CN104867537B - Low lead high square resistance silicon solar cell front silver electrode paste and preparation method thereof - Google Patents
Low lead high square resistance silicon solar cell front silver electrode paste and preparation method thereof Download PDFInfo
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- CN104867537B CN104867537B CN201510197287.6A CN201510197287A CN104867537B CN 104867537 B CN104867537 B CN 104867537B CN 201510197287 A CN201510197287 A CN 201510197287A CN 104867537 B CN104867537 B CN 104867537B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 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 16
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 16
- 239000010703 silicon Substances 0.000 title claims abstract description 16
- 239000002003 electrode paste Substances 0.000 title claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 95
- 239000002002 slurry Substances 0.000 claims abstract description 36
- 239000006185 dispersion Substances 0.000 claims abstract description 22
- 239000011521 glass Substances 0.000 claims abstract description 21
- 239000000654 additive Substances 0.000 claims abstract description 15
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002270 dispersing agent Substances 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
- 238000009736 wetting Methods 0.000 claims abstract description 9
- 239000000956 alloy Substances 0.000 claims abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 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
- 238000005096 rolling process Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 15
- 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
- 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
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 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
- 238000000034 method Methods 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
- 239000011734 sodium Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 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
- 235000021355 Stearic acid Nutrition 0.000 claims description 9
- 239000000787 lecithin Substances 0.000 claims description 9
- 229940067606 lecithin Drugs 0.000 claims description 9
- 235000010445 lecithin Nutrition 0.000 claims description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 9
- 239000008117 stearic acid Substances 0.000 claims description 9
- 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 8
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 8
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 8
- 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 8
- 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
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims description 8
- 235000020778 linoleic acid Nutrition 0.000 claims description 8
- 235000021313 oleic acid Nutrition 0.000 claims description 8
- 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 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000005639 Lauric acid Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910020218 Pb—Zn Inorganic materials 0.000 claims description 4
- 229910003069 TeO2 Inorganic materials 0.000 claims description 4
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 239000004359 castor oil Substances 0.000 claims description 4
- 235000019438 castor oil Nutrition 0.000 claims description 4
- 229920001727 cellulose butyrate Polymers 0.000 claims description 4
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 4
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 4
- 229960001826 dimethylphthalate Drugs 0.000 claims description 4
- 125000005456 glyceride group Chemical group 0.000 claims description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 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
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 claims description 4
- 229940116411 terpineol Drugs 0.000 claims description 4
- PZTAGFCBNDBBFZ-UHFFFAOYSA-N tert-butyl 2-(hydroxymethyl)piperidine-1-carboxylate Chemical group CC(C)(C)OC(=O)N1CCCCC1CO PZTAGFCBNDBBFZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 4
- 239000002253 acid Substances 0.000 claims 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- 239000011347 resin Substances 0.000 claims 2
- 229920005989 resin Polymers 0.000 claims 2
- 238000003682 fluorination reaction Methods 0.000 claims 1
- 229940116364 hard fat Drugs 0.000 claims 1
- 239000000428 dust Substances 0.000 abstract description 9
- 238000005245 sintering Methods 0.000 abstract description 8
- 238000011049 filling Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process 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
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000012798 spherical particle Substances 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
- 229910052789 astatine Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 208000014674 injury Diseases 0.000 description 1
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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
Abstract
The invention discloses a kind of low lead high square resistance silicon solar cell front silver electrode paste and preparation method thereof, slurry is by 85% 95% argentum powder, 1% 5% frits, 5% 10% organic carriers and 0.002% 0.5% inorganic additives are through mixing dispersion, three-roller rolling and filtration are made, argentum powder is different particle diameters, specific surface, tap density, the argentum powder of pattern and dispersion mixes, frit adopts Te Bi Pb Zn system and/or Te Bi Zn system glass dust, organic carrier is by organic solvent, thickening agent, organic thixotropic agents and wetting dispersing agent are according to mass ratio (70 90)：(2‑15)：(2‑10)：(1 5) make, inorganic additive is at least one in the oxide containing U, Th, Ru, Pt, Rh, Cr, Ca, Zn, W, Fe, Co, Ni, Te, Mo or Mn, fluoride, carbonation, simple substance and alloy, has lower contact resistance, high pulling force, high filling, wide sintering window and the electrical performance characteristics fair with external slurry using after the sintered test of the cell piece of slurry of the present invention preparation.
