CN117410010A - Low-temperature conductive silver paste for HJT battery and preparation method thereof - Google Patents
Low-temperature conductive silver paste for HJT battery and preparation method thereof Download PDFInfo
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- CN117410010A CN117410010A CN202311336565.2A CN202311336565A CN117410010A CN 117410010 A CN117410010 A CN 117410010A CN 202311336565 A CN202311336565 A CN 202311336565A CN 117410010 A CN117410010 A CN 117410010A
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- epoxy resin
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 241
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000007822 coupling agent Substances 0.000 claims abstract description 69
- 239000003822 epoxy resin Substances 0.000 claims abstract description 65
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 65
- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 59
- 239000002270 dispersing agent Substances 0.000 claims abstract description 58
- 239000000843 powder Substances 0.000 claims abstract description 48
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims description 80
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 39
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 31
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 24
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 24
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 24
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 24
- 239000005642 Oleic acid Substances 0.000 claims description 24
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 24
- -1 alcohol ester Chemical class 0.000 claims description 24
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 24
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 24
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 24
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 150000002460 imidazoles Chemical class 0.000 claims description 13
- 239000012948 isocyanate Substances 0.000 claims description 13
- 150000002513 isocyanates Chemical class 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 5
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 5
- 229910001887 tin oxide Inorganic materials 0.000 claims description 5
- 229910015900 BF3 Inorganic materials 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 3
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- PSXWNITXWWECNY-LPVGZGSHSA-N dTDP-4-dehydro-beta-L-rhamnose Chemical compound O[C@@H]1[C@H](O)C(=O)[C@H](C)O[C@@H]1OP(O)(=O)OP(O)(=O)OC[C@@H]1[C@@H](O)C[C@H](N2C(NC(=O)C(C)=C2)=O)O1 PSXWNITXWWECNY-LPVGZGSHSA-N 0.000 claims description 3
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 abstract description 24
- 239000004332 silver Substances 0.000 abstract description 24
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 description 45
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 21
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 21
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 21
- 239000003607 modifier Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 239000011812 mixed powder Substances 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000005274 electronic transitions Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000011882 ultra-fine particle Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229940023462 paste product Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—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 low-temperature conductive silver paste for HJT batteries, which comprises the following components in percentage by mass: 2 to 10 percent of epoxy resin, 0.5 to 2 percent of curing agent, 0.1 to 0.3 percent of curing accelerator, 85 to 92 percent of silver powder, 2 to 12 percent of organic solvent, 0.5 to 2 percent of dispersing agent, 0.1 to 0.3 percent of coupling agent and 0.03 to 1.35 percent of modified nano antimony tin oxide powder. According to the invention, the modified nano antimony tin oxide powder is added into the conductive silver paste, so that the silver gate electrode formed after the silver paste is solidified has the advantages of low resistivity, good conductivity, good durability and low production cost. The invention also discloses a preparation method of the low-temperature conductive silver paste for the HJT battery.
Description
Technical Field
The invention relates to the field of solar cells, in particular to low-temperature conductive silver paste for HJT cells and a preparation method thereof.
Background
HJT solar cells are the most efficient solar cell structures among known commercial cells. The conversion efficiency of the traditional crystalline silicon battery is 20.2%, the efficiency of the high-efficiency crystalline silicon battery can only reach 22%, and the highest efficiency of the HJT battery can reach 27%. However, the actual mass production efficiency of the current HJT battery is basically the same as that of the high-efficiency crystalline silicon battery, and the main technical difficulty is that the low-temperature silver paste has lower conductivity and the paste product accounts for more than 50% of the non-silicon product manufactured by the battery. Therefore, the breakthrough of HJT silver paste is important to the industrialization of batteries. The technical requirements of HJT silver paste such as high conductivity and rapid printing are difficult to meet simultaneously, so that the existing HJT battery silver paste industrialization technology is monopoly monopolized by foreign enterprises, the price is high, and the development of HJT battery technology in China is severely restricted.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide low-temperature conductive silver paste for HJT batteries and a preparation method thereof, and the modified nano antimony tin oxide powder is added into the conductive silver paste, so that a silver gate electrode formed after the silver paste is solidified has the advantages of low resistivity, good conductivity, good durability and low production cost.
The aim of the invention is achieved by the following technical scheme:
the low-temperature conductive silver paste for the HJT battery comprises the following components in percentage by mass: 2 to 10 percent of epoxy resin, 0.5 to 2 percent of curing agent, 0.1 to 0.3 percent of curing accelerator, 85 to 92 percent of silver powder, 2 to 12 percent of organic solvent, 0.5 to 2 percent of dispersing agent, 0.1 to 0.3 percent of coupling agent and 0.03 to 1.35 percent of modified nano antimony tin oxide powder.
Further, the epoxy resin includes one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, and alicyclic epoxy resin.
Further, the curing agent comprises one or more of dicyandiamide, blocked isocyanate, organoborane amine complex, latent imidazole modifier.
Further, the curing accelerator comprises one or more of DBU octoate, modified imidazole, acetylacetone metal salt and boron trifluoride complex.
Further, the dispersing agent is one or more of polyether phosphate, oleic acid, TDO and lauryl phosphate.
Further, the organic solvent is one or more of alcohol ester twelve, diethylene glycol diethyl ether acetate, diethylene glycol butyl ether and triethylene glycol butyl ether.
Further, the coupling agent is one or more of silane coupling agent, titanate coupling agent, aluminate coupling agent, bimetallic coupling agent, phosphate coupling agent and borate coupling agent.
