CN114822909B - Silver-aluminum paste for low-temperature sintering crystalline silicon solar cell, preparation method and application - Google Patents
Silver-aluminum paste for low-temperature sintering crystalline silicon solar cell, preparation method and application Download PDFInfo
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- -1 Silver-aluminum Chemical compound 0.000 title claims abstract description 100
- 229910021419 crystalline silicon Inorganic materials 0.000 title claims abstract description 89
- 238000009766 low-temperature sintering Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 125
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000011521 glass Substances 0.000 claims abstract description 42
- 239000002270 dispersing agent Substances 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 28
- 229910052709 silver Inorganic materials 0.000 claims abstract description 26
- 239000004332 silver Substances 0.000 claims abstract description 26
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 239000002245 particle 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 13
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 15
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 6
- 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
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- 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
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- 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
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- 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
- 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
- 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
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims 1
- 150000001241 acetals Chemical class 0.000 claims 1
- 239000012748 slip agent Substances 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 17
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- 230000004927 fusion Effects 0.000 abstract description 4
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- 230000000694 effects Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229920005591 polysilicon Polymers 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
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- 230000006698 induction Effects 0.000 description 3
- 238000002161 passivation Methods 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
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- 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
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- 239000011265 semifinished product Substances 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
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- 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
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 1
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- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
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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
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 to 90.0 parts of conductive silver powder, 0.7 to 5.0 parts of nano aluminum powder pre-dispersion, 2.0 to 8.0 parts of glass powder, 4.0 to 9.0 parts of organic solvent, 0.1 to 1.0 parts of resin, 0.1 to 1.0 parts of organic dispersing agent, 0.05 to 1.0 parts of thixotropic agent and 0.1 to 1.0 parts of slipping agent; the conductive silver powder is submicron or micron silver powder, and the particle size of the nanometer aluminum powder is 50-300 nm. The silver-aluminum paste of the crystalline silicon solar cell is introduced with 50-300 nm nano aluminum powder, the fusion temperature of the nano aluminum powder and the conductive silver powder is reduced by utilizing the irregular atomic ordering characteristic of the surface of the nano aluminum powder, and the sintering temperature of the original front silver-aluminum paste can be reduced from 760-780 ℃ to 720-750 ℃, so that the sintering temperature is obviously reduced. By matching the nano aluminum powder with the conductive silver powder, silver-aluminum alloying 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 crystalline silicon solar cell silver-aluminum paste 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 main stream of the photovoltaic industry by virtue of the characteristics of high conversion efficiency, long service life and the like, and relatively low-efficiency conventional cells gradually exit the market. At present, PERC high-efficiency crystalline silicon solar cells are a main technical route, and n-type cell technology is also rapidly developed. According to the ITRPV research institute in 2020, the photovoltaic market predicts that n-type batteries in 2020 account for about 10% of the photovoltaic market, and will account for 42% of the market share after 2029.
The N-type solar cell mainly comprises a HJT cell, an N-type Topcon crystalline silicon solar cell and an IBC cell, wherein the rest cells except the HJT cell use low-temperature silver paste are all made of high Wen Yinlv paste/silver paste. The N-type Topcon crystalline silicon solar cell is firstly developed in front hofure solar research institute, combines novel technologies such as thermal oxide film passivation and polysilicon film contact, has the characteristics of high open voltage, high current, high FF and the like, and becomes an important subject of domestic large photovoltaic cell company/research institution research in recent two years. N-TOPCon batteries are a further upgrade of N-PERT technology, and manufacturers of the current scale industrialization mainly comprise medium-energy photovoltaic, lin Yang technology, crystal energy, tongwei solar energy, british and the like. Although the prior art has more problems and more complex process, the batch efficiency reaches about 24.0 percent. New world records with the highest efficiency of 24.58% of large-scale N-type polycrystalline i-TOPCO batteries prepared by the zenithal light energy show potential competitiveness for the N-type TOPCO batteries.