Description
Technical field
The invention belongs to solar cell size field is and in particular to a kind of high square resistance silicon solar cell front silver electrode is starched
Material and preparation method thereof.
Background technology
Solaode is the device by photoelectric effect, luminous energy being changed into electric energy.Incident in the P-N junction of quasiconductor
Suitable wavelength radiation serve as in this quasiconductor produce hole-electron pair exterior source of energy.Due to there is electricity at P-N junction
Potential difference, hole and electronics move across this knot in a reverse direction.Electronics moves to cathode contact, and hole moves to positive pole and touches
Point, thus produce the electric current that can transmit electric power to external circuit.The electrode contacts of solaode are very heavy for the performance of battery
Will.
Front electrode of solar battery slurry is to make the important basic material of photovoltaic solar cells, for making crystal
The front electrode of silicon solar cell.Front electrode of solar battery by glass dust, argentum powder, organic carrier, inorganic additive, have
Machine additive forms；Wherein glass dust Main Function is to burn the silicon nitride anti-reflection film of insulation, help formation Ag/Si ohm to connect
Touch, adhesive force is provided；Argentum powder Main Function is to make argentum powder sintering densification, forms low grid line resistance, the conductive electricity providing
Pole；Organic carrier Main Function is moistening between powder body, printing, outward appearance, depth-width ratio；Inorganic additive and organic additive master
It is used for the modified improvement with size performance.
With the development of technology, in order to improve conversion efficiency and reduce surface recombination, each battery manufacturer adopts battery one after another
The shallow junction of piece and the close gate technique of thin grid.Shallow junction refers to that solaode P-N junction junction depth is less than 0.3 μm, can be notable using shallow junction
Reduce the minority carrier recombination speed on solar battery sheet surface, improve the spectral response of short-wave band.The thin close grid of grid refer to too
Sun can battery pass through to reduce grid line width using the close gate technique of thin grid, reaches depth-width ratio and maximizes, at utmost to reduce electricity
The shading-area in pond, to improve the whole efficiency of battery.Due to using shallow junction (high square resistance) technology, leading to during sintering due to P-N
Tie very shallow it is easy to burn, this requires that slurry has wider sintering window and suitable corrosion rate, and affects to sinter window
Depend primarily on the characteristic of glass dust in positive silver paste with corrosion rate：Glass dust will have different corrosion in different temperatures interval
Speed, corrosion resistance, mobility, wettability, heat stability.Due to using the close gate technique of thin grid, leading to levelling, the stream of slurry
Extension, between grid line width, grid line height, difficult to reach preferably balances, so lead to battery grid line break grid, grid line width wide,
Grid line height low printing problem excessively occurs, and affect the impressionability of slurry, depth-width ratio depends primarily in positive silver paste
The characteristic of organic system：Have confidential there is preferable mobility and thixotropy, slurry needs high viscosity when static, after being sheared
Low viscosity.
Content of the invention
In order to solve above-mentioned technical problem, the invention provides a kind of low lead high square resistance silicon solar cell front silver electrode
Slurry and preparation method thereof, has lower contact resistance, height using after the sintered test of the cell piece of slurry of the present invention preparation
Pulling force, high filling, wide sintering window and the electrical performance characteristics maintaining an equal level with external slurry.
The present invention be employed technical scheme comprise that to solve its technical problem：
A kind of low lead high square resistance silicon solar cell front silver electrode paste, is made up of following four kinds of compositions：
A, conductive powder：Conducting powder by 2-3 kind different-shape, different-grain diameter, different specific surface and different dispersion
End is constituted, and mass percent in whole slurry system for the described conductive powder is 85%-93%；
B, frit：It is made up of the frit of 2-4 kind difference Tg, different-grain diameter and different system, described frit is whole
Mass percent in individual slurry system is 1%-5%；
C, organic carrier：It is made up of organic solvent, thickening agent, organic thixotropic agents and wetting dispersing agent and these four compositions
Mass ratio be (70-90)：(2-15)：(2-10)：(1-5), quality hundred in whole slurry system for the described organic carrier
Divide ratio for 5%-10%；
D, inorganic additive：Oxide containing U, Th, Ru, Pt, Rh, Cr, Ca, Zn, W, Fe, Co, Ni, Te, Mo or Mn,
At least one in fluoride, carbonation, simple substance and alloy, percent mass in whole slurry system for the described inorganic additive
Than for 0.002%-0.5%.
