CN117275798A - Conductive paste and battery - Google Patents
Conductive paste and battery Download PDFInfo
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- CN117275798A CN117275798A CN202311146593.8A CN202311146593A CN117275798A CN 117275798 A CN117275798 A CN 117275798A CN 202311146593 A CN202311146593 A CN 202311146593A CN 117275798 A CN117275798 A CN 117275798A
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- conductive paste
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- 239000002904 solvent Substances 0.000 claims description 60
- 238000009835 boiling Methods 0.000 claims description 57
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 13
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 claims description 2
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 claims description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 2
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 2
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- 239000005642 Oleic acid Substances 0.000 claims description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229960000541 cetyl alcohol Drugs 0.000 claims description 2
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 claims description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000000787 lecithin Substances 0.000 claims description 2
- 235000010445 lecithin Nutrition 0.000 claims description 2
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- 229910052751 metal Inorganic materials 0.000 claims description 2
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 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
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052710 silicon Inorganic materials 0.000 abstract description 13
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- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
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- 238000004519 manufacturing process Methods 0.000 description 3
- 239000005360 phosphosilicate glass Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
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- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- PEJVLWCOQVHCAF-UHFFFAOYSA-N dioctyl oxalate Chemical compound CCCCCCCCOC(=O)C(=O)OCCCCCCCC PEJVLWCOQVHCAF-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
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- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Sustainable Development (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Conductive Materials (AREA)
Abstract
The invention provides a conductive paste and a battery comprising the conductive paste. Through the special design of the components and the content of the organic carrier, on one hand, the wettability of the conductive paste to the film groove is ensured, so that the conductive paste is fully filled, the thin grid line after laser transfer is ensured to have no defects such as break points, broken lines and the like, the line type is fully filled, and the excellent grid line height-width ratio can be obtained, thereby improving the conversion efficiency of the battery; on the other hand, the conductive paste obtains better yield stress, ensures that the edge of the conductive paste is less splashed when the conductive paste falls on the silicon wafer, reduces the shading area, improves the utilization rate of the conductive paste, and reduces the use cost of the conductive paste.
Description
Technical Field
The invention relates to the technical field of conductive paste, in particular to conductive paste and a battery comprising the same.
Background
The N-type TOPCon battery (Tunnel Oxide Passivated Contact solar cell) has the advantages of high theoretical photoelectric conversion efficiency, high compatibility with PERC equipment, high double-sided rate, good low-temperature coefficient, low attenuation and the like, and the market share of the N-type TOPCon battery is rapidly improved in recent years; the current mass production efficiency of the N-type TOPCon battery is 25 percent, which is still a larger improvement space than the theoretical efficiency of the N-type TOPCon battery is 28.7 percent; the fine grid of the N-type TOPCO battery generally adopts silver-aluminum paste on the front side and silver paste on the back side, and the cost of conductive paste required by the fine grid is higher than that of PERC, so that the problem of efficiency improvement and cost reduction is important to consider when the N-type TOPCO battery is produced in a large scale.
The laser transfer technique (Pattern Transfer Printing) is a non-contact type printing conductive paste technique, which fills the required conductive paste in the grooves of a specific transparent flexible material, and then transfers the conductive paste to the surface of the silicon wafer by high-energy laser; the technology can print ultra-fine grid lines to obtain electrode grid lines with better height-width ratio, thereby reducing the front shading area and improving the short-circuit current of the battery; meanwhile, the electrode grid line obtained by the technology has excellent height-width ratio, so that the electrode can still keep better line resistance and contact resistance, and higher battery conversion efficiency can be obtained; in addition, the laser transfer printing technology can reduce the printing consumption of the conductive paste of the single-chip battery and reasonably reduce the use cost of the conductive paste, so that the technology is very suitable for being used as a fine grid printing technology of an N-type TOPCON battery.
However, in the practical application process, the problems of break points, broken lines and the like often occur in the conductive paste thin grid line printed by the laser transfer printing technology, and the poor quality of the grid line on the electrode surface directly affects the benefit of the battery, so that the laser transfer printing technology cannot be widely applied, and the industrial development of the N-type TOPCO battery is limited.