Further, the preparation method of the modified nano antimony tin oxide powder comprises the following steps:
s11: mixing a silane coupling agent, methanol and water according to a certain proportion to form a mixed solution, and regulating the PH value to be acidic or alkaline;
s12: mixing nano antimony oxide and nano tin oxide according to a certain proportion, adding the mixture into the mixed solution, and uniformly stirring to obtain modified nano antimony tin oxide slurry;
s13: and drying the slurry, and stirring and dispersing uniformly to obtain the modified nano antimony tin oxide powder.
Further, the silver powder comprises submicron silver powder and micron silver powder, wherein the D50 of the submicron silver powder is 500-800nm, and the D50 of the micron silver powder is 2-5 mu m.
The invention also provides a preparation method of the low-temperature conductive silver paste for the HJT battery, which comprises the following steps:
s21: uniformly mixing and stirring epoxy resin, a curing agent, a curing accelerator, a coupling agent, a dispersing agent, an organic solvent and modified nano antimony tin oxide powder according to a proportion to obtain a first mixture;
s22: adding silver powder into the first mixture, and uniformly stirring to obtain a second mixture;
s23: grinding the second mixture to obtain the required conductive silver paste.
The invention has the beneficial effects that: the dispersing agent enables the modified nano antimony tin oxide to have extremely high interfacial stability activity, can be firmly adsorbed on the surfaces of solid particles, effectively solves the particle agglomeration effect, can effectively exclude the interfacial adsorption of water on a substrate, improves the wet adhesion of a coating product, enables the nano antimony tin oxide to be well dispersed in slurry and to be in good contact with a bottom substrate, reduces the electronic transition difficulty, enables the bridging effect among conductive silver powder particles to be more frequent, and enables the conductive performance to be better and increased; the modified nano antimony tin oxide has strong chemical stability, small physical property change caused by external environments such as heat, humidity and the like, can keep permanent conductive property and has good durability; the silver gate electrode formed by curing the conductive silver paste has the advantages of low resistivity, good conductivity and good durability by adding the modified nano antimony tin oxide, and the modified nano antimony tin oxide powder can replace part of silver powder, so that the cost is reduced.
Detailed Description
The invention provides low-temperature conductive silver paste for HJT batteries, which comprises the following components in percentage by mass: 2 to 10 percent of epoxy resin, 0.5 to 2 percent of curing agent, 0.1 to 0.3 percent of curing accelerator, 85 to 92 percent of silver powder, 2 to 12 percent of organic solvent, 0.5 to 2 percent of dispersing agent, 0.1 to 0.3 percent of coupling agent and 0.03 to 1.35 percent of modified nano antimony tin oxide powder. In the embodiment, the dispersing agent enables the modified nano antimony tin oxide to have extremely high interfacial stability activity, can be firmly adsorbed on the surfaces of solid particles, effectively solves the particle agglomeration effect, can effectively exclude the interfacial adsorption of moisture on a substrate, improves the wet adhesion of a coating product, enables the nano antimony tin oxide to be well dispersed in slurry and to be in good contact with the substrate on the bottom surface, reduces the electronic transition difficulty, and has the advantages of more frequent bridging action among conductive silver powder particles, better conductive performance and increased conductive performance; the modified nano antimony tin oxide has strong chemical stability, small physical property change caused by external environments such as heat, humidity and the like, can keep permanent conductive property and has good durability. According to the invention, the silver gate electrode formed after the conductive silver paste is solidified by adding the modified nano antimony tin oxide has the advantages of low resistivity, good conductivity and good durability, and the modified nano antimony tin oxide can replace part of silver powder, so that the cost is reduced.
Further, the epoxy resin includes one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, and alicyclic epoxy resin. The epoxy resin contains various functional groups, has good mechanical strength after solidification, and meets the function of further welding the HJT battery on the silver grid line.
Further, the curing agent comprises one or more of dicyandiamide, blocked isocyanate, organoborane amine complex, latent imidazole modifier. The curing agent can promote the curing and hardening of the silver paste. The epoxy resin can react with epoxy groups of epoxy resin in silver paste to form a high-strength network structure, so that the tensile strength, bending strength and impact strength of the silver paste are obviously improved. Meanwhile, the curing agent can improve the binding force and stability of the silver paste, so that the service life and reliability of the silver paste are prolonged.
Further, the curing accelerator comprises one or more of DBU octoate, modified imidazole, acetylacetone metal salt and boron trifluoride complex. The curing accelerator can accelerate the action of the curing agent, so that the reaction speed of the curing agent is higher, the curing process of the material is accelerated, polymer molecules are more tightly combined, and the hardness and the strength of the material are enhanced in a short time
Further, the dispersing agent is one or more of polyether phosphate, oleic acid, TDO and lauryl phosphate, so that the raw materials can be uniformly dispersed.
Further, the organic solvent is one or more of alcohol ester twelve, diethylene glycol diethyl ether acetate, diethylene glycol butyl ether and triethylene glycol butyl ether. By adding a solvent, the conductive silver paste can be diluted to adjust the viscosity and fluidity of the paste so that it is suitable for the printing process.
Further, the coupling agent is one or more of silane coupling agent, titanate coupling agent, aluminate coupling agent, bimetallic coupling agent, phosphate coupling agent and borate coupling agent.
