CN104867537A - Low-lead high-sheet-resistance silicon solar battery front-surface silver electrode slurry and preparation method thereof - Google Patents
Low-lead high-sheet-resistance silicon solar battery front-surface silver electrode slurry and preparation method thereof Download PDFInfo
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- CN104867537A CN104867537A CN201510197287.6A CN201510197287A CN104867537A CN 104867537 A CN104867537 A CN 104867537A CN 201510197287 A CN201510197287 A CN 201510197287A CN 104867537 A CN104867537 A CN 104867537A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 21
- 239000004332 silver Substances 0.000 title claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 18
- 239000010703 silicon Substances 0.000 title claims abstract description 18
- 239000011267 electrode slurry Substances 0.000 title abstract 2
- 239000002002 slurry Substances 0.000 claims abstract description 37
- 239000011521 glass Substances 0.000 claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 238000009736 wetting Methods 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 238000012360 testing method Methods 0.000 claims abstract description 9
- 239000002562 thickening agent Substances 0.000 claims abstract description 9
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000000956 alloy Substances 0.000 claims abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910020218 Pb—Zn Inorganic materials 0.000 claims abstract description 5
- 229910052776 Thorium Inorganic materials 0.000 claims abstract description 5
- 229910052770 Uranium Inorganic materials 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 5
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000005096 rolling process Methods 0.000 claims abstract description 4
- 239000006185 dispersion Substances 0.000 claims description 21
- 239000002003 electrode paste Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims description 10
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 10
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 10
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 10
- 239000005642 Oleic acid Substances 0.000 claims description 10
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 10
- 235000021355 Stearic acid Nutrition 0.000 claims description 10
- 239000000428 dust Substances 0.000 claims description 10
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 10
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 10
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims description 10
- 235000020778 linoleic acid Nutrition 0.000 claims description 10
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 10
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 10
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 10
- 235000021313 oleic acid Nutrition 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 239000008117 stearic acid Substances 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 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 9
- 235000010445 lecithin Nutrition 0.000 claims description 9
- 239000000787 lecithin Substances 0.000 claims description 9
- 229940067606 lecithin Drugs 0.000 claims description 9
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 8
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 5
- 229940070765 laurate Drugs 0.000 claims description 5
- 229940083542 sodium Drugs 0.000 claims description 5
- 239000012798 spherical particle Substances 0.000 claims description 5
- 229960004274 stearic acid Drugs 0.000 claims description 5
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 4
- 229920000180 alkyd Polymers 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 229920001727 cellulose butyrate Polymers 0.000 claims description 4
- 235000010985 glycerol esters of wood rosin Nutrition 0.000 claims description 4
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 claims description 4
- -1 lauryl alcohol ester Chemical class 0.000 claims description 4
- 229920000193 polymethacrylate Polymers 0.000 claims description 4
- PZTAGFCBNDBBFZ-UHFFFAOYSA-N tert-butyl 2-(hydroxymethyl)piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCCC1CO PZTAGFCBNDBBFZ-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 238000005245 sintering Methods 0.000 abstract description 13
- 238000011049 filling Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000003068 static effect Effects 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
- H01B1/14—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
- 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
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- 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
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- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Conductive Materials (AREA)
- Powder Metallurgy (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a low-lead high-sheet-resistance silicon solar battery front-surface silver electrode slurry and a preparation method thereof. The slurry is prepared by performing mixed dispersing, three-roller rolling and filtering on 85%-95% of silver powder, 1%-5% of glass frit, 5%-10% of an organic carrier and 0.002%-0.5% of an inorganic additive, wherein the silver powder is formed by mixing silver powder with different particle sizes, different specific surfaces, different tap densities, different morphologies and different disperse systems; the frit employs frit of a Te-Bi-Pb-Zn system and/or a Te-Bi-Zn system; the organic carrier is prepared by use of an organic solvent, a thickening agent, an organic thixotropic agent and a wetting dispersant according to a mass ratio of (70-90):(2-15):(2-10):(1-5); and the inorganic additive is at least one from an oxide, a fluoride, a carbonic acid substance, a simple substance and an alloy which comprise U, Th, Ru, Pt, Rh, Cr, Ca, Zn, W, Fe, Co, Ni, Te, Mo or Mn. A battery sheet prepared by use of the slurry, after a sintering test, has lower contact resistance, higher tension, higher filling performance, wide sintering windows and an electrical property characteristic comparable with that of an overseas slurry.