Disclosure of Invention
In order to improve the above-described problems in the prior art, the present invention provides a conductive paste and a battery including the same. According to the invention, through the special design of the components and the content of the organic carrier, on one hand, the wettability of the conductive paste to the film groove is ensured, so that the conductive paste is fully filled, the defects of no break points, broken lines and the like of thin grid lines after laser transfer are ensured, the line type is fully filled, and the excellent grid line height-width ratio can be obtained, thereby improving the conversion efficiency of the battery; on the other hand, the conductive paste obtains better yield stress, ensures that the edge of the conductive paste is less splashed when the conductive paste falls on the silicon wafer, improves the utilization rate of the conductive paste, and reduces the use cost of the conductive paste.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a conductive paste, which comprises conductive powder, glass powder and an organic carrier, wherein the weight content of the conductive powder is 80.5-95 wt%, the weight content of the glass powder is 2-8 wt%, and the weight content of the organic carrier is 5-10 wt%, and the organic carrier comprises a surfactant, a high polymer binder, a thixotropic agent, a multi-component solvent and other optional auxiliary agents;
the weight percentage of the organic carrier is calculated, the weight content of the surfactant is 1-5 wt%, the weight content of the high polymer binder is 1-10 wt%, the weight content of the thixotropic agent is 1-10 wt%, the weight content of the multi-component solvent is 80-90 wt%, and the weight content of the other auxiliary agents is 0-2 wt%;
the total weight content of the high polymer binder and the thixotropic agent is 5-15 wt%.
A second aspect of the invention provides the use of the electroconductive paste according to the first aspect of the invention in laser transfer.
A third aspect of the present invention provides a battery comprising a substrate and a gate line disposed on a surface of the substrate, the gate line being formed by laser transfer of the conductive paste according to the first aspect of the present invention.
Through the technical scheme, compared with the prior art, the invention has at least the following advantages:
(1) According to the conductive paste provided by the invention, the content of each component is regulated, so that the grid line obtained through transfer printing has excellent height-width ratio, the front shading area is smaller, and the photoelectric efficiency of the battery is improved.
(2) According to the conductive paste provided by the invention, the surfactant is added, so that the wettability of the conductive paste to the film groove is ensured, and the conductive paste fills the film groove more fully, so that the defects of no break point, broken line and the like of a thin grid line after transfer printing are ensured, the line type of the grid line is ensured to be fully, and the photoelectric conversion efficiency of the battery is further improved.
(3) According to the conductive paste, the contents of the polymer binder and the thixotropic agent are adjusted, so that the conductive paste obtains better yield stress, and less edge splashing is ensured when the conductive paste falls on a silicon wafer, so that the shading area of a substrate is reduced, and the photoelectric conversion efficiency of a battery is improved; on the other hand, the utilization rate of the conductive paste is improved, and the use cost of the conductive paste is reduced.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
A first aspect of the present invention provides a conductive paste comprising a conductive powder, a glass frit, and an organic vehicle comprising a surfactant, a polymeric binder, a thixotropic agent, a multi-component solvent, and other optional adjuvants; the surfactant is present in an amount of 1wt% to 5wt% based on the weight of the organic carrier (e.g.: 1wt%, 2wt%, 3wt%, 4wt%, 5 wt%), the weight content of the polymeric binder being 1wt% to 10wt% (for example: 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, the thixotropic agent is 1wt% -10wt% (e.g., 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10 wt%), the polybasic solvent is 80wt% -90wt% (e.g., 80wt%, 81wt%, 82wt%, 83wt%, 84wt%, 85wt%, 86wt%, 87wt%, 88wt%, 89wt%, 90 wt%), and the other optional auxiliary agent is 0wt% -2wt% (e.g., 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt 1.9wt%, 2 wt%); the total weight content of the polymeric binder and the thixotropic agent is 5wt% to 15wt% (e.g., 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15 wt%).
