CN118039250B - Heterojunction silver paste preparation method - Google Patents
Heterojunction silver paste preparation method Download PDFInfo
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- CN118039250B CN118039250B CN202410341461.9A CN202410341461A CN118039250B CN 118039250 B CN118039250 B CN 118039250B CN 202410341461 A CN202410341461 A CN 202410341461A CN 118039250 B CN118039250 B CN 118039250B
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- hydroxyethyl cellulose
- methacrylic acid
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 69
- 239000004332 silver Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- 239000003822 epoxy resin Substances 0.000 claims abstract description 93
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 93
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000002156 mixing Methods 0.000 claims abstract description 45
- 238000003756 stirring Methods 0.000 claims abstract description 40
- 239000000654 additive Substances 0.000 claims abstract description 33
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 32
- 239000002270 dispersing agent Substances 0.000 claims abstract description 32
- 239000004094 surface-active agent Substances 0.000 claims abstract description 32
- 239000003960 organic solvent Substances 0.000 claims abstract description 31
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 31
- 238000009736 wetting Methods 0.000 claims abstract description 30
- 239000002562 thickening agent Substances 0.000 claims abstract description 29
- 238000001816 cooling Methods 0.000 claims abstract description 26
- 239000012745 toughening agent Substances 0.000 claims abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 78
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 65
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 65
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 65
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 54
- 239000002904 solvent Substances 0.000 claims description 49
- -1 polyethylene Polymers 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 39
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 30
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 28
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 239000012265 solid product Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000004698 Polyethylene Substances 0.000 claims description 15
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 claims description 15
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 15
- 229920000573 polyethylene Polymers 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- 229940116411 terpineol Drugs 0.000 claims description 15
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 14
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 14
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 14
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 14
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 14
- 238000010559 graft polymerization reaction Methods 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 14
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000440 bentonite Substances 0.000 claims description 12
- 229910000278 bentonite Inorganic materials 0.000 claims description 12
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000004108 freeze drying Methods 0.000 claims description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000000378 calcium silicate Substances 0.000 claims description 4
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 4
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000080 wetting agent Substances 0.000 claims description 2
- 238000000502 dialysis Methods 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 238000010907 mechanical stirring Methods 0.000 claims 1
- 125000005395 methacrylic acid group Chemical group 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 238000002390 rotary evaporation Methods 0.000 claims 1
- 230000000996 additive effect Effects 0.000 abstract description 28
- 230000007547 defect Effects 0.000 abstract description 2
- 238000013461 design Methods 0.000 abstract description 2
- 238000006073 displacement reaction Methods 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- 239000002002 slurry Substances 0.000 description 10
- 238000000967 suction filtration Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010025 steaming Methods 0.000 description 9
- 239000002390 adhesive tape Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Epoxy Resins (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a preparation method of heterojunction silver paste, which comprises the steps of (1) mixing and stirring 8-14 parts of organic solvent, 2-6 parts of methacrylic acid modified epoxy resin and 2-10 parts of auxiliary agent at 40-50 ℃ for 40-60 min, then cooling to room temperature to obtain an organic carrier, (2) mixing 20-95 parts of silver powder and 10-15 parts of oxide nano additive with the organic carrier prepared in the step (1), and stirring and uniformly mixing to prepare the silver paste, wherein the auxiliary agent comprises (1-4) of (2-5) of (1-5) of thickener, toughener, thixotropic agent, surfactant and wetting dispersant in a weight ratio of (1-5). The invention overcomes the defects of the prior art, provides a simple, efficient and low-cost heterojunction silver paste preparation method, has reasonable design and has higher social use value and application prospect.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a preparation method of heterojunction silver paste.
Background
Along with the continuous progress of technology, silver paste is used as an important conductive material, and is increasingly widely applied to the fields of electronics, photovoltaics, touch screens, printed circuit boards and the like. In particular, in the field of heterojunction solar cells, silver paste is used as an electrode material, and plays a vital role in improving the photoelectric conversion efficiency and long-term stability of the cell. However, the conventional silver paste preparation method generally adopts a physical mixing or simple chemical synthesis method, and the silver paste prepared by the method often has the problems of poor conductive performance, weak adhesive force, poor stability and the like, so that the wide application of the silver paste in heterojunction solar cells is limited.
In order to solve these problems, researchers have made a great deal of research on the preparation technology of silver paste, and various preparation methods and modification means have been proposed. For example, the dispersibility and conductivity of silver paste are improved by adding different surfactants, dispersants or nanoparticles. Although the methods improve the performance of silver paste to a certain extent, the problems of complicated preparation process, higher cost, insufficient stability and the like still exist.
In recent years, with the rapid development of nano technology, the use of nano materials to improve the performance of silver paste has become a research hotspot. The nano material has excellent physical and chemical properties, such as high specific surface area, good conductivity, stability and the like, and provides new possibility for improving the performance of silver paste. However, how to effectively incorporate nanomaterials into silver paste and ensure uniform distribution in the silver paste remains a major challenge facing the current technology.
Therefore, developing a simple, efficient and low-cost heterojunction silver paste preparation method becomes a current urgent problem to be solved. The method needs to be capable of preparing silver paste with good dispersibility, high conductivity and long-term stability so as to meet the application requirements of high-end fields such as heterojunction solar cells.
Based on the background, the invention provides a novel heterojunction silver paste preparation method, which aims to solve the problems in the prior art and provides more reliable technical support for the application of silver paste in the fields of heterojunction solar cells and the like.
