CN114038610A - Organic carrier for battery silicon wafer metallization process and preparation method thereof - Google Patents
Organic carrier for battery silicon wafer metallization process and preparation method thereof Download PDFInfo
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- CN114038610A CN114038610A CN202210019295.1A CN202210019295A CN114038610A CN 114038610 A CN114038610 A CN 114038610A CN 202210019295 A CN202210019295 A CN 202210019295A CN 114038610 A CN114038610 A CN 114038610A
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 55
- 239000010703 silicon Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 53
- 230000008569 process Effects 0.000 title claims abstract description 45
- 238000001465 metallisation Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000001913 cellulose Substances 0.000 claims abstract description 68
- 229920002678 cellulose Polymers 0.000 claims abstract description 68
- 229920002545 silicone oil Polymers 0.000 claims abstract description 65
- ICLYJLBTOGPLMC-KVVVOXFISA-N (z)-octadec-9-enoate;tris(2-hydroxyethyl)azanium Chemical compound OCCN(CCO)CCO.CCCCCCCC\C=C/CCCCCCCC(O)=O ICLYJLBTOGPLMC-KVVVOXFISA-N 0.000 claims abstract description 62
- 239000004147 Sorbitan trioleate Substances 0.000 claims abstract description 62
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound 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 abstract description 62
- 229960000391 sorbitan trioleate Drugs 0.000 claims abstract description 62
- 235000019337 sorbitan trioleate Nutrition 0.000 claims abstract description 62
- 229940117013 triethanolamine oleate Drugs 0.000 claims abstract description 62
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 48
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 43
- 229920000570 polyether Polymers 0.000 claims abstract description 43
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 39
- 239000003960 organic solvent Substances 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims description 109
- 239000002002 slurry Substances 0.000 claims description 90
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 82
- 238000002156 mixing Methods 0.000 claims description 76
- -1 carboxyethyl Chemical class 0.000 claims description 66
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 64
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 62
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 55
- 239000008367 deionised water Substances 0.000 claims description 50
- 229910021641 deionized water Inorganic materials 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 239000011259 mixed solution Substances 0.000 claims description 34
- 239000000377 silicon dioxide Substances 0.000 claims description 32
- 235000012239 silicon dioxide Nutrition 0.000 claims description 32
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 30
- 239000011121 hardwood Substances 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 30
- 239000013008 thixotropic agent Substances 0.000 claims description 26
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 22
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 22
- 238000000227 grinding Methods 0.000 claims description 21
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- 229910052709 silver Inorganic materials 0.000 claims description 19
- 239000004332 silver Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 14
- 239000004952 Polyamide Substances 0.000 claims description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 229920002647 polyamide Polymers 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- IFPMZBBHBZQTOV-UHFFFAOYSA-N 1,3,5-trinitro-2-(2,4,6-trinitrophenyl)-4-[2,4,6-trinitro-3-(2,4,6-trinitrophenyl)phenyl]benzene Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C(C=2C(=C(C=3C(=CC(=CC=3[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)C(=CC=2[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)=C1[N+]([O-])=O IFPMZBBHBZQTOV-UHFFFAOYSA-N 0.000 claims description 12
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 11
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 11
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 11
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 11
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 229960002798 cetrimide Drugs 0.000 claims description 10
- 238000007865 diluting Methods 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 4
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims description 3
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 235000012431 wafers Nutrition 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- 238000007873 sieving Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000007639 printing Methods 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 238000005286 illumination Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 241000409201 Luina Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940008099 dimethicone Drugs 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000010792 warming 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
- C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Dispersion Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides an organic carrier for a battery silicon chip metallization process and a preparation method thereof, wherein the organic carrier is kept to be volatilized hierarchically by limiting the components and the contents of an organic solvent and other additives in the organic carrier; the following relationships exist: w (sorbitan trioleate) + W (triethanolamine oleate) is not less than 5W (release agent); the ratio of the sum of the sorbitan trioleate and the triethanolamine oleate to the organic carrier is 3.2-5.7 percent by weight, the moderate viscosity is kept, the leveling property of the organic carrier is improved, the film layer is more smooth and compact, and the film layer does not sag after being printed; the silicone oil is subjected to amino polyether modification treatment, and a large amount of polyether chain segments, amino groups and hydroxyl groups are added to the side chain, so that the rapid leveling property is improved; the total addition of the amino polyether modified silicone oil and the silicone oil in the organic carrier is limited to be lower than the total addition of sorbitan trioleate and triethanolamine oleate, and the modified microfibrillated cellulose is used as a binder, so that the battery efficiency is improved, and the service life of the battery is prolonged.
Description
Technical Field
The invention relates to the field of battery silicon chips, in particular to an organic carrier for a battery silicon chip metallization process and a preparation method thereof.
Background
A solar cell is a semiconductor device that converts light energy into electrical energy using a photochemical effect or a photovoltaic effect; the development of solar cells began from the first discovery of potential difference generated by illumination energy in solution by a french scientist beckerel in 1839, and by 1954, american scientists made single crystal silicon solar cells with a photoelectric conversion efficiency of 4.5%, and the first real silicon p-n junction solar cell was formally landed on the historical stage. The solar cell has the advantages of free fuel, no harmful gas emission, environmental protection, and the like, and has the characteristics of difficult damage, easy maintenance, rapid installation, no noise and the like.
With the trend of global energy and the obvious problems of global warming, ecological environment deterioration and the like, solar power generation attracts much attention as a sustainable energy substitution mode, and with the continuous improvement of the technical level of the photovoltaic industry and the enlargement of the production scale, the newly increased demand of the solar cell increases year by year from 2011; according to the prediction of the European photovoltaic industry society, solar power generation occupies an important seat of world energy consumption in the 21 st century, not only replaces part of conventional energy, but also becomes a main body of world energy supply.
The solar cell collects and guides electrons through silver grid lines printed on a silicon wafer, and the conversion efficiency of the solar cell is determined by the quality of front silver paste in the solar cell; the front silver paste is a suspension system formed by adding silver powder and glass powder in a specific ratio into an organic carrier serving as a base material. The organic carrier is a carrier medium, and is prepared by dissolving a high molecular substance in an organic solvent, and plays a role in determining the rheology and the printing performance of the slurry, and generally accounts for 5-15% of the total weight.
In the preparation of the silicon wafer solar cell, printing slurry on the back surface of a silicon wafer, drying and sintering the slurry, and forming a back electrode on the back surface of the silicon wafer; the contact resistance between the silver back electrode and the aluminum back electrode formed after sintering is small, and the adhesive force between the back silver paste and the silicon wafer is strong. However, the rheological property of the organic carrier used in the prior art is poor, so that the shaping capability of the grid line of the back silver paste is poor, the height-to-width ratio of the sintered electrode to the grid line is small, the light receiving area occupied by the cell is reduced, and the efficiency of the solar cell is reduced.
Disclosure of Invention
The invention aims to provide an organic carrier for a battery silicon chip metallization process and a preparation method thereof, which aim to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
an organic carrier for a battery silicon chip metallization process comprises the following components in parts by weight: 65-80 parts of organic solvent, 5-15 parts of modified carboxyethyl microfibrillated cellulose, 0.5-3 parts of thixotropic agent, 0.1-3 parts of sorbitan trioleate, 0.1-3 parts of triethanolamine oleate and 0.1-0.8 part of release agent.
Further, the organic solvent is one or more of butyl carbitol, alcohol ester dodeca, butyl carbitol acetate, dimethyl adipate and tributyl citrate.