However, the structural design of the back surface of the N-type TOPCon crystalline silicon solar cell by adopting a 1-2 nm tunnel oxide layer-100 nm polycrystalline silicon film-passivation layer requires that the corrosiveness of back surface silver paste is lower; meanwhile, the doping concentration of the surface of the p+ layer on the front side is low, good ohmic contact cannot be formed by pure positive silver paste, and good work function matching can be formed by adopting positive silver aluminum paste.
The existing solar battery silver-aluminum paste 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 realization of the characteristics of high open pressure and high conversion efficiency is not facilitated. The existing silver-aluminum paste formula has poor contact performance, high contact resistivity and low conversion efficiency if sintered at 720-750 ℃. Along with the development of the N-type TOPCon crystalline silicon solar cell, the polysilicon film on the back surface of the N-type TOPCon crystalline silicon solar cell is thinner and thinner, is more sensitive to sintering temperature, and has higher requirements on the matching property of the 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 the sintering temperature of the solar cell silver-aluminum paste in the prior art is high, and a back polycrystalline silicon film and a tunnel oxide layer are easy to burn through.
To achieve the purpose, the invention adopts the following technical scheme:
the invention provides 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 nanometer 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 mu m, the tap density of the conductive silver powder is 4.0-7.0 g/cm < 3 >, 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 organic silicon dispersing agents, alkane dispersing agents and siloxane dispersing agents.
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 includes one or more combinations of Li2O, na2O, sb O3, V2O5, teO2, ga2O3, in2O3, geO2, mgO, baO, caO, ni2O3, ag2O, and Tl2O 3.
In the silver-aluminum paste for the crystalline silicon solar cell 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 crystalline silicon solar cell silver-aluminum paste for low-temperature sintering, the resin comprises one or more of ethyl cellulose, polyvinyl alcohol Ding Quanzhi, acrylic resin and aldehyde ketone resin; the organic solvent comprises any two or more of diethylene glycol butyl ether acetate, alcohol ester twelve, terpineol, diethylene glycol butyl ether acetate, dimethyl adipate, N-methylpyrrolidone, dimethyl phthalate and dimethyl terephthalate; the organic dispersant comprises one or more combinations of dispersants containing amine functional groups and dispersants containing fatty acid functional groups.
The silver-aluminum paste for the crystalline silicon solar cell for low-temperature sintering further comprises 0-1.0 part of organic auxiliary agent, wherein the organic auxiliary agent comprises one or more of leveling agent, organosilicon defoamer, silane coupling agent and 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 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 nano aluminum powder pre-dispersion;
batching and mixing: weighing conductive silver powder, nano aluminum powder pre-dispersion, glass powder, an organic solvent, resin, an organic dispersing agent, a thixotropic agent, a slipping agent and an organic auxiliary agent according to the proportion, and mixing and stirring to obtain semi-finished silver paste;
rolling: grinding the semi-finished silver paste to obtain the silver aluminum paste of the crystalline silicon solar cell for low-temperature sintering.
The invention also provides application of the crystalline silicon solar cell silver-aluminum paste 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 of the invention has the following beneficial effects:
the crystalline silicon solar cell silver-aluminum paste for low-temperature sintering is introduced with 50-300 nm nano aluminum powder, the fusion temperature of the nano aluminum powder and the conductive silver powder is reduced by utilizing the irregular atomic ordering 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. By matching the nano aluminum powder with the conductive silver powder, silver-aluminum alloying is formed, so that the contact resistance between the silver layer and the crystalline silicon solar cell substrate is effectively reduced, and the metal induction compounding speed of the crystalline silicon solar cell substrate is reduced.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. The present invention is described more fully below in order to facilitate an understanding of the present invention. This 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 are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
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 herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The invention provides 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 nanometer aluminum powder is 50-300 nm.
