CN108010602B - Preparation process of nano glass powder - Google Patents
Preparation process of nano glass powder Download PDFInfo
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- CN108010602B CN108010602B CN201711229802.XA CN201711229802A CN108010602B CN 108010602 B CN108010602 B CN 108010602B CN 201711229802 A CN201711229802 A CN 201711229802A CN 108010602 B CN108010602 B CN 108010602B
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- 239000011521 glass Substances 0.000 title claims abstract description 82
- 239000000843 powder Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002270 dispersing agent Substances 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 24
- 238000000227 grinding Methods 0.000 claims description 53
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 39
- 229910052726 zirconium Inorganic materials 0.000 claims description 39
- 239000000725 suspension Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 239000003607 modifier Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- -1 polyoxyethylene Polymers 0.000 claims description 10
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 229920001897 terpolymer Polymers 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- CSYSJPRFLYSSOB-UHFFFAOYSA-N butyl 2-methylprop-2-enoate;furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1.CCCCOC(=O)C(C)=C CSYSJPRFLYSSOB-UHFFFAOYSA-N 0.000 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229940116411 terpineol Drugs 0.000 claims description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- SZTBMYHIYNGYIA-UHFFFAOYSA-N 2-chloroacrylic acid Chemical compound OC(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-N 0.000 claims description 2
- 229940022682 acetone Drugs 0.000 claims description 2
- 229960004132 diethyl ether Drugs 0.000 claims description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 2
- 229960004756 ethanol Drugs 0.000 claims description 2
- 229940093476 ethylene glycol Drugs 0.000 claims description 2
- 229960004592 isopropanol Drugs 0.000 claims description 2
- 239000011858 nanopowder Substances 0.000 claims description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 2
- 229940044603 styrene Drugs 0.000 claims description 2
- JRSCGPHVSNGOMK-UHFFFAOYSA-N 3-[methyl(propyl)amino]propyl 2-methylprop-2-enoate Chemical compound CCCN(C)CCCOC(=O)C(C)=C JRSCGPHVSNGOMK-UHFFFAOYSA-N 0.000 claims 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 22
- 238000007641 inkjet printing Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000713 high-energy ball milling Methods 0.000 abstract description 2
- 238000000498 ball milling Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
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- 238000006243 chemical reaction Methods 0.000 description 3
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- 238000002844 melting Methods 0.000 description 3
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- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
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- 238000005265 energy consumption Methods 0.000 description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
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- 238000003980 solgel method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical group CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- 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
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- 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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- Sustainable Development (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Chemical & Material Sciences (AREA)
- Sustainable Energy (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
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Abstract
The invention relates to a preparation process of nano glass powder, which is characterized in that the nano glass powder is prepared by matching a high-energy ball milling method with a dispersing agent, has an average particle size of 60-120 nm, is not easy to settle and agglomerate, can be dispersed in nano silver conductive ink and is used for ink-jet printing of a solar cell electrode. Compared with the prior art, the nano glass powder prepared by the invention has high purity, uniform granularity, small particle size and simple process, solves the problem that the nano glass phase in the solar cell ink-jet printing ink is difficult to prepare, and finally can prepare the solar cell electrode ink-jet printing ink which has good dispersibility, high stability and no blockage of a nozzle.
Description
Technical Field
The invention belongs to the field of inorganic non-metallic materials, and particularly relates to a preparation process of nano glass powder.
Background
Since the oil crisis of the last century, countries have been discussing a new energy source to alleviate the energy crisis. Solar cells directly convert sunlight into electricity, which is a clean energy source, and thus the novel energy source is receiving more and more attention. With the improvement of the photoelectric conversion efficiency of the solar cell, the cost of photovoltaic power generation is close to that of thermal power generation in a place with sufficient sunlight, the power generation capacity of solar energy predicted by international energy deployment accounts for about 16% of the global power generation capacity in 2050, and the solar power generation capacity is one of the main forms of future energy acquisition.