The invention achieves the purpose of controlling the volatilization rate of the silver paste by limiting the components and the contents of the organic solvent and other additives in the organic carrier, so that the organic carrier can be kept to be volatilized in a layered manner, and uneven holes are prevented from appearing on the surface of the grid line; and each temperature section is uniformly volatilized during high-temperature sintering, so that cracks generated by concentrated volatilization are avoided.
The sorbitan trioleate has a large molecular weight, is mainly used for dispersing and wetting the silver powder through steric hindrance effect, has a lipophilic group, is uniformly dispersed in an organic carrier, and is anchored on the surface of the silver powder through an oleophobic group, so that the wetting property of the silver powder is effectively promoted, the viscosity is reduced, and meanwhile, the leveling of a film layer is promoted; the triethanolamine oleate disperses the silver powder through the mutual exclusion effect of double electric layers, has larger molecular weight, has certain steric hindrance effect, and improves the dispersion effect on the silver powder.
Further, the release agent is prepared from dimethyl silicone oil and amino polyether modified silicone oil according to the mass ratio of 1: 1.
Further, the preparation method of the amino polyether modified silicone oil comprises the following steps: mixing hydrogen-containing silicone oil, allyl glycidyl ether and allyl polyoxyethylene ether, ultrasonically stirring, and stirring for 2-5min under the protection of nitrogen; heating to 80-90 ℃, dripping a platinum catalyst solution, and reacting for 1-2 h; reducing the pressure, then adding ethylenediamine, introducing nitrogen, heating to 80-90 ℃ and reacting for 1-2 h; decompressing, washing with cyclohexane and chloroform in sequence to obtain the amino polyether modified silicone oil.
Furthermore, the mass ratio of the hydrogen-containing silicone oil to the allyl glycidyl ether to the allyl polyoxyethylene ether is 10:1: 1.
Carrying out amino polyether modification treatment on the silicone oil, and adding a large amount of polyether chain segments, amino and hydroxyl on side chains; the silicone oil has better conditioning property; the added polyether chain segment has good hydrophilicity, and is matched with sorbitan trioleate and triethanolamine oleate to adjust the thixotropy and the leveling property; the amino group has good flexibility, and the polysiloxane has high film-forming property, so that the rapid leveling property of the organic carrier is improved; however, the total addition amount of the amino polyether modified silicone oil and the silicone oil in the organic carrier is lower than that of the sorbitan trioleate and the triethanolamine oleate, the addition amount concentration of the sorbitan trioleate and the triethanolamine oleate is too high, the surface amino polyether modified silicone oil film is thickened, the viscosity is too high, and the leveling property is poor.
The following relations exist by limiting the sorbitan trioleate, the triethanolamine oleate and the release agent: w (sorbitan trioleate) + W (triethanolamine oleate) is not less than 5W (release agent), namely the total addition amount of the sorbitan trioleate and the triethanolamine oleate is not less than 5 times of the addition amount of the release agent in parts by weight; when the content is less than 5 times, the viscosity is too high and the leveling property is reduced in parts by weight;
when the total content of sorbitan trioleate and triethanolamine oleate added into the organic carrier in the invention is lower than 3.2 percent in the organic carrier, silver particles cannot be well wetted and dispersed, the phenomenon of conglobation and serious aggregation of silver particles occurs, the viscosity is too high, the leveling property of a film layer is poor, the shrinkage or closure rate of holes of the film layer is greatly reduced, the phenomena of porosity, unevenness and larger holes of the film layer are caused, and the phenomenon of difficulty in passing through a screen during printing is caused;
therefore, the content of the sorbitan trioleate and the triethanolamine oleate is limited, the ratio of the total amount of the sorbitan trioleate and the triethanolamine oleate to the organic carrier is 3.2-5.7% by weight, the thixotropy of the organic carrier is improved, the synergistic capability of all components on the leveling property is improved, the moderate viscosity is kept, the quick leveling property of the organic carrier is improved, the film layer is more smooth and compact, the phenomenon that the printed grid line is not sagging after printing is ensured, no sharp head exists, the printed grid line is ensured to be regular and flat, and the photoelectric conversion efficiency of the battery is improved.
Furthermore, the thixotropic agent is prepared from polyvinyl alcohol and polyamide wax according to the mass ratio of (1-3) to 1.
The mass ratio of polyvinyl alcohol to polyamide wax is limited to (1-3): 1, so that the organic carrier and the paste become thinner when subjected to external force, and the viscosity is increased after the external force is removed, thereby ensuring that the printed silver grid line has a large height-width ratio.
Further, the preparation of the modified carboxyethyl microfibrillated cellulose comprises the following steps:
(1) crushing bleached sulfate hardwood pulp, adding the crushed bleached sulfate hardwood pulp into a sodium hydroxide solution, performing ultrasonic stirring, adding an acrylamide solution to obtain a slurry, concentrating the slurry until the slurry concentration is 22%, putting the slurry into a high-concentration mixing reactor, reacting at the temperature of 80-90 ℃ for 1-2h, washing the slurry to be neutral by using deionized water, diluting the slurry to the slurry concentration of 2% by using the deionized water, and grinding the slurry at the rotating speed of 1600r/min to obtain the carboxyethyl microfibrillated cellulose;
(2) mixing cetrimide, diethyl ether, ethanol, ammonia water and deionized water, ultrasonically stirring, adding ethyl orthosilicate and 3-aminopropyltriethoxysilane after 5-10min, and ultrasonically stirring for 0.5-1 h; adding hydrochloric acid to adjust pH to 6-7, centrifuging, washing with ethanol and deionized water, and drying at 50-60 deg.C to obtain dendritic silicon dioxide;
(3) mixing and stirring carboxyethyl microfibrillated cellulose, dendritic silicon dioxide, a silane coupling agent and deionized water, and performing ultrasonic dispersion to obtain the modified carboxyethyl microfibrillated cellulose.
Further, the mass ratio of the bleached sulfate hardwood pulp to the sodium hydroxide solution to the acrylamide solution in the step (1) is 1:5: 3; in the step (2), the volume ratio of the diethyl ether to the ethanol to the ethyl orthosilicate is 2:1: 0.25; in the step (3), the mass ratio of the carboxyethyl microfibrillated cellulose to the dendritic silicon dioxide is 10: 1.
A preparation method of an organic carrier for a battery silicon chip metallization process comprises the following steps:
s1: mixing, stirring and ultrasonically dispersing modified carboxyethyl microfibrillated cellulose, a thixotropic agent and an organic solvent, and preserving heat for 0.5-1h at 70-80 ℃ to obtain a modified mixed solution;
s2: and mixing and stirring sorbitan trioleate and triethanolamine oleate, adding the modified mixed solution and the release agent, mixing and stirring, performing ultrasonic dispersion, grinding and sieving to obtain the organic carrier for the battery silicon wafer metallization process.
Further, in step S2, the powder is sieved through a 200-350-mesh sieve.
The organic carrier for the metallization process of the silicon wafer of the battery, which is prepared by the invention, is used for preparing the back silver slurry of the silicon wafer solar battery: and stirring the organic carrier, the nano silver powder and the flake silver powder in a planetary stirrer until the three-roller grinder disperses the mixture to the fineness of 2-5 mu m to obtain the back silver slurry.