According to the invention, 50-300 nm nano aluminum powder is introduced, the fusion temperature of the nano aluminum powder and the conductive silver powder is reduced by utilizing the irregular atomic ordering 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. By matching the nano aluminum powder with the conductive silver powder, silver-aluminum alloying is formed, so that the contact resistance between the silver layer and the crystalline silicon solar cell substrate is effectively reduced, and the metal induction compounding speed of the crystalline silicon solar cell substrate is reduced.
In the specific application process, the polycrystalline silicon film thickness of the N-type TOPCO crystalline silicon solar cell and the infrared light absorption effect of the back surface of the N-type TOPCO crystalline silicon solar cell can be reduced by matching with the back surface silver paste suitable for low-temperature sintering at 720-750 ℃, and the productivity and the conversion efficiency of the N-type TOPCO crystalline silicon solar cell can be effectively improved.
The surface of aluminum powder in the silver-aluminum paste contains a large amount of hydroxyl groups, so that the solvent and the resin are easy to adsorb, the content of the 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 large, the pinning effect is also large, and the open-circuit voltage is obviously reduced.
The crystalline silicon solar cell silver-aluminum paste provided by the invention uses nano aluminum powder with the particle size of 50-300 nm. Compared with micron-sized aluminum powder, the nanometer-sized aluminum powder can be more effectively contacted with the conductive silver powder, so that the use amount of the aluminum powder can be reduced, and the effects of improving the printability of balanced silver-aluminum paste and reducing the contact resistivity are achieved. In the specific embodiment of the invention, the particle size of the nano aluminum powder is preferably 100-200 nm. When the grain diameter of the nano aluminum powder is larger than 300nm, the silver aluminum paste cannot effectively realize the effect of low-temperature sintering at 720-750 ℃. When the grain diameter of the nanometer aluminum powder is smaller than 50nm, the specific surface area is larger, the silver-containing aluminum paste is easy to agglomerate, and the printability of the silver-aluminum paste is reduced.
The nano aluminum powder with the activity of 50 nm-300 nm is strong, and the nano aluminum powder can be rapidly oxidized in the naked air, even spontaneously burned and exploded. According to the silver-aluminum paste for the crystalline silicon solar cell, the surface of the nano aluminum powder is modified and coated 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 720-750 ℃, the nano aluminum powder coated with the nano aluminum powder coating agent at the outer side can be 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 can be subjected to silver-aluminum alloying with the conductive silver powder to form a silver-aluminum electrode, so that ohmic contact between the silver-aluminum electrode and a p+ layer substrate is realized. Meanwhile, the nano aluminum powder coated with the nano aluminum powder coating agent has small size and large quantity, can be uniformly distributed in a silver aluminum paste system, realizes more ohmic contact points, reduces the use amount of the aluminum powder, and achieves the aim of reducing the bulk resistivity of the silver aluminum electrode.
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 can be realized at the temperature of 720-750 ℃ by the conductive silver powder and the nano aluminum powder, the contact resistance of the silver layer and the substrate is reduced, and the metal induction compounding of the substrate is realized. In a preferred embodiment of the present invention, the conductive silver powder is spherical or spheroid, the particle size of the conductive silver powder is 1.0-2.5 μm, and the tap density of the conductive silver powder is 4.5-6.0g/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 an organosilicon dispersing agent, an alkane dispersing agent and a siloxane dispersing agent.
The preparation method of the nano aluminum powder comprises but is not limited to nitrogen atomization, an electric explosion method and a chemical reduction method. The organosilicon dispersing agent, the alkane dispersing agent and the siloxane dispersing agent belong to low-activity substances, do not react with nano aluminum powder, and volatilize at the temperature of 720-750 ℃. The nano aluminum powder coating agent is coated on the surface of the nano silver powder, so that the surface of the nano silver powder is modified and coated, the nano aluminum powder is passivated at normal temperature, and 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 the exposure of the nano aluminum powder to 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 portions 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 of the above).