Further, the preparation method of the modified nano antimony tin oxide powder comprises the following steps:
s11: mixing a silane coupling agent, methanol and water according to a certain proportion to form a mixed solution, and regulating the PH value to be acidic or alkaline; specifically, firstly, hydrolyzing a silane coupling agent, optionally adding 10-20% of methoxy silane coupling agent, 65-75% of methanol and 5-20% of pure water, wherein the silane is hydrolyzed at a speed related to the PH value, the neutrality is slowest, the meta-acid and meta-alkali are both faster, and a small amount of acetic acid can be added to enable the PH value of the mixed solution to be between 4 and 5, and standing for 15-30min for hydrolysis;
s12: mixing nano antimony oxide and nano tin oxide according to a certain proportion, adding the mixture into the mixed solution, and uniformly stirring to obtain modified nano antimony tin oxide slurry; specifically, 85% of nano antimony oxide powder (30-50 nm) and 15% of nano tin oxide powder (30-50 nm) are added to form mixed powder (nano antimony tin oxide mixed powder), and after the mixed powder is added to the mixed liquid for wetting, a V-shaped solid stirrer is added, and stirring is carried out for 1-2h at 15-20 rpm;
s13: drying the slurry, drying at 80-100 ℃ for 2-4h, stirring, adding a V-shaped solid stirrer, stirring at 15-20rpm for 30min, and dispersing uniformly to obtain the modified nano antimony tin oxide powder. The surface modification of the nano antimony tin oxide can improve the dispersity of the nano antimony tin oxide, reduce agglomeration and improve the performance. The nano antimony tin oxide has large specific surface area, so that the nano antimony tin oxide can be uniformly dispersed in an organic solvent when the conductive silver paste is prepared; however, the addition amount is not excessive, which results in excessive viscosity of silver paste and inability to carry out screen printing.
Further, the silver powder comprises submicron silver powder and micron silver powder, wherein the D50 of the submicron silver powder is 500-800nm, and the D50 of the micron silver powder is 2-5 mu m. The silver powder includes plate-like silver powder and spherical silver powder.
The invention also provides a method for preparing the low-temperature conductive silver paste for HJT batteries, which comprises the following steps:
s21: uniformly mixing and stirring epoxy resin, a curing agent, a curing accelerator, a coupling agent, a dispersing agent, an organic solvent and modified nano antimony tin oxide powder according to a proportion to obtain a first mixture; manual stirring or stirrer stirring can be selected;
s22: adding silver powder into the first mixture, and uniformly stirring to obtain a second mixture; manual stirring or stirring by a stirrer can be selected, and uniformly mixing can be performed at the rotation speed of 550-1000rpm of the vacuum homogenizer;
s23: grinding the second mixture to obtain the required conductive silver paste; the grinding can be carried out by a three-roller mill, and the minimum clearance is not smaller than 10 mu m.
The beneficial effects of the invention are as follows:
(1) The conductivity is high: the silver paste comprises a dispersing agent, when the modified nano antimony tin oxide powder is added, the dispersing agent (such as TDO) can enable the modified nano antimony tin oxide to have extremely high interfacial stability activity, can be firmly adsorbed on the surfaces of solid particles, effectively solves the particle agglomeration effect, can effectively exclude the interfacial adsorption of water on a substrate, improves the wet adhesion of a coating product, enables the nano antimony tin oxide to be well dispersed in the paste, has good contact with the substrate on the bottom surface, reduces the electronic transition difficulty, enables bridging among conductive silver powder particles to be more frequent, has better conductivity and increases conductivity; the conductive film is formed by the interaction of the uniformly dispersed conductive nano ultrafine particles, and the high transmittance and antistatic effect can be realized by the movement of charges in the conductive film;
(2) The durability is good: the nano ultra-fine particle modified nano antimony tin oxide powder with stable chemical property has small physical property change caused by external environment such as heat, humidity and the like, and can keep permanent conductive property; oxygen vacancies or electrons formed when antimony doped tin is used for forming a defect solid are used as carriers for conduction, the conductivity is not influenced by environmental humidity, and the defect of dependence of an organic antistatic agent on the environment is avoided;
(3) The cost is low: 3-6% of silver powder can be replaced by adding modified nano antimony tin oxide powder, so that the cost is reduced.
The present invention will be further elucidated with reference to the following embodiments, which should be understood as merely illustrative of the invention and not as limiting the scope of the invention.
Examples 1 to 20:
example 1
The invention provides a low-temperature conductive silver paste for HJT batteries, which comprises the following components in percentage by mass: 3.7% of epoxy resin, 1.2% of curing agent, 0.1% of curing accelerator, 0.12% of dispersing agent, 2.65% of solvent, 0.2% of coupling agent, 92% of silver powder and 0.03% of modified nano antimony tin oxide powder;
the epoxy resin comprises 15% bisphenol a epoxy resin, 35% cycloaliphatic epoxy resin and 50% bisphenol F epoxy resin;
the curing agent is a latent imidazole modifier;
the curing accelerator is DBU octoate;
the dispersing agent is a mixture of TDO and oleic acid;
the coupling agent is a silane coupling agent;
the solvent is a mixture of alcohol ester twelve, diethylene glycol diethyl ether acetate and diethylene glycol butyl ether acetate;
the silver powder is a mixture of silver powder with D50 of 500-800nm and D50 of 2-5 μm, and comprises spherical silver powder and flake silver powder.
The manufacturing steps of the low-temperature conductive silver paste for HJT battery of the embodiment comprise: uniformly mixing epoxy resin, a curing agent, a curing accelerator, a dispersing agent, a solvent, a coupling agent and modified nano antimony tin oxide powder in a homogenizer at a rotating speed of 550-1000rpm; adding silver powder into the prepared mixture, mixing uniformly at 550-1000rpm; and grinding the mixed slurry by a three-roller mill until the fineness of the slurry is below 10 mu m, thus obtaining the required conductive silver slurry.