According to the invention, modified microfibrillated cellulose is used as a binder, dendritic silicon dioxide is used for modifying the microfibrillated cellulose, and spherical silicon dioxide is prepared by utilizing a synergistic effect theory, a molecular accumulation theory and a charge density matching mechanism to increase the dispersibility; the escape of ether and the addition of 3-aminopropyltriethoxysilane are utilized to form a dendritic pore channel, a compact network structure with a surface rich in hydroxyl is constructed, and the viscosity is adjusted together with sorbitan trioleate, triethanolamine oleate and a release agent, so that the prepared silver paste has excellent leveling property, thixotropy and printability, and the photoelectric conversion efficiency of the battery is improved.
The invention has the beneficial effects that:
the invention provides an organic carrier for a battery silicon chip metallization process and a preparation method thereof, which can control the volatilization rate of silver paste by limiting the components and the contents of an organic solvent and other additives in the organic carrier, and uniformly volatilizes at each temperature section of high-temperature sintering, so that the organic carrier can be kept to be volatilized hierarchically, and cracks generated by concentrated volatilization and uneven holes on the surface of a grid line are prevented;
the battery front silver paste prepared by the organic carrier has high resolution, excellent transfer characteristic, flat and compact silver layer and excellent storage performance, has excellent linear shaping capability by optimizing the organic carrier for the battery silicon wafer metallization process, greatly improves the silk-screen quality on the silicon wafer, improves the height-width ratio of sintered electrodes and grid lines, and prolongs the service life of the battery while improving the battery efficiency when being applied to a solar battery.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that if directional indications such as up, down, left, right, front, and back … … are involved in the embodiment of the present invention, the directional indications are only used to explain a specific posture, such as a relative positional relationship between components, a motion situation, and the like, and if the specific posture changes, the directional indications also change accordingly. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The technical solutions of the present invention are further described in detail with reference to specific examples, which should be understood that the following examples are only illustrative of the present invention and are not intended to limit the present invention.
Example 1
A preparation method of an organic carrier for a battery silicon chip metallization process comprises the following steps:
s1: mixing 65 parts of organic solvent, 5 parts of modified carboxyethyl microfibrillated cellulose and 2.5 parts of thixotropic agent, stirring, ultrasonically dispersing, and preserving heat at 70 ℃ for 1h to obtain a modified mixed solution;
the preparation of the modified carboxyethyl microfibrillated cellulose comprises the following steps:
crushing bleached sulfate hardwood pulp, adding the crushed bleached sulfate hardwood pulp into a sodium hydroxide solution, performing ultrasonic stirring, adding an acrylamide solution to obtain a slurry, concentrating the slurry until the slurry concentration is 22%, putting the slurry into a high-concentration mixing reactor, reacting at 80 ℃ for 2 hours, washing the slurry to be neutral by using deionized water, diluting the slurry to be 2% by using the deionized water, and grinding the slurry at the rotating speed of 1600r/min to obtain carboxyethyl microfibrillated cellulose;
the mass ratio of the bleached sulfate hardwood pulp to the sodium hydroxide solution to the acrylamide solution is 1:5: 3;
mixing cetrimide, diethyl ether, ethanol, ammonia water and deionized water, ultrasonically stirring, adding ethyl orthosilicate and 3-aminopropyltriethoxysilane after 5min, and ultrasonically stirring for 0.5 h; adding hydrochloric acid to adjust pH to 6, centrifuging, washing with ethanol and deionized water, and drying at 50 deg.C to obtain dendritic silicon dioxide;
the volume ratio of the diethyl ether to the ethanol to the ethyl orthosilicate is 2:1: 0.25;
mixing and stirring carboxyethyl microfibrillated cellulose, dendritic silicon dioxide, a silane coupling agent and deionized water, and performing ultrasonic dispersion to obtain modified carboxyethyl microfibrillated cellulose;
the mass ratio of the carboxyethyl microfibrillated cellulose to the dendritic silicon dioxide is 10: 1;
the thixotropic agent is prepared from polyvinyl alcohol and polyamide wax in a mass ratio of 1: 1;
the organic solvent is a mixed solution of butyl carbitol, alcohol ester dodeca and tributyl citrate;
s2: mixing and stirring sorbitan trioleate and triethanolamine oleate, adding the modified mixed solution and a release agent, mixing and stirring, performing ultrasonic dispersion, grinding and sieving by a 200-mesh sieve to obtain an organic carrier for a battery silicon wafer metallization process;
1.2 parts of sorbitan trioleate, 1.2 parts of triethanolamine oleate and 0.1 part of a release agent; the total content of the sorbitan trioleate and the triethanolamine oleate in the organic carrier is 3.2 percent;
the release agent is prepared from dimethyl silicone oil and amino polyether modified silicone oil according to the mass ratio of 1: 1;
the preparation method of the amino polyether modified silicone oil comprises the following steps: mixing hydrogen-containing silicone oil, allyl glycidyl ether and allyl polyoxyethylene ether, ultrasonically stirring, and stirring for 2min under the protection of nitrogen; heating to 80 ℃, and dripping a platinum catalyst solution to react for 2 hours; reducing the pressure, then adding ethylenediamine, introducing nitrogen, heating to 80 ℃ and reacting for 2 hours; decompressing, washing with cyclohexane and chloroform in sequence to obtain the amino polyether modified silicone oil.
And stirring the prepared organic carrier in a planetary stirrer according to the proportion of 8% of the organic carrier, 12% of the nano silver powder and 80% of the flaky silver powder until the mixture is dispersed by a three-roll grinder to the fineness of 2 mu m, thus obtaining the slurry.
Example 2
A preparation method of an organic carrier for a battery silicon chip metallization process comprises the following steps:
s1: mixing 75 parts of organic solvent, 10 parts of modified carboxyethyl microfibrillated cellulose and 1 part of thixotropic agent, stirring, ultrasonically dispersing, and preserving heat at 75 ℃ for 0.8h to obtain a modified mixed solution;
the preparation of the modified carboxyethyl microfibrillated cellulose comprises the following steps:
crushing bleached sulfate hardwood pulp, adding the crushed bleached sulfate hardwood pulp into a sodium hydroxide solution, performing ultrasonic stirring, adding an acrylamide solution to obtain a slurry, concentrating the slurry until the slurry concentration is 22%, putting the slurry into a high-concentration mixing reactor, reacting at 85 ℃ for 1.5h, washing the slurry to be neutral by deionized water, diluting the slurry to be 2% by deionized water, and grinding the slurry at the rotating speed of 1600r/min to obtain the carboxyethyl microfibrillated cellulose;
the mass ratio of the bleached sulfate hardwood pulp to the sodium hydroxide solution to the acrylamide solution is 1:5: 3;
mixing cetrimide, diethyl ether, ethanol, ammonia water and deionized water, ultrasonically stirring, adding ethyl orthosilicate and 3-aminopropyltriethoxysilane after 8min, and ultrasonically stirring for 0.8 h; adding hydrochloric acid to adjust pH to 6.5, centrifuging, washing with ethanol and deionized water, and drying at 55 deg.C to obtain dendritic silicon dioxide;
the volume ratio of the diethyl ether to the ethanol to the ethyl orthosilicate is 2:1: 0.25;
mixing and stirring carboxyethyl microfibrillated cellulose, dendritic silicon dioxide, a silane coupling agent and deionized water, and performing ultrasonic dispersion to obtain modified carboxyethyl microfibrillated cellulose;
the mass ratio of the carboxyethyl microfibrillated cellulose to the dendritic silicon dioxide is 10: 1;
the thixotropic agent is prepared from polyvinyl alcohol and polyamide wax in a mass ratio of 2: 1;
the organic solvent is a mixed solution of alcohol ester dodeca, butyl carbitol acetate and tributyl citrate;
s2: mixing and stirring sorbitan trioleate and triethanolamine oleate, adding the modified mixed solution and a release agent, mixing and stirring, performing ultrasonic dispersion, grinding and sieving by a 300-mesh sieve to obtain an organic carrier for a battery silicon wafer metallization process;
1.6 parts of sorbitan trioleate, 2 parts of triethanolamine oleate and 0.6 part of a release agent; the total content of the sorbitan trioleate and the triethanolamine oleate in the organic carrier is 4 percent;
the release agent is prepared from dimethyl silicone oil and amino polyether modified silicone oil according to the mass ratio of 1: 1;
the preparation method of the amino polyether modified silicone oil comprises the following steps: mixing hydrogen-containing silicone oil, allyl glycidyl ether and allyl polyoxyethylene ether, ultrasonically stirring, and stirring for 4min under the protection of nitrogen; heating to 85 ℃, and dripping a platinum catalyst solution to react for 1.5 h; reducing the pressure, then adding ethylenediamine, introducing nitrogen, heating to 85 ℃ and reacting for 1.5 h; decompressing, washing with cyclohexane and chloroform in sequence to obtain amino polyether modified silicone oil;
and stirring the prepared organic carrier in a planetary stirrer according to the proportion of 8% of the organic carrier, 12% of the nano silver powder and 80% of the flaky silver powder until the mixture is dispersed by a three-roll grinder to the fineness of 3 mu m, thus obtaining the slurry.