Description
Technical field
The invention belongs to solar cell size field, be specifically related to a kind of high square resistance silicon solar cell front silver electrode paste and preparation method thereof.
Background technology
Solar cell is the device by photoelectric effect, light energy conversion being become electric energy.The radiation of suitable wavelength incident in the P-N junction of semiconductor is served as produce the right exterior source of energy of hole-electron in this semiconductor.Due to P-N junction there is electrical potential difference in place, and hole and electronics stride across this knot with contrary direction and move.Electronics moves to cathode contact, and hole moves to cathode contact, thus produce can the externally electric current that transmits electric power of circuit.The electrode contacts of solar cell is very important for the performance of battery.
Front electrode of solar battery slurry makes the important basic material of photovoltaic solar cells, for making the front electrode of crystal silicon solar energy battery.Front electrode of solar battery is made up of glass dust, silver powder, organic carrier, inorganic additive, organic additive; Wherein glass dust Main Function be burn insulation silicon nitride anti-reflection film, help to form Ag/Si ohmic contact, adhesive force is provided; Silver powder Main Function makes silver powder sintering densification, forms low grid line resistance, the conductive electrode provided; Organic carrier Main Function is wetting, printing, outward appearance, depth-width ratio between powder; Inorganic additive and organic additive are mainly used in the improvement of modification and size performance.
Along with the development of technology, in order to improve conversion efficiency and reduce surface recombination, each battery manufacturer adopts the shallow junction of cell piece and the thin close gate technique of grid one after another.Shallow junction refers to that solar cell P-N junction junction depth is less than 0.3 μm, utilizes shallow junction significantly can reduce the minority carrier recombination speed on solar battery sheet surface, improves the spectral response of short-wave band.The close grid of thin grid refer to that solar cell passes through to adopt the close gate technique of thin grid to reduce grid line width, reach depth-width ratio and maximize, at utmost to reduce the shading-area of battery, to improve the whole efficiency of battery.Owing to adopting shallow junction (high square resistance) technology, because P-N junction is very shallow when causing sintering, be easy to burn, this just requires that slurry has wider sintering window and suitable corrosion rate, and impact sintering window and corrosion rate depend primarily on the characteristic of glass dust in positive silver paste: glass dust will have different corrosion rates, corrosion resistance, mobility, wetability, thermal stability in different temperatures interval.Owing to adopting the close gate technique of thin grid, cause being difficult to reach desirable balance between the levelling of slurry, sagging, grid line width, grid line height, and then cause battery grid line break the printing problems such as grid, grid line width is wide, grid line height is too low occur, and affect the impressionability of slurry, characteristic that depth-width ratio depends primarily on organic system in positive silver paste: have confidential have good mobility and thixotropy, slurry needs high viscosity when static, is sheared rear low viscosity.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of low plumbous high square resistance silicon solar cell front silver electrode paste and preparation method thereof, the electrical performance characteristics that the cell piece using slurry of the present invention to prepare has lower contact resistance, high pulling force, high filling, wide sintering window and maintains an equal level with external slurry after sintering test.
The present invention in order to the technical scheme solving its technical problem and adopt is:
A kind of low plumbous high square resistance silicon solar cell front silver electrode paste, is made up of following four kinds of compositions:
A, conductive powder: be made up of the conductive powder of 1-3 kind different-shape, different-grain diameter, different specific surface and different dispersion, the mass percent of described conductive powder in whole slurry system is 85%-95%;
B, frit: be made up of the frit of 1-4 kind different Tg, different-grain diameter and different system, the mass percent of described frit in whole slurry system is 1%-5%;
C, organic carrier: be made up of organic solvent, thickener, organic thixotropic agents and wetting dispersing agent and the mass ratio of these four kinds of compositions for (70-90): (2-15): (2-10): (1-5), the mass percent of described organic carrier in whole slurry system is 5%-10%;
D, inorganic additive: at least one in the oxide containing U, Th, Ru, Pt, Rh, Cr, Ca, Zn, W, Fe, Co, Ni, Te, Mo or Mn, fluoride, carbonic acid thing, simple substance and alloy, the mass percent of described inorganic additive in whole slurry system is 0.002%-0.5%.