The preparation method of the modified nano antimony tin oxide powder comprises the following steps:
(1) Firstly, hydrolyzing a silane coupling agent, and mixing 10-20% of a methoxy silane coupling agent, 65-75% of methanol and 5-20% of pure water; because the hydrolysis speed of the silane is related to the PH value, the neutrality is slowest, the meta-acid and the meta-alkali are both faster, a small amount of acetic acid can be added to enable the PH value of the mixed solution to be between 4 and 5, and the mixed solution is placed for 15 to 30 minutes to wait for hydrolysis;
(2) Adding 85% of nano antimony oxide (30-50 nm) and 15% of nano tin oxide (30-50 nm) to form mixed powder (nano antimony tin oxide mixed powder), adding the prepared mixed liquid to wet, adding a V-shaped solid stirrer, and stirring at 15-20rpm for 1-2h;
(3) Taking out, and drying at 80-100deg.C for 2-4 hr;
(4) Adding into V-shaped solid stirrer, stirring at 15-20rpm for 30min; taking out the powder which is the surface modified nano antimony tin oxide for standby.
Example 2
The invention provides a low-temperature conductive silver paste for HJT batteries, which comprises the following components in percentage by mass: 3.7% of epoxy resin, 1.2% of curing agent, 0.1% of curing accelerator, 0.125% of dispersing agent, 2.6% of solvent, 0.2% of coupling agent, 92% of silver powder and 0.075% of modified nano antimony tin oxide powder;
the epoxy resin comprises 15% bisphenol a epoxy resin, 35% cycloaliphatic epoxy resin and 50% bisphenol F epoxy resin;
the curing agent is a latent imidazole modifier;
the curing accelerator is DBU octoate;
the dispersing agent is a mixture of TDO and oleic acid;
the coupling agent is a silane coupling agent;
the solvent is a mixture of alcohol ester twelve, diethylene glycol diethyl ether acetate and diethylene glycol butyl ether acetate;
the silver powder is a mixture of silver powder with D50 of 500-800nm and D50 of 2-5 μm, and comprises spherical silver powder and flake silver powder.
Example 3
The invention provides a low-temperature conductive silver paste for HJT batteries, which comprises the following components in percentage by mass: 3.7% of epoxy resin, 1.2% of curing agent, 0.1% of curing accelerator, 0.13% of dispersing agent, 2.55% of solvent, 0.2% of coupling agent, 92% of silver powder and 0.12% of modified nano antimony tin oxide powder;
the epoxy resin comprises 15% bisphenol a epoxy resin, 35% cycloaliphatic epoxy resin and 50% bisphenol F epoxy resin;
the curing agent is a latent imidazole modifier;
the curing accelerator is DBU octoate;
the dispersing agent is a mixture of TDO and oleic acid;
the coupling agent is a silane coupling agent;
the solvent is a mixture of alcohol ester twelve, diethylene glycol diethyl ether acetate and diethylene glycol butyl ether acetate;
the silver powder is a mixture of silver powder with D50 of 500-800nm and D50 of 2-5 μm, and comprises spherical silver powder and flake silver powder.
Example 4
The invention provides a low-temperature conductive silver paste for HJT batteries, which comprises the following components in percentage by mass: 3.7% of epoxy resin, 1.2% of curing agent, 0.1% of curing accelerator, 0.135% of dispersing agent, 2.515% of solvent, 0.2% of coupling agent, 92% of silver powder and 0.15% of modified nano antimony tin oxide powder;
the epoxy resin comprises 15% bisphenol a epoxy resin, 35% cycloaliphatic epoxy resin and 50% bisphenol F epoxy resin;
the curing agent is a latent imidazole modifier;
the curing accelerator is DBU octoate;
the dispersing agent is a mixture of TDO and oleic acid;
the coupling agent is a silane coupling agent;
the solvent is a mixture of alcohol ester twelve, diethylene glycol diethyl ether acetate and diethylene glycol butyl ether acetate;
the silver powder is a mixture of silver powder with D50 of 500-800nm and D50 of 2-5 μm, and comprises spherical silver powder and flake silver powder.
Example 5
The invention provides a low-temperature conductive silver paste for HJT batteries, which comprises the following components in percentage by mass: 3.7% of epoxy resin, 1.2% of curing agent, 0.1% of curing accelerator, 0.137% of dispersing agent, 2.483% of solvent, 0.2% of coupling agent, 92% of silver powder and 0.18% of modified nano antimony tin oxide powder;
the epoxy resin comprises 15% bisphenol a epoxy resin, 35% cycloaliphatic epoxy resin and 50% bisphenol F epoxy resin;
the curing agent is a latent imidazole modifier;
the curing accelerator is DBU octoate;
the dispersing agent is a mixture of TDO and oleic acid;
the coupling agent is a silane coupling agent;
the solvent is a mixture of alcohol ester twelve, diethylene glycol diethyl ether acetate and diethylene glycol butyl ether acetate;
the silver powder is a mixture of silver powder with D50 of 500-800nm and D50 of 2-5 μm, and comprises spherical silver powder and flake silver powder.
