 to 2wt% of alloy powder for N-zone metallization.
In a preferred embodiment, the silver-coated copper conductive paste has a copper diffusion inhibitor content of 0.1 to 5wt% for N-zone metallization.
More preferably, the silver-coated copper conductive paste has a copper diffusion inhibitor content of 0.1 to 0.4wt% for N-region metallization.
In a preferred embodiment, the silver-coated copper conductive paste has an antioxidant content of 0.1 to 4wt% for N-zone metallization.
More preferably, the silver-coated copper conductive paste has an antioxidant content of 0.1 to 0.4wt% for N-zone metallization.
Preferably, the TOPCon solar cell comprises a front side P region and a back side N region, a front side N region and a back side P region solar cell, and a back side P region and a back side N region BC back contact solar cell.
In a second aspect, the present invention provides a solar cell, which is implemented by adopting the following technical scheme:
a solar cell is prepared by the TOPCON solar cell metallization method using silver-coated copper paste.
In summary, the invention has the following beneficial effects:
1. according to the invention, low-cost silver-coated copper powder is adopted to replace silver powder for TOPCO solar cell metallization, so that the production cost is reduced, and the electrical performance of the TOPCO solar cell is improved by adopting a laser enhanced sintering process, and meanwhile, the requirements of TOPCO solar cell cost reduction and efficiency improvement are met.
2. According to the invention, the copper diffusion inhibitor and the antioxidant are added into the silver-coated copper paste, so that the composite loss caused by copper diffusion into the silicon body at high temperature and the resistance loss caused by copper oxidation at high temperature are avoided, and the negative influence of high-temperature sintering of the silver-coated copper paste on the electrical performance of the TOPCO solar cell is avoided.
Detailed Description
The present invention will be described in further detail with reference to examples.
Examples
Embodiment 1 provides a method for metallizing a TOPCO solar cell by silver-coated copper paste, which comprises the following steps:
s1, screen printing silver-coated copper conductive paste for N-zone metallization on the N-zone of the back surface of a TOPCO battery piece, and drying for 30S at the temperature peak value of 200 ℃ under the condition of the belt speed of 12000 mm/min.
The preparation method of the silver-coated copper conductive paste for N-region metallization comprises the following steps:
sa, weighing 60g of silver-coated copper powder, 30g of silver powder, 0.05g of alloy powder, 2g of glass powder, 1.5g of organic resin, 0.5g of dispersing agent, 0.2g of copper diffusion inhibitor, 0.2g of antioxidant and 5.55g of solvent;
sb, firstly, putting the weighed alloy powder, glass powder, organic resin, dispersing agent, copper diffusion inhibitor, antioxidant and solvent into a wide-mouth bottle of a planetary stirrer, then adding silver-coated copper powder and silver powder into the wide-mouth bottle, and uniformly stirring by using a scraper; and then mixed for 3min at 800rpm by a planetary mixer to obtain sample slurry. And grinding the sample slurry for 5 times by using a three-roller grinder, and testing that the grinding fineness is less than 10 mu m and the Brookfield viscosity is between 300 and 350Pa.s to obtain the silver-coated copper conductive slurry for N-zone metallization.
The silver content of the silver-coated copper powder of the silver-coated copper conductive paste for N-zone metallization is 40wt%; the alloy powder is silicon-phosphorus alloy (the phosphorus content is 44.87wt percent and the silicon content is 55.13wt percent); the glass powder comprises the following components: pbO 8.7wt%, bi 2 O 3 5.5wt%、SiO 2 1.5wt%、Li 2 O 4.5wt%、ZnO 5.5wt%、MgO 4wt%、WO 3 9wt%、Fe 2 O 3 0.8wt% and TeO 2 60.5wt%; the organic resin is ethyl cellulose; the dispersant is oleic acid; the copper diffusion inhibitor is titanium nitride; the antioxidant is 2-mercaptobenzimidazole; the solvent is a mixture of butyl carbitol acetate and alcohol ester 12 according to the mass ratio of 1:1.
S2, screen printing silver-coated copper conductive paste for P area metallization on the front P area of the TOPCO battery piece printed with the back N area grid line by adopting a screen printing mode, and drying for 30S at the temperature peak value of 200 ℃ under the condition of the belt speed of 12000 mm/min.