Example 3
A preparation method of an organic carrier for a battery silicon chip metallization process comprises the following steps:
s1: mixing, stirring and ultrasonically dispersing 80 parts of organic solvent, 15 parts of modified carboxyethyl microfibrillated cellulose and 3 parts of thixotropic agent, and preserving heat at 80 ℃ for 0.5h to obtain a modified mixed solution;
the preparation of the modified carboxyethyl microfibrillated cellulose comprises the following steps:
crushing bleached sulfate hardwood pulp, adding the crushed bleached sulfate hardwood pulp into a sodium hydroxide solution, performing ultrasonic stirring, adding an acrylamide solution to obtain a slurry, concentrating the slurry until the slurry concentration is 22%, putting the slurry into a high-concentration mixing reactor, reacting at 90 ℃ for 1h, washing the slurry to be neutral by using deionized water, diluting the slurry to be 2% by using the deionized water, and grinding the slurry at the rotating speed of 1600r/min to obtain carboxyethyl microfibrillated cellulose;
the mass ratio of the bleached sulfate hardwood pulp to the sodium hydroxide solution to the acrylamide solution is 1:5: 3;
mixing cetrimide, diethyl ether, ethanol, ammonia water and deionized water, ultrasonically stirring, adding ethyl orthosilicate and 3-aminopropyltriethoxysilane after 10min, and ultrasonically stirring for 1 h; adding hydrochloric acid to adjust pH to 7, centrifuging, washing with ethanol and deionized water, and drying at 60 deg.C to obtain dendritic silicon dioxide;
the volume ratio of the diethyl ether to the ethanol to the ethyl orthosilicate is 2:1: 0.25;
mixing and stirring carboxyethyl microfibrillated cellulose, dendritic silicon dioxide, a silane coupling agent and deionized water, and performing ultrasonic dispersion to obtain modified carboxyethyl microfibrillated cellulose;
the mass ratio of the carboxyethyl microfibrillated cellulose to the dendritic silicon dioxide is 10: 1;
the thixotropic agent is prepared from polyvinyl alcohol and polyamide wax in a mass ratio of 3: 1;
the organic solvent is a mixed solution of butyl carbitol, alcohol ester dodeca and dimethyl adipate;
s2: mixing and stirring sorbitan trioleate and triethanolamine oleate, adding the modified mixed solution and a release agent, mixing and stirring, performing ultrasonic dispersion, grinding and sieving with a 350-mesh sieve to obtain an organic carrier for a battery silicon wafer metallization process;
3 parts of sorbitan trioleate, 3 parts of triethanolamine oleate and 0.8 part of a release agent; the total content of the sorbitan trioleate and the triethanolamine oleate in the organic carrier is 5.7 percent;
the release agent is prepared from dimethyl silicone oil and amino polyether modified silicone oil according to the mass ratio of 1: 1;
the preparation method of the amino polyether modified silicone oil comprises the following steps: mixing hydrogen-containing silicone oil, allyl glycidyl ether and allyl polyoxyethylene ether, ultrasonically stirring, and stirring for 5min under the protection of nitrogen; heating to 90 ℃, and dripping a platinum catalyst solution to react for 2 hours; reducing the pressure, then adding ethylenediamine, introducing nitrogen, heating to 90 ℃ and reacting for 1 h; decompressing, washing with cyclohexane and chloroform in sequence to obtain amino polyether modified silicone oil;
and stirring the prepared organic carrier in a planetary stirrer according to the proportion of 8% of the organic carrier, 12% of the nano silver powder and 80% of the flaky silver powder until the mixture is dispersed by a three-roll grinder to the fineness of 5 mu m, thus obtaining the slurry.
Comparative example 1
A preparation method of an organic carrier for a battery silicon chip metallization process comprises the following steps:
s1: mixing 75 parts of organic solvent, 10 parts of carboxyethyl microfibrillated cellulose and 1 part of thixotropic agent, stirring, ultrasonically dispersing, and preserving heat at 75 ℃ for 0.8h to obtain a modified mixed solution;
the thixotropic agent is prepared from polyvinyl alcohol and polyamide wax in a mass ratio of 2: 1;
the organic solvent is a mixed solution of alcohol ester dodeca, butyl carbitol acetate and tributyl citrate;
s2: mixing and stirring sorbitan trioleate and triethanolamine oleate, adding the modified mixed solution and a release agent, mixing and stirring, performing ultrasonic dispersion, grinding and sieving by a 300-mesh sieve to obtain an organic carrier for a battery silicon wafer metallization process;
1.6 parts of sorbitan trioleate, 2 parts of triethanolamine oleate and 0.6 part of a release agent; the total content of the sorbitan trioleate and the triethanolamine oleate in the organic carrier is 4 percent;
the release agent is prepared from dimethyl silicone oil and amino polyether modified silicone oil according to the mass ratio of 1: 1;
the preparation method of the amino polyether modified silicone oil comprises the following steps: mixing hydrogen-containing silicone oil, allyl glycidyl ether and allyl polyoxyethylene ether, ultrasonically stirring, and stirring for 4min under the protection of nitrogen; heating to 85 ℃, and dripping a platinum catalyst solution to react for 1.5 h; reducing the pressure, then adding ethylenediamine, introducing nitrogen, heating to 85 ℃ and reacting for 1.5 h; decompressing, washing with cyclohexane and chloroform in sequence to obtain amino polyether modified silicone oil;
and stirring the prepared organic carrier in a planetary stirrer according to the proportion of 8% of the organic carrier, 12% of the nano silver powder and 80% of the flaky silver powder until the mixture is dispersed by a three-roll grinder to the fineness of 3 mu m, thus obtaining the slurry.