Disclosure of Invention
The invention aims to provide a simple, efficient and low-cost heterojunction silver paste preparation method.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the heterojunction silver paste comprises the following steps:
(1) Mixing and stirring 8-14 parts of organic solvent, 2-6 parts of methacrylic acid modified epoxy resin and 2-10 parts of auxiliary agent at 40-50 ℃ for 40-60min, and then cooling to room temperature to obtain an organic carrier;
(2) Mixing 20-95 parts of silver powder and 10-15 parts of oxide nano additive with the organic carrier prepared in the step (1), and uniformly stirring and mixing to prepare silver paste;
wherein the auxiliary agent comprises (1-4) thickening agent, toughening agent, thixotropic agent, surfactant and wetting dispersant in a weight ratio of (2-5) to (1-5).
Preferably, the organic solvent comprises terpineol, tributyl citrate and ethyl acetate in a mass ratio of (2-3) (1-2).
Preferably, the preparation method of the methacrylic acid modified epoxy resin comprises the steps of taking 30-35 parts of methacrylic acid as a functional monomer, taking 0.7-1wt% of benzoyl peroxide as an initiator, taking 25-28 parts of butyl acrylate and 5-8 parts of styrene as raw materials, and carrying out graft polymerization on 10-14 parts of epoxy resin in the presence of 35-42 parts of solvent, wherein the reaction temperature is 110-120 ℃, and the reaction time is 5-6 hours, so that the methacrylic acid modified epoxy resin is prepared.
Preferably, the silver powder comprises spherical silver powder with a D50 particle size of 0.5-2.5 microns and a specific surface area of 0.25-0.5m 2/g.
Preferably, the oxide nano-additive comprises one or more of alumina, titania or zinc oxide, and the particle size of the oxide nano-additive is 5-30 nanometers.
Preferably, the thickener comprises poly isobutyl ester and modified hydroxyethyl cellulose in a weight ratio of (1-3).
Preferably, the preparation method of the modified hydroxyethyl cellulose comprises the steps of weighing 0.5-3g of hydroxyethyl cellulose, dissolving in 20-60mL of dehydrated dimethyl sulfoxide, adding 0.5-2g of ethylene oxide into the hydroxyethyl cellulose solution, stirring, heating the mixed solution to 50-70 ℃, adding 0.01-1g of SnCl 4 and 5-20mL of dimethyl sulfoxide mixed solution as a catalyst for reaction for 0.1-1h, cooling the reaction solution to room temperature after completion, then carrying out solvent displacement with ethyl acetate to remove solvent DMSO and suction filtration to obtain a solid product, redispersing the solid product in distilled water, dialyzing for 20-28h, steaming at least a small amount of water in a spinning way, and freeze-drying to obtain the modified hydroxyethyl cellulose.
Preferably, the thixotropic agent is at least one of bentonite, calcium silicate, colloidal alumina and polyamide wax.
Preferably, the surfactant is span 85.
Preferably, the wet dispersant polyethylene wax.
Preferably, the epoxy resin comprises epoxy resin E-44 and epoxy resin E-51 in a weight ratio of 1:2, and the solvent comprises n-butanol and ethylene glycol butyl ether in a weight ratio of 2:1.
Compared with the prior art, the invention has the beneficial effects that:
1. The heterojunction silver paste is prepared by using an organic solvent, methacrylic acid modified epoxy resin, an auxiliary agent, silver powder and an oxide nano additive as raw materials, wherein the auxiliary agent comprises (1-4) 2-5 (1-5) 1-5 of a thickening agent, a toughening agent, a thixotropic agent, a surfactant and a wetting dispersant in parts by weight, the thixotropic agent is at least one of bentonite, calcium silicate, colloidal alumina and polyamide wax, the surfactant is span 85, and the wetting dispersant polyethylene wax is used for effectively improving the performance of the heterojunction silver paste;
2. The invention selects terpineol, tributyl citrate and ethyl acetate with the mass ratio of (2-3) as (1-2) as a mixed organic solvent, and adopts methacrylic acid modified epoxy resin as base resin in a matching way, thereby effectively promoting the slurry to be in close contact with a substrate, promoting the slurry to form bonding between the substrates, leading the silver slurry to better wet and permeate to the surface of the substrate, being beneficial to forming a compact silver slurry/substrate interface and improving the integral performance of a heterojunction, wherein acrylic ester structural units in the methacrylic acid modified epoxy resin can provide more crosslinking points, thereby improving the conductivity of the silver slurry after curing, and the modified epoxy resin can possibly form a conductive network, further improving the conductivity of the silver slurry;
3. According to the invention, alumina, titanium oxide or zinc oxide with the particle size of 5-30 nanometers is used as an oxide nano additive, so that the use amount of silver powder is reduced, the production cost is reduced, the stability of silver paste is improved on the basis of the reduction of the production cost, and the influence of oxidation and environmental factors is effectively resisted;
4. The invention selects the poly isobutyl ester and modified hydroxyethyl cellulose thickener with the weight ratio of 1 (1-3), the poly isobutyl ester can form a reticular structure in silver paste by a unique chemical structure, thereby increasing the viscosity of the silver paste, the modified hydroxyethyl cellulose can also effectively increase the viscosity of the silver paste by entanglement of a high molecular chain of the poly isobutyl ester and the modified hydroxyethyl cellulose, when the poly isobutyl ester and the modified hydroxyethyl cellulose are mixed and used in a proper proportion, the viscosity of the silver paste can be increased more, in addition, the ethylene oxide is adopted as the modifier, and the prepared ethylene oxide modified hydroxyethyl cellulose can lead silver particles in the silver paste to be distributed in the paste more uniformly, form a denser conductive network, thereby improving the conductive performance of a heterojunction battery, reducing resistance loss, and indirectly improving the photoelectric conversion efficiency of the heterojunction battery by improving the performance of the silver paste;
5. The preparation process adopted by the invention is simple and efficient, reduces the production cost, makes the heterojunction silver paste easier to popularize and apply, and is suitable for various electronic devices such as solar cells, touch screens, LEDs and the like, and has wide market prospect.