Say further, described conductive powder comprises silver powder, and described silver powder is made up of the first silver powder and the second silver powder two kinds of silver powder, and described first silver powder and the second silver powder all have spherical particle, and the blending ratio of the first silver powder and the second silver powder is 1-6; The tap density of the first silver powder is 3.5-4.5, specific surface is 0.6-0.8m
2/ gm, d10 are 1.0-1.5um, D50 be 2.0-2.5um and D90 is 4.0-8.0um, and the dispersion on described first silver powder surface is selected from least one in oleic acid, linoleic acid, linoleic acid sodium, stearic acid and phosphorous surfactant; The tap density of the second silver powder is more than 5, specific surface is 0.5-0.8m
2/ gm, d10 are 1.0-1.5um, D50 is 2.0-3.0um and D903.0-5.0um, and the dispersion on described second silver powder surface is selected from least one in oleic acid, linoleic acid, linoleic acid sodium, stearic acid, laurate, lecithin and phosphorous surfactant.
Say further, described frit comprises following component and weight percentage: TeO
2: 30-80%, PbO:0-5%, Bi
2o
3: 1-20%, ZnO:0-50%.Furthermore, described frit can adopt the hybrid glass powder be made up of Te-Bi-Pb-Zn system and Te-Bi-Zn system; Described frit also can adopt Te-Bi-Zn system glass dust.
Say further, the selection of described organic carrier is as follows:
Described organic solvent is selected from least one in dipropylene glycol dibenzoate, lauryl alcohol ester, butyl carbitol, terpinol, diethyl phthalate and repefral;
Described thickener is selected from least one in ester gum, maleic rosin ester, cerinic acid cellulose butyrate, poly-methacrylate ester and alkyd resins;
Described organic thixotropic agents is selected from least one in rilanit special and polyolefin-wax;
Described wetting dispersing agent is selected from least one in lecithin and tributylcitrate.
The preparation method of above-mentioned low plumbous high square resistance silicon solar cell front silver electrode paste, comprises the steps:
One, silver powder preparation: silver powder is made up of the first silver powder and the second silver powder, and the first silver powder and the second silver powder all have spherical particle, and the blending ratio of the first silver powder and the second silver powder is 1-6; The tap density of the first silver powder is 3.5-4.5, specific surface is 0.6-0.8m
2/ gm, d10 are 1.0-1.5um, D50 be 2.0-2.5um and D90 is 4.0-8.0um, and the dispersion on the first silver powder surface is selected from least one in oleic acid, linoleic acid, linoleic acid sodium, stearic acid and phosphorous surfactant; The tap density of the second silver powder is more than 5, specific surface is 0.5-0.8m
2/ gm, d10 are 1.0-1.5um, D50 is 2.0-3.0um and D903.0-5.0um, and the dispersion on the second silver powder surface is selected from least one in oleic acid, linoleic acid, linoleic acid sodium, stearic acid, laurate, lecithin and phosphorous surfactant;
First silver powder and the second silver powder are prepared burden according to above blending ratio scope and control overflow, and prepare according to following flow process: surface modifier → the first silver powder of preparing burden → add mixes → ball milling → oven dry → screening with the second silver powder;
Two, frit preparation: frit comprises following component and percentage by weight thereof: TeO
2: 30-80%, PbO:0-5, Bi
2o
3: 1-20%, ZnO:0-50%;
Three, organic carrier preparation: organic carrier is made up of organic solvent, thickener, organic thixotropic agents and wetting dispersing agent and the mass ratio of these four kinds of compositions is (70-90): (2-15): (2-10): (1-5);
Described organic solvent is selected from least one in dipropylene glycol dibenzoate, lauryl alcohol ester, butyl carbitol, terpinol, diethyl phthalate and repefral;
Described thickener is selected from least one in ester gum, maleic rosin ester, cerinic acid cellulose butyrate, poly-methacrylate ester and alkyd resins;
Described organic thixotropic agents is selected from least one in rilanit special and polyolefin-wax;