In the laser transfer process of the conductive paste, the yield stress of the conductive paste is insufficient, so that after the effect of laser, the cohesive force of each component of the conductive paste is insufficient when the conductive paste is transferred to a silicon wafer, the edge of a substrate is increased due to splashing, the shading area is increased, and then the short circuit or the current drop of a battery is caused, so that the photoelectric conversion efficiency of the battery is finally affected.
The inventor of the invention discovers that the total weight and the thixotropic agent of the polymer binder are controlled within a specific range, so that the conductive paste can obtain better yield stress, and the cohesive force among all components of the conductive paste can be improved, thereby ensuring that the conductive paste splashed on the edge of a substrate is reduced when laser transfer printing is performed on a silicon wafer, reducing the shading area of the substrate and improving the photoelectric conversion efficiency of a battery.
In the present invention, the multi-component solvent may include a low boiling point solvent having a boiling point of 180 to 220℃ (e.g., 180℃, 185℃, 190℃, 195℃, 200℃, 205℃, 210℃, 215℃, 220℃), a medium boiling point solvent having a boiling point of 221 to 260℃ (e.g., 221℃, 225℃, 230℃, 235℃, 240℃, 245℃, 250℃, 255℃, 260℃), and a high boiling point solvent having a boiling point of 261 to 350℃ (e.g., 261℃, 265℃, 270℃, 275℃, 280℃, 285℃, 290℃, 295℃, 300℃, 305℃, 310℃, 315℃, 320℃, 325℃, 330℃, 335℃, 340℃, 345℃, 350℃).
In the invention, the multi-element solvent comprises three solvents with low, medium and high boiling points designed according to a gradient relation, the boiling point ranges of the low boiling point solvent, the medium boiling point solvent and the high boiling point solvent are not overlapped, and the inventor of the invention discovers that the boiling point of the solvent in the conductive paste adopts the gradient design, so that the conductive paste can volatilize to generate proper vapor pressure when the laser acts on the conductive paste, and the conductive paste is transferred onto a silicon wafer under the lower laser power; meanwhile, compared with the conductive paste which only adopts two boiling point gradient solvents, the vapor pressure is continuous and easier to control, stable vapor pressure can be generated at different temperatures, the surface temperature of the paste caused by laser power is higher in improving tolerance, the action window of laser is wider, and the accuracy and operability of laser transfer printing are improved.
In the present invention, each of the solvents of the boiling point ranges contains one or more solvents within the boiling point range, and the solvent is an organic solvent, and when each of the solvents of the boiling point ranges contains a plurality of solvents within the boiling point range, a plurality of solvents having a gradient relationship may be selected according to the boiling points of different solvents, for example: the low boiling point solvent can be 1, 2-propylene glycol (boiling point 187 ℃), dimethyl sulfoxide (boiling point 189 ℃), N-methyl pyrrolidone (boiling point 202 ℃) and ethyl benzoate (boiling point 212 ℃) in combination, and each adjacent boiling point solvent has a certain boiling point difference to form a gradient relation.
In one example, the weight ratio between the low boiling point solvent, the medium boiling point solvent and the high boiling point solvent is 1: (0.5-1): (0.3-1).
In yet another example, the weight ratio between the low boiling point solvent, the medium boiling point solvent, and the high boiling point solvent is 1: (0.5-0.8): (0.3-0.2).
The inventor of the present invention found that controlling the weight ratio of the low boiling point solvent, the medium boiling point solvent and the high boiling point solvent within a specific range can generate more suitable and stable vapor pressure, accelerate the transfer of the conductive paste, enable the conductive paste to be transferred onto the silicon wafer under a smaller laser power, and promote the efficiency of laser transfer.
In the present invention, the low boiling point solvent comprises one or more of 1, 2-propanediol, dimethylsulfoxide, N-methylpyrrolidone, ethyl benzoate, 1, 4-butyrolactone, ethylene glycol diacetate or diethyl oxalate; the medium boiling point solvent comprises one or a combination of more of ethylene glycol monophenyl ether, alcohol ester twelve, diphenyl ether, propylene glycol phenyl ether, diethylene glycol monobutyl ether or diethylene glycol butyl ether acetate; the high boiling point solvent comprises one or more of glycerol, cetyl alcohol or dibutyl phthalate.