Further say, described conductive powder comprises argentum powder, and described argentum powder is by the first argentum powder and the second argentum powder two
Plant argentum powder to constitute, described first argentum powder and the second argentum powder are respectively provided with spherical particle, the blending ratio of the first argentum powder and the second argentum powder
For 1-6；The tap density of the first argentum powder is 3.5-4.5g/cm3, specific surface be 0.6-0.8m2/ g, D10 are 1.0-1.5 μm, D50
It is 4.0-8.0 μm for 2.0-2.5 μm and D90, the dispersion on described first argentum powder surface is selected from Oleic acid, linoleic acid, sub- oil
At least one in sour sodium, stearic acid and phosphorous surfactant；The tap density of the second argentum powder is 5g/cm3Above, compare table
Face is 0.5-0.8m2/ g, D10 are 1.0-1.5 μm, D50 is 2.0-3.0 μm and D90 and is 3.0-5.0 μm, described second argentum powder table
The dispersion in face is selected from Oleic acid, linoleic acid, linoleic acid sodium, stearic acid, lauric acid, lecithin and phosphorous surfactant
At least one.
Further say, described frit includes following components and weight percentage：TeO2:30-80%, PbO:0-
5%th, Bi2O3:1-20%, ZnO:0-50%.Furthermore, described frit can using by Te-Bi-Pb-Zn system with
The hybrid glass powder of Te-Bi-Zn system composition.
Further say, the selection of described organic carrier is as follows：
Described organic solvent is selected from dipropylene glycol dibenzoate, lauryl alcohol ester, butyl carbitol, terpineol, adjacent benzene two
At least one in formic acid diethylester and dimethyl phthalate；
Described thickening agent is selected from rosin glyceride, maleic rosin ester, cerinic acid cellulose butyrate, poly- methacrylate ester
With at least one in alkyd resin；
Described organic thixotropic agents are selected from least one in castor oil hydrogenated and polyolefin-wax；
Described wetting dispersing agent is selected from least one in lecithin and tributyl citrate.
The preparation method of above-mentioned low lead high square resistance silicon solar cell front silver electrode paste, comprises the steps：
First, argentum powder preparation：Argentum powder is made up of with the second argentum powder the first argentum powder, and the first argentum powder and the second argentum powder are respectively provided with spherical
Granule, the blending ratio of the first argentum powder and the second argentum powder is 1-6；The tap density of the first argentum powder is 3.5-4.5g/cm3, compare table
Face is 0.6-0.8m2/ g, D10 are 1.0-1.5 μm, D50 is 2.0-2.5 μm and D90 and is 4.0-8.0 μm, the first argentum powder surface
Dispersion be selected from Oleic acid, linoleic acid, linoleic acid sodium, at least one in stearic acid and phosphorous surfactant；Second
The tap density of argentum powder is 5g/cm3Above, specific surface is 0.5-0.8m2/ g, D10 be 1.0-1.5 μm, D50 be 2.0-3.0 μm and
D90 is 3.0-5.0 μm, the dispersion on the second argentum powder surface be selected from Oleic acid, linoleic acid, linoleic acid sodium, stearic acid, lauric acid,
At least one in lecithin and phosphorous surfactant；
First argentum powder and the second argentum powder carry out dispensing according to above blending ratio scope with controlling requirement, and according to following
Prepared by flow process：Dispensing → addition surface modifier → the first argentum powder mixs homogeneously → ball milling → drying → screening with the second argentum powder；
2nd, frit preparation:Frit includes following components and its percentage by weight：TeO2:30-80%, PbO:0-
5%th, Bi2O3:1-20%, ZnO:0-50%；
3rd, organic carrier preparation:Organic carrier is made up of organic solvent, thickening agent, organic thixotropic agents and wetting dispersing agent
And the mass ratio of these four compositions is (70-90)：(2-15)：(2-10)：(1-5)；
Described organic solvent is selected from dipropylene glycol dibenzoate, lauryl alcohol ester, butyl carbitol, terpineol, adjacent benzene two
At least one in formic acid diethylester and dimethyl phthalate；
Described thickening agent is selected from rosin glyceride, maleic rosin ester, cerinic acid cellulose butyrate, poly- methacrylate ester