The preparation method of the silver-coated copper conductive paste for P region metallization comprises the following steps:
sc, weighing 60g of silver-coated copper powder, 30g of silver powder, 0.12g of aluminum powder, 0.05g of alloy powder, 2g of glass powder, 1.5g of organic resin, 0.5g of dispersing agent, 0.2g of copper diffusion inhibitor, 0.2g of antioxidant and 5.43g of solvent;
sd, firstly placing the weighed aluminum powder, alloy powder, glass powder, organic resin, dispersing agent, copper diffusion inhibitor, antioxidant and solvent into a wide-mouth bottle of a planetary stirrer, then adding silver-coated copper powder and silver powder into the wide-mouth bottle, and uniformly stirring by using a scraper; and then mixed for 3min at 800rpm by a planetary mixer to obtain sample slurry. And grinding the sample slurry for 5 times by using a three-roller grinder, and testing that the grinding fineness is less than 10 mu m and the Brookfield viscosity is between 300 and 350Pa.s to obtain the silver-coated copper conductive slurry for P-region metallization.
The silver content of the silver-coated copper powder of the silver-coated copper conductive paste for P region metallization is 40wt%; the alloy powder is AlSi 10 An alloy; the glass powder comprises the following components: 40.5wt% of PbO and Bi 2 O 3 1.5wt%、SiO 2 5wt%、Li 2 O 2wt%、Na 2 O 0.5wt%、ZnO 4wt%、Al 2 O 3 1.5wt%、B 2 O 3 30wt%, baO 7.5wt% and TiO 2 7.5wt%; the organic resin is ethyl cellulose; the dispersant is oleic acid; the copper diffusion inhibitor is titanium nitride; the antioxidant is 2-mercaptobenzimidazole; the solvent is a mixture of butyl carbitol acetate and alcohol ester 12 according to the mass ratio of 1:1.
And S3, placing the TOPCO battery piece prepared in the step S2 in a sintering furnace, and sintering under the condition of the belt speed of 12000mm/min in an air atmosphere, wherein the temperature peak value is 600 ℃, and the sintering time is 1.5min, so as to obtain the first sintered battery piece.
And S4, performing laser enhanced sintering on the first sintered battery piece, and simultaneously applying reverse deflection voltage to finish metallization of the TOPCON solar battery piece, wherein the laser enhanced sintering corresponds to the laser beam with the power of 30W, the scanning time of the laser beam is 1S, and the reverse deflection voltage is 20V.
Example 2 provides a TOPCon solar cell metallization process with silver-coated copper paste, differing from example 1 only in that: the mass of the alloy powder of the silver-coated copper conductive paste for N-zone metallization is 0g, and the mass of the solvent is 5.6g; the mass of the alloy powder of the silver-coated copper conductive paste for the P region metallization is 0g, the mass of the aluminum powder is 0g, and the mass of the solvent is 5.6g.
Example 3 provides a TOPCon solar cell metallization process with silver-coated copper paste, differing from example 1 only in that: the mass of the alloy powder of the silver-coated copper conductive paste for N-zone metallization is 2g, and the mass of the solvent is 3.6g; the mass of the alloy powder of the silver-coated copper conductive paste for the P region metallization is 2g, the mass of the aluminum powder is 2g, and the mass of the solvent is 1.6g.
Example 4 provides a TOPCon solar cell metallization process with silver-coated copper paste, differing from example 1 only in that: the mass of the glass powder of the silver-coated copper conductive paste for N-zone metallization is 1g, and the mass of the solvent is 6.55g; the mass of the glass powder of the silver-coated copper conductive paste for the P-zone metallization was 1g, and the mass of the solvent was 6.43g.
Example 5 provides a TOPCon solar cell metallization process with silver-coated copper paste, differing from example 1 only in that: the mass of the glass powder of the silver-coated copper conductive paste for N-zone metallization is 5g, and the mass of the solvent is 2.55g; the mass of the glass powder of the silver-coated copper conductive paste for the P-zone metallization was 5g and the mass of the solvent was 2.43g.
Example 6 provides a TOPCon solar cell metallization process with silver-coated copper paste, differing from example 1 only in that: the mass of the copper diffusion inhibitor of the silver-coated copper conductive paste for N-region metallization is 0g, and the mass of the solvent is 5.75g; the mass of the copper diffusion inhibitor of the silver-coated copper conductive paste for P-zone metallization was 0g, and the mass of the solvent was 5.63g.