In one example, the low boiling point solvent comprises one or more of 1, 2-propanediol, dimethylsulfoxide, N-methylpyrrolidone, ethyl benzoate; the medium boiling point solvent comprises one or a combination of more of ethylene glycol monophenyl ether, alcohol ester dodecanol and diphenyl ether; the high boiling point solvent comprises glycerol.
In the invention, the total weight content of the polymer binder and the thixotropic agent is 8-13 wt%.
In one example, the weight content ratio of the polymeric binder to the thixotropic agent is 1: (1-5), for example: 1:1, 1:2, 1:3, 1:4, 1:5.
In yet another example, the polymeric binder and the thixotropic agent are present in a weight ratio of 1: (1-3).
The inventor of the invention finds that when the yield stress of the conductive paste is high, the conductive paste can be ensured to be less in edge splashing when falling on a silicon wafer, but when the yield stress is too high, the wettability of the conductive paste is poor, so that the conductive paste is not fully filled, the line type of a grid line after transfer is influenced, and defects such as break points, broken lines and the like are very easy to occur; the wettability and the yield stress of the conductive paste can be more accurately regulated by further controlling the weight content ratio of the high molecular binder to the thixotropic agent, so that the wettability deterioration of the conductive paste caused by the increase of the yield stress is avoided.
In one example, the surfactant comprises one or more of linoleic acid, ethyl hydroxy acid, decanoic acid, fatty acid glycerides, oleic acid, or lecithin; the high polymer binder comprises one or more of ethyl cellulose, hydroxyethyl cellulose, hydrogenated rosin resin, phenolic resin, acrylic resin or polyvinyl butyral; the thixotropic agent comprises one or more of hydrogenated castor oil, polyamide wax, polyvinyl alcohol, polyacrylate, fumed silica, or organobentonite.
In yet another example, the surfactant includes a combination of one or more of linoleic acid, ethyl hydroxy acid, decanoic acid, fatty acid glycerides; the high molecular binder comprises one or a combination of more of ethyl cellulose, hydroxyethyl cellulose, hydrogenated rosin resin, phenolic resin and acrylic resin; the thixotropic agent comprises one or more of hydrogenated castor oil, polyamide wax, polyvinyl alcohol and polyacrylate.
In the invention, the conductive paste also comprises other optional auxiliary agents, and mainly plays roles in thickening, plasticizing, dispersing and leveling. The auxiliary agent comprises one or a combination of a plurality of organic matters with the same function, such as dioctyl oxalate, polyethylene glycol, glyceryl stearate, polydimethylsiloxane, polymethylphenylsiloxane and the like.
In the present invention, the conductive powder includes a metal powder, such as silver powder, aluminum powder, or a combination powder of silver and aluminum powder.
In one example, the conductive powder is a combined powder of silver powder and aluminum powder.
In the present invention, the silver powder is spherical or spheroid, the particle size D50 is 1 μm to 1.5 μm (e.g., 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm), and the tap density is 5g/cm 3 -6g/cm 3 (e.g., 5 g/cm) 3 、5.1g/cm 3 、5.2g/cm 3 、5.3g/cm 3 、5.4g/cm 3 、5.5g/cm 3 、5.6g/cm 3 、5.7g/cm 3 、5.8g/cm 3 、5.9g/cm 3 、6g/cm 3 ) Silver powder having a specific surface area of 0.3m 2 /g-1m 2 /g (e.g., 0.3 m) 2 /g、0.4m 2 /g、0.5m 2 /g、0.6m 2 /g、0.7m 2 /g、0.8m 2 /g、0.9m 2 /g、1m 2 /g)。
In the present invention, the aluminum powder is spherical or spheroid, and has a particle size D50 of 2 μm to 5 μm (e.g., 2 μm, 3 μm, 4 μm, 5 μm) and an activity of 99% to 99.9% (e.g., 99%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%).