In conclusion, the invention overcomes the defects of the prior art, has reasonable design and higher social use value and application prospect.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a preparation method of heterojunction silver paste, which comprises the following steps:
(1) Mixing and stirring 10 parts of an organic solvent, 4 parts of methacrylic acid modified epoxy resin and 6 parts of an auxiliary agent at 45 ℃ for 50min, and then cooling to room temperature to obtain an organic carrier;
Wherein the organic solvent comprises terpineol, tributyl citrate and ethyl acetate with the mass ratio of (2.5) (2) (1.5);
The preparation method of the methacrylic acid modified epoxy resin comprises the steps of taking 32 parts of methacrylic acid as a functional monomer, taking 0.8wt% of benzoyl peroxide as an initiator, 26 parts of butyl acrylate, 6 parts of styrene as raw materials and 12 parts of epoxy resin, and carrying out graft polymerization under the condition that 38 parts of solvent exists, wherein the reaction temperature is 115 ℃ and the reaction time is 5.5 hours, so that the methacrylic acid modified epoxy resin is prepared;
wherein the auxiliary agent comprises (2): 3): 4): 3: (3) thickener, flexibilizer, thixotropic agent, surfactant and wetting dispersant in part by weight;
the thickener comprises (2) poly isobutyl ester and modified hydroxyethyl cellulose with the weight ratio of 1, (2), bentonite as the thixotropic agent, span 85 as the surfactant, polyethylene wax as the wetting dispersant, and epoxy resin E-44 and epoxy resin E-51 with the weight ratio of 1:2, wherein the solvent comprises n-butanol and ethylene glycol butyl ether with the weight ratio of 2:1;
The preparation method of the modified hydroxyethyl cellulose comprises the steps of weighing 1g of hydroxyethyl cellulose, dissolving in 40mL of dehydrated dimethyl sulfoxide, adding 1g of ethylene oxide into the hydroxyethyl cellulose solution, stirring, heating the mixed solution to 60 ℃, adding 0.05g of SnC l 4 and 10mL of dimethyl sulfoxide mixed solution as a catalyst for reaction for 0.5h, cooling the reaction solution to room temperature after completion, then carrying out solvent displacement with ethyl acetate to remove solvent DMSO, carrying out suction filtration to obtain a solid product, re-dispersing the solid product in distilled water, dialyzing for 24h, steaming to a residual amount of water, and freeze-drying to obtain the modified hydroxyethyl cellulose;
(2) Mixing 80 parts of silver powder and 12 parts of oxide nano additive with the organic carrier prepared in the step (1), and uniformly stirring and mixing to prepare silver paste;
Wherein the silver powder comprises spherical silver powder with a D50 particle size of 1.5 microns and a specific surface area of 0.4m 2/g, the oxide nano additive is alumina, and the particle size is 18 nanometers.
Example 2
The embodiment provides a preparation method of heterojunction silver paste, which comprises the following steps:
(1) 11 parts of organic solvent, 5 parts of methacrylic acid modified epoxy resin and 5 parts of auxiliary agent are mixed and stirred for 45min at 40 ℃, and then cooled to room temperature to obtain an organic carrier;
Wherein the organic solvent comprises terpineol, tributyl citrate and ethyl acetate in the mass ratio of (2) (1) (2);
The preparation method of the methacrylic acid modified epoxy resin comprises the steps of taking 30 parts of methacrylic acid as a functional monomer, taking 0.7wt% of benzoyl peroxide as an initiator, taking 25 parts of butyl acrylate and 5 parts of styrene as raw materials and 10 parts of epoxy resin, and carrying out graft polymerization under the condition that 35 parts of solvent exists, wherein the reaction temperature is 110 ℃ and the reaction time is 6 hours, so that the methacrylic acid modified epoxy resin is prepared;
wherein the auxiliary agent comprises (1) and (2) and (1) thickening agent, toughening agent, thixotropic agent, surfactant and wetting dispersant in parts by weight;
The thickener comprises (1) poly isobutyl ester and modified hydroxyethyl cellulose in a weight ratio of (1), calcium silicate as the thixotropic agent, span 85 as the surfactant, polyethylene wax as the wetting dispersant, E-44 and E-51 epoxy resins in a weight ratio of (1:2), and n-butanol and ethylene glycol butyl ether in a weight ratio of (2:1);
The preparation method of the modified hydroxyethyl cellulose comprises the steps of weighing 1g of hydroxyethyl cellulose, dissolving in 40mL of dehydrated dimethyl sulfoxide, adding 1g of ethylene oxide into the hydroxyethyl cellulose solution, stirring, heating the mixed solution to 60 ℃, adding 0.05g of SnC l 4 and 10mL of dimethyl sulfoxide mixed solution as a catalyst for reaction for 0.5h, cooling the reaction solution to room temperature after completion, then carrying out solvent displacement with ethyl acetate to remove solvent DMSO, carrying out suction filtration to obtain a solid product, re-dispersing the solid product in distilled water, dialyzing for 24h, steaming to a residual amount of water, and freeze-drying to obtain the modified hydroxyethyl cellulose;
(2) Mixing 90 parts of silver powder and 11 parts of oxide nano additive with the organic carrier prepared in the step (1), and uniformly stirring and mixing to prepare silver paste;
Wherein the silver powder comprises spherical silver powder with the D50 particle size of 0.5 micron and the specific surface area of 0.25m 2/g, the oxide nano additive is titanium oxide, and the particle size is 10 nanometers.