In the specific embodiment of the invention, the glass powder is prepared by adopting 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, the raw materials are put into a high temperature resistant crucible for smelting at 1000-1300 ℃ 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; pulverizing into glass powder by water quenching ball milling method or jet milling method, and oven drying. The average particle size of the glass frit is 0.5 to 5 μm, and in a preferred embodiment, the average particle size of the glass frit is 1 to 2 μm.
In the sintering process, the glass powder can effectively melt silicon nitride, and form a layer of ultrathin glass layer at the interface of the silicon substrate, and a large number of nano silver microcrystals are formed in the glass layer, so that the volume resistivity of the glass layer 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 friction resistance between silver-aluminum paste and a screen, improve the screen passing characteristic of paste and avoid the screen blocking after long-time printing. The thixotropic agent can enable the low viscosity characteristic of the silver-aluminum paste under high shearing acting force, improve the surface leveling characteristic of the paste after passing through the net and ensure good leveling line type.
Specifically, the resin comprises one or more combinations of ethyl cellulose, polyvinyl alcohol Ding Quanzhi, acrylic resin and aldehyde ketone resin; the organic solvent comprises any two or more of diethylene glycol butyl ether acetate, alcohol ester twelve, terpineol, diethylene glycol butyl ether acetate, dimethyl adipate, N-methylpyrrolidone, dimethyl phthalate and dimethyl terephthalate; the organic dispersant comprises one or more combinations of dispersants containing amine functional groups and dispersants containing fatty acid functional groups.
By adopting the resin, the paste printing effect can be effectively improved, the good aspect 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 particular embodiments of the present invention, the organic dispersant may be a commercially available BYK110 organic dispersant, or a commercially available Tego655 organic dispersant.
Optionally, the crystalline silicon solar cell silver-aluminum paste for low-temperature sintering further comprises 0-1.0 parts of organic auxiliary agent, wherein the organic auxiliary agent comprises one or more of leveling agent, organosilicon defoamer, silane coupling agent and titanate coupling agent.
The organic auxiliary agent can be added according to actual production requirements, 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 defoamer can reduce the surface tension of silver-aluminum paste and prevent foam formation; the silane coupling agent and the titanate coupling agent play a role in improving the dispersity 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 of:
preparing 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 nano aluminum powder pre-dispersion;
batching and mixing: weighing conductive silver powder, nano aluminum powder pre-dispersion, glass powder, an organic solvent, resin, an organic dispersing agent, a thixotropic agent, a slipping agent and an organic auxiliary agent according to the proportion, and mixing and stirring to obtain semi-finished silver paste;
rolling: grinding the semi-finished silver paste to obtain the silver aluminum paste of the crystalline silicon solar cell for low-temperature sintering.
In the step of preparing the nano aluminum powder pre-dispersion, firstly, soft nano aluminum powder agglomerates are fully opened and uniformly distributed in the nano aluminum powder coating agent to prevent the surface of the nano aluminum powder from being excessively oxidized. Subsequently, the conductive silver powder, the nano aluminum powder pre-dispersion, the glass powder, the organic solvent, the resin, the organic dispersing agent, the thixotropic agent, the slipping agent and the organic aid are fully mixed through the steps of batching and mixing, so that the conductive silver powder and the nano aluminum powder pre-dispersion are wetted by the resin and the organic solvent. The rolling process can adjust parameters such as different roller gaps, grinding speed, grinding times and the like according to actual demands, so that the semi-finished silver paste is ground to fineness below 10 mu m, and the silver-aluminum paste of the crystalline silicon solar cell for low-temperature sintering is obtained.