In the invention, the particle size D50, tap density and specific surface area have the conventional meaning in the field, the particle size D50 testing method is to test the particle size distribution condition of the powder by using a laser particle sizer, and the testing result comprises particle size distribution parameters such as D10, D50, D90 and the like, wherein D50 is a main evaluation index, namely the powder with the particle size smaller than 50 percent; the method for measuring the tap density uses a tap density meter to test the density of the powder after tapping; the specific surface area is tested by adopting a BET (nitrogen adsorption) specific surface tester; the activity was measured by an oxygen content tester.
In the invention, the glass powder is PbO-ZnO-Bi 2 O 3 -B 2 O 3 The system is prepared by adopting a high-temperature melt quenching process, and the granularity D50 of the glass powder is 0.8-1.5 mu m.
In the invention, the weight content of the conductive powder is 80.5-95 wt%, the weight content of the glass powder is 2-8 wt% and the weight content of the organic carrier is 5-10 wt% based on the weight percentage of the conductive paste.
In an example, the silver powder is 80wt% to 90wt%, the aluminum powder is 0.5wt% to 5wt%, the glass frit is 2wt% to 8wt%, and the organic carrier is 5wt% to 10wt% based on the weight percentage of the conductive paste.
The inventor of the present invention has found that by mixing silver powder and aluminum powder in a specific weight content, the transfer-printed conductive paste grid line can have a more excellent aspect ratio, the front light shielding area is smaller, and the photoelectric efficiency of the battery can be improved.
The invention also provides a manufacturing process of the conductive paste, which comprises the following steps:
(1) The multi-element solvent, the surfactant, the high molecular binder, the thixotropic agent and other optional auxiliary agents are mixed and heated in a water bath at the temperature of 50-80 ℃ for dissolution and activation to form a uniform organic carrier.
(2) Mixing the silver powder, the aluminum powder, the glass powder and the organic carrier according to the weight portion, and grinding by using a three-roller grinder to ensure that the fineness of the conductive paste is below 5 mu m.
A second aspect of the present invention provides the use of the conductive paste according to the first aspect of the present invention in laser transfer, in particular in the preparation of battery grids using laser transfer techniques.
In the invention, the process steps for preparing the battery grid line by using the laser transfer printing technology comprise the following steps:
firstly, cleaning and texturing a substrate n-type silicon wafer, and then performing high-temperature boron expansion. And secondly, after alkali polishing, preparing a tunneling oxide layer and a poly polysilicon layer, and cleaning PSG (phosphosilicate glass) on the surface by a wet chemical cleaning method (RCA). Then, an aluminum oxide layer and a silicon nitride passivation layer are plated on the front surface, a silicon nitride layer is plated on the back surface, a back main grid, a fine grid and a front main grid are printed after a blue film is plated, then the front fine grid is printed by using the slurry prepared in the first aspect of the invention through a laser transfer printing mode, finally sintering and light injection are carried out, and the prepared battery piece is tested and sorted, and finally the battery is manufactured.
A third aspect of the present invention provides a battery comprising a substrate and a gate line disposed on a surface of the substrate, the gate line being formed by laser transfer of the conductive paste according to the first aspect of the present invention.
The battery may be an N-type TOPCon battery.
The substrate may be a silicon wafer.
The technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
The invention is described in detail below in connection with specific embodiments, which are intended to be illustrative rather than limiting.
In the examples below, unless otherwise specified, all of the ingredients used were commercially available analytical grade. 1 part by weight represents 1g.
Example 1
Preparation of conductive paste
The raw materials of the organic carrier are accurately weighed according to the proportion shown in the table 1, are put into a water bath heater to be heated at the constant temperature of 60 ℃ and are stirred for 20 minutes to obtain the organic carrier.
