CN114014972A - Ketone hydrazine crosslinking system for organic carrier in photovoltaic silver paste - Google Patents
Ketone hydrazine crosslinking system for organic carrier in photovoltaic silver paste Download PDFInfo
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- CN114014972A CN114014972A CN202111345594.6A CN202111345594A CN114014972A CN 114014972 A CN114014972 A CN 114014972A CN 202111345594 A CN202111345594 A CN 202111345594A CN 114014972 A CN114014972 A CN 114014972A
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- silver paste
- reagent
- hydrazine
- acrylic resin
- acid dihydrazide
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 61
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 25
- 239000004332 silver Substances 0.000 title claims abstract description 25
- 238000004132 cross linking Methods 0.000 title claims abstract description 21
- 150000002576 ketones Chemical class 0.000 title claims abstract description 17
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 32
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 32
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 20
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001412 amines Chemical class 0.000 claims abstract description 18
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 3
- MDJZGXRFYKPSIM-JCYAYHJZSA-N (2r,3r)-2,3-dihydroxybutanedihydrazide Chemical compound NNC(=O)[C@H](O)[C@@H](O)C(=O)NN MDJZGXRFYKPSIM-JCYAYHJZSA-N 0.000 claims description 2
- SNVRDQORMVVQBI-UPHRSURJSA-N (z)-but-2-enedihydrazide Chemical compound NNC(=O)\C=C/C(=O)NN SNVRDQORMVVQBI-UPHRSURJSA-N 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- -1 aliphatic tertiary amine Chemical class 0.000 claims description 2
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 claims description 2
- ALHNLFMSAXZKRC-UHFFFAOYSA-N benzene-1,4-dicarbohydrazide Chemical compound NNC(=O)C1=CC=C(C(=O)NN)C=C1 ALHNLFMSAXZKRC-UHFFFAOYSA-N 0.000 claims description 2
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 claims description 2
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 claims description 2
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 claims description 2
- ZWLFGLCGZUVIEA-UHFFFAOYSA-N nonanedihydrazide Chemical compound NNC(=O)CCCCCCCC(=O)NN ZWLFGLCGZUVIEA-UHFFFAOYSA-N 0.000 claims description 2
- LGYJSPMYALQHBL-UHFFFAOYSA-N pentanedihydrazide Chemical compound NNC(=O)CCCC(=O)NN LGYJSPMYALQHBL-UHFFFAOYSA-N 0.000 claims description 2
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 claims 1
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000007639 printing Methods 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 235000012431 wafers Nutrition 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- SHOTZAAGWLBZQV-UHFFFAOYSA-N aminoazanium;carbonate Chemical compound NN.NN.OC(O)=O SHOTZAAGWLBZQV-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Sustainable Energy (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Development (AREA)
- Polymers & Plastics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
- Conductive Materials (AREA)
Abstract
The invention provides a ketone hydrazine crosslinking system for an organic carrier in photovoltaic silver paste, which consists of acrylic resin, a hydrazine reagent and an amine reagent, wherein the ketone hydrazine crosslinking system comprises the following components in parts by weight: the total molar ratio of the acrylic resin to the acrylic resin, the hydrazine reagent and the amine reagent is (0.05-0.2): 1, the molar ratio of the amine reagent to the hydrazine reagent is (0.5-2): 1, and diacetone acrylamide (DAAM) is used as a monomer in the synthesis of the acrylic resin. The organic carrier for the photovoltaic silver paste comprises acrylic resin, a hydrazine reagent and an amine reagent, and when the organic carrier is used in the photovoltaic silver paste, the printed grid line can not collapse when being heated and dried, so that the narrow line width and the good height-width ratio are kept.
Description
Technical Field
The invention relates to a ketone hydrazine crosslinking system for an organic carrier in photovoltaic silver paste.
Background
The photovoltaic industry is currently developing vigorously and silicon solar cells occupy more than 80% of the current market. The electrode grid lines for receiving the light surface of the silicon solar cell are formed by screen printing, drying and sintering conductive paste, so that the electrode grid lines are as narrow as possible and have a good height-width ratio, and the reduction of photovoltaic conversion efficiency caused by shielding of incident light can be reduced. The conductive silver paste for the silicon solar cell generally comprises an organic carrier, glass powder and conductive metal powder, the organic carrier part of the conductive paste generally comprises resin and an auxiliary agent, and the organic components generally soften or decompose gradually along with the heating temperature, so that the width of a grid line is widened and the cell efficiency is reduced. The ketone hydrazine crosslinking system is generally applied to water-based coatings, and has no disclosed application in the field of oily photovoltaic silver paste.