The traditional preparation method of the solar cell electrode is screen printing. In the screen printing technology, the opening of the screen is about 30-45 μm, the width of the paste after single printing and sintering is 50-60 μm or even wider, the height is generally 12-20 μm, the ratio of the height to the width is below 0.4, and the possibility of electrode wire breakage is caused by the blockage of printing meshes. If an ink-jet printing technology is adopted, the thin grid lines with the width of 30-50 microns and the height of 30-50 microns can be formed by printing, stacking and forming layer by layer, the height-to-width ratio can be 1, the shading area can be reduced, the internal resistance of the electrode can be reduced, the conversion efficiency can be improved, and the consumption of silver paste can be reduced. The forming mechanism is that the ink is sprayed and printed on the substrate battery piece by the ink-jet printing head, the surface temperature of the battery piece is 150-200 ℃ due to the heating of the base platform, the solvent is quickly volatilized when the ink drops are sprayed on the surface of the battery piece, the remaining solid particles are accumulated on the surface, and the grid lines are gradually increased and the line width is kept unchanged when the ink is sprayed and printed at the same place for many times.
In the inkjet printing, the diameter of the nozzle of the inkjet head is in the range of 10 to 60 μm, and in order to avoid the occurrence of a plug during the inkjet printing process, the particles of the substances in the ink must be strictly limited, and the metal powder, the glass frit and the organic vehicle particles in the ink are made to be less than 1 μm as much as possible. Meanwhile, in order to avoid particle precipitation in the ink, the particle diameters of the metal powder and the glass frit are practically required to be less than 200 nm. At present, the technology for preparing nano metal powder is relatively mature, but for glass frit, the industrial preparation of nano glass powder has certain difficulty, and the method is one of the key technologies of solar cell electrode ink-jet printing.
At present, three main ways are available for preparing the glass powder for the electronic paste: high temperature melting method, spray pyrolysis method, sol-gel method. The high-temperature melting method is characterized in that glass raw materials are uniformly mixed according to a certain metering ratio, then are heated and melted, are rapidly cooled to form glass frits or are quenched into glass slag, and then the glass frits or the glass slag are crushed to obtain glass powder. However, this method is not easy to prepare nano-scale glass powder; the method is characterized in that the glass powder is prepared by the micro-reaction of liquid drops, is relatively uniform in size and components, is spherical and has better dispersibility. The spray thermal decomposition method is suitable for large-scale industrial production, but has high requirements on equipment and high production cost; the superfine glass powder prepared by the sol-gel method is generally homogeneous and high in purity, the composition proportion is well controlled, the preparation temperature is much lower than that of the traditional method, and the superfine glass powder has certain rheological property.
The chinese patent publication No. CN102815870A discloses a method for preparing nano glass powder by laser-resistance composite heating evaporation; the chinese patent publication No. CN105060722A discloses a method for preparing nano glass powder by water quenching, high shear dispersion and centrifugal spraying. The two methods need to completely melt the glass powder and then treat the glass powder, have the defects of complex process, high requirement on equipment, high energy consumption and the like, and are easy to introduce pollution during melting. The Chinese patent with publication number CN106082682A discloses a method for preparing glass powder suspension for glass inkjet, which does not use proper dispersant, the preparation process is as long as 24-48h, and the obtained suspension inevitably has the phenomena of sedimentation and agglomeration.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation process of nano glass powder.
The purpose of the invention can be realized by the following technical scheme:
a preparation process of nano glass powder comprises the following steps:
(1) mixing a glass powder raw material, a solvent and coarse grinding zirconium balls according to a weight ratio of 1-10: 10-50, and performing coarse grinding at 200-500 rpm for 30-120 min;
(2) taking out the coarse grinding zirconium balls, adding the fine grinding zirconium balls, mixing the glass powder raw material, the solvent, the fine grinding zirconium balls and the dispersing agent according to the weight ratio of 1-10: 10-50: 0.1-2, fine grinding at 400-800 rpm for 30-60 min, and taking out the zirconium balls to obtain the nano glass powder suspension.
The dispersant is compounded by a dispersant main agent and a surface modifier, wherein the dispersant main agent accounts for 80-90% of the total weight, and the surface modifier accounts for 10-20% of the total weight.
The main agent of the dispersing agent is one or more of a methacrylic acyloxy ethyl Dimethylamine (DM) -1, 3-propane sultone copolymer, a 3- (2-methacrylic acyloxy ethyl dimethylamino) propane sulfonic acid-methyl allyl polyoxyethylene ether copolymer, a humic acid-sodium allylsulfonate-dimethyl diallyl ammonium chloride terpolymer, a methyl methacrylate-maleic anhydride copolymer or a maleic anhydride-butyl methacrylate-styrene terpolymer. Preferably, a 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonic acid-methallyl polyoxyethylene ether copolymer or a maleic anhydride-butyl methacrylate-styrene terpolymer may be used.