Comparative example 2
A preparation method of an organic carrier for a battery silicon chip metallization process comprises the following steps:
s1: mixing 75 parts of organic solvent, 10 parts of modified carboxyethyl microfibrillated cellulose and 1 part of thixotropic agent, stirring, ultrasonically dispersing, and preserving heat at 75 ℃ for 0.8h to obtain a modified mixed solution;
the preparation of the modified carboxyethyl microfibrillated cellulose comprises the following steps:
crushing bleached sulfate hardwood pulp, adding the crushed bleached sulfate hardwood pulp into a sodium hydroxide solution, performing ultrasonic stirring, adding an acrylamide solution to obtain a slurry, concentrating the slurry until the slurry concentration is 22%, putting the slurry into a high-concentration mixing reactor, reacting at 85 ℃ for 1.5h, washing the slurry to be neutral by deionized water, diluting the slurry to be 2% by deionized water, and grinding the slurry at the rotating speed of 1600r/min to obtain the carboxyethyl microfibrillated cellulose;
the mass ratio of the bleached sulfate hardwood pulp to the sodium hydroxide solution to the acrylamide solution is 1:5: 3;
mixing cetrimide, diethyl ether, ethanol, ammonia water and deionized water, ultrasonically stirring, adding ethyl orthosilicate and 3-aminopropyltriethoxysilane after 8min, and ultrasonically stirring for 0.8 h; adding hydrochloric acid to adjust pH to 6.5, centrifuging, washing with ethanol and deionized water, and drying at 55 deg.C to obtain dendritic silicon dioxide;
the volume ratio of the diethyl ether to the ethanol to the ethyl orthosilicate is 2:1: 0.25;
mixing and stirring carboxyethyl microfibrillated cellulose, dendritic silicon dioxide, a silane coupling agent and deionized water, and performing ultrasonic dispersion to obtain modified carboxyethyl microfibrillated cellulose;
the mass ratio of the carboxyethyl microfibrillated cellulose to the dendritic silicon dioxide is 10: 1;
the thixotropic agent is prepared from polyvinyl alcohol and polyamide wax in a mass ratio of 2: 1;
the organic solvent is a mixed solution of alcohol ester dodeca, butyl carbitol acetate and tributyl citrate;
s2: mixing and stirring sorbitan trioleate and triethanolamine oleate, adding the modified mixed solution and a release agent, mixing and stirring, performing ultrasonic dispersion, grinding and sieving by a 300-mesh sieve to obtain an organic carrier for a battery silicon wafer metallization process;
1.6 parts of sorbitan trioleate, 2 parts of triethanolamine oleate and 0.6 part of a release agent; the total content of the sorbitan trioleate and the triethanolamine oleate in the organic carrier is 4 percent; the release agent is dimethyl silicone oil;
and stirring the prepared organic carrier in a planetary stirrer according to the proportion of 8% of the organic carrier, 12% of the nano silver powder and 80% of the flaky silver powder until the mixture is dispersed by a three-roll grinder to the fineness of 3 mu m, thus obtaining the slurry.
Comparative example 3
A preparation method of an organic carrier for a battery silicon chip metallization process comprises the following steps:
s1: mixing 75 parts of organic solvent, 10 parts of modified carboxyethyl microfibrillated cellulose and 1 part of thixotropic agent, stirring, ultrasonically dispersing, and preserving heat at 75 ℃ for 0.8h to obtain a modified mixed solution;
the preparation of the modified carboxyethyl microfibrillated cellulose comprises the following steps:
crushing bleached sulfate hardwood pulp, adding the crushed bleached sulfate hardwood pulp into a sodium hydroxide solution, performing ultrasonic stirring, adding an acrylamide solution to obtain a slurry, concentrating the slurry until the slurry concentration is 22%, putting the slurry into a high-concentration mixing reactor, reacting at 85 ℃ for 1.5h, washing the slurry to be neutral by deionized water, diluting the slurry to be 2% by deionized water, and grinding the slurry at the rotating speed of 1600r/min to obtain the carboxyethyl microfibrillated cellulose;
the mass ratio of the bleached sulfate hardwood pulp to the sodium hydroxide solution to the acrylamide solution is 1:5: 3;
mixing cetrimide, diethyl ether, ethanol, ammonia water and deionized water, ultrasonically stirring, adding ethyl orthosilicate and 3-aminopropyltriethoxysilane after 8min, and ultrasonically stirring for 0.8 h; adding hydrochloric acid to adjust pH to 6.5, centrifuging, washing with ethanol and deionized water, and drying at 55 deg.C to obtain dendritic silicon dioxide;
the volume ratio of the diethyl ether to the ethanol to the ethyl orthosilicate is 2:1: 0.25;
mixing and stirring carboxyethyl microfibrillated cellulose, dendritic silicon dioxide, a silane coupling agent and deionized water, and performing ultrasonic dispersion to obtain modified carboxyethyl microfibrillated cellulose;
the mass ratio of the carboxyethyl microfibrillated cellulose to the dendritic silicon dioxide is 10: 1;
the thixotropic agent is prepared from polyvinyl alcohol and polyamide wax in a mass ratio of 2: 1;
the organic solvent is a mixed solution of alcohol ester dodeca, butyl carbitol acetate and tributyl citrate;
s2: mixing and stirring sorbitan trioleate and triethanolamine oleate, adding the modified mixed solution and a release agent, mixing and stirring, performing ultrasonic dispersion, grinding and sieving by a 300-mesh sieve to obtain an organic carrier for a battery silicon wafer metallization process;
1.3 parts of sorbitan trioleate, 1.38 parts of triethanolamine oleate and 0.6 part of a release agent; the total content of the sorbitan trioleate and the triethanolamine oleate in the organic carrier is 3 percent;
the release agent is prepared from dimethyl silicone oil and amino polyether modified silicone oil according to the mass ratio of 1: 1;
the preparation method of the amino polyether modified silicone oil comprises the following steps: mixing hydrogen-containing silicone oil, allyl glycidyl ether and allyl polyoxyethylene ether, ultrasonically stirring, and stirring for 4min under the protection of nitrogen; heating to 85 ℃, and dripping a platinum catalyst solution to react for 1.5 h; reducing the pressure, then adding ethylenediamine, introducing nitrogen, heating to 85 ℃ and reacting for 1.5 h; decompressing, washing with cyclohexane and chloroform in sequence to obtain amino polyether modified silicone oil;
and stirring the prepared organic carrier in a planetary stirrer according to the proportion of 8% of the organic carrier, 12% of the nano silver powder and 80% of the flaky silver powder until the mixture is dispersed by a three-roll grinder to the fineness of 3 mu m, thus obtaining the slurry.