The organic carrier 8 weight portions, glass powder 5 weight portions, silver powder 85 weight portions and aluminum powder 2 weight portions are weighed and mixed uniformly, and a three-roller grinder is used for grinding to obtain a finished conductive paste with fineness less than 5 mu m, and the number is P1.
OTHER EMBODIMENTS
Other examples referring to example 1, the organic vehicle was different in the composition ratios, see in particular table 1, and the resulting finished conductive paste was designated with the number Pn, n=2, 3, 4, 5, 6.
Comparative example 1 group
Comparative example 1 the group of reference example 1 was modified in that the total weight content of the polymeric binder and thixotropic agent, see specifically table 1, was varied and the resulting conductive pastes were numbered D1-1, D1-2.
Comparative example 2 group
Comparative example 2 the comparative example 1 was conducted except that the solvent components and proportions of the polyvalent solvents were changed, and specifically, referring to table 1, the resulting electroconductive pastes were numbered D2-1, D2-2.
Comparative example 3
Comparative example 3 referring to example 1, except that no surfactant was added to the organic vehicle, see specifically table 1, the resulting conductive paste was numbered D3.
Table 1 (Table 1 shows 1 part by weight, and blank space indicates that the component is not added)
The electroconductive pastes obtained in the above examples and comparative examples were prepared into batteries, and the procedure was as follows:
after a substrate n-type silicon wafer is subjected to a cleaning texturing process, performing high-temperature boron expansion, wherein the diffusion sheet resistance is 150-170 Ω/≡; after alkali polishing, preparing a tunneling oxide layer and a poly polysilicon layer, and cleaning to remove PSG through RCA; plating a front aluminum oxide layer, a silicon nitride passivation layer and a back silicon nitride layer; printing a back main grid, a fine grid and a front main grid after a blue film, printing the front fine grid by using the slurry in a laser transfer printing mode, finally sintering and light injection, testing and sorting the prepared battery piece, and finally manufacturing the battery.
The battery and the gate linear energy test of the battery sheet of the battery prepared from the conductive paste prepared in each of the above examples and comparative examples are shown below.
The testing method comprises the following steps:
(1) Electrode gate line width testing
The heights, widths, and printing qualities of the fine grid lines of the battery sheets prepared from the conductive pastes obtained in the above examples and comparative examples were measured by a 3D microscope, and the results are shown in table 2.
(2) Battery conversion efficiency test
The front surfaces of the batteries prepared by the conductive pastes prepared in the above examples and comparative examples were tested for efficiency using an I-V tester after sintering in an infrared chain sintering furnace, and the results including photoelectric conversion efficiency (Eta), open circuit voltage (Voc), short circuit current (Isc), and Fill Factor (FF) are shown in table 2.
Table 2 battery test results
As shown in Table 2, the silver conductive paste P1-P7 of the invention is used together with the laser transfer printing technology, the thin grid line has a smaller width, the shading area is small, the short circuit of the battery is higher, and meanwhile, due to the excellent aspect ratio, the good line resistance and contact resistance of the electrode can be ensured, so that the battery can obtain higher efficiency.
In comparative example 1, the total amount of the polymer resin and the thixotropic agent is 4%, so that the yield stress of the conductive paste is insufficient, and after the laser action, the cohesion of each component of the conductive paste is insufficient when the conductive paste is transferred to a silicon wafer, so that the edge of an electrode is splashed and increased, the shading area is increased, the short-circuit current of a battery is reduced, and the efficiency is reduced; since the sum of the polymer resin and the thixotropic agent is 18% in the conductive paste D1-2, the viscosity of the paste becomes large due to the excessively large yield stress of the conductive paste, the paste is excessively dry, a large number of holes are generated due to insufficient wetting when the film grooves are filled, the electrode is not compact, the line resistance is increased, the contact performance of the battery is deteriorated, the FF is reduced, and the gate breakage is caused by the excessively high viscosity of the paste.
In comparative example 2, the boiling point of the organic solvent is not designed in a gradient manner, two solvents are selected to prepare the conductive paste, and the low boiling point solvent is less, so that the vapor pressure generated by volatilization of the solvent is insufficient when the conductive paste acts on the laser, the conductive paste is not easy to strip, and gate breakage is caused.