Example 3
The embodiment provides a preparation method of heterojunction silver paste, which comprises the following steps:
(1) Mixing and stirring 12 parts of an organic solvent, 5 parts of methacrylic acid modified epoxy resin and 3 parts of an auxiliary agent at 50 ℃ for 60 minutes, and then cooling to room temperature to obtain an organic carrier;
Wherein the organic solvent comprises terpineol, tributyl citrate and ethyl acetate in the mass ratio of (3) (2);
the preparation method of the methacrylic acid modified epoxy resin comprises the steps of taking 35 parts of methacrylic acid as a functional monomer, taking benzoyl peroxide of 1wt% as an initiator, 28 parts of butyl acrylate and 8 parts of styrene as raw materials and 14 parts of epoxy resin, and carrying out graft polymerization under the condition of 42 parts of solvent, wherein the reaction temperature is 120 ℃, and the reaction time is 6 hours, so as to obtain the methacrylic acid modified epoxy resin;
wherein the auxiliary agent comprises a thickening agent, a toughening agent, a thixotropic agent, a surfactant and a wetting dispersing agent in a weight ratio of (4): 5: (5);
the thickener comprises (3) poly isobutyl ester and modified hydroxyethyl cellulose with the weight ratio of 1, (3), the thixotropic agent is colloidal alumina, the surfactant is span 85, the wetting dispersant polyethylene wax, the epoxy resin comprises epoxy resin E-44 and epoxy resin E-51 with the weight ratio of 1:2, and the solvent comprises n-butanol and ethylene glycol butyl ether with the weight ratio of 2:1;
The preparation method of the modified hydroxyethyl cellulose comprises the steps of weighing 1g of hydroxyethyl cellulose, dissolving in 40mL of dehydrated dimethyl sulfoxide, adding 1g of ethylene oxide into the hydroxyethyl cellulose solution, stirring, heating the mixed solution to 60 ℃, adding 0.05g of SnC l 4 and 10mL of dimethyl sulfoxide mixed solution as a catalyst for reaction for 0.5h, cooling the reaction solution to room temperature after completion, then carrying out solvent displacement with ethyl acetate to remove solvent DMSO, carrying out suction filtration to obtain a solid product, re-dispersing the solid product in distilled water, dialyzing for 24h, steaming to a residual amount of water, and freeze-drying to obtain the modified hydroxyethyl cellulose;
(2) Mixing 70 parts of silver powder and 14 parts of oxide nano additive with the organic carrier prepared in the step (1), and uniformly stirring and mixing to prepare silver paste;
Wherein the silver powder comprises spherical silver powder with the D50 particle size of 2.5 microns and the specific surface area of 0.5m 2/g, the oxide nano additive is zinc oxide, and the particle size is 30 nanometers.
Example 4
The embodiment provides a preparation method of heterojunction silver paste, which comprises the following steps:
(1) Mixing and stirring 14 parts of an organic solvent, 6 parts of methacrylic acid modified epoxy resin and 8 parts of an auxiliary agent at 40 ℃ for 60 minutes, and then cooling to room temperature to obtain an organic carrier;
Wherein the organic solvent comprises terpineol, tributyl citrate and ethyl acetate in the mass ratio of (2) (1) (2);
The preparation method of the methacrylic acid modified epoxy resin comprises the steps of taking 35 parts of methacrylic acid as a functional monomer, taking 0.9wt% of benzoyl peroxide as an initiator, 26 parts of butyl acrylate, 7 parts of styrene as raw materials and 11 parts of epoxy resin, and carrying out graft polymerization under the condition that 40 parts of solvent exists, wherein the reaction temperature is 115 ℃ and the reaction time is 5 hours, so that the methacrylic acid modified epoxy resin is prepared;
Wherein the auxiliary agent comprises (1): 3): 5): 1: (3) thickener, flexibilizer, thixotropic agent, surfactant and wetting dispersant in part by weight;
The thickener comprises (2) poly isobutyl ester and modified hydroxyethyl cellulose with the weight ratio of 1, (2), the thixotropic agent is polyamide wax, the surfactant is span 85, the wetting dispersant is polyethylene wax, the epoxy resin comprises epoxy resin E-44 and epoxy resin E-51 with the weight ratio of 1:2, and the solvent comprises n-butanol and ethylene glycol butyl ether with the weight ratio of 2:1;
The preparation method of the modified hydroxyethyl cellulose comprises the steps of weighing 1g of hydroxyethyl cellulose, dissolving in 40mL of dehydrated dimethyl sulfoxide, adding 1g of ethylene oxide into the hydroxyethyl cellulose solution, stirring, heating the mixed solution to 60 ℃, adding 0.05g of SnC l 4 and 10mL of dimethyl sulfoxide mixed solution as a catalyst for reaction for 0.5h, cooling the reaction solution to room temperature after completion, then carrying out solvent displacement with ethyl acetate to remove solvent DMSO, carrying out suction filtration to obtain a solid product, re-dispersing the solid product in distilled water, dialyzing for 24h, steaming to a residual amount of water, and freeze-drying to obtain the modified hydroxyethyl cellulose;
(2) Mixing 82 parts of silver powder and 11 parts of oxide nano additive with the organic carrier prepared in the step (1), and uniformly stirring and mixing to prepare silver paste;
wherein the silver powder comprises spherical silver powder with the D50 particle size of 2 microns and the specific surface area of 0.4m 2/g, the oxide nano additive is alumina, and the particle size is 20 nanometers.