The invention also provides application of the crystalline silicon solar cell silver-aluminum paste 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 silver-aluminum paste for the low-temperature sintered crystalline silicon solar cell can be used as front silver-aluminum paste of a TOPCO crystalline silicon solar cell and used for preparing the TOPCO crystalline silicon solar cell. The silver-aluminum paste of the crystalline silicon solar cell utilizes the irregular atomic ordering characteristic of the aluminum powder surface with nanoscale 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 low-temperature sintering requirement 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 glass for 60min at 1200 ℃ by using a high-temperature smelting furnace, and rapidly cooling glass liquid by using a water quenching method after the glass is fully melted to obtain glass slag; quickly ball-milling glass slag by using a planetary ball mill provided with zirconium beads, and filtering glass liquid by using a 250-mesh screen after the particle size of glass powder is 2.5-3.0 mu m; and (5) drying the glass liquid by adopting an oven to obtain glass powder.
TABLE 1 formula of glass powder raw materials in weight portion
Example group B
Preparing silver-aluminum paste of a crystalline silicon solar cell, which comprises the following steps:
preparing nano aluminum powder pre-dispersion: mixing and stirring the nano aluminum powder and the nano aluminum powder coating agent according to the proportion of the table 2 to obtain nano aluminum powder pre-dispersion;
batching and mixing: weighing conductive silver powder, nano aluminum powder pre-dispersion, glass powder, an organic solvent, resin, an organic dispersing agent, a thixotropic agent, a slipping agent and an organic auxiliary agent according to the proportion of the table 2, and mixing and stirring to obtain semi-finished silver paste;
rolling: grinding the semi-finished silver paste by using a three-roller grinder, and evaluating fineness by using a scraper fineness gauge, wherein the grinding fineness of the paste is below 10 mu m, so as to obtain the silver-aluminum paste of the crystalline silicon solar cell for low-temperature sintering.
TABLE 2 silver aluminum paste Components
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 And/g. Example 4 used the glass frit described in example 1, examples 5 and examples 7 to 9 used the glass frit described in example 2, and example 6 used the glass frit described in example 3.
In examples 4 to 6, the average particle diameter of the nano aluminum powder is 50 to 60nm, the nano aluminum powder coating agent is an organosilicon dispersing agent, the slipping agent is silicone oil, the thixotropic agent is hydrogenated castor oil, the resin is ethyl cellulose, the organic solvent is dodecyl diethylene glycol butyl ether acetate and alcohol ester, and the commercial model of the organic dispersing agent is BYK 110.
In examples 7 to 9, the average particle diameter of the nano aluminum powder is 80 to 100nm, the nano aluminum powder coating agent is a siloxane dispersing agent, the slipping agent is erucamide, the thixotropic agent is polyamide wax, the resin is aldehyde ketone resin, the organic solvent is terpineol and dimethyl adipate, the commercial model of the organic dispersing agent is Tego655, and the organic auxiliary agent is an organosilicon defoaming agent.
Comparative example 1
The preparation method of comparative example 1 was identical to that of example 1 except that the components of comparative example 1 include 83 parts of conductive silver powder, 7 parts of the glass frit described in example 1, 1 part of aluminum powder having an average particle diameter of 1.5 to 2.0um, and the remaining other components were identical to that of example 1.
Comparative example 2
The preparation method of comparative example 1 was identical to that of example 1 except that the components of comparative example 2 include 83 parts of conductive silver powder, 5 parts of glass frit as described in example 2, 2 parts of aluminum powder having an average particle size of 2.0 to 3.0um, and the remaining other components were identical to that of example 1.
Comparative example 3
The preparation method of comparative example 1 was identical to that of example 1, except that the composition of comparative example 3 comprised 84 parts of conductive silver powder, 3 parts of the glass frit of example 3, 3 parts of aluminum powder having an average particle size of 3.0 to 4.0um, and the remaining other components were identical to that of example 1.