Example 7 provides a TOPCon solar cell metallization process with silver-coated copper paste, differing from example 1 only in that: the mass of the copper diffusion inhibitor of the silver-coated copper conductive paste for N-region metallization is 5g, and the mass of the solvent is 0.75g; the mass of the copper diffusion inhibitor of the silver-coated copper conductive paste for P-zone metallization was 5g, and the mass of the solvent was 0.63g.
Example 8 provides a TOPCon solar cell metallization process with silver-coated copper paste, differing from example 1 only in that: the mass of the antioxidant of the silver-coated copper conductive paste for N-zone metallization is 0g, and the mass of the solvent is 5.75g; the mass of the antioxidant of the silver-coated copper conductive paste for P-zone metallization was 0g and the mass of the solvent was 5.63g.
Example 9 provides a TOPCon solar cell metallization process with silver-coated copper paste, differing from example 1 only in that: the mass of the antioxidant of the silver-coated copper conductive paste for N-zone metallization is 5g, and the mass of the solvent is 0.75g; the mass of the antioxidant of the silver-coated copper conductive paste for P-zone metallization was 5g and the mass of the solvent was 0.63g.
Example 10 provides a TOPCon solar cell metallization process with silver-coated copper paste, differing from example 1 only in that: the copper diffusion inhibitor was dicyclohexyl-18-crown-6 (CAS number 16069-36-6).
Example 11 provides a TOPCon solar cell metallization process with silver-coated copper paste, differing from example 1 only in that: the antioxidant is germanium powder.
Example 12 provides a TOPCon solar cell metallization process with silver-coated copper paste, differing from example 1 only in that: and S3, the temperature peak value in the step is 400 ℃, and the sintering time is 1.5min.
Example 13 provides a TOPCon solar cell metallization process with silver-coated copper paste, differing from example 1 only in that: and S3, the temperature peak value in the step S3 is 740 ℃, and the sintering time is 1.5min.
Comparative example
Comparative example 1 provides a TOPCon solar cell metallization process with silver-coated copper paste, differing from example 1 only in that: in the step S3, the temperature peak value is 350 ℃, and the sintering time is 1.5min.
Comparative example 2 provides a TOPCon solar cell metallization process with silver-coated copper paste, differing from example 1 only in that: and S3, the temperature peak value in the step S3 is 800 ℃, and the sintering time is 1.5min.
Comparative example 3 provides a TOPCon solar cell metallization process with silver-coated copper paste, differing from example 1 only in that: there is no step S4.
Comparative example 4 provides a TOPCon solar cell metallization process comprising the steps of:
s1, screen printing AX101 silver paste produced by the company of the photoelectric technology of the ocean wave (Jiangsu) on an N area on the back surface of a TOPCO battery piece, and drying for 30S at the temperature peak value of 200 ℃ under the condition of the belt speed of 12000 mm/min.
S2, screen printing AX301 type silver aluminum paste produced by the photoelectric technology (Jiangsu) limited company on the front P area of the TOPCO battery piece printed with the back grid line, and drying for 30S at the temperature peak value of 200 ℃ under the condition of the belt speed of 12000 mm/min.
And S3, placing the TOPCO battery piece prepared in the step S2 in a sintering furnace, and sintering under the condition of the belt speed of 12000mm/min in an air atmosphere, wherein the temperature peak value is 600 ℃, and the sintering time is 1.5min, so as to obtain the first sintered battery piece.
And S4, performing laser enhanced sintering on the first sintered battery piece, and simultaneously applying reverse deflection voltage to finish metallization of the TOPCON solar battery piece, wherein the laser enhanced sintering corresponds to the laser beam with the power of 30W, the scanning time of the laser beam is 1S, and the reverse deflection voltage is 20V.
Comparative example 5 provides a TOPCon solar cell metallization process comprising the steps of:
s1, screen printing AX101 silver paste produced by the company of the photoelectric technology of the ocean wave (Jiangsu) on an N area on the back surface of a TOPCO battery piece, and drying for 30S at the temperature peak value of 200 ℃ under the condition of the belt speed of 12000 mm/min.
S2, screen printing AX301 type silver aluminum paste produced by the photoelectric technology (Jiangsu) limited company on the front P area of the TOPCO battery piece printed with the back grid line, and drying for 30S at the temperature peak value of 200 ℃ under the condition of the belt speed of 12000 mm/min.
And S3, placing the TOPCO battery piece prepared in the step S2 in a sintering furnace, and sintering under the condition of the belt speed of 12000mm/min in an air atmosphere, wherein the temperature peak value is 740 ℃, and the sintering time is 1.5min, so as to obtain the first sintered battery piece.