Comparative example 1
The embodiment provides a preparation method of heterojunction silver paste, which comprises the following steps:
(1) Mixing and stirring 10 parts of an organic solvent, 4 parts of epoxy resin and 6 parts of an auxiliary agent at 45 ℃ for 50min, and then cooling to room temperature to obtain an organic carrier;
Wherein the organic solvent comprises terpineol, tributyl citrate and ethyl acetate with the mass ratio of (2.5) (2) (1.5);
The preparation method of the methacrylic acid modified epoxy resin comprises the steps of taking 32 parts of methacrylic acid as a functional monomer, taking 0.8wt% of benzoyl peroxide as an initiator, 26 parts of butyl acrylate, 6 parts of styrene as raw materials and 12 parts of epoxy resin, and carrying out graft polymerization under the condition that 38 parts of solvent exists, wherein the reaction temperature is 115 ℃ and the reaction time is 5.5 hours, so that the methacrylic acid modified epoxy resin is prepared;
wherein the auxiliary agent comprises (2): 3): 4): 3: (3) thickener, flexibilizer, thixotropic agent, surfactant and wetting dispersant in part by weight;
The thickener comprises (2) poly isobutyl ester and modified hydroxyethyl cellulose in a weight ratio of 1, (2) bentonite as thixotropic agent, span 85 as surfactant, and polyethylene wax as wetting dispersant, wherein the preparation method of the modified hydroxyethyl cellulose comprises the steps of weighing 1g of hydroxyethyl cellulose, dissolving in 40mL of dehydrated dimethyl sulfoxide, adding 1g of ethylene oxide into the hydroxyethyl cellulose solution, stirring, heating the mixed solution to 60 ℃, adding 0.05g of SnC l 4 and 10mL of dimethyl sulfoxide mixed solution as a catalyst for reaction for 0.5h, cooling the reaction solution to room temperature after completion, then carrying out solvent displacement with ethyl acetate to remove the solvent DMSO, carrying out suction filtration to obtain a solid product, redispersing the solid product in distilled water, dialyzing for 24h, steaming at least a small amount of water, and freeze-drying to obtain the modified hydroxyethyl cellulose;
The epoxy resin comprises epoxy resin E-44 and epoxy resin E-51 in a weight ratio of 1:2;
(2) Mixing 80 parts of silver powder and 12 parts of oxide nano additive with the organic carrier prepared in the step (1), and uniformly stirring and mixing to prepare silver paste;
Wherein the silver powder comprises spherical silver powder with a D50 particle size of 1.5 microns and a specific surface area of 0.4m 2/g, the oxide nano additive is alumina, and the particle size is 18 nanometers.
Comparative example 2
The embodiment provides a preparation method of heterojunction silver paste, which comprises the following steps:
(1) Mixing and stirring 10 parts of an organic solvent, 4 parts of methacrylic acid modified epoxy resin and 6 parts of an auxiliary agent at 45 ℃ for 50min, and then cooling to room temperature to obtain an organic carrier;
Wherein the organic solvent comprises terpineol, tributyl citrate and ethyl acetate with the mass ratio of (2.5) (2) (1.5);
The preparation method of the methacrylic acid modified epoxy resin comprises the steps of taking 32 parts of methacrylic acid as a functional monomer, taking 0.8wt% of benzoyl peroxide as an initiator, 26 parts of butyl acrylate, 6 parts of styrene as raw materials and 12 parts of epoxy resin, and carrying out graft polymerization under the condition that 38 parts of solvent exists, wherein the reaction temperature is 115 ℃ and the reaction time is 5.5 hours, so that the methacrylic acid modified epoxy resin is prepared;
wherein the auxiliary agent comprises (2): 3): 4): 3: (3) thickener, flexibilizer, thixotropic agent, surfactant and wetting dispersant in part by weight;
The thickener comprises (2) poly isobutyl ester and modified hydroxyethyl cellulose in a weight ratio of 1, (2) bentonite as thixotropic agent, span 85 as surfactant, polyethylene wax as wetting dispersant, E-44 as epoxy resin and n-butanol as solvent, wherein the preparation method of the modified hydroxyethyl cellulose comprises the steps of weighing 1g of hydroxyethyl cellulose to be dissolved in 40mL of dehydrated dimethyl sulfoxide, adding 1g of ethylene oxide into the hydroxyethyl cellulose solution, stirring, heating the mixed solution to 60 ℃, adding 0.05g of SnC l 4 and 10mL of dimethyl sulfoxide mixed solution as catalyst for reaction for 0.5h, cooling the reaction solution to room temperature after completion, then carrying out solvent displacement with ethyl acetate to remove the DMSO, carrying out suction filtration to obtain a solid product, redispersing the solid product in distilled water, dialyzing for 24h, screwing at least a small amount of water, evaporating to obtain the modified hydroxyethyl cellulose by freeze drying;
(2) Mixing 80 parts of silver powder and 12 parts of oxide nano additive with the organic carrier prepared in the step (1), and uniformly stirring and mixing to prepare silver paste;
Wherein the silver powder comprises spherical silver powder with a D50 particle size of 1.5 microns and a specific surface area of 0.4m 2/g, the oxide nano additive is alumina, and the particle size is 18 nanometers.