Example 6
The invention provides a low-temperature conductive silver paste for HJT batteries, which comprises the following components in percentage by mass: 3.7% of epoxy resin, 1.2% of curing agent, 0.1% of curing accelerator, 0.138% of dispersing agent, 2.437% of solvent, 0.2% of coupling agent, 92% of silver powder and 0.225% of modified nano antimony tin oxide powder;
the epoxy resin comprises 15% bisphenol a epoxy resin, 35% cycloaliphatic epoxy resin and 50% bisphenol F epoxy resin;
the curing agent is a latent imidazole modifier;
the curing accelerator is DBU octoate;
the dispersing agent is a mixture of TDO and oleic acid;
the coupling agent is a silane coupling agent;
the solvent is a mixture of alcohol ester twelve, diethylene glycol diethyl ether acetate and diethylene glycol butyl ether acetate;
the silver powder is a mixture of silver powder with D50 of 500-800nm and D50 of 2-5 μm, and comprises spherical silver powder and flake silver powder.
Example 7
The invention provides a low-temperature conductive silver paste for HJT batteries, which comprises the following components in percentage by mass: 3.7% of epoxy resin, 1.2% of curing agent, 0.1% of curing accelerator, 0.14% of dispersing agent, 2.39% of solvent, 0.2% of coupling agent, 92% of silver powder and 0.27% of modified nano antimony tin oxide powder;
the epoxy resin comprises 15% bisphenol a epoxy resin, 35% cycloaliphatic epoxy resin and 50% bisphenol F epoxy resin;
the curing agent is a latent imidazole modifier;
the curing accelerator is DBU octoate;
the dispersing agent is a mixture of TDO and oleic acid;
the coupling agent is a silane coupling agent;
the solvent is a mixture of alcohol ester twelve, diethylene glycol diethyl ether acetate and diethylene glycol butyl ether acetate;
the silver powder is a mixture of silver powder with D50 of 500-800nm and D50 of 2-5 μm, and comprises spherical silver powder and flake silver powder.
Example 8
The invention provides a low-temperature conductive silver paste for HJT batteries, which comprises the following components in percentage by mass: 3.7% of epoxy resin, 1.2% of curing agent, 0.1% of curing accelerator, 0.142% of dispersing agent, 2.358% of solvent, 0.2% of coupling agent, 92% of silver powder and 0.3% of modified nano antimony tin oxide powder;
the epoxy resin comprises 15% bisphenol a epoxy resin, 35% cycloaliphatic epoxy resin and 50% bisphenol F epoxy resin;
the curing agent is a latent imidazole modifier;
the curing accelerator is DBU octoate;
the dispersing agent is a mixture of TDO and oleic acid;
the coupling agent is a silane coupling agent;
the solvent is a mixture of alcohol ester twelve, diethylene glycol diethyl ether acetate and diethylene glycol butyl ether acetate;
the silver powder is a mixture of silver powder with D50 of 500-800nm and D50 of 2-5 μm, and comprises spherical silver powder and flake silver powder.
Example 9
The invention provides a low-temperature conductive silver paste for HJT batteries, which comprises the following components in percentage by mass: 2.8% of epoxy resin, 1% of curing agent, 0.1% of curing accelerator, 0.142% of dispersing agent, 3.458% of solvent, 0.2% of coupling agent, 92% of silver powder and 0.3% of modified nano antimony tin oxide powder;
the epoxy resin comprises 15% bisphenol a epoxy resin, 35% cycloaliphatic epoxy resin and 50% bisphenol F epoxy resin;
the curing agent is a latent imidazole modifier;
the curing accelerator is DBU octoate;
the dispersing agent is a mixture of TDO and oleic acid;
the coupling agent is a silane coupling agent;
the solvent is a mixture of alcohol ester twelve, diethylene glycol diethyl ether acetate and diethylene glycol butyl ether acetate;
the silver powder is a mixture of silver powder with D50 of 500-800nm and D50 of 2-5 μm, and comprises spherical silver powder and flake silver powder.
Example 10
The invention provides a low-temperature conductive silver paste for HJT batteries, which comprises the following components in percentage by mass: 2.8% of epoxy resin, 1% of curing agent, 0.1% of curing accelerator, 0.142% of dispersing agent, 3.458% of solvent, 0.2% of coupling agent, 92% of silver powder and 0.3% of modified nano antimony tin oxide powder;
the epoxy resin comprises 15% bisphenol a epoxy resin, 35% cycloaliphatic epoxy resin and 50% bisphenol F epoxy resin;
the curing agent is closed isocyanate;
the curing accelerator is modified imidazole;
the dispersing agent is a mixture of TDO and oleic acid;
the coupling agent is a silane coupling agent;
the solvent is a mixture of alcohol ester twelve, diethylene glycol diethyl ether acetate and diethylene glycol butyl ether acetate;
the silver powder is a mixture of silver powder with D50 of 500-800nm and D50 of 2-5 μm, and comprises spherical silver powder and flake silver powder.
Example 11
The invention provides a low-temperature conductive silver paste for HJT batteries, which comprises the following components in percentage by mass: 2.8% of epoxy resin, 1% of curing agent, 0.1% of curing accelerator, 0.142% of dispersing agent, 3.458% of solvent, 0.2% of coupling agent, 92% of silver powder and 0.3% of modified nano antimony tin oxide powder;
the epoxy resin comprises 15% bisphenol a epoxy resin, 35% cycloaliphatic epoxy resin and 50% bisphenol F epoxy resin;
the curing agent is an organoboron amine complex;
the curing accelerator is modified imidazole;
the dispersing agent is a mixture of TDO and oleic acid;
the coupling agent is a silane coupling agent;
the solvent is a mixture of alcohol ester twelve, diethylene glycol diethyl ether acetate and diethylene glycol butyl ether acetate; the silver powder is a mixture of silver powder with D50 of 500-800nm and D50 of 2-5 μm, and comprises spherical silver powder and flake silver powder.