Comparative example 4
A preparation method of an organic carrier for a battery silicon chip metallization process comprises the following steps:
s1: mixing 68 parts of organic solvent, 10 parts of modified carboxyethyl microfibrillated cellulose and 2 parts of thixotropic agent, stirring, ultrasonically dispersing, and preserving heat at 75 ℃ for 0.8h to obtain a modified mixed solution;
the preparation of the modified carboxyethyl microfibrillated cellulose comprises the following steps:
crushing bleached sulfate hardwood pulp, adding the crushed bleached sulfate hardwood pulp into a sodium hydroxide solution, performing ultrasonic stirring, adding an acrylamide solution to obtain a slurry, concentrating the slurry until the slurry concentration is 22%, putting the slurry into a high-concentration mixing reactor, reacting at 85 ℃ for 1.5h, washing the slurry to be neutral by deionized water, diluting the slurry to be 2% by deionized water, and grinding the slurry at the rotating speed of 1600r/min to obtain the carboxyethyl microfibrillated cellulose;
the mass ratio of the bleached sulfate hardwood pulp to the sodium hydroxide solution to the acrylamide solution is 1:5: 3;
mixing cetrimide, diethyl ether, ethanol, ammonia water and deionized water, ultrasonically stirring, adding ethyl orthosilicate and 3-aminopropyltriethoxysilane after 8min, and ultrasonically stirring for 0.8 h; adding hydrochloric acid to adjust pH to 6.5, centrifuging, washing with ethanol and deionized water, and drying at 55 deg.C to obtain dendritic silicon dioxide;
the volume ratio of the diethyl ether to the ethanol to the ethyl orthosilicate is 2:1: 0.25;
mixing and stirring carboxyethyl microfibrillated cellulose, dendritic silicon dioxide, a silane coupling agent and deionized water, and performing ultrasonic dispersion to obtain modified carboxyethyl microfibrillated cellulose;
the mass ratio of the carboxyethyl microfibrillated cellulose to the dendritic silicon dioxide is 10: 1;
the thixotropic agent is prepared from polyvinyl alcohol and polyamide wax in a mass ratio of 2: 1;
the organic solvent is a mixed solution of alcohol ester dodeca, butyl carbitol acetate and tributyl citrate;
s2: mixing and stirring sorbitan trioleate and triethanolamine oleate, adding the modified mixed solution and a release agent, mixing and stirring, performing ultrasonic dispersion, grinding and sieving by a 300-mesh sieve to obtain an organic carrier for a battery silicon wafer metallization process;
2.5 parts of sorbitan trioleate, 2.64 parts of triethanolamine oleate and 0.6 part of a release agent; the total content of the sorbitan trioleate and the triethanolamine oleate in the organic carrier is 6 percent;
the release agent is prepared from dimethyl silicone oil and amino polyether modified silicone oil according to the mass ratio of 1: 1;
the preparation method of the amino polyether modified silicone oil comprises the following steps: mixing hydrogen-containing silicone oil, allyl glycidyl ether and allyl polyoxyethylene ether, ultrasonically stirring, and stirring for 4min under the protection of nitrogen; heating to 85 ℃, and dripping a platinum catalyst solution to react for 1.5 h; reducing the pressure, then adding ethylenediamine, introducing nitrogen, heating to 85 ℃ and reacting for 1.5 h; decompressing, washing with cyclohexane and chloroform in sequence to obtain amino polyether modified silicone oil;
and stirring the prepared organic carrier in a planetary stirrer according to the proportion of 8% of the organic carrier, 12% of the nano silver powder and 80% of the flaky silver powder until the mixture is dispersed by a three-roll grinder to the fineness of 3 mu m, thus obtaining the slurry.
Comparative example 5
A preparation method of an organic carrier for a battery silicon chip metallization process comprises the following steps:
s1: mixing 75 parts of organic solvent, 10 parts of modified carboxyethyl microfibrillated cellulose and 1 part of thixotropic agent, stirring, ultrasonically dispersing, and preserving heat at 75 ℃ for 0.8h to obtain a modified mixed solution;
the preparation of the modified carboxyethyl microfibrillated cellulose comprises the following steps:
crushing bleached sulfate hardwood pulp, adding the crushed bleached sulfate hardwood pulp into a sodium hydroxide solution, performing ultrasonic stirring, adding an acrylamide solution to obtain a slurry, concentrating the slurry until the slurry concentration is 22%, putting the slurry into a high-concentration mixing reactor, reacting at 85 ℃ for 1.5h, washing the slurry to be neutral by deionized water, diluting the slurry to be 2% by deionized water, and grinding the slurry at the rotating speed of 1600r/min to obtain the carboxyethyl microfibrillated cellulose;
the mass ratio of the bleached sulfate hardwood pulp to the sodium hydroxide solution to the acrylamide solution is 1:5: 3;
mixing cetrimide, diethyl ether, ethanol, ammonia water and deionized water, ultrasonically stirring, adding ethyl orthosilicate and 3-aminopropyltriethoxysilane after 8min, and ultrasonically stirring for 0.8 h; adding hydrochloric acid to adjust pH to 6.5, centrifuging, washing with ethanol and deionized water, and drying at 55 deg.C to obtain dendritic silicon dioxide;
the volume ratio of the diethyl ether to the ethanol to the ethyl orthosilicate is 2:1: 0.25;
mixing and stirring carboxyethyl microfibrillated cellulose, dendritic silicon dioxide, a silane coupling agent and deionized water, and performing ultrasonic dispersion to obtain modified carboxyethyl microfibrillated cellulose;
the mass ratio of the carboxyethyl microfibrillated cellulose to the dendritic silicon dioxide is 10: 1;
the thixotropic agent is prepared from polyvinyl alcohol and polyamide wax in a mass ratio of 2: 1;
the organic solvent is a mixed solution of alcohol ester dodeca, butyl carbitol acetate and tributyl citrate;
s2: mixing and stirring sorbitan trioleate and triethanolamine oleate, adding the modified mixed solution and a release agent, mixing and stirring, performing ultrasonic dispersion, grinding and sieving by a 300-mesh sieve to obtain an organic carrier for a battery silicon wafer metallization process;
1.8 parts of sorbitan trioleate, 1.8 parts of triethanolamine oleate and 0.8 part of a release agent; the total content of the sorbitan trioleate and the triethanolamine oleate in the organic carrier is 4 percent;
the release agent is prepared from dimethyl silicone oil and amino polyether modified silicone oil according to the mass ratio of 1: 1;
the preparation method of the amino polyether modified silicone oil comprises the following steps: mixing hydrogen-containing silicone oil, allyl glycidyl ether and allyl polyoxyethylene ether, ultrasonically stirring, and stirring for 4min under the protection of nitrogen; heating to 85 ℃, and dripping a platinum catalyst solution to react for 1.5 h; reducing the pressure, then adding ethylenediamine, introducing nitrogen, heating to 85 ℃ and reacting for 1.5 h; decompressing, washing with cyclohexane and chloroform in sequence to obtain amino polyether modified silicone oil;
and stirring the prepared organic carrier in a planetary stirrer according to the proportion of 8% of the organic carrier, 12% of the nano silver powder and 80% of the flaky silver powder until the mixture is dispersed by a three-roll grinder to the fineness of 3 mu m, thus obtaining the slurry.