The active groups in the main agent of the dispersant for dispersion mainly comprise a plurality of amino, quaternary ammonium, sulfonic acid, propanesulfonic acid ester, acrylic ester, phosphoric acid, carboxyl and hydroxyphenyl.
The action mechanism of the dispersant is as follows: carboxyl, sulfonic group, phosphate group, hydroxyl, amino and the like or compounds thereof are combined with the surface of the nano powder, so that good hydrophilic performance and electrostatic repulsion are provided; in addition, functional groups such as propanesulfonic acid group, propanesulfonic acid ester, acrylic ester and linear or branched alkyl form a third monomer, so that the steric hindrance effect of the dispersing agent can be improved, and the dispersing effect of the dispersing agent is further enhanced.
The dispersing agent disclosed by the patent can greatly reduce the time consumed in the preparation process, and the prepared nano glass powder turbid liquid is not easy to settle and agglomerate.
The surface modifier is one or more of silane coupling agent, polyacrylic acid, OP-10, 2-chloroacrylic acid or polyvinylpyrrolidone.
The solvent is one or more selected from water, ethanol, ethylene glycol, diethylene glycol monobutyl ether, diethyl ether, acetone, styrene, isopropanol or terpineol.
The diameter of the zirconium ball for coarse grinding is 3-20 mm, and the diameter of the zirconium ball for fine grinding is 0.5-3 mm. On the one hand, the larger the grinding ball particle size is, the larger the energy of feeding is transferred from the ball in each ball and material collision, which is beneficial to crushing the material, so that if the small-diameter ball is directly used for ball milling, a lot of glass materials can not be crushed, and the large ball needs to be used for primary grinding. On the other hand, because the large ball gap is large, the glass powder can be hidden in the grinding ball gap to a certain fineness, and the ball milling process can not be continued, the glass material is ground to a nanometer size by using small zirconium balls after being smashed.
Glass powder raw materials: solvent: the zirconium balls for coarse grinding are 1-10: 10-50, and the ball-to-material ratio is preferably 10:1 and the solid-to-liquid ratio is preferably 1: 0.8. The ball-material ratio is increased, so that the collision frequency of the grinding ball and the glass powder can be increased, the mean free path of the grinding ball is reduced, and the probability of capturing powder particles by the grinding ball is increased. The occurrence of agglomeration can be effectively inhibited; if the ball-material ratio is too large, along with the increase of the number of the grinding balls, the collision of the grinding balls and the probability of collision of the grinding balls and the ball-milling tank are increased, and the ball-milling tank and the grinding balls are greatly abraded. When the solid-liquid ratio is low, solid particles in the slurry are less, the probability of being impacted by the balls is small, and therefore, the production efficiency is low; while high solid-to-liquid ratio can cause the slurry Reynolds number ReThe impact force and the shearing force of the slurry are gradually reduced, and a powder particle layer is formed between the media, so that the trend of particle size reduction is slowed down.
In the step (1), the rotation speed of the coarse grinding is 200-500 rpm, and the time is 30-120 min; in the step (2), the fine grinding speed is 400-800 rpm, and the time is 30-60 min. The longer the time and the higher the rotating speed, the better the ball milling effect, but the longer the time and the higher the rotating speed, the higher the cost, so the proper rotating speed and time should be selected.
The average particle size of the nano glass powder in the nano glass powder turbid liquid is 60-120 nm, and a self-made dispersing agent is used, so that the phenomena of agglomeration and sedimentation are avoided. The glass powder is an important functional phase in the solar cell electrode, is a bottleneck material which is easy to cause the blockage of a spray head in the ink-jet printing ink, and therefore, the particle size of the glass powder is reduced as much as possible and agglomeration is prevented so as not to block a spray nozzle. In addition, the smaller grain size can reduce the sintering temperature in the subsequent ohmic contact forming process, which is beneficial to reducing the loss of the solar cell efficiency.
Compared with the prior art, the method adopts the high-energy ball milling process and uses the self-made dispersing agent to prepare the nano glass powder, has the characteristics of simple process, short time consumption, low requirement on equipment and the like, does not need to melt the glass powder in the preparation process, prevents the pollution possibly caused by introduction, reduces the energy consumption, and has green and high-efficiency preparation process. The self-made dispersing agent can greatly reduce the ball milling time and effectively disperse the nano glass powder to prevent agglomeration and sedimentation. The prepared nano glass powder has small and uniform particle size, good dispersibility and strong stability, and can effectively solve the problem of nozzle blockage during the preparation of solar cell electrodes by ink-jet printing.