And S4, performing laser enhanced sintering on the first sintered battery piece, and simultaneously applying reverse deflection voltage to finish metallization of the TOPCON solar battery piece, wherein the laser enhanced sintering corresponds to the laser beam with the power of 30W, the scanning time of the laser beam is 1S, and the reverse deflection voltage is 20V.
Comparative example 6 provides a TOPCon solar cell metallization process comprising the steps of:
s1, screen printing AX101 silver paste produced by the company of the photoelectric technology of the ocean wave (Jiangsu) on an N area on the back surface of a TOPCO battery piece, and drying for 30S at the temperature peak value of 200 ℃ under the condition of the belt speed of 12000 mm/min.
S2, screen printing AX301 type silver aluminum paste produced by the photoelectric technology (Jiangsu) limited company on the front P area of the TOPCO battery piece printed with the back grid line, and drying for 30S at the temperature peak value of 200 ℃ under the condition of the belt speed of 12000 mm/min.
And S3, placing the TOPCO battery piece prepared in the step S2 into a sintering furnace, and sintering under the condition of the belt speed of 12000mm/min and the air atmosphere, wherein the temperature peak value is 740 ℃, and the sintering time is 1.5min.
The same screen was used for examples 1-13 and comparative examples 1-6, and the screen parameters were: 480 mesh 11 μm wire mesh diameter, 14 μm yarn thickness, 4 μm latex thickness, 148 22 μm secondary grid lines and 16 primary grid lines.
Performance test
The TOPCON solar cells prepared by the metallization methods of examples 1-13 and comparative examples 1-6 of the present invention were tested for performance as follows.
1. Electrical properties
The solar cells were characterized using a commercially available IV tester "YP-CX5000" obtained from spectral intelligence at 25 ℃ + -1.0 ℃. The stroboscopic pulsed light was used to simulate sunlight, which was known to have an AM1.5 intensity of 1000W/m on the battery surface 2 . To have this intensity the strobe light flashes several times in a short time until a steady level is reached as monitored by the "1.0.0.0" software of the IV tester. The spectrum IV tester uses a multi-point contact method to measure current (I) and voltage (V) to determine the IV curve of the battery. All values are automatically determined from the curve by means of the running software package. As a reference standard, calibrated solar cells obtained from ISE Freiburg and made of the same area size, the same wafer material and using the same front side pattern were tested and the data compared with certified values. At least 5 wafers processed in very identical fashion were measured and the data was analyzed by calculating the average of the values. The software provides values for conversion efficiency, fill factor, short circuit current, series resistance, gate line resistance, and open circuit voltage.
The grid line resistance is calibrated by resistance values between two adjacent main grids, specifically selecting resistance values between 1 st and 2 nd main grids, resistance values between 2 nd and 3 rd main grids, resistance values between 3 rd and 4 th main grids, resistance values between 4 th and 5 th main grids, and average values of resistance values between 5 th and 6 th main grids and resistance values between 6 th and 7 th main grids to represent grid line resistance.
The conversion efficiency, open circuit voltage, short circuit current, fill factor and gate line resistance test data for examples 1-13 and comparative examples 1-6 are shown in Table 1. Where Ncell denotes a conversion efficiency value, uoc denotes an open circuit voltage value, isc denotes a short circuit current value, FF denotes a fill factor value, and Rgl denotes a gate line resistance value.