Described wetting dispersing agent is selected from least one in lecithin and tributylcitrate;
Organic carrier is prepared burden according to above mass ratio and material, and prepares according to following flow process: batching → dissolve → dispersion → dry preparation;
The organic carrier prepared through above method presents milky;
Four, slurry preparation: slurry is made up of the mass percent scope of following material: quality of cathode silver hundred is than being 85%-95%, frit quality hundred is than being 1%-5%, organic carrier quality hundred is than being 5%-10%, inorganic additive quality hundred is than for 0.002-0.5%, and wherein inorganic additive is selected from least one in the oxide of U, Th, Ru, Pt, Rh, Cr, Ca, Zn, W, Fe, Co, Ni, Te, Mo or Mn, fluoride, carbonic acid thing, simple substance and alloy;
Slurry preparation is prepared burden according to mass percent scope and the material of above each material, and makes in conjunction with following preparation flow: batching → mix the rolling → filtration → test of dispersion → three-roller.
The granularity of the described slurry prepared through above technique is less than 8um, and be under the condition of 20 in shear rate, the viscosity of slurry is 150 ± 5pa/s.
The invention has the beneficial effects as follows:
1) silver powder adopt the silver powder of different large small particle diameter, different specific surface, different tap density, different-shape, different dispersion carry out mixed and modified after, can effectively realize the tightly packed of silver powder, to reduce the gap between powder, reduce the contraction of the rear silver powder of sintering, reduce the body resistance of grid line with entirety;
2) silver powder of different large small particle diameter, different specific surface, different tap density, different-shape, different dispersion carry out mixed and modified after, also helped by modified mixing silver powder and reduce grid line width, improve depth-width ratio, improve printing quality;
3) when the hybrid glass powder be made up of Te-Bi-Pb-Zn system and Te-Bi-Zn system taked by frit, owing to adopting the collocation of high/low temperature glass dust, thus can be good at by the effect of high/low temperature glass dust and particular design purposes the speed and the degree of depth that solve corroding silicon nitride, simultaneously in conjunction with the characteristic of semiconductor of Te-Bi-Pb-Zn system and Te-Bi-Zn system glass, be conducive to forming good contact and low Rs;
4) when frit adopts Te-Bi-Zn system single kind glass dust, lead-free systems is adopted to be conducive to environmental protection and to reduce the plumbous injury to the person; The Te-Bi-Zn system glass dust simultaneously designed can low temperature from show different viscosity B coefficent and glassy phase during high temperature, can solve speed and the degree of depth of corroding silicon nitride, simultaneously in conjunction with the characteristic of semiconductor of Te-Bi-Zn system glass material, be conducive to forming good contact and low Rs, while Te-Bi-Zn system glass VOC, ISC, FF of showing in the slurry all higher than there being plumbous system glass;
5) electrical performance characteristics that the cell piece using slurry of the present invention to prepare has lower contact resistance, high pulling force, high filling, wide sintering window and maintains an equal level with external slurry after sintering test.
Embodiment
Embodiment:
The formula of frit of the present invention exemplifies embodiment A 1-A6 six kinds of execution modes (but being not limited thereto), refers to following table 1 (unit: percentage by weight, %):
The formula of organic carrier of the present invention exemplifies embodiment Z1-Z6 six kinds of execution modes (but being not limited thereto), refers to following table 2 (unit: percentage by weight, %):
Organic carrier is prepared burden according to above mass ratio and material, and prepares according to following flow process: batching → dissolve → dispersion → dry preparation.