Comparative example 3
The embodiment provides a preparation method of heterojunction silver paste, which comprises the following steps:
(1) Mixing and stirring 10 parts of an organic solvent, 4 parts of methacrylic acid modified epoxy resin and 6 parts of an auxiliary agent at 45 ℃ for 50min, and then cooling to room temperature to obtain an organic carrier;
Wherein the organic solvent comprises terpineol, tributyl citrate and ethyl acetate with the mass ratio of (2.5) (2) (1.5);
The preparation method of the methacrylic acid modified epoxy resin comprises the steps of taking 32 parts of methacrylic acid as a functional monomer, taking 0.8wt% of benzoyl peroxide as an initiator, 26 parts of butyl acrylate, 6 parts of styrene as raw materials and 12 parts of epoxy resin, and carrying out graft polymerization under the condition that 38 parts of solvent exists, wherein the reaction temperature is 115 ℃ and the reaction time is 5.5 hours, so that the methacrylic acid modified epoxy resin is prepared;
wherein the auxiliary agent comprises (2): 3): 4): 3: (3) thickener, flexibilizer, thixotropic agent, surfactant and wetting dispersant in part by weight;
the thickener comprises (2) poly isobutyl ester and modified hydroxyethyl cellulose in a weight ratio of 1, (2) bentonite as thixotropic agent, span 85 as surfactant, polyethylene wax as wetting dispersant, E-51 as epoxy resin and ethylene glycol butyl ether as solvent, wherein the preparation method of the modified hydroxyethyl cellulose comprises the steps of weighing 1g of hydroxyethyl cellulose, dissolving in 40mL of dehydrated dimethyl sulfoxide, adding 1g of ethylene oxide into the hydroxyethyl cellulose solution, stirring, heating the mixed solution to 60 ℃, adding 0.05g of SnC l 4 and 10mL of dimethyl sulfoxide mixed solution as catalyst for reaction for 0.5h, cooling the reaction solution to room temperature after completion, then carrying out solvent displacement with ethyl acetate to remove solvent DMSO, carrying out suction filtration to obtain a solid product, re-dispersing the solid product in distilled water, dialyzing for 24h, steaming to a small amount of water, and freeze-drying to obtain the modified hydroxyethyl cellulose;
(2) Mixing 80 parts of silver powder and 12 parts of oxide nano additive with the organic carrier prepared in the step (1), and uniformly stirring and mixing to prepare silver paste;
Wherein the silver powder comprises spherical silver powder with a D50 particle size of 1.5 microns and a specific surface area of 0.4m 2/g, the oxide nano additive is alumina, and the particle size is 18 nanometers.
Comparative example 4
The embodiment provides a preparation method of heterojunction silver paste, which comprises the following steps:
(1) Mixing and stirring 10 parts of an organic solvent, 4 parts of methacrylic acid modified epoxy resin and 6 parts of an auxiliary agent at 45 ℃ for 50min, and then cooling to room temperature to obtain an organic carrier;
wherein the organic solvent comprises (2.5) terpineol and tributyl citrate in a mass ratio of (2);
The preparation method of the methacrylic acid modified epoxy resin comprises the steps of taking 32 parts of methacrylic acid as a functional monomer, taking 0.8wt% of benzoyl peroxide as an initiator, 26 parts of butyl acrylate, 6 parts of styrene as raw materials and 12 parts of epoxy resin, and carrying out graft polymerization under the condition that 38 parts of solvent exists, wherein the reaction temperature is 115 ℃ and the reaction time is 5.5 hours, so that the methacrylic acid modified epoxy resin is prepared;
wherein the auxiliary agent comprises (2): 3): 4): 3: (3) thickener, flexibilizer, thixotropic agent, surfactant and wetting dispersant in part by weight;
The thickener comprises (2) poly isobutyl ester and modified hydroxyethyl cellulose with the weight ratio of 1, (2), bentonite as thixotropic agent, span 85 as surfactant, polyethylene wax as wetting dispersant, E-44 and E-51 as epoxy resin with the weight ratio of 1:2, wherein the solvent comprises n-butyl alcohol and ethylene glycol butyl ether with the weight ratio of 2:1, the preparation method of the modified hydroxyethyl cellulose comprises the steps of weighing 1g of hydroxyethyl cellulose, dissolving in 40mL of dehydrated dimethyl sulfoxide, adding 1g of ethylene oxide into the hydroxyethyl cellulose solution, stirring, heating the mixed solution to 60 ℃, adding 0.05g of SnC l 4 and 10mL of dimethyl sulfoxide mixed solution as a catalyst, reacting for 0.5h, cooling the reaction solution to room temperature after the completion, then performing solvent displacement with ethyl acetate to remove the solvent, pumping to obtain a solid product, redissolving the solid product in distilled water, evaporating at least for 24h, drying to obtain modified hydroxyethyl cellulose;
(2) Mixing 80 parts of silver powder and 12 parts of oxide nano additive with the organic carrier prepared in the step (1), and uniformly stirring and mixing to prepare silver paste;
Wherein the silver powder comprises spherical silver powder with a D50 particle size of 1.5 microns and a specific surface area of 0.4m 2/g, the oxide nano additive is alumina, and the particle size is 18 nanometers.