Drawings
FIG. 1 is a graph showing laser particle size analysis of the nano glass frit suspension prepared in example 1;
FIG. 2 is a graph showing laser particle size analysis of the nano glass frit suspension prepared in example 2.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
100g of glass powder raw material, 200g of 10mm zirconium balls and 100g of diethylene glycol dibutyl ether are added into a ball milling tank, a cooling water loop is opened, grinding is carried out for 50min at 300rpm, and the zirconium balls are filtered by a 200-mesh screen.
5g of dispersant was prepared by the specific method: 2g of methacryloyloxyethyl Dimethylamine (DM) -1, 3-propane sultone copolymer, 2g of methyl methacrylate-maleic anhydride copolymer, 0.5g of polyacrylic acid and 0.5-0.5 gOP-10 are taken and stirred uniformly.
The glass powder suspension after the initial grinding was poured back into the ball mill pot, and 1000g of 3mm zirconium balls and 5g of the prepared dispersant were added.
Grinding at 600rpm for 80min, and taking out the zirconium balls by using a 400-mesh screen to obtain a nano glass powder suspension.
The obtained nano glass powder suspension was subjected to particle size analysis using a nano laser particle size analyzer, and the average particle size was 101nm, and the specific particle size was as shown in table 1, and the obtained results are shown in fig. 1.
TABLE 1
Characteristic parameter of granularity
Example 2
100g of glass powder raw material, 200g of 7mm zirconium balls and 100g of ethanol are added into a ball milling tank, a cooling water loop is opened, grinding is carried out for 60min at 200rpm, and the zirconium balls are filtered by a 200-mesh screen.
5g of dispersant was prepared by the specific method: 4g of 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonic acid-methallyl polyoxyethylene ether copolymer, 0.5g of humic acid-sodium allylsulfonate-dimethyl di-allylammonium chloride terpolymer and 0.5g of polyvinylpyrrolidone are uniformly stirred.
The glass powder suspension after the initial grinding was poured back into the ball mill pot, and 1000g of 1mm zirconium balls and 5g of the prepared dispersant were added.
Grinding at 500rpm for 60min, and taking out the zirconium balls by using a 400-mesh screen to obtain a nano glass powder suspension.
The obtained nano glass powder suspension was subjected to particle size analysis using a nano laser particle size analyzer, and the average particle size was 109nm, and the specific particle size was as shown in table 2, and the obtained results are shown in fig. 2.
TABLE 2
Characteristic parameter of granularity
Example 3
A preparation process of nano glass powder comprises the following steps:
(1) mixing a glass powder raw material, a water solvent and a zirconium ball for coarse grinding with the ball diameter of 3mm according to the weight ratio of 1:1:10, and performing coarse grinding for 120min at 200 rpm;
(2) taking out the rough grinding zirconium balls, adding the fine grinding zirconium balls with the ball diameter of 0.5mm, mixing the glass powder raw material, the solvent, the fine grinding zirconium balls and the dispersing agent according to the weight ratio of 1:1:10:0.1, carrying out fine grinding for 60min at 400rpm, compounding the used dispersing agent by a main dispersing agent methacryloyloxyethyl dimethyl amine (DM) -1, 3-propane sultone copolymer and a surface modifier silane coupling agent, wherein the main dispersing agent accounts for 80% of the total weight, the surface modifier accounts for 20% of the total weight, and then taking out the zirconium balls to obtain a nano glass powder suspension, wherein the average particle size of the nano glass powder is 60 nm.
Example 4
A preparation process of nano glass powder comprises the following steps:
(1) mixing glass powder raw materials, terpineol alcohol solvent and zirconium balls for coarse grinding with the ball diameter of 10mm according to the weight ratio of 3:7:40, and performing coarse grinding at 300rpm for 60 min;
(2) taking out the zirconium balls for coarse grinding, adding the zirconium balls for fine grinding with the ball diameter of 1mm, mixing glass powder raw materials, a solvent, the zirconium balls for fine grinding and a dispersing agent according to the weight ratio of 3:2:40:1, fine grinding for 40min at 600rpm, compounding a main agent of the dispersing agent, namely methyl methacrylate-maleic anhydride copolymer, and a surface modifier OP-10, wherein the main agent of the dispersing agent accounts for 85% of the total weight, and the surface modifier accounts for 15% of the total weight, and then taking out the zirconium balls to obtain a nano glass powder suspension, wherein the average particle size of the nano glass powder is 100 nm.