The crystalline silicon solar cell silver aluminum pastes for low temperature sintering prepared in examples 2 to 7 and comparative examples 1 to 3 were applied to TOPCon crystalline silicon solar cells, and specific cell preparation includes:
and (3) performing pre-cleaning, texturing and post-cleaning on the N-type crystalline silicon wafer, forming a front p+ layer through high-temperature diffusion or plasma doping process, forming a tunnel oxide layer on the back through oxidation process, and depositing by LPCVD or APCVD equipment to form a back polysilicon film. The front and back passivation dielectric films are formed through LPCVD or ALD and other processes. And printing the silver-aluminum paste of the crystalline silicon solar cell on the front surface of the TOPCO semi-finished product blue film by a screen printing or ink-jet printing mode, and printing the silver paste on the back surface of the TOPCO semi-finished product blue film. After the drying and sintering process, the silver-aluminum paste of the crystalline silicon solar cell and the silver paste on the back are volatilized organically, the glass powder is softened, and the silver powder, the aluminum powder or other inorganic powder is wetted. Glass powder of silver-aluminum paste of crystalline silicon solar cell melts front surface dielectric film and a small amount of p+ layer substrate at high temperature, and simultaneously conductive silver powder and nano aluminum powder are alloyed to promote the formation of good ohmic contact between silver-aluminum alloy and substrate, ultrathin glass film and substrate. The back side silver paste also melts the dielectric film such as back side silicon nitride and forms good ohmic contact with the back side polysilicon film. After the process, the complete TOPCon crystalline silicon solar cell is formed.
The bulk resistivity of the silver layer was evaluated by using an ohmic resistance tester by evaluating the contact resistivity of the silver layer with the substrate using a conventional four probe method (TLM). The conversion efficiency of the solar cell was evaluated by using a current-voltage electrical tester (IV tester) commonly used for solar cells, and the test results are shown in table 3.
TABLE 3 electrical properties and contact resistivity of TOPCON crystalline silicon solar cells
The sintering temperature is 750 ℃, voc is open circuit voltage, isc is short circuit current, FF is filling factor, rs is series resistance, rsh is parallel resistance, eta is conversion efficiency, irev2 is saturated leakage current in electric performance.
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 a silicon substrate can be reduced, the damage effect of active aluminum on a p-n junction is reduced, and meanwhile, 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, comparative examples 1 to 3 were designed with micro aluminum powder, and as the content of micro aluminum powder increases, the content of aluminum actually involved in contact with the silicon substrate increases, the contact resistivity drastically decreases, and the series resistance becomes smaller. In contrast, in comparative examples 4 to 6 and examples 7 to 9, the contact resistivity was decreased as the content of the nano-alumina powder was increased in the content range of the nano-alumina powder. As can be seen from the embodiment group B and the comparative examples 1 to 3, the introduction of the nano aluminum powder can effectively balance the relationship between the open circuit voltage and the contact resistance, and improve the filling factor, thereby improving the conversion efficiency of the TOPCon crystalline silicon solar cell, while the effect cannot be achieved by the micro aluminum powder.
The crystalline silicon solar cell silver aluminum pastes prepared using example 8 and comparative example 2 were sintered at 730 ℃ and 750 ℃ to prepare a TOPCon crystalline silicon solar cell, and electrical property data and contact resistivity tests were performed on the prepared TOPCon crystalline silicon solar cell, 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 micro aluminum powder resulted in a significant increase in series resistance with a decrease in sintering temperature, a significant decrease in the filled silver FF, and a large fluctuation in conversion efficiency. Whereas low temperature sintering has little effect on example 8 using nano-aluminum powder. Therefore, the silver-aluminum paste of the crystalline silicon solar cell is applied to the preparation of the TOPCO crystalline silicon solar cell, so that the sintering temperature can be effectively reduced, the higher conversion efficiency is ensured, and the development requirement of the TOPCO crystalline silicon solar cell for low-temperature sintering can be met.
The technical principle of the present invention is described above in connection with the specific embodiments. The description is made for the purpose of illustrating the general 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 from consideration of this specification without the exercise of inventive faculty, and such equivalent modifications and alternatives are intended to be included within the scope of the invention as defined in the claims.