Disclosure of Invention
The invention aims to provide a ketone hydrazine crosslinking system for an organic carrier in photovoltaic silver paste, wherein the organic carrier is conductive silver paste for a solar cell, and can prevent linear collapse of the paste in a heating process, so that the line width of a printed grid line is narrow.
The invention provides a ketone hydrazine crosslinking system for an organic carrier in photovoltaic silver paste, which comprises acrylic resin, a hydrazine reagent and an amine reagent, wherein the ketone hydrazine crosslinking system comprises the following components in parts by weight: the total molar ratio of the acrylic resin to the acrylic resin, the hydrazine reagent and the amine reagent is (0.05-0.2): 1, the molar ratio of the amine reagent to the hydrazine reagent is (0.5-2): 1, and diacetone acrylamide (DAAM) is used as a monomer in the synthesis of the acrylic resin.
In the invention, the hydrazine reagent is one or a combination of more of adipic acid dihydrazide, oxalic acid dihydrazide, maleic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, tartaric acid dihydrazide, lauric acid dihydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide and carbonic acid hydrazine.
In the invention, the amine reagent is an aliphatic tertiary amine reagent, and is one or a combination of triethanolamine and triethylamine.
In the present invention, the molar ratio of the hydrazine reagent to DAAM used for synthesizing the acrylic resin is (0.25-1): 1.
The ketone hydrazine crosslinking system for the organic carrier in the photovoltaic silver paste comprises acrylic resin containing ketone carbonyl, a hydrazine reagent and an amine reagent, wherein the ketone carbonyl of the acrylic resin is introduced by using a monomer diacetone acrylamide during synthesis, and at normal temperature or low temperature, the conductive silver paste can be prepared by adding glass powder and conductive metal powder into the organic carrier; when the grid line is heated, along with the volatilization of the amine reagent, the ketone carbonyl group and the hydrazine reagent in the acrylic resin are subjected to a crosslinking reaction, so that the printed grid line does not collapse in the drying and sintering stage, and the narrower line width and the better height-to-width ratio are kept.
The invention has the beneficial effects that:
the ketone hydrazine crosslinking system for the organic carrier in the photovoltaic silver paste comprises acrylic resin, a hydrazine reagent and an amine reagent, and when the ketone hydrazine crosslinking system is used in the photovoltaic silver paste, the printed grid line can not collapse when being heated and dried, so that the narrow line width and the good height-width ratio are kept.
Detailed Description
The invention is further illustrated by the following examples.
Example 1:
synthesis of acrylic resin
236.31 g of deionized water, 0.22 g of sodium lauryl sulfate and 7.12 g of a 0.7% aqueous potassium dihydrogen phosphate solution (neutralized to a pH of about 7 with potassium hydroxide) were added sequentially to a 500ml three-necked flask under a nitrogen blanket to obtain a mixture, which was then heated to 85 deg.foC was stirred for half an hour, and in a separate beaker, 55.18 g of n-butyl methacrylate monomer, 12.95 g of methyl methacrylate, 8.77 g of diacetone acrylamide and 0.26 g of ethylene glycol dimethacrylate as a crosslinking agent were added in this order to obtain a monomer mixture. At 85oC, 28.58 g of the monomer mixture in the beaker was charged into the three-necked flask, and after stirring for 15 minutes, 1.11 g of a 2.5% aqueous ammonium persulfate solution was added thereto, followed by 85 goAnd C, under the protection of nitrogen, dropwise adding the residual monomer mixture in the beaker into the three-neck flask at a constant speed, and finishing dropwise adding for 1 hour. After which the mixture continues at 85oStirring is continued for 2 hours under C, then 1.11 g of 2.5 percent aqueous ammonium persulfate solution is added, and the temperature is kept at 85 DEGoC, stirring for 2 hours, cooling, filtering the reacted mixed solution by a filter screen, pouring the filtered mixed solution into an aluminum pot, standing at 30 ℃ for 10 hours, and mechanically crushing to obtain white powder acrylic resin R1.