Example 5
A preparation process of nano glass powder comprises the following steps:
(1) mixing the glass powder raw material, an ether solvent and a zirconium ball for coarse grinding with the ball diameter of 20mm according to the weight ratio of 10:10:50, and performing coarse grinding for 30min at 500 rpm;
(2) taking out the zirconium balls for coarse grinding, adding the zirconium balls for fine grinding with the ball diameter of 3mm, mixing the glass powder raw materials, the solvent, the zirconium balls for fine grinding and the dispersing agent according to the weight ratio of 10:10:50:2, fine grinding for 40min at 600rpm, compounding the used dispersing agent by maleic anhydride-butyl methacrylate-styrene terpolymer serving as a main dispersing agent and polyvinylpyrrolidone serving as a surface modifier, wherein the main dispersing agent accounts for 90% of the total weight, and the surface modifier accounts for 10% of the total weight, and then taking out the zirconium balls to obtain a nano glass powder suspension, wherein the average particle size of the nano glass powder is 120 nm.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (5)
1. The preparation process of the nano glass powder is characterized by comprising the following steps of:
(1) mixing a glass powder raw material, a solvent and coarse grinding zirconium balls according to a weight ratio of 1-10: 10-50, and performing coarse grinding at 200-500 rpm for 30-120 min;
(2) taking out the zirconium balls for coarse grinding, adding the zirconium balls for fine grinding, mixing the glass powder raw material, the solvent, the zirconium balls for fine grinding and the dispersing agent according to the weight ratio of 1-10: 10-50: 0.1-2, fine grinding at 400-800 rpm for 30-60 min, and taking out the zirconium balls to obtain a nano glass powder suspension;
the dispersing agent is compounded by a dispersing agent main agent and a surface modifier, wherein the dispersing agent main agent accounts for 80-90% of the total weight, the surface modifier accounts for 10-20% of the total weight, and the dispersing agent main agent is one or more of a methacryloyloxyethyl Dimethylamine (DM) -1, 3-propane sultone copolymer, a 3- (2-methacryloyloxyethyl dimethylamino) propane sulfonic acid-methallyl polyoxyethylene ether copolymer, a humic acid-sodium allylsulfonate-dimethyl diallyl ammonium chloride terpolymer, a methyl methacrylate-maleic anhydride copolymer or a maleic anhydride-butyl methacrylate-styrene terpolymer;
the surface modifier is one or more of silane coupling agent, polyacrylic acid, alkylphenol polyoxyethylene, 2-chloropropenoic acid or polyvinylpyrrolidone;
the solvent is one or more selected from water, ethanol, ethylene glycol, diethylene glycol monobutyl ether, diethyl ether, acetone, styrene, isopropanol or terpineol.
2. The process for preparing glass nano-powder according to claim 1, wherein the dispersant main agent is 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonic acid-methallyl polyoxyethylene ether copolymer or maleic anhydride-butyl methacrylate-styrene terpolymer.
3. The process for preparing nano glass powder according to claim 1, wherein the ball diameter of the rough grinding zirconium ball is 3-20 mm.
4. The process for preparing nano glass powder according to claim 1, wherein the diameter of the zirconium balls for fine grinding is 0.5-3 mm.
5. The process for preparing nano glass powder according to claim 1, wherein the average particle size of the nano glass powder in the nano glass powder suspension is 60 to 120 nm.
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| CN108922647A (en) * | 2018-05-24 | 2018-11-30 | 江苏时瑞电子科技有限公司 | A kind of Zinc-oxide piezoresistor low-shrinkage electrode silver plasm and preparation method thereof |
| CN110600162B (en) * | 2019-10-23 | 2021-04-02 | 河南农业大学 | Solar cell conductive paste and preparation method thereof |
| CN110950540B (en) * | 2019-11-11 | 2023-03-14 | 上海银浆科技有限公司 | Surface modification method of glass for front silver paste of solar cell |
| CN112499977B (en) * | 2020-11-30 | 2023-03-31 | 华东理工大学 | Superfine silicate glass powder and preparation method thereof |
| CN113461338A (en) * | 2021-08-05 | 2021-10-01 | 江苏正能电子科技有限公司 | Nano glass powder for PERC back silver and preparation method thereof |
| CN113617496B (en) * | 2021-08-06 | 2023-01-10 | Oppo广东移动通信有限公司 | Preparation method of nano glass powder, nano glass powder and glass product |
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