Table 1 test data for examples 1-13 and comparative examples 1-6
| Ncell(%) | Uoc(mV) | Isc(A) | FF(%) | Rgl(mohm) | |
| Example 1 | 26.061 | 727.514 | 13.930 | 84.827 | 50.880 |
| Example 2 | 26.042 | 727.111 | 13.944 | 84.719 | 56.723 |
| Example 3 | 26.053 | 727.802 | 14.001 | 84.334 | 50.255 |
| Example 4 | 26.043 | 731.189 | 13.989 | 83.982 | 51.878 |
| Example 5 | 26.055 | 723.403 | 13.909 | 85.412 | 51.070 |
| Example 6 | 26.034 | 724.578 | 14.022 | 84.520 | 52.187 |
| Example 7 | 26.053 | 730.529 | 13.919 | 84.516 | 54.368 |
| Example 8 | 26.047 | 733.249 | 13.966 | 83.899 | 103.352 |
| Example 9 | 26.053 | 727.558 | 13.871 | 85.150 | 36.254 |
| Example 10 | 26.342 | 731.888 | 13.931 | 85.219 | 48.403 |
| Example 11 | 26.365 | 715.212 | 13.941 | 87.219 | 21.261 |
| Example 12 | 26.026 | 732.055 | 13.859 | 84.615 | 48.107 |
| Example 13 | 26.026 | 725.051 | 13.910 | 85.118 | 49.869 |
| Comparative example 1 | 1.698 | 714.612 | 2.993 | 26.190 | 68.189 |
| Comparative example 2 | 18.374 | 611.842 | 13.415 | 73.837 | 81.338 |
| Comparative example 3 | 1.065 | 732.223 | 2.030 | 23.634 | 47.433 |
| Comparative example 4 | 23.502 | 733.059 | 13.743 | 76.947 | 35.869 |
| Comparative example 5 | 26.001 | 728.358 | 13.890 | 84.776 | 21.505 |
| Comparative example 6 | 25.749 | 726.911 | 13.881 | 84.176 | 21.819 |
The test data of table 1 are used in the following to describe the present application in detail.
From the test data of examples 1, 12-13 and comparative examples 1-2, the silver-coated copper paste of the present application was sintered in air at 400-740 ℃ and combined with a laser enhanced sintering process, and a TOPCon solar cell with a silver-coated copper paste having high conversion efficiency could be obtained, because the sintered silver-coated copper paste at 400 ℃ or lower could not form good ohmic contact with silicon, and the copper oxidation and diffusion effects of the sintered silver-coated copper paste at 740 ℃ or higher were all aggravated, which resulted in a decrease in the conversion efficiency of TOPCon solar cells.
From the test data of example 1 and comparative example 3, the present application improved the electrical performance of TOPCon solar cells using low cost silver-coated copper paste in combination with a laser enhanced sintering process, with the conversion efficiency of example 1 being 24.996% higher than that of comparative example 3. The method is characterized in that the contact between the silver-coated copper paste and silicon can be obviously improved due to the laser enhanced sintering process matched with the sintering of the silver-coated copper paste, and the filling factor and the conversion efficiency are greatly improved.
From the test data of examples 1-11 and comparative example 4, the conversion efficiency of the sintering of the silver-coated copper paste in 600 ℃ air and the laser-enhanced sintering process is 2.532-2.863% higher than that of the silver paste or silver aluminum paste in 600 ℃ air and the laser-enhanced sintering process, because the sintering of the silver-coated copper paste in 600 ℃ air can form a denser fine grid structure, can form better contact with silicon and realize a higher filling factor. Meanwhile, the structural design of copper particles in the silver-coated copper paste is beneficial to the solar cell to absorb more light energy and realize higher short-circuit current. And the silver content of the TOPCO solar cell prepared in the embodiments 1-11 is only 54%, so that the requirements of the TOPCO solar cell on cost reduction and efficiency improvement can be met at the same time.
From the test data of example 13 and comparative example 6, the conversion efficiency of the TOPCN solar cell prepared by sintering silver-coated copper paste in 740 ℃ air and combining the laser enhanced sintering process in example 13 is 0.277% higher than that of the TOPCN solar cell prepared by sintering pure silver paste or silver-aluminum paste at 740 ℃ in comparative example 6, and the silver content of the TOPCN solar cell prepared in example 13 of the application is only 54%, so that the requirements of reducing cost and improving efficiency of the TOPCN solar cell can be simultaneously met.
From the test data of example 13 and comparative example 5, the conversion efficiency of the TOPCO solar cell prepared by sintering silver-coated copper paste in 740 ℃ air and then combining the laser enhanced sintering process in example 13 is 0.025% higher than that of the TOPCO solar cell prepared by sintering pure silver paste or silver-aluminum paste at 740 ℃ and combining the laser enhanced sintering process in comparative example 5, and the silver content of example 13 is only 54%, which indicates that the high conversion efficiency is realized at low cost according to the present invention.
From the test data of examples 1, 7 and 6, it is known that the copper diffusion inhibitor can increase the open circuit voltage of the TOPCon solar cell, thereby increasing the conversion efficiency of the TOPCon solar cell.
From the test data of examples 1 and 8, it is known that the antioxidant can reduce the grid line resistance of the TOPCon solar cell, thereby improving the conversion efficiency of the TOPCon solar cell.