With at least one in alkyd resin；
Described organic thixotropic agents are selected from least one in castor oil hydrogenated and polyolefin-wax；
Described wetting dispersing agent is selected from least one in lecithin and tributyl citrate；
Organic carrier carries out dispensing according to above mass ratio and material, and according to below scheme preparation：Dispensing → dissolving
→ dispersion → dry preparation；
Organic carrier through above method preparation presents milky；
4th, slurry preparation：Slurry is made up of the mass percent scope of following material：Quality of cathode silver hundred ratio is 85%-
93%, frit quality hundred ratio is 1%-5%, and organic carrier quality hundred ratio is 5%-10%, and inorganic additive quality hundred ratio is
0.002-0.5%, wherein inorganic additive are selected from the oxygen of U, Th, Ru, Pt, Rh, Cr, Ca, Zn, W, Fe, Co, Ni, Te, Mo or Mn
At least one in compound, fluoride, carbonation, simple substance and alloy；
Slurry preparation carries out dispensing according to the mass percent scope of each material above with material, and combines following preparation stream
Cheng Jinhang makes：Dispensing → mixing dispersion → three-roller rolling → filter → test.
It is less than 8 μm through the granularity of the described slurry of process above preparation, under conditions of shear rate is for 20/s, slurry
Viscosity be 150 ± 5Pa s.
The invention has the beneficial effects as follows：
1) argentum powder adopts different size particle diameter, different specific surface, different tap density, different-shape, different dispersion
Argentum powder carry out mixed and modified after, can effectively realize the tightly packed of argentum powder, to reduce the gap between powder body, after reducing sintering
The contraction of argentum powder, with the overall body resistance reducing grid line；
2) different size particle diameter, different specific surface, different tap density, different-shape, the argentum powder of different dispersion enter
After row is mixed and modified, also helps reduction grid line width, improve depth-width ratio, improve printing quality by modified mixing argentum powder
Amount；
3) when the hybrid glass powder being made up of Te-Bi-Pb-Zn system taken with Te-Bi-Zn system by frit, due to
Using the collocation of high/low temperature glass dust, thus can be good at solving corruption by the effect of high/low temperature glass dust and particular design purposes
The speed of erosion silicon nitride and depth, in combination with the characteristic of semiconductor of Te-Bi-Pb-Zn system and Te-Bi-Zn system glass, have
Beneficial to the good contact of formation and low Rs；
4) when frit adopts Te-Bi-Zn system single kind glass dust, be conducive to environmental protection and subtract using lead-free systems
Few lead is to personal injury；The Te-Bi-Zn system glass dust simultaneously designing can show different viscosity when low temperature is from high temperature
Change and glass phase, can solve speed and the depth of corroding silicon nitride, in combination with Te-Bi-Zn system glass material
Characteristic of semiconductor, advantageously form good contact and low Rs, Te-Bi-Zn system glass shows in the slurry simultaneously
VOC, ISC, FF have been above lead system glass；
5) using slurry of the present invention preparation cell piece sintered test after have lower contact resistance, high pulling force,
High filling, wide sintering window and the electrical performance characteristics maintaining an equal level with external slurry.
Specific embodiment
Embodiment：
The formula of the frit of the present invention enumerates six kinds of embodiment (but not limited to) of embodiment A1-A6, refers to table 1 below
(unit：Percentage by weight, %)：
The formula of the organic carrier of the present invention enumerates six kinds of embodiment (but not limited to) of embodiment Z1-Z6, refers to down
Table 2 (unit：Percentage by weight, %)：
Organic carrier carries out dispensing according to above mass ratio and material, and according to below scheme preparation：Dispensing → dissolving
→ dispersion → dry preparation.