Example 12
The invention provides a low-temperature conductive silver paste for HJT batteries, which comprises the following components in percentage by mass: 2.8% of epoxy resin, 1% of curing agent, 0.1% of curing accelerator, 0.142% of dispersing agent, 3.458% of solvent, 0.2% of coupling agent, 92% of silver powder and 0.3% of modified nano antimony tin oxide powder;
the epoxy resin comprises 15% bisphenol a epoxy resin, 35% cycloaliphatic epoxy resin and 50% bisphenol F epoxy resin;
the curing agent is dicyandiamide;
the curing accelerator is acetylacetone metal salt;
the dispersing agent is a mixture of TDO and oleic acid;
the coupling agent is a silane coupling agent;
the solvent is a mixture of alcohol ester twelve, diethylene glycol diethyl ether acetate and diethylene glycol butyl ether acetate;
the silver powder is a mixture of silver powder with D50 of 500-800nm and D50 of 2-5 μm, and comprises spherical silver powder and flake silver powder.
Example 13
The invention provides a low-temperature conductive silver paste for HJT batteries, which comprises the following components in percentage by mass:
2.8% of epoxy resin, 1% of curing agent, 0.1% of curing accelerator, 0.142% of dispersing agent, 3.458% of solvent, 0.2% of coupling agent, 92% of silver powder and 0.3% of modified nano antimony tin oxide powder;
the epoxy resin comprises 15% bisphenol a epoxy resin, 35% cycloaliphatic epoxy resin and 50% bisphenol F epoxy resin;
the curing agent is blocked isocyanate;
the curing accelerator is boron trifluoride complex;
the dispersing agent is a mixture of TDO and oleic acid;
the coupling agent is a silane coupling agent;
the solvent is a mixture of alcohol ester twelve, diethylene glycol diethyl ether acetate and diethylene glycol butyl ether acetate;
the silver powder is a mixture of silver powder with D50 of 500-800nm and D50 of 2-5 μm, and comprises spherical silver powder and flake silver powder.
Example 14
The invention provides a low-temperature conductive silver paste for HJT batteries, which comprises the following components in percentage by mass:
2.8% of epoxy resin, 1% of curing agent, 0.1% of curing accelerator, 0.15% of dispersing agent, 4.3% of solvent, 0.2% of coupling agent, 91% of silver powder and 0.45% of modified nano antimony tin oxide powder;
the epoxy resin comprises 15% bisphenol a epoxy resin, 35% cycloaliphatic epoxy resin and 50% bisphenol F epoxy resin;
the curing agent is closed isocyanate;
the curing accelerator is modified imidazole;
the dispersing agent is a mixture of TDO and oleic acid;
the coupling agent is a silane coupling agent;
the solvent is a mixture of alcohol ester twelve, diethylene glycol diethyl ether acetate and diethylene glycol butyl ether acetate;
the silver powder is a mixture of silver powder with D50 of 500-800nm and D50 of 2-5 μm, and comprises spherical silver powder and flake silver powder.
Example 15
The invention provides a low-temperature conductive silver paste for HJT batteries, which comprises the following components in percentage by mass:
2.8% of epoxy resin, 1% of curing agent, 0.1% of curing accelerator, 0.16% of dispersing agent, 5.14% of solvent, 0.2% of coupling agent, 90% of silver powder and 0.6% of modified nano antimony tin oxide powder;
the epoxy resin comprises 15% bisphenol a epoxy resin, 35% cycloaliphatic epoxy resin and 50% bisphenol F epoxy resin;
the curing agent is closed isocyanate;
the curing accelerator is modified imidazole;
the dispersing agent is a mixture of TDO and oleic acid;
the coupling agent is a silane coupling agent;
the solvent is a mixture of alcohol ester twelve, diethylene glycol diethyl ether acetate and diethylene glycol butyl ether acetate;
the silver powder is a mixture of silver powder with D50 of 500-800nm and D50 of 2-5 μm, and comprises spherical silver powder and flake silver powder.
Example 16
The invention provides a low-temperature conductive silver paste for HJT batteries, which comprises the following components in percentage by mass:
2.8% of epoxy resin, 1% of curing agent, 0.1% of curing accelerator, 0.17% of dispersing agent, 5.98% of solvent, 0.2% of coupling agent, 89% of silver powder and 0.75% of modified nano antimony tin oxide powder;
the epoxy resin comprises 15% bisphenol a epoxy resin, 35% cycloaliphatic epoxy resin and 50% bisphenol F epoxy resin;
the curing agent is closed isocyanate;
the curing accelerator is modified imidazole;
the dispersing agent is a mixture of TDO and oleic acid;
the coupling agent is a silane coupling agent;
the solvent is a mixture of alcohol ester twelve, diethylene glycol diethyl ether acetate and diethylene glycol butyl ether acetate;
the silver powder is a mixture of silver powder with D50 of 500-800nm and D50 of 2-5 μm, and comprises spherical silver powder and flake silver powder.
Example 17
The invention provides a low-temperature conductive silver paste for HJT batteries, which comprises the following components in percentage by mass:
2.8% of epoxy resin, 1% of curing agent, 0.1% of curing accelerator, 0.18% of dispersing agent, 6.82% of solvent, 0.2% of coupling agent, 88% of silver powder and 0.9% of modified nano antimony tin oxide powder;
the epoxy resin comprises 15% bisphenol a epoxy resin, 35% cycloaliphatic epoxy resin and 50% bisphenol F epoxy resin;
the curing agent is closed isocyanate;
the curing accelerator is modified imidazole;
the dispersing agent is a mixture of TDO and oleic acid;
the coupling agent is a silane coupling agent;
the solvent is a mixture of alcohol ester twelve, diethylene glycol diethyl ether acetate and diethylene glycol butyl ether acetate;
the silver powder is a mixture of silver powder with D50 of 500-800nm and D50 of 2-5 μm, and comprises spherical silver powder and flake silver powder.