Example 14 provides a method for metallizing a BC back contact solar cell using silver-coated copper paste, comprising the steps of:
s1, screen printing silver-coated copper conductive paste for N-zone metallization on the back N zone of a BC back contact solar cell by adopting a screen printing mode, and drying for 30S at the temperature peak value of 200 ℃ under the condition of the belt speed of 12000 mm/min; wherein the silver copper-clad conductive paste for N-region metallization is the same as in example 1.
S2, screen printing silver-coated copper conductive paste for metallization of the P region on the back side of the BC back contact solar cell sheet prepared in the step S1 by screen printing, and drying for 30S at the temperature peak value of 200 ℃ under the condition of the belt speed of 12000 mm/min; wherein the silver copper-clad conductive paste for P-region metallization is the same as in example 1.
And S3, placing the BC back contact solar cell sheet dried in the step S1 and the step S2 in a sintering furnace, and sintering under the condition of the belt speed of 12000mm/min in an air atmosphere, wherein the temperature peak value is 600 ℃, and the sintering time is 1.5min, so as to obtain a first sintered cell sheet.
And S4, performing laser enhanced sintering on the first sintered battery piece, and simultaneously applying reverse deflection voltage to finish metallization of the BC back contact solar battery piece, wherein the laser enhanced sintering corresponds to the laser beam with the power of 30W, the scanning time of the laser beam is 1S, and the reverse deflection voltage is 20V.
Example 15 provides a BC back contact solar cell metallization process with silver-coated copper paste, differing from example 14 only in that: the mass of the silver-coated copper powder of the silver-coated copper conductive paste for N-zone metallization is 95g, the mass of the silver powder is 0g, and the mass of the solvent is 0.55g; the mass of the silver-coated copper powder of the silver-coated copper conductive paste for the P region metallization is 95g, the mass of the silver powder is 0g, and the mass of the solvent is 0.43g; and the silver content in the silver-coated copper powder is 10wt%.
Example 16 provides a BC back contact solar cell metallization process with silver-coated copper paste, differing from example 14 only in that: the mass of the silver-coated copper powder of the silver-coated copper conductive paste for N-zone metallization is 5g, the mass of the silver powder is 75g, and the mass of the solvent is 15.55g; the mass of the silver-coated copper powder of the silver-coated copper conductive paste for the P region metallization is 5g, the mass of the silver powder is 75g, and the mass of the solvent is 15.43g; and the silver content in the silver-coated copper powder is 90wt%.
Comparative example 7 provides a BC back contact solar cell metallization process with silver-coated copper paste differing from example 14 only in that: there is no step S4.
Comparative example 8 provides a BC back contact solar cell metallization method, comprising the steps of:
s1, screen printing AX101 silver paste produced by Jingsu photoelectric technology (Jiangsu) on an N area on the back of a BC back contact solar cell, and drying for 30S at the temperature peak value of 200 ℃ under the condition of the belt speed of 12000 mm/min.
S2, screen printing AX301 silver aluminum paste produced by the photoelectric technology (Jiangsu) limited company is adopted on the back P area of the BC back contact solar cell sheet prepared in the step S1 through screen printing, and the silver aluminum paste is dried for 30S at the temperature peak value of 200 ℃ under the condition of the belt speed of 12000 mm/min.
And S3, placing the BC back contact solar cell sheet dried in the step S1 and the step S2 in a sintering furnace, and sintering under the condition of the belt speed of 12000mm/min in an air atmosphere, wherein the temperature peak value is 600 ℃, and the sintering time is 1.5min, so as to obtain a first sintered cell sheet.
And S4, performing laser enhanced sintering on the first sintered battery piece, and simultaneously applying reverse deflection voltage to finish metallization of the BC back contact solar battery piece, wherein the laser enhanced sintering corresponds to the laser beam with the power of 30W, the scanning time of the laser beam is 1S, and the reverse deflection voltage is 20V.
The same screen was used for examples 14-16 and comparative examples 7-8, and the screen parameters were: a wire diameter of a 430 mesh 13 μm screen, a yarn thickness of 14 μm, and a latex thickness of 4 μm.
The BC back contact solar cells prepared in examples 14-16 and comparative examples 7-8 of the present invention were tested for electrical performance, and the conversion efficiency, open circuit voltage, short circuit current, fill factor, and gate line resistance of examples 14-16 and comparative examples 7-8 were tested as shown in table 2.