The above is for the synthesis of acrylic resin R1, wherein the molar ratio of n-Butyl Methacrylate (BMA) to Methyl Methacrylate (MMA) is 3:1, wherein the molar ratio of active monomer diacetone acrylamide (DAAM) to the total amount of monomers BMA and MMA is 0.1:1, denoted as content 10%, and the molar ratio of crosslinking agent Ethylene Glycol Dimethacrylate (EGDMA) to the total amount of monomers BMA and MMA is 0.0025:1, denoted as content 0.25%. The synthesis of the acrylic resin R2 and the acrylic resin R3 both adopt the same synthesis method as that of the example 1, but the content is adjusted, based on the acrylic resin R1, wherein the content of the acrylic resin R2 and the acrylic resin R3 using active monomers is adjusted to be 5 percent and 20 percent; the synthesis of each acrylic resin is shown in table 1.
The composition ratio of the monomer and the cross-linking agent in the synthesis of the acrylic resin R1-R3
Example 2:
preparation of conductive silver paste P1-P20 containing acrylic resin
Mixing the acrylic resin R1-R3 with other organic components according to the content in Table 2, and heating to 90 goC is cooled to 25 ℃ after being stirred for 2 hoursoC, adding glass powder and silver powder according to the content in the table 1, stirring the mixture into paste, adding an amine reagent and a hydrazine reagent (the specific content and the reagent name are shown in the table 3), finally adding a diethylene glycol monobutyl ether acetate and a diethylene glycol monobutyl ether mixed solution, adjusting the proportion of the two, repeatedly grinding and dispersing the mixture by using a three-roll machine until the Fineness (FOG) is less than 10 mu m and the viscosity is 83-88 Pa S (Brookfield VISCOMETER, available from BROOKFLE VISCOMETER, model HBDV 2T) at the rotating speed of 50rpm respectively obtain P1-P20 slurries.
TABLE 2 fixed content of paste components in silver paste P1-P6 formulation
TABLE 3 silver paste formulations P1-P6 with varying component names and amounts
Example 3:
observation of viscosity change of conductive silver paste
The viscosities of the conductive silver pastes P1-P5 at 50rpm were measured using a brookfield VISCOMETER (available from brookfield mill, model HBDV 2T) using spindle 14 after 0.5 hours and 48 hours, respectively, after the sample preparation, and the specific viscosity values are given in table 4. After the conductive silver paste samples P1-P5 are configured for 0.5 hour, the viscosities are basically close to each other and are all about 84mPa S, after the conductive silver paste samples P1-P5 are configured for 48 hours, the viscosity changes of the conductive silver paste P2 and the conductive silver paste P3 are not large, the viscosity increase of the conductive silver paste P1 is large, and therefore the conductive silver paste P1 is unstable, and probably due to the fact that a ketone carbonyl unit introduced into acrylic resin through DAAM and adipic acid dihydrazide are subjected to a cross-linking reaction; the viscosity of the conductive silver paste P2-P5 is not changed greatly, which indicates that amine substances are adopted and the molar ratio of the used amount to the hydrazine substances is (0.5-2): 1, the cross-linking chemical reaction change in the silver paste can be avoided.
TABLE 4 viscosity Change Observation of conductive silver paste P1-P3
Example 4:
tracking of line type changes during printing, baking and sintering of conductive silver paste P2, conductive silver paste P3 and comparative conductive silver paste P20
After the conductive silver paste was dispensed, conductive silver paste P2, conductive silver paste P3 and comparative conductive silver paste P20 were each printed by screen printing onto 158.75 μm by 158.75 μm P-type single crystal silicon wafers with backside silver and aluminum pastes using screen parameters of 520 mesh, 17 μm wire diameter, 8 μm film thickness and 22 μm opening, which was labeled as the printing process. The printed silicon wafer is immediately subjected to line type parameter observation through a 3D microscope (purchased from Keynes, model VHX-970F), the line height and the line width of the printed fine grid silver line on the solar cell wafer are mainly measured, and the height-width ratio is calculated. 3 battery pieces are taken from each battery piece printed by the paste, linear parameters of fixed positions on the battery pieces are measured, and then an average value is taken; heating the silicon wafer subjected to line measurement at the temperature of 280-350 ℃ for about 10 seconds by a multi-temperature-zone tunnel furnace, marking the process as a drying process, taking out the silicon wafer, and observing line parameters by a 3D microscope according to the same method; after the test is finished, the silicon wafer is subjected to 830 ℃ heating treatment for about 20 seconds through a multi-temperature-zone tunnel furnace at 750-. The line type parameters of the grid lines in the printing, drying and sintering processes are shown in table 5.