Example 18
The invention provides a low-temperature conductive silver paste for HJT batteries, which comprises the following components in percentage by mass:
2.8% of epoxy resin, 1% of curing agent, 0.1% of curing accelerator, 0.19% of dispersing agent, 7.66% of solvent, 0.2% of coupling agent, 87% of silver powder and 1.05% of modified nano antimony tin oxide powder;
the epoxy resin comprises 15% bisphenol a epoxy resin, 35% cycloaliphatic epoxy resin and 50% bisphenol F epoxy resin;
the curing agent is blocked isocyanate.
The curing accelerator is modified imidazole.
The dispersing agent is a mixture of TDO and oleic acid.
The coupling agent is a silane coupling agent;
the solvent is a mixture of alcohol ester twelve, diethylene glycol diethyl ether acetate and diethylene glycol butyl ether acetate.
The silver powder is a mixture of silver powder with D50 of 500-800nm and D50 of 2-5 μm, and comprises spherical silver powder and flake silver powder.
Example 19
The invention provides a low-temperature conductive silver paste for HJT batteries, which comprises the following components in percentage by mass:
2.8% of epoxy resin, 1% of curing agent, 0.1% of curing accelerator, 0.2% of dispersing agent, 8.5% of solvent, 0.2% of coupling agent, 86% of silver powder and 1.2% of modified nano antimony tin oxide powder;
the epoxy resin comprises 15% bisphenol a epoxy resin, 35% cycloaliphatic epoxy resin and 50% bisphenol F epoxy resin;
the curing agent is closed isocyanate;
the curing accelerator is modified imidazole;
the dispersing agent is a mixture of TDO and oleic acid;
the coupling agent is a silane coupling agent;
the solvent is a mixture of alcohol ester twelve, diethylene glycol diethyl ether acetate and diethylene glycol butyl ether acetate;
the silver powder is a mixture of silver powder with D50 of 500-800nm and D50 of 2-5 μm, and comprises spherical silver powder and flake silver powder.
Example 20
The invention provides a low-temperature conductive silver paste for HJT batteries, which comprises the following components in percentage by mass:
2.8% of epoxy resin, 1% of curing agent, 0.1% of curing accelerator, 0.21% of dispersing agent, 9.34% of solvent, 0.2% of coupling agent, 85% of silver powder and 1.35% of modified nano antimony tin oxide powder;
the epoxy resin comprises 15% bisphenol a epoxy resin, 35% cycloaliphatic epoxy resin and 50% bisphenol F epoxy resin;
the curing agent is closed isocyanate;
the curing accelerator is modified imidazole;
the dispersing agent is a mixture of TDO and oleic acid;
the coupling agent is a silane coupling agent;
the solvent is a mixture of alcohol ester twelve, diethylene glycol diethyl ether acetate and diethylene glycol butyl ether acetate.
The silver powder is a mixture of silver powder with D50 of 500-800nm and D50 of 2-5 μm, and comprises spherical silver powder and flake silver powder.
Wherein, the preparation method of the low-temperature conductive silver paste for HJT battery of examples 2-20 and the preparation method of the modified nano antimony tin oxide are the same as example 1, and each component is adjusted according to the requirement.
Comparative example 1
The invention provides conventional conductive silver paste, which comprises the following components in percentage by mass:
4.2% of epoxy resin, 1.2% of curing agent, 0.1% of curing accelerator, 0.1% of dispersing agent, 2.2% of solvent, 0.2% of coupling agent and 92% of silver powder;
the epoxy resin comprises 15% bisphenol a epoxy resin, 35% cycloaliphatic epoxy resin and 50% bisphenol F epoxy resin;
the curing agent is a latent imidazole modifier;
the curing accelerator is DBU octoate;
the dispersing agent is a mixture of polyether phosphate and oleic acid;
the coupling agent is a silane coupling agent;
the solvent is a mixture of alcohol ester twelve, diethylene glycol diethyl ether acetate and diethylene glycol butyl ether acetate;
the silver powder is a mixture of silver powder with D50 of 500-800nm and D50 of 2-5 μm, and comprises spherical silver powder and flake silver powder.
The invention mixes the epoxy resin, the curing agent, the curing accelerator, the dispersing agent, the coupling agent and the solvent uniformly in a homogenizer with the rotating speed of 550-1000rpm; adding silver powder into the prepared mixture, mixing uniformly at 550-1000rpm; and grinding the mixed slurry by a three-roller mill until the fineness of the slurry is below 10 mu m, thus obtaining the conventional conductive silver slurry.
Testing
Using the low-temperature conductive silver pastes of example 1 to example 20 and comparative example 1 as samples, each sample was printed on the same substrate to perform a related property test, and the test procedure was as follows:
1. resistivity test: the resistance at both ends of the electrode was tested using a four-probe ohmmeter.
2. Viscosity test: the viscosity test is to test the viscosity value at stirring for 4min with a Bowler-Nordheim viscometer at 10 revolutions per minute.
3. Contact resistance: printing a specific pattern on the heterojunction battery piece by the low-temperature silver paste, and then drying and curing; cutting out a battery piece with a printed pattern area of a preset size by using a laser slicer; contact resistance was measured using a TLM contact resistance device.