Table 2 test data for examples 14-16 and comparative examples 7-8
| Ncell(%) | Uoc(mV) | Isc(A) | FF(%) | Rgl(mohm) | |
| Example 14 | 26.652 | 728.629 | 14.212 | 84.896 | 52.336 |
| Example 15 | 24.227 | 725.898 | 14.006 | 78.603 | 134.329 |
| Example 16 | 26.767 | 729.001 | 14.217 | 85.188 | 28.956 |
| Comparative example 7 | 1.350 | 732.467 | 2.497 | 24.339 | 50.029 |
| Comparative example 8 | 24.205 | 734.098 | 14.098 | 77.146 | 22.119 |
From the test data of example 14 and comparative example 7, it is understood that the use of low cost silver-coated copper paste in example 14 in combination with the laser enhanced sintering process improves the electrical performance of BC back contact solar cells, and the conversion efficiency of example 14 is 25.302% higher than that of comparative example 7.
From the test data of example 14 and comparative example 8, it is understood that example 14 uses silver-coated copper paste, comparative example 8 uses pure silver paste or silver-aluminum paste, the silver content of example 14 is 54%, and the conversion efficiency is improved by 2.447%. From the test data of example 15 and comparative example 8, the silver content of example 15 was only 9.5%, and the conversion efficiency was 0.022% higher than that of comparative example 8. From the test data of example 16 and comparative example 8, the silver content of example 16 was 79.5%, but the conversion efficiency was 2.562% higher than that of comparative example 8. The BC back contact solar cell can meet the requirements of cost reduction and efficiency improvement of the BC back contact solar cell.
The above examples and comparative examples of the present application only exemplify one kind of glass frit and alloy powder for the silver-coated copper conductive paste for P region/N region metallization, but the present application is not limited to the kinds of glass frit and alloy powder mentioned in the above examples and comparative examples, and those skilled in the art can adjust according to the kinds of claims, and also obtain superior effects.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (15)
1. A method for metallizing a TOPCON solar cell with silver-coated copper paste, comprising the steps of:
screen printing silver-coated copper conductive paste on the surface of the TOPCON solar cell, drying, and sintering in air at 400-740 ℃ to obtain a first sintered cell;
performing laser enhanced sintering on the first sintered cell, and simultaneously applying reverse deflection voltage to finish metallization of the TOPCON solar cell;
the silver-coated copper conductive paste comprises, by mass, 5-95% of silver-coated copper powder, 0-75% of silver powder, 0-2% of alloy powder, 1-6% of glass powder, 0.1-3% of organic resin, 0.1-1% of dispersing agent, 0.1-5% of copper diffusion inhibitor, 0-5% of antioxidant and the balance of solvent.
2. A method of metallizing a TOPCon solar cell with a silver-coated copper paste according to claim 1, wherein the copper diffusion inhibitor is selected from one or more of silicon or silicon-containing alloy powder, organic substances containing adsorbed chelating groups, silicates or aluminates having the effect of adsorbing copper ions, glass powder reactive with copper oxide, metal or metal alloy powder, nitride.
3. A method of metallizing a TOPCon solar cell with silver-coated copper paste according to claim 2, characterized in that the organic substance containing adsorbed chelating groups is a small molecule, surfactant or macromolecular resin containing one or more of carboxylic acid, phosphoric acid or sulphonic acid groups, or a mixture containing one or more of crown ether, EDTA and organic substances containing EDTA groups complexed with copper.
4. The method for metallizing the TOPCO solar cell with the silver-coated copper paste according to claim 1, wherein the antioxidant is one or more selected from carbon materials, nitrogen heterocyclic compounds, phosphoric acid and phosphite compounds, compounds with reducibility, metals which are more noble than copper, boron powder and germanium powder.
5. The method for metallizing a TOPCon solar cell with silver-coated copper paste according to claim 1, wherein the silver content of the silver-coated copper powder is 10-90wt%.
6. The method for metallizing the TOPCO solar cell with the silver-coated copper paste according to claim 1, wherein the composition of the silver-coated copper conductive paste for the metallization of the P region comprises, in mass percent, 5-95% of silver-coated copper powder, 0-75% of silver powder, 0-2% of aluminum powder, 0-2% of alloy powder, 1-6% of glass frit, 0.1-3% of organic resin, 0.1-1% of dispersing agent, 0.1-5% of copper diffusion inhibitor, 0-5% of antioxidant and the balance of solvent.