TABLE 5 tracking of line type changes in drying and sintering processes after printing of conductive silver paste
As can be seen from table 5, the line width of the line pattern printed with the conductive silver paste P20 of comparative example was expanded, the line height was reduced, and the line pattern collapse was confirmed during the period from printing to drying. Compared with the conductive silver paste P20 of the comparative example, the line widths of the conductive silver paste P2 and the conductive silver paste P3 from printing to drying to sintering are narrowed, and the aspect ratio is not changed greatly, which indicates that the ketohydrazine crosslinking system applied in the conductive silver paste P2 and the conductive silver paste P3 can effectively inhibit the linear collapse in the heating process.
Example 5
Screen printing and line inspection of conductive silver paste
All slurries of examples and comparative examples were printed by screen printing 1 hour after slurry placement onto P-type single crystal silicon wafers of 158.75 μm by 158.75 μm size with backside silver and aluminum pastes using screen parameters of 520 mesh, 17 μm wire diameter, 8 μm film thickness and 22 μm openings, respectively. And (3) heating the printed silicon wafer by using a multi-temperature-zone tunnel furnace to obtain a stable solar cell, wherein the temperature of the initial heating section of the tunnel furnace is 280 ℃, and the temperature of the final heating section is 900 ℃.
The line height, line width and aspect ratio of the fine grid silver line printed on the solar cell sheet were mainly measured by observing the line parameters after sintering with a 3D microscope (from keyence, model VHX-970F). And 3 battery pieces printed by each paste are respectively taken, the linear parameters of the fixed positions on the battery pieces are measured, and then the average value is taken. Specific linetype parameters are shown in Table 6.
TABLE 6 grid line profile parameters of solar cells made from conductive silver pastes P3-P11 and comparative example P20
In table 6, from the printing results of the conductive silver paste P3 and the conductive silver paste P4, it can be seen that the amine reagent is used in an increased amount, which results in an increased line width; from the printing results of the conductive silver paste P6 and the conductive silver paste P7, it was found that when the molar ratio of the hydrazine-based agent to the DAAM deviates from 0.5:1, the effect of suppressing the linear collapse is reduced; from the printing results of the conductive silver paste P8-P11, it can be known that when the content of DAAM and hydrazine is correspondingly reduced or increased, the effect of inhibiting linear collapse is correspondingly reduced or enhanced; from the printing results of the conductive silver paste P12-P19, compared with the conductive silver paste P20 of the comparative example, the application of different hydrazines can play the roles of narrowing the line width and improving the aspect ratio due to the fact that the linear collapse in the heating process can be inhibited; further, the longer the linking structure between dihydrazides is, the weaker the effect of suppressing linear collapse is.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (4)
1. A ketone hydrazine crosslinking system for an organic carrier in photovoltaic silver paste is characterized in that: the ketone hydrazine crosslinking system comprises acrylic resin, a hydrazine reagent and an amine reagent, wherein: the total molar ratio of the acrylic resin to the acrylic resin, the hydrazine reagent and the amine reagent is (0.05-0.2): 1, the molar ratio of the amine reagent to the hydrazine reagent is (0.5-2): 1, and diacetone acrylamide (DAAM) is used as a monomer in the synthesis of the acrylic resin.
2. The ketone hydrazine crosslinking system for the organic carrier in the photovoltaic silver paste as claimed in claim 1, wherein: the hydrazine reagent is one or more of adipic acid dihydrazide, oxalic acid dihydrazide, maleic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, tartaric acid dihydrazide, lauric acid dihydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide or carbohydrazide.
3. The ketone hydrazine crosslinking system for the organic carrier in the photovoltaic silver paste as claimed in claim 1, wherein: the amine reagent is an aliphatic tertiary amine reagent and is one or a combination of triethanolamine and triethylamine.
4. The ketone hydrazine crosslinking system for the organic carrier in the photovoltaic silver paste as claimed in claim 1, wherein: the molar ratio of the hydrazine reagent to DAAM used in the synthesis of the acrylic resin is (0.25-1): 1.
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