Comparative example 5
The embodiment provides a preparation method of heterojunction silver paste, which comprises the following steps:
(1) Mixing and stirring 10 parts of an organic solvent, 4 parts of methacrylic acid modified epoxy resin and 6 parts of an auxiliary agent at 45 ℃ for 50min, and then cooling to room temperature to obtain an organic carrier;
Wherein the organic solvent comprises terpineol, tributyl citrate and ethyl acetate with the mass ratio of (2.5) (2) (1.5);
The preparation method of the methacrylic acid modified epoxy resin comprises the steps of taking 32 parts of methacrylic acid as a functional monomer, taking 0.8wt% of benzoyl peroxide as an initiator, 26 parts of butyl acrylate, 6 parts of styrene as raw materials and 12 parts of epoxy resin, and carrying out graft polymerization under the condition that 38 parts of solvent exists, wherein the reaction temperature is 115 ℃ and the reaction time is 5.5 hours, so that the methacrylic acid modified epoxy resin is prepared;
wherein the auxiliary agent comprises (2): 3): 4): 3: (3) thickener, flexibilizer, thixotropic agent, surfactant and wetting dispersant in part by weight;
the thickener comprises (2) poly isobutyl ester and modified hydroxyethyl cellulose with the weight ratio of 1, (2), bentonite as the thixotropic agent, span 85 as the surfactant, polyethylene wax as the wetting dispersant, and epoxy resin E-44 and epoxy resin E-51 with the weight ratio of 1:2, wherein the solvent comprises n-butanol and ethylene glycol butyl ether with the weight ratio of 2:1;
The preparation method of the modified hydroxyethyl cellulose comprises the steps of weighing 1g of hydroxyethyl cellulose, dissolving in 40mL of dehydrated dimethyl sulfoxide, adding 1g of ethylene oxide into the hydroxyethyl cellulose solution, stirring, heating the mixed solution to 60 ℃, adding 0.05g of SnC l 4 and 10mL of dimethyl sulfoxide mixed solution as a catalyst for reaction for 0.5h, cooling the reaction solution to room temperature after completion, then carrying out solvent displacement with ethyl acetate to remove solvent DMSO, carrying out suction filtration to obtain a solid product, re-dispersing the solid product in distilled water, dialyzing for 24h, steaming to a residual amount of water, and freeze-drying to obtain the modified hydroxyethyl cellulose;
(2) Mixing 80 parts of silver powder and 12 parts of oxide nano additive with the organic carrier prepared in the step (1), and uniformly stirring and mixing to prepare silver paste;
Wherein the silver powder comprises spherical silver powder with a D50 particle size of 1.5 microns and a specific surface area of 0.4m 2/g, the oxide nano additive is copper oxide, and the particle size is 18 nanometers.
Comparative example 6
The embodiment provides a preparation method of heterojunction silver paste, which comprises the following steps:
(1) Mixing and stirring 10 parts of an organic solvent, 4 parts of methacrylic acid modified epoxy resin and 6 parts of an auxiliary agent at 45 ℃ for 50min, and then cooling to room temperature to obtain an organic carrier;
Wherein the organic solvent comprises terpineol, tributyl citrate and ethyl acetate with the mass ratio of (2.5) (2) (1.5);
The preparation method of the methacrylic acid modified epoxy resin comprises the steps of taking 32 parts of methacrylic acid as a functional monomer, taking 0.8wt% of benzoyl peroxide as an initiator, 26 parts of butyl acrylate, 6 parts of styrene as raw materials and 12 parts of epoxy resin, and carrying out graft polymerization under the condition that 38 parts of solvent exists, wherein the reaction temperature is 115 ℃ and the reaction time is 5.5 hours, so that the methacrylic acid modified epoxy resin is prepared;
wherein the auxiliary agent comprises (2): 3): 4): 3: (3) thickener, flexibilizer, thixotropic agent, surfactant and wetting dispersant in part by weight;
The thickener is poly isobutyl ester, the thixotropic agent is bentonite, the surfactant is span 85, the wetting dispersant is polyethylene wax, the epoxy resin comprises epoxy resin E-44 and epoxy resin E-51 with the weight ratio of 1:2, and the solvent comprises n-butyl alcohol and ethylene glycol butyl ether with the weight ratio of 2:1;
(2) Mixing 80 parts of silver powder and 12 parts of oxide nano additive with the organic carrier prepared in the step (1), and uniformly stirring and mixing to prepare silver paste;
Wherein the silver powder comprises spherical silver powder with a D50 particle size of 1.5 microns and a specific surface area of 0.4m 2/g, the oxide nano additive is alumina, and the particle size is 18 nanometers.
Comparative example 7
The embodiment provides a preparation method of heterojunction silver paste, which comprises the following steps:
(1) Mixing and stirring 10 parts of an organic solvent, 4 parts of methacrylic acid modified epoxy resin and 6 parts of an auxiliary agent at 45 ℃ for 50min, and then cooling to room temperature to obtain an organic carrier;
Wherein the organic solvent comprises terpineol, tributyl citrate and ethyl acetate with the mass ratio of (2.5) (2) (1.5);
The preparation method of the methacrylic acid modified epoxy resin comprises the steps of taking 32 parts of methacrylic acid as a functional monomer, taking 0.8wt% of benzoyl peroxide as an initiator, 26 parts of butyl acrylate, 6 parts of styrene as raw materials and 12 parts of epoxy resin, and carrying out graft polymerization under the condition that 38 parts of solvent exists, wherein the reaction temperature is 115 ℃ and the reaction time is 5.5 hours, so that the methacrylic acid modified epoxy resin is prepared;
wherein the auxiliary agent comprises (2): 3): 4): 3: (3) thickener, flexibilizer, thixotropic agent, surfactant and wetting dispersant in part by weight;
the thickener is modified hydroxyethyl cellulose, the thixotropic agent is bentonite, the surfactant is span 85, the wetting dispersant is polyethylene wax, the epoxy resin comprises epoxy resin E-44 and epoxy resin E-51 with the weight ratio of 1:2, and the solvent comprises n-butanol and ethylene glycol butyl ether with the weight ratio of 2:1;
The preparation method of the modified hydroxyethyl cellulose comprises the steps of weighing 1g of hydroxyethyl cellulose, dissolving in 40mL of dehydrated dimethyl sulfoxide, adding 1g of ethylene oxide into the hydroxyethyl cellulose solution, stirring, heating the mixed solution to 60 ℃, adding 0.05g of SnC l 4 and 10mL of dimethyl sulfoxide mixed solution as a catalyst for reaction for 0.5h, cooling the reaction solution to room temperature after completion, then carrying out solvent displacement with ethyl acetate to remove solvent DMSO, carrying out suction filtration to obtain a solid product, re-dispersing the solid product in distilled water, dialyzing for 24h, steaming to a residual amount of water, and freeze-drying to obtain the modified hydroxyethyl cellulose;
(2) Mixing 80 parts of silver powder and 12 parts of oxide nano additive with the organic carrier prepared in the step (1), and uniformly stirring and mixing to prepare silver paste;
Wherein the silver powder comprises spherical silver powder with a D50 particle size of 1.5 microns and a specific surface area of 0.4m 2/g, the oxide nano additive is alumina, and the particle size is 18 nanometers.