The pulp furnish of the low plumbous high square resistance silicon solar cell front silver electrode paste of embodiment of the present invention J1-J10 refers to following table 3:
Table 3 (unit: mass percent, %):
In upper table 3, described first silver powder and the second silver powder all have spherical particle, and the tap density of the first silver powder is 3.5-4.5, specific surface is 0.6-0.8m
2/ gm, d10 are 1.0-1.5um, D50 be 2.0-2.5um and D90 is 4.0-8.0um, and the dispersion on described first silver powder surface is selected from least one in oleic acid, linoleic acid, linoleic acid sodium, stearic acid and phosphorous surfactant; The tap density of the second silver powder is more than 5, specific surface is 0.5-0.8m
2/ gm, d10 are 1.0-1.5um, D50 is 2.0-3.0um and D903.0-5.0um, and the dispersion on described second silver powder surface is selected from least one in oleic acid, linoleic acid, linoleic acid sodium, stearic acid, laurate, lecithin and phosphorous surfactant.
Inorganic additive in upper table 3 refers to the oxide, fluoride, carbonic acid thing, simple substance or the alloy that contain element in table.
The preparation method of the low plumbous high square resistance silicon solar cell front silver electrode paste of embodiment of the present invention J1-J10 carries out in the steps below:
1) silver powder preparation:
First silver powder and the second silver powder are proportionally prepared burden, and prepare according to following flow process: surface modifier → the first silver powder of preparing burden → add mixes → ball milling → oven dry → screening with the second silver powder;
2) frit preparation:
Frit is proportionally prepared burden, and through molten system, water-cooled, ball milling, oven dry preparation;
3) organic carrier preparation:
Each components in certain proportion batching of organic carrier, and warp: batching, dissolving, dispersion, oven dry preparation;
Prepare organic carrier through above method and present milky, and show good thixotropy, printing;
4) slurry preparation: silver powder, frit, organic carrier and inorganic additive are prepared burden in proportion, and makes in conjunction with following preparation flow: batching → mixing dispersion → three-roller rolling → filtration → test.
The slurry prepared through above technique requires that granularity is less than 8um, and viscosity is in shear rate 20, and the viscosity recorded is 150pa/s.
The test result of slurry in polycrystalline 80 sheet resistance of slurry test result: embodiment J1-J10 sees the following form 4:
In upper table 4: VOC---volatile organic matter; ISC---short circuit current;
RS---string resistance; RSH---and hinder;
FF---fill factor, curve factor; Ncell---photoelectric conversion efficiency;
Irev2---reverse current.
From upper table 4, the electrical performance characteristics that the cell piece prepared by slurry of the present invention has lower contact resistance, high pulling force, high filling, wide sintering window and maintains an equal level with external slurry after sintering test.
Should be understood that above-described embodiment is only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within claims of the present invention limited range equally after the content of having read the present invention's instruction.
Claims (8)
1. a low plumbous high square resistance silicon solar cell front silver electrode paste, is characterized in that, be made up of following four kinds of compositions:
A, conductive powder: be made up of the conductive powder of 1-3 kind different-shape, different-grain diameter, different specific surface and different dispersion, the mass percent of described conductive powder in whole slurry system is 85%-95%;
B, frit: be made up of the frit of 1-4 kind different Tg, different-grain diameter and different system, the mass percent of described frit in whole slurry system is 1%-5%;
C, organic carrier: be made up of organic solvent, thickener, organic thixotropic agents and wetting dispersing agent and the mass ratio of these four kinds of compositions for (70-90): (2-15): (2-10): (1-5), the mass percent of described organic carrier in whole slurry system is 5%-10%;
D, inorganic additive: at least one in the oxide containing U, Th, Ru, Pt, Rh, Cr, Ca, Zn, W, Fe, Co, Ni, Te, Mo or Mn, fluoride, carbonic acid thing, simple substance and alloy, the mass percent of described inorganic additive in whole slurry system is 0.002%-0.5%.