Comparative example 6
A preparation method of an organic carrier for a battery silicon chip metallization process comprises the following steps:
s1: mixing 65 parts of organic solvent, 5 parts of modified carboxyethyl microfibrillated cellulose and 0.5 part of thixotropic agent, stirring, ultrasonically dispersing, and preserving heat at 75 ℃ for 0.8h to obtain a modified mixed solution;
the preparation of the modified carboxyethyl microfibrillated cellulose comprises the following steps:
crushing bleached sulfate hardwood pulp, adding the crushed bleached sulfate hardwood pulp into a sodium hydroxide solution, performing ultrasonic stirring, adding an acrylamide solution to obtain a slurry, concentrating the slurry until the slurry concentration is 22%, putting the slurry into a high-concentration mixing reactor, reacting at 85 ℃ for 1.5h, washing the slurry to be neutral by deionized water, diluting the slurry to be 2% by deionized water, and grinding the slurry at the rotating speed of 1600r/min to obtain the carboxyethyl microfibrillated cellulose;
the mass ratio of the bleached sulfate hardwood pulp to the sodium hydroxide solution to the acrylamide solution is 1:5: 3;
mixing cetrimide, diethyl ether, ethanol, ammonia water and deionized water, ultrasonically stirring, adding ethyl orthosilicate and 3-aminopropyltriethoxysilane after 8min, and ultrasonically stirring for 0.8 h; adding hydrochloric acid to adjust pH to 6.5, centrifuging, washing with ethanol and deionized water, and drying at 55 deg.C to obtain dendritic silicon dioxide;
the volume ratio of the diethyl ether to the ethanol to the ethyl orthosilicate is 2:1: 0.25;
mixing and stirring carboxyethyl microfibrillated cellulose, dendritic silicon dioxide, a silane coupling agent and deionized water, and performing ultrasonic dispersion to obtain modified carboxyethyl microfibrillated cellulose;
the mass ratio of the carboxyethyl microfibrillated cellulose to the dendritic silicon dioxide is 10: 1;
the thixotropic agent is prepared from polyvinyl alcohol and polyamide wax in a mass ratio of 2: 1;
the organic solvent is a mixed solution of alcohol ester dodeca, butyl carbitol acetate and tributyl citrate;
s2: mixing and stirring sorbitan trioleate and triethanolamine oleate, adding the modified mixed solution and a release agent, mixing and stirring, performing ultrasonic dispersion, grinding and sieving by a 300-mesh sieve to obtain an organic carrier for a battery silicon wafer metallization process;
1.1 parts of sorbitan trioleate, 1.1 parts of triethanolamine oleate and 0.8 part of a release agent; the total content of the sorbitan trioleate and the triethanolamine oleate in the organic carrier is 3 percent;
the release agent is prepared from dimethyl silicone oil and amino polyether modified silicone oil according to the mass ratio of 1: 1;
the preparation method of the amino polyether modified silicone oil comprises the following steps: mixing hydrogen-containing silicone oil, allyl glycidyl ether and allyl polyoxyethylene ether, ultrasonically stirring, and stirring for 4min under the protection of nitrogen; heating to 85 ℃, and dripping a platinum catalyst solution to react for 1.5 h; reducing the pressure, then adding ethylenediamine, introducing nitrogen, heating to 85 ℃ and reacting for 1.5 h; decompressing, washing with cyclohexane and chloroform in sequence to obtain amino polyether modified silicone oil;
and stirring the prepared organic carrier in a planetary stirrer according to the proportion of 8% of the organic carrier, 12% of the nano silver powder and 80% of the flaky silver powder until the mixture is dispersed by a three-roll grinder to the fineness of 3 mu m, thus obtaining the slurry.
Comparative example 7
A preparation method of an organic carrier for a battery silicon chip metallization process comprises the following steps:
s1: mixing 65 parts of organic solvent, 5 parts of carboxyethyl microfibrillated cellulose and 0.5 part of thixotropic agent, stirring, ultrasonically dispersing, and preserving heat at 75 ℃ for 0.8h to obtain a modified mixed solution;
the thixotropic agent is prepared from polyvinyl alcohol and polyamide wax in a mass ratio of 2: 1;
the organic solvent is a mixed solution of alcohol ester dodeca, butyl carbitol acetate and tributyl citrate;
s2: mixing and stirring sorbitan trioleate and triethanolamine oleate, adding the modified mixed solution and a release agent, mixing and stirring, performing ultrasonic dispersion, grinding and sieving by a 300-mesh sieve to obtain an organic carrier for a battery silicon wafer metallization process;
1.1 parts of sorbitan trioleate, 1.1 parts of triethanolamine oleate and 0.8 part of a release agent; the total content of the sorbitan trioleate and the triethanolamine oleate in the organic carrier is 3 percent; the release agent is dimethyl silicone oil;
and stirring the prepared organic carrier in a planetary stirrer according to the proportion of 8% of the organic carrier, 12% of the nano silver powder and 80% of the flaky silver powder until the mixture is dispersed by a three-roll grinder to the fineness of 3 mu m, thus obtaining the slurry.
And (3) performance testing: the performance of the slurries prepared in the examples 1 to 3 and the comparative examples 1 to 7 is tested, and the adhesion is determined by referring to a noble metal slurry test method for GB/T17473.4-2008 microelectronic technology; the measurement results are shown in Table 1;
the slurries prepared in the embodiments 1 to 3 and the comparative examples 1 to 7 are printed by using HJT silicon wafers with the same specification and the same screen printing plate and printing parameters, cured at 200 ℃ for 20min, and the surface condition of the electrode grid line is observed;
measuring the height-width ratio of the electrode and the grid line by referring to the measurement of the height-width ratio of the electrode grid line of the SJ/T11759-2020 photovoltaic cell; testing the data of series resistance and photoelectric conversion efficiency by an I-V tester, and controlling the testing environment to be 22 +/-3 ℃ by a cooling controller; the illumination intensity of the light source used by the I-V tester needs to be calibrated and calibrated, the illumination intensity needs to be adjusted to AM1.5G through a standard plate during testing, and the illumination intensity is 1000Mw/cm2The results are shown in Table 1;
| example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | |
| Surface condition of electrode grid line | The lines are regular and smooth | The lines are regular and smooth | The lines are regular and smooth | Is smoother | Is smoother | Is smoother | The situation of wire break occurs | The situation of wire break occurs | The situation of wire break occurs | Wire break |
| Electrode adhesion (N/mm)2） | 22.9 | 23.4 | 21.8 | 17.9 | 17.4 | 16.5 | 16.9 | 16.1 | 15.8 | 15.5 |
| Series resistance (omega) | 0.922 | 0.826 | 0.913 | 1.021 | 1.032 | 1.063 | 1.072 | 1.102 | 1.098 | 1.202 |
| Electrode and grid line aspect ratio | 0.33 | 0.38 | 0.35 | 0.30 | 0.29 | 0.27 | 0.28 | 0.26 | 0.26 | 0.25 |
| Photoelectric conversion efficiency | 21.1% | 22.9% | 21.6% | 19.6% | 19.8% | 18.6% | 18.9% | 17.4% | 17.6% | 17.1% |
TABLE 1
Examples 1-3 were prepared according to the process of the present invention, comparative example 1 was prepared without modification treatment of carboxyethyl microfibrillated cellulose; the release agent in comparative example 2 was dimethicone; comparative example 3 is a total of 3% sorbitan trioleate, triethanolamine oleate in the organic vehicle; comparative example 4 is a total sorbitan trioleate, triethanolamine oleate content of 6% in the organic vehicle; comparative example 5 is sorbitan trioleate, triethanolamine oleate, release agent do not satisfy the defined relationship: w (sorbitan trioleate) + W (triethanolamine oleate) is not less than 5W (release agent); comparative example 6 is that sorbitan trioleate, triethanolamine oleate, and release agent do not satisfy the defined relationship W (sorbitan trioleate) + W (triethanolamine oleate) of not less than 5W (release agent), and the total content of sorbitan trioleate and triethanolamine oleate in the organic vehicle is 3%; comparing the example 2 with the comparative examples 1 to 7, it can be known that the total content of the sorbitan trioleate and the triethanolamine oleate in the organic carrier is limited to 3.2 to 5.7 percent, so that the synergistic capability on the leveling property is improved, the moderate viscosity is maintained, the leveling property of the organic carrier is improved, the film layer is more smooth and compact, and the phenomenon that the film layer does not sag after being printed is ensured;
carrying out amino polyether modification treatment on the silicone oil, and adding a large amount of polyether chain segments, amino and hydroxyl on side chains; the silicone oil has better conditioning property; the added polyether chain segment has good hydrophilicity, so that the polyether chain segment has excellent compatibility with sorbitan trioleate and triethanolamine oleate, and the rapid leveling property of the organic carrier is improved; the total addition amount of the amino polyether modified silicone oil and the silicone oil in the organic carrier is limited to be lower than the total addition amount of sorbitan trioleate and triethanolamine oleate, and the addition amount concentration of the sorbitan trioleate and the triethanolamine oleate is too high, so that the viscosity is too high and the leveling property is poor;
the battery front silver paste prepared by the organic carrier has high resolution, excellent transfer characteristic, flat and compact silver layer and excellent storage performance, has excellent linear shaping capability by optimizing the organic carrier for the battery silicon wafer metallization process, greatly improves the silk-screen quality on the silicon wafer, improves the height-width ratio of electrodes and grid lines after sintering, and prolongs the service life of the battery while improving the efficiency of the solar battery.