Comparative example 8
The embodiment provides a preparation method of heterojunction silver paste, which comprises the following steps:
(1) Mixing and stirring 10 parts of an organic solvent, 4 parts of methacrylic acid modified epoxy resin and 6 parts of an auxiliary agent at 45 ℃ for 50min, and then cooling to room temperature to obtain an organic carrier;
Wherein the organic solvent comprises terpineol, tributyl citrate and ethyl acetate with the mass ratio of (2.5) (2) (1.5);
The preparation method of the methacrylic acid modified epoxy resin comprises the steps of taking 32 parts of methacrylic acid as a functional monomer, taking 0.8wt% of benzoyl peroxide as an initiator, 26 parts of butyl acrylate, 6 parts of styrene as raw materials and 12 parts of epoxy resin, and carrying out graft polymerization under the condition that 38 parts of solvent exists, wherein the reaction temperature is 115 ℃ and the reaction time is 5.5 hours, so that the methacrylic acid modified epoxy resin is prepared;
Wherein the auxiliary agent comprises (3), (4), (3) a toughening agent, a thixotropic agent, a surfactant and a wetting dispersant in a weight ratio of (3), (3) a wetting agent;
The thixotropic agent is bentonite, the surfactant is span 85, the wetting dispersant is polyethylene wax, the epoxy resin comprises epoxy resin E-44 and epoxy resin E-51 with the weight ratio of 1:2, and the solvent comprises n-butanol and ethylene glycol butyl ether with the weight ratio of 2:1;
(2) Mixing 80 parts of silver powder and 12 parts of oxide nano additive with the organic carrier prepared in the step (1), and uniformly stirring and mixing to prepare silver paste;
Wherein the silver powder comprises spherical silver powder with a D50 particle size of 1.5 microns and a specific surface area of 0.4m 2/g, the oxide nano additive is alumina, and the particle size is 18 nanometers.
The performance test method comprises the following steps:
(1) The volume resistivity of the slurries prepared in examples 1 to 4 and comparative examples 1 to 8 was measured;
(2) Coating silver paste on a crystalline silicon heterojunction battery through screen printing, drying at 200 ℃ for 8min, curing at 200 ℃ for 20min, and measuring photoelectric conversion efficiency, open-circuit voltage and series resistance of the battery by adopting equipment with model number HSC 1/XSCM-9 manufactured by Shanghai-Jia Dahur technology Co., ltd;
(3) The method for measuring the adhesive force of the conductive silver paste comprises the steps of adopting a hundred-grid test method, printing or smearing the conductive silver paste on the surface of an ITO substrate, drying, then measuring the adhesive force according to a scratch experiment of national standard GBT9286-1998 colored paint and varnish film, namely, using a hundred-grid knife to scratch 100 small grids of 1mm multiplied by 1mm on the surface of a test sample, enabling each scribing line to be deep and reach the surface of the ITO substrate, brushing fragments of a test area cleanly by using a brush, firmly adhering the tested small grids by using a 3M600 adhesive tape produced by 3M company of the United states or an adhesive tape with equal efficacy, and wiping the adhesive tape by using an eraser to enlarge the contact area and strength of the adhesive tape and the tested area, grasping one end of the adhesive tape by hand, rapidly and downwards adhering the adhesive tape in the vertical direction of the adhesive tape, judging that the adhered part occupies the number ratio of the hundred grids when the edge of a notch (the notch) is completely smooth, judging that the adhesive force of the conductive silver paste is 5B when the edge of the lattice is not peeled, and the adhesive force of the conductive silver paste is actually broken in the area is not more than 5B when the small grid is peeled at the intersection of the notch;
(4) The method for testing the abrasion resistance (scraping times) of the slurry comprises the steps of uniformly coating the slurry on a substrate, curing the slurry according to process conditions, selecting a friction rod with a smooth circular bottom (with the diameter of 1 mm), carrying out reciprocating friction test on the surface of the electrode, observing the change of the surface of the electrode until falling off, and recording the friction times, wherein the specific friction times are average values obtained after three sample tests;
the specific test results of the above tests are shown in table 1 below:
TABLE 1
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
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| CN115798783A (en) * | 2022-11-14 | 2023-03-14 | 四川东树新材料有限公司 | Heterojunction slurry for superfine line printing and preparation method thereof |
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| CN110692126B (en) * | 2018-03-30 | 2023-06-13 | 京瓷株式会社 | Resin composition for bonding electronic component, method for bonding small chip component, electronic circuit board, and method for manufacturing electronic circuit board |
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| CN107207835A (en) * | 2015-01-19 | 2017-09-26 | 京瓷株式会社 | Conductive resin composition and semiconductor device |
| CN115798783A (en) * | 2022-11-14 | 2023-03-14 | 四川东树新材料有限公司 | Heterojunction slurry for superfine line printing and preparation method thereof |
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