7. The method for metallizing TOPCO solar cells with silver-coated copper paste according to claim 6, wherein the composition of the glass frit comprises, in mass percent, pbO 30-90%, bi 2 O 3 0-20%、SiO 2 0-35%、Li 2 O 0-7%、Na 2 O 0-10%、ZnO 0-15%、Al 2 O 3 0-35%、B 2 O 3 5-60%, baO 0-50% and TiO 2 0-30%。
8. A method of metallizing a TOPCon solar cell with a silver-coated copper paste according to claim 7, wherein the composition of the glass frit further comprises one or more of the following elements or compounds containing the elements: te, se, sn, ag, ce, cs, cu, fe, K, rb, W, ge, ga, in, ni, ca, mg, sr, mo, Y, as, la, nd, co, pr, gd, sm, dy, eu, ho, yb, lu, ta, V, hf, cr, cd, sb, F, zr, mn, ru, re, P and Nb.
9. A TOPCon solar cell metallization process with silver-coated copper paste according to claim 6, wherein the composition of the alloy powder contains one or more of Al, si, B, mg, ti, ni and Fe.
10. The method for metallizing the TOPCO solar cell with the silver-coated copper paste according to claim 1, wherein the composition of the silver-coated copper conductive paste for N-zone metallization comprises, in mass percent, 5-95% of silver-coated copper powder, 0-75% of silver powder, 0-2% of alloy powder, 1-6% of glass frit, 0.1-3% of organic resin, 0.1-1% of dispersant, 0.1-5% of copper diffusion inhibitor, 0-5% of antioxidant and the balance of solvent.
11. The method for metallizing TOPCO solar cells with silver-coated copper paste according to claim 10, wherein the composition of the glass frit comprises, in mass percent, teO 0-80%, pbO 0-50%, bi 2 O 3 0-50%、SiO 2 0-50% and Li 2 O0-50%; the contents of TeO and PbO cannot be 0% at the same time.
12. A method of metallizing a TOPCon solar cell with a silver-coated copper paste according to claim 11, wherein the composition of the glass frit further comprises one or more of the following elements or compounds containing the elements: zn, B, sn, ti, ag, al, ce, cs, cu, fe, K, na, rb, W, ge, ga, in, ni, ca, mg, sr, ba, se, mo, Y, as, la, nd, co, pr, gd, sm, dy, eu, ho, yb, lu, ta, V, hf, cr, cd, sb, F, zr, mn, P, ru, re and Nb.
13. A method of metallizing a TOPCon solar cell with a silver-coated copper paste according to claim 10, wherein the composition of said alloy powder contains one or more of P, sb and Bi.
14. A method of metallizing a TOPCon solar cell with silver-coated copper paste according to any of claims 1-13, wherein the TOPCon solar cell comprises a front side P-region and back side N-region, a front side N-region and back side P-region solar cell, and a back side P-region and back side N-region BC back contact solar cell.
15. A solar cell produced by the TOPCon solar cell metallization method of any one of claims 1-14 with silver-coated copper paste.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090110739A (en) * | 2008-04-18 | 2009-10-22 | 계명대학교 산학협력단 | Printing paste composition for electrode of solar cell and electrode forming method using the same |
| CN115602355A (en) * | 2022-10-14 | 2023-01-13 | 三一硅能（株洲）有限公司（Cn） | Conductive paste and solar cell prepared from same |
| CN116543948A (en) * | 2023-06-30 | 2023-08-04 | 浙江晶科新材料有限公司 | Silver-aluminum paste for N-type TOPCON solar cell and preparation method thereof |
| CN117079860A (en) * | 2023-10-12 | 2023-11-17 | 上海银浆科技有限公司 | Low-temperature silver paste for low-consumption silver heterojunction solar cell, and preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090110739A (en) * | 2008-04-18 | 2009-10-22 | 계명대학교 산학협력단 | Printing paste composition for electrode of solar cell and electrode forming method using the same |
| CN115602355A (en) * | 2022-10-14 | 2023-01-13 | 三一硅能（株洲）有限公司（Cn） | Conductive paste and solar cell prepared from same |
| CN116543948A (en) * | 2023-06-30 | 2023-08-04 | 浙江晶科新材料有限公司 | Silver-aluminum paste for N-type TOPCON solar cell and preparation method thereof |
| CN117079860A (en) * | 2023-10-12 | 2023-11-17 | 上海银浆科技有限公司 | Low-temperature silver paste for low-consumption silver heterojunction solar cell, and preparation method and application thereof |
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