Claims (9)
1. The silver-aluminum paste for the low-temperature sintering crystalline silicon solar cell is characterized by comprising the following components in parts by weight:
84.0 to 90.0 portions of conductive silver powder
0.7 to 5.0 parts of nano aluminum powder pre-dispersion
2.0 to 8.0 portions of glass powder
4.0 to 9.0 portions of organic solvent
0.1 to 1.0 part of resin
0.1 to 1.0 part of organic dispersant
Thixotropic agent 0.05-1.0 parts
0.1 to 1.0 part of slipping agent;
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-sized silver powder, and the particle size of the nanometer aluminum powder is 50-300 nm; the ratio of the nano aluminum powder coating agent to the nano aluminum powder is 1:9-9:1.
2. The crystalline silicon solar cell silver-aluminum paste for low-temperature sintering according to claim 1, wherein the particle size of the conductive silver powder is 0.5 to 3.0 μm, and the tap density of the conductive silver powder is 4.0 to 7.0g/cm 3 The specific surface area of the conductive silver powder is 0.1-2.0 cm 2 /g。
3. The crystalline silicon solar cell silver aluminum paste for low temperature sintering according to claim 1, wherein the nano aluminum powder coating agent comprises one or more combinations of organosilicon dispersing agents, alkane dispersing agents and siloxane dispersing agents.
4. The crystalline silicon solar cell silver aluminum paste for low-temperature sintering according to 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 to 6 portions 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 of the above).
5. A crystalline silicon solar cell silver aluminum paste for low temperature sintering according to claim 1, wherein the slip agent comprises one or more combinations of silicone oil, oleamide and erucamide; the thixotropic agent comprises one or more combinations of hydrogenated castor oil, polyamide wax, and polyurea.
6. A crystalline silicon solar cell silver aluminum paste for low temperature sintering according to claim 1, wherein the resin comprises one or more combinations of ethyl cellulose, polyvinyl acetal Ding Quanzhi, acrylic resin and aldehyde ketone resin; the organic solvent comprises any two or more of diethylene glycol butyl ether acetate, alcohol ester twelve, terpineol, diethylene glycol butyl ether acetate, dimethyl adipate, N-methylpyrrolidone, dimethyl phthalate and dimethyl terephthalate; the organic dispersant comprises one or more combinations of dispersants containing amine functional groups and dispersants containing fatty acid functional groups.
7. The crystalline silicon solar cell silver-aluminum paste for low-temperature sintering according to claim 1, further comprising 0 to 1.0 parts of an organic auxiliary agent, wherein the organic auxiliary agent comprises one or more of a leveling agent, an organosilicon antifoaming agent, a silane coupling agent and a titanate coupling agent.
8. A method for preparing crystalline silicon solar cell silver-aluminum paste for low temperature sintering, which is used for preparing crystalline silicon solar cell silver-aluminum paste for low temperature sintering according to any one of claims 1 to 7, and is characterized by comprising the following steps:
preparing 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 nano aluminum powder pre-dispersion;
batching and mixing: weighing conductive silver powder, nano aluminum powder pre-dispersion, glass powder, an organic solvent, resin, an organic dispersing agent, a thixotropic agent, a slipping agent and an organic auxiliary agent according to the proportion, and mixing and stirring to obtain semi-finished silver paste;
rolling: grinding the semi-finished silver paste to obtain the silver aluminum paste of the crystalline silicon solar cell for low-temperature sintering.
9. Use of a crystalline silicon solar cell silver-aluminum paste for low temperature sintering, characterized in that a TOPCon crystalline silicon solar cell is prepared using the crystalline silicon solar cell silver-aluminum paste for low temperature sintering according to any one of claims 1 to 7, the TOPCon crystalline silicon solar cell sintering temperature being 720 to 750 ℃.
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