4. Durability test: and printing a specific pattern on the heterojunction battery piece by the low-temperature silver paste, drying and solidifying, putting the heterojunction battery piece into a constant temperature (65 ℃) constant humidity (65%) box, and taking out the heterojunction battery piece after 720 hours of constant temperature (65%). The resistance was tested and the difference between the front and rear resistances was compared.
The test data are shown in tables 1-3.
Table 1 resistivity test comparative tables for examples 1-13 and comparative example 1
| Numbering device | Resistivity/10 -6 Ω·cm |
| Example 1 | 6.3 |
| Example 2 | 6.2 |
| Example 3 | 6.1 |
| Example 4 | 5.8 |
| Example 5 | 5.8 |
| Example 6 | 5.7 |
| Example 7 | 5.7 |
| Example 8 | 5.6 |
| Example 9 | 5.6 |
| Example 10 | 5.5 |
| Example 11 | 5.9 |
| Example 12 | 5.7 |
| Example 13 | 6.0 |
| Comparative example 1 | 6.5 |
As can be seen from Table 1, the resistivity of examples 1 to 13 was reduced as compared with comparative example 1, i.e., the silver gate electrode formed after curing the conductive silver paste had excellent conductivity by adding the modified nano-antimony tin oxide powder. Of these, example 10 had the least resistivity. And when the curing agent is closed isocyanate and the curing accelerator is modified imidazole, the conductive silver paste has better performances.
Table 2 comparative table of resistivity, viscosity and contact resistance tests of example 10 and examples 14-20
Comparing examples 14-20 with example 10, and comparing the silver powder reduction test, it is clear from Table 2 that when the mass percentage of the modified nano antimony tin oxide powder to replace silver powder is between 3-6%, the conductivity is slightly increased, and the viscosity is increased but can be ensured to be within the printing range; the addition amount is more than 8%, and the conductivity is reduced due to the insufficient filling amount of the main conductive silver powder; therefore, when the conductivity of the silver paste is enhanced and the viscosity is within the printing range, 3-6% of silver powder can be replaced by adding the modified nano antimony tin oxide powder, so that the overall cost of the paste is reduced.
TABLE 3 durability test results for examples 15-20 and comparative example 1
As can be seen from table 3, the low-temperature silver paste was printed with a specific pattern on the heterojunction cell, dried and cured, and then put into a constant temperature (65 ℃) and constant humidity (65%) box for 720 hours, and then taken out. By comparing the difference between the resistances before and after, it is known that the increase rate of the resistance is reduced and the durability is improved by adding the nano antimony tin oxide powder.
It should be noted that, in the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described as different from other embodiments, and identical and similar parts between the embodiments are all enough to be referred to each other.
The present invention is not limited to the preferred embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (10)
1. The low-temperature conductive silver paste for HJT battery is characterized by comprising the following components in percentage by mass: 2 to 10 percent of epoxy resin, 0.5 to 2 percent of curing agent, 0.1 to 0.3 percent of curing accelerator, 85 to 92 percent of silver powder, 2 to 12 percent of organic solvent, 0.5 to 2 percent of dispersing agent, 0.1 to 0.3 percent of coupling agent and 0.03 to 1.35 percent of modified nano antimony tin oxide powder.
2. The low temperature conductive silver paste for HJT cells of claim 1, wherein the epoxy resin comprises one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, and cycloaliphatic epoxy resin.
3. The low temperature conductive silver paste for HJT cells of claim 1, wherein said curing agent comprises one or more of dicyandiamide, blocked isocyanate, organoborane amine complex, latent imidazole modification.
4. The low temperature conductive silver paste for HJT cells of claim 1, wherein said curing accelerator comprises one or more of DBU octoate, modified imidazole, acetylacetonate metal salt, boron trifluoride complex.
5. The low temperature conductive silver paste for HJT cells of claim 1, wherein said dispersant is one or more of polyether phosphate, oleic acid, TDO, lauryl phosphate.
6. The low temperature conductive silver paste for HJT cells of claim 1, wherein the organic solvent is one or more of alcohol ester twelve, diethylene glycol diethyl ether acetate, diethylene glycol butyl ether and triethylene glycol butyl ether.
7. The low temperature conductive silver paste for HJT cells of claim 1, wherein the coupling agent is one or more of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a bimetallic coupling agent, a phosphate coupling agent, a borate coupling agent.
8. The low-temperature conductive silver paste for HJT cells of claim 1, wherein the preparation method of the modified nano-antimony tin oxide powder comprises the following steps:
s11: mixing a silane coupling agent, methanol and water according to a certain proportion to form a mixed solution, and regulating the PH value to be acidic or alkaline;
s12: mixing nano antimony oxide and nano tin oxide according to a certain proportion, adding the mixture into the mixed solution, and uniformly stirring to obtain modified nano antimony tin oxide slurry;
s13: and drying the slurry, and stirring and dispersing uniformly to obtain the modified nano antimony tin oxide powder.
9. The low temperature conductive silver paste for HJT cells of claim 1, wherein said silver powder comprises submicron silver powder having a D50 of 500 to 800nm and micron silver powder having a D50 of 2 to 5 μm.
10. A method for preparing the low-temperature conductive silver paste for HJT batteries based on any one of claims 1 to 9, which comprises the following steps:
s21: uniformly mixing and stirring epoxy resin, a curing agent, a curing accelerator, a coupling agent, a dispersing agent, an organic solvent and modified nano antimony tin oxide powder according to a proportion to obtain a first mixture;
s22: adding silver powder into the first mixture, and uniformly stirring to obtain a second mixture;
s23: grinding the second mixture to obtain the required conductive silver paste.
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