In the comparative example 3, no surfactant was added to the organic carrier, so that the wettability of the conductive paste to the thin film grooves was insufficient, and the conductive paste was not fully filled, resulting in defects such as broken lines of the thin gate lines after transfer.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The conductive paste is characterized by comprising conductive powder, glass powder and an organic carrier, wherein the weight content of the conductive powder is 80.5-95 wt% and the weight content of the glass powder is 2-8 wt% based on the weight percentage of the conductive paste, and the weight content of the organic carrier is 5-10 wt%, and the organic carrier comprises a surfactant, a high polymer binder, a thixotropic agent, a multi-element solvent and other optional auxiliary agents;
the weight percentage of the organic carrier is calculated, the weight content of the surfactant is 1-5 wt%, the weight content of the high polymer binder is 1-10 wt%, the weight content of the thixotropic agent is 1-10 wt%, the weight content of the multi-component solvent is 80-90 wt%, and the weight content of the auxiliary agent is 0-2 wt%;
the total weight content of the high polymer binder and the thixotropic agent is 5-15 wt%.
2. The conductive paste of claim 1, wherein the multi-component solvent comprises a low boiling point solvent, a medium boiling point solvent, and a high boiling point solvent;
and/or the boiling point of the low boiling point solvent is 180 ℃ to 220 ℃, the boiling point of the medium boiling point solvent is 221 ℃ to 260 ℃, and the boiling point of the high boiling point solvent is 261 ℃ to 350 ℃.
3. The conductive paste according to claim 2, wherein a weight ratio between the low boiling point solvent, the medium boiling point solvent and the high boiling point solvent is 1: (0.5-1): (0.3-1), preferably 1: (0.5-0.8): (0.3-0.2).
4. The conductive paste of claim 2 or 3, wherein the low boiling point solvent comprises one or more of 1, 2-propanediol, dimethylsulfoxide, N-methylpyrrolidone, ethyl benzoate, 1, 4-butyrolactone, ethylene glycol diacetate, or diethyl oxalate;
and/or the medium boiling point solvent comprises one or a combination of more of ethylene glycol monophenyl ether, alcohol ester twelve, diphenyl ether, propylene glycol phenyl ether, diethylene glycol monobutyl ether or diethylene glycol butyl ether acetate;
and/or the high boiling point solvent comprises one or more of glycerol, cetyl alcohol or dibutyl phthalate.
5. The conductive paste according to claim 1, wherein the total weight content of the polymeric binder and the thixotropic agent is 8wt% to 13wt%,
and/or the weight content ratio of the high polymer binder to the thixotropic agent is 1: (1-5), more preferably 1: (1-3).
6. The conductive paste of claim 1, wherein the surfactant comprises a combination of one or more of linoleic acid, ethyl hydroxy acid, decanoic acid, fatty acid glycerides, oleic acid, or lecithin;
and/or the polymer binder comprises one or more of ethyl cellulose, hydroxyethyl cellulose, hydrogenated rosin resin, phenolic resin, acrylic resin or polyvinyl butyral;
and/or the thixotropic agent comprises one or more combinations of hydrogenated castor oil, polyamide wax, polyvinyl alcohol, polyacrylate, fumed silica, or organobentonite.
7. The conductive paste of claim 1, wherein the conductive powder comprises a metal powder; preferably, the conductive powder includes silver powder and aluminum powder.
8. The conductive paste according to claim 7, wherein the silver powder is 80wt% to 90wt%, the aluminum powder is 0.5wt% to 5wt%, the glass frit is 2wt% to 8wt%, and the organic vehicle is 5wt% to 10wt%, based on the weight percentage of the conductive paste.
9. Use of the electroconductive paste according to any one of claims 1-8 in laser transfer.
10. A battery comprising a substrate and a grid line provided on a surface of the substrate, the grid line being formed by laser transfer of the electroconductive paste according to any one of claims 1 to 8.
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