2. low plumbous high square resistance silicon solar cell front as claimed in claim 1 silver electrode paste, it is characterized in that, described conductive powder comprises silver powder, and described silver powder is made up of the first silver powder and the second silver powder two kinds of silver powder, described first silver powder and the second silver powder all have spherical particle, and the blending ratio of the first silver powder and the second silver powder is 1-6; The tap density of the first silver powder is 3.5-4.5, specific surface is 0.6-0.8m
2/ gm, d10 are 1.0-1.5um, D50 be 2.0-2.5um and D90 is 4.0-8.0um, and the dispersion on described first silver powder surface is selected from least one in oleic acid, linoleic acid, linoleic acid sodium, stearic acid and phosphorous surfactant; The tap density of the second silver powder is more than 5, specific surface is 0.5-0.8m
2/ gm, d10 are 1.0-1.5um, D50 is 2.0-3.0um and D903.0-5.0um, and the dispersion on described second silver powder surface is selected from least one in oleic acid, linoleic acid, linoleic acid sodium, stearic acid, laurate, lecithin and phosphorous surfactant.
3. low plumbous high square resistance silicon solar cell front as claimed in claim 1 silver electrode paste, it is characterized in that, described frit comprises following component and weight percentage: TeO
2: 30-80%, PbO:0-5%, Bi
2o
3: 1-20%, ZnO:0-50%.
4. low plumbous high square resistance silicon solar cell front as claimed in claim 1 silver electrode paste, it is characterized in that, the selection of described organic carrier is as follows:
Described organic solvent is selected from least one in dipropylene glycol dibenzoate, lauryl alcohol ester, butyl carbitol, terpinol, diethyl phthalate and repefral;
Described thickener is selected from least one in ester gum, maleic rosin ester, cerinic acid cellulose butyrate, poly-methacrylate ester and alkyd resins;
Described organic thixotropic agents is selected from least one in rilanit special and polyolefin-wax;
Described wetting dispersing agent is selected from least one in lecithin and tributylcitrate.
5. low plumbous high square resistance silicon solar cell front as claimed in claim 3 silver electrode paste, it is characterized in that, described frit adopts the hybrid glass powder be made up of Te-Bi-Pb-Zn system and Te-Bi-Zn system.
6. low plumbous high square resistance silicon solar cell front as claimed in claim 3 silver electrode paste, is characterized in that, described frit adopts Te-Bi-Zn system glass dust.
7. a preparation method for the low plumbous high square resistance silicon solar cell front silver electrode paste according to any one of claim 1 to 6, is characterized in that, comprise the steps:
One, silver powder preparation: silver powder is made up of the first silver powder and the second silver powder, and the first silver powder and the second silver powder all have spherical particle, and the blending ratio of the first silver powder and the second silver powder is 1-6; The tap density of the first silver powder is 3.5-4.5, specific surface is 0.6-0.8m
2/ gm, d10 are 1.0-1.5um, D50 be 2.0-2.5um and D90 is 4.0-8.0um, and the dispersion on the first silver powder surface is selected from least one in oleic acid, linoleic acid, linoleic acid sodium, stearic acid and phosphorous surfactant; The tap density of the second silver powder is more than 5, specific surface is 0.5-0.8m
2/ gm, d10 are 1.0-1.5um, D50 is 2.0-3.0um and D903.0-5.0um, and the dispersion on the second silver powder surface is selected from least one in oleic acid, linoleic acid, linoleic acid sodium, stearic acid, laurate, lecithin and phosphorous surfactant;
First silver powder and the second silver powder are prepared burden according to above blending ratio scope and control overflow, and prepare according to following flow process: surface modifier → the first silver powder of preparing burden → add mixes → ball milling → oven dry → screening with the second silver powder;
Two, frit preparation: frit comprises following component and percentage by weight thereof: TeO
2: 30-80%, PbO:0-5, Bi
2o
3: 1-20%, ZnO:0-50%;
Three, organic carrier preparation: organic carrier is made up of organic solvent, thickener, organic thixotropic agents and wetting dispersing agent and the mass ratio of these four kinds of compositions is (70-90): (2-15): (2-10): (1-5);
Described organic solvent is selected from least one in dipropylene glycol dibenzoate, lauryl alcohol ester, butyl carbitol, terpinol, diethyl phthalate and repefral;
Described thickener is selected from least one in ester gum, maleic rosin ester, cerinic acid cellulose butyrate, poly-methacrylate ester and alkyd resins;
Described organic thixotropic agents is selected from least one in rilanit special and polyolefin-wax;
Described wetting dispersing agent is selected from least one in lecithin and tributylcitrate;
Organic carrier is prepared burden according to above mass ratio and material, and prepares according to following flow process: batching → dissolve → dispersion → dry preparation;
The organic carrier prepared through above method presents milky;
Four, slurry preparation: slurry is made up of the mass percent scope of following material: quality of cathode silver hundred is than being 85%-95%, frit quality hundred is than being 1%-5%, organic carrier quality hundred is than being 5%-10%, inorganic additive quality hundred is than for 0.002-0.5%, and wherein inorganic additive is selected from least one in the oxide of U, Th, Ru, Pt, Rh, Cr, Ca, Zn, W, Fe, Co, Ni, Te, Mo or Mn, fluoride, carbonic acid thing, simple substance and alloy;
Slurry preparation is prepared burden according to mass percent scope and the material of above each material, and makes in conjunction with following preparation flow: batching → mix the rolling → filtration → test of dispersion → three-roller.