The above description is only an example of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A preparation method of an organic carrier for a battery silicon chip metallization process is characterized by comprising the following steps:
s1: mixing, stirring and ultrasonically dispersing modified carboxyethyl microfibrillated cellulose, a thixotropic agent and an organic solvent, and preserving heat for 0.5-1h at 70-80 ℃ to obtain a modified mixed solution;
s2: and mixing and stirring sorbitan trioleate and triethanolamine oleate, adding the modified mixed solution and the release agent, mixing and stirring, and performing ultrasonic dispersion to obtain the organic carrier for the battery silicon wafer metallization process.
2. The method for preparing the organic carrier for the battery silicon wafer metallization process according to claim 1, wherein the organic carrier comprises the following components in parts by weight: 65-80 parts of organic solvent, 5-15 parts of modified carboxyethyl microfibrillated cellulose, 0.5-3 parts of thixotropic agent, 0.1-3 parts of sorbitan trioleate, 0.1-3 parts of triethanolamine oleate and 0.1-0.8 part of release agent.
3. The method for preparing an organic carrier used in battery silicon wafer metallization process according to claim 1, wherein the organic solvent is one or more of butyl carbitol, alcohol ester dodeca, butyl carbitol acetate, dimethyl adipate and tributyl citrate.
4. The method for preparing the organic carrier for the metallization process of the battery silicon wafer as claimed in claim 1, wherein the sorbitan trioleate, the triethanolamine oleate and the release agent have the following relations: w (sorbitan trioleate) + W (triethanolamine oleate) is not less than 5W (release agent); the ratio of the total of the sorbitan trioleate and the triethanolamine oleate to the organic carrier is 3.2-5.7% in parts by weight.
5. The method for preparing the organic carrier for the battery silicon wafer metallization process according to claim 1, wherein the thixotropic agent is prepared from polyvinyl alcohol and polyamide wax in a mass ratio of (1-3): 1.
6. The method for preparing the organic carrier for the battery silicon wafer metallization process according to claim 1, wherein the release agent is prepared from dimethyl silicone oil and amino polyether modified silicone oil in a mass ratio of 1: 1.
7. The preparation method of the organic carrier for the battery silicon wafer metallization process according to claim 6, wherein the preparation method of the amino polyether modified silicone oil comprises the following steps: mixing hydrogen-containing silicone oil, allyl glycidyl ether and allyl polyoxyethylene ether, ultrasonically stirring, and stirring for 2-5min under the protection of nitrogen; heating to 80-90 ℃, dripping a platinum catalyst solution, and reacting for 1-2 h; reducing the pressure, then adding ethylenediamine, introducing nitrogen, heating to 80-90 ℃ and reacting for 1-2 h; decompressing, washing with cyclohexane and chloroform in sequence to obtain the amino polyether modified silicone oil.
8. The method for preparing the organic carrier for the battery silicon wafer metallization process according to claim 1, wherein the preparation of the modified carboxyethyl microfibrillated cellulose comprises the following steps:
crushing bleached sulfate hardwood pulp, adding the crushed bleached sulfate hardwood pulp into a sodium hydroxide solution, performing ultrasonic stirring, adding an acrylamide solution to obtain a slurry, concentrating the slurry until the slurry concentration is 22%, putting the slurry into a high-concentration mixing reactor, reacting at the temperature of 80-90 ℃ for 1-2h, washing the slurry to be neutral by using deionized water, diluting the slurry to be 2% by using the deionized water, and stirring and grinding the slurry to obtain carboxyethyl microfibrillated cellulose;
mixing cetrimide, diethyl ether, ethanol, ammonia water and deionized water, ultrasonically stirring, adding ethyl orthosilicate and 3-aminopropyltriethoxysilane after 5-10min, and ultrasonically stirring for 0.5-1 h; adding hydrochloric acid to adjust pH to 6-7, centrifuging, washing with ethanol and deionized water, and drying at 50-60 deg.C to obtain dendritic silicon dioxide;
mixing and stirring carboxyethyl microfibrillated cellulose, dendritic silicon dioxide, a silane coupling agent and deionized water, and performing ultrasonic dispersion to obtain the modified carboxyethyl microfibrillated cellulose.
9. The method for preparing the organic carrier used for the metallization process of the battery silicon wafer as claimed in claim 8, wherein the mass ratio of the bleached sulfate hardwood pulp, the sodium hydroxide solution and the acrylamide solution in the step (1) is 1:5: 3; in the step (2), the volume ratio of the diethyl ether to the ethanol to the ethyl orthosilicate is 2:1: 0.25; in the step (3), the mass ratio of the carboxyethyl microfibrillated cellulose to the dendritic silicon dioxide is 10: 1.
10. The use of the organic vehicle for battery silicon wafer metallization process prepared by the method for preparing the organic vehicle for battery silicon wafer metallization process according to any one of claims 1 to 9, characterized in that the prepared organic vehicle is used for preparing a back silver paste of a silicon wafer solar cell: and stirring the organic carrier, the nano silver powder and the flake silver powder in a planetary stirrer until the three-roller grinder disperses the mixture to the fineness of 2-5 mu m to obtain the back silver slurry.
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| CN103435854A (en) * | 2013-08-29 | 2013-12-11 | 中国人民解放军国防科学技术大学 | Organic carrier for crystalline silicon solar cell electrode slurry and preparation method thereof |
| CN106928605A (en) * | 2017-02-20 | 2017-07-07 | 江苏瑞德新能源科技有限公司 | A kind of organic carrier for solar cell positive silver paste and preparation method thereof |
| CN108641123A (en) * | 2018-03-28 | 2018-10-12 | 山东建邦胶体材料有限公司 | The nanocrystalline organic carrier preparation method of containing cellulose and the application in silver paste |
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| CN103435854A (en) * | 2013-08-29 | 2013-12-11 | 中国人民解放军国防科学技术大学 | Organic carrier for crystalline silicon solar cell electrode slurry and preparation method thereof |
| CN106928605A (en) * | 2017-02-20 | 2017-07-07 | 江苏瑞德新能源科技有限公司 | A kind of organic carrier for solar cell positive silver paste and preparation method thereof |
| CN108641123A (en) * | 2018-03-28 | 2018-10-12 | 山东建邦胶体材料有限公司 | The nanocrystalline organic carrier preparation method of containing cellulose and the application in silver paste |
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