8. the preparation method of low plumbous high square resistance silicon solar cell front as claimed in claim 7 silver electrode paste, it is characterized in that, the granularity of described slurry is less than 8um, is under the condition of 20 in shear rate, and the viscosity of slurry is 150 ± 5pa/s.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510197287.6A CN104867537B (en) | 2015-04-23 | 2015-04-23 | Low lead high square resistance silicon solar cell front silver electrode paste and preparation method thereof |
| PCT/CN2016/079985 WO2016169512A1 (en) | 2015-04-23 | 2016-04-22 | Glass frit, preparation method therefor and electrode paste containing glass frit |
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|---|---|---|---|
| CN201510197287.6A CN104867537B (en) | 2015-04-23 | 2015-04-23 | Low lead high square resistance silicon solar cell front silver electrode paste and preparation method thereof |
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| CN104867537A true CN104867537A (en) | 2015-08-26 |
| CN104867537B CN104867537B (en) | 2017-03-01 |
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| WO2016169512A1 (en) * | 2015-04-23 | 2016-10-27 | 江苏欧耐尔新型材料股份有限公司 | Glass frit, preparation method therefor and electrode paste containing glass frit |
| CN106816203A (en) * | 2017-03-20 | 2017-06-09 | 北京市合众创能光电技术有限公司 | Crystal silicon solar energy battery high-tensile strength positive silver paste and preparation method thereof |
| CN109378108A (en) * | 2018-12-06 | 2019-02-22 | 中国科学院山西煤炭化学研究所 | Positive silver paste and preparation method for perc crystal silicon solar energy battery |
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| JP5955791B2 (en) * | 2013-02-12 | 2016-07-20 | 株式会社ノリタケカンパニーリミテド | Paste composition and solar cell |
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| CN104036844A (en) * | 2014-02-28 | 2014-09-10 | 深圳市银和新材料科技有限公司 | Environment-friendly water-soluble solar cell anode silver paste and preparation method thereof |
| CN104867537B (en) * | 2015-04-23 | 2017-03-01 | 江苏欧耐尔新型材料有限公司 | Low lead high square resistance silicon solar cell front silver electrode paste and preparation method thereof |
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| JPH06295616A (en) * | 1993-04-05 | 1994-10-21 | Alps Electric Co Ltd | Conductive paste for forming film capable of applying soldering |
| CN102543260A (en) * | 2012-02-27 | 2012-07-04 | 江苏科技大学 | Silver paste for electrode of solar cell and method for preparing silver paste |
| CN103440897A (en) * | 2013-08-06 | 2013-12-11 | 浙江光达电子科技有限公司 | Silicon solar cell front silver electrode high-square-resistance slurry and manufacturing method thereof |
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| CN113677458A (en) * | 2019-03-29 | 2021-11-19 | 大洲电子材料株式会社 | Mixed silver powder and conductive paste containing the same |
| CN110217992A (en) * | 2019-05-24 | 2019-09-10 | 江苏大学 | A kind of preparation method of environment-friendly glass frit |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2016169512A1 (en) | 2016-10-27 |
| CN104867537B (en) | 2017-03-01 |
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