The proportioning raw materials of the low lead high square resistance silicon solar cell front silver electrode paste of embodiment of the present invention J1-J10 are detailed
See table 3：
Table 3 (unit：Mass percent, %)：
In upper table 3, described first argentum powder and the second argentum powder are respectively provided with spherical particle, and the tap density of the first argentum powder is 3.5-
4.5g/cm3, specific surface be 0.6-0.8m2/ g, D10 are 1.0-1.5 μm, D50 is 2.0-2.5 μm and D90 and is 4.0-8.0 μm,
The dispersion on described first argentum powder surface is selected from Oleic acid, linoleic acid, linoleic acid sodium, stearic acid and phosphorous surfactant
At least one；The tap density of the second argentum powder is 5g/cm3Above, specific surface is 0.5-0.8m2/ g, D10 be 1.0-1.5 μm,
D50 is 2.0-3.0 μm and D90 and is 3.0-5.0 μm, and the dispersion on described second argentum powder surface is selected from Oleic acid, linoleic acid, sub- oil
At least one in sour sodium, stearic acid, lauric acid, lecithin and phosphorous surfactant.
Inorganic additive in upper table 3 refers to containing the oxide of element, fluoride, carbonation, simple substance or alloy in table.
The preparation method of the low lead high square resistance silicon solar cell front silver electrode paste of embodiment of the present invention J1-J10 is pressed
Following step is carried out：
1) argentum powder preparation：
First argentum powder and the second argentum powder proportionally carry out dispensing, and according to below scheme preparation：Dispensing → addition surface
Modifying agent → the first argentum powder mixs homogeneously → ball milling → drying → screening with the second argentum powder；
2) frit preparation：
Frit proportionally carries out dispensing, and through molten system, water-cooled, ball milling, drying preparation；
3) organic carrier preparation：
Each components in certain proportion dispensing of organic carrier, and warp：Dispensing, dissolving, dispersion, drying preparation；
Prepare organic carrier through above method and present milky, and show good thixotropy, printing；
4) slurry preparation：By argentum powder, frit, organic carrier and inorganic additive dispensing in proportion, and combine following system
Standby flow process is made：Dispensing → mixing dispersion → three-roller rolling → filter → test.
Granularity is required to be less than 8 μm through the slurry of process above preparation, viscosity in shear rate 20/s, the viscosity recording is
150Pa·s.
Slurry test result：Test result in polycrystalline 80 sheet resistance for the slurry of embodiment J1-J10 see table 4：
In upper table 4：VOC volatile organic matter；ISC short circuit current；
RS string resistance；RSH simultaneously hinders；
FF fill factor, curve factor；Ncell photoelectric transformation efficiency；
Irev2 reverse current.
From upper table 4, after the sintered test of the cell piece prepared by slurry of the present invention, there is lower contact resistance, height
Pulling force, high filling, wide sintering window and the electrical performance characteristics maintaining an equal level with external slurry.
It should be understood that above-described embodiment is only illustrative of the invention and is not intended to limit the scope of the invention.In addition, it is to be understood that
After having read the content of present invention instruction, those skilled in the art can make various changes or modifications to the present invention, these
The equivalent form of value equally falls within claims of the present invention limited range.
Claims (6)
1. a kind of low lead high square resistance silicon solar cell front silver electrode paste is it is characterised in that be made up of following four kinds of compositions：
A, conductive powder：Conductive powder structure by 2-3 kind different-shape, different-grain diameter, different specific surface and different dispersion
Become, mass percent in whole slurry system for the described conductive powder is 85%-93%；Described conductive powder comprises argentum powder,
And described argentum powder is to be made up of the first argentum powder and two kinds of argentum powder of the second argentum powder, and described first argentum powder and the second argentum powder are respectively provided with ball
Shape granule, the blending ratio of the first argentum powder and the second argentum powder is 1-6；The tap density of the first argentum powder is 3.5-4.5g/cm3, ratio
Surface is 0.6-0.8m2/ g, D10 are 1.0-1.5 μm, D50 is 2.0-2.5 μm and D90 and is 4.0-8.0 μm, described first silver medal
The dispersion on powder surface is selected from least in Oleic acid, linoleic acid, linoleic acid sodium, stearic acid and phosphorous surfactant
Kind；The tap density of the second argentum powder is 5g/cm3Above, specific surface is 0.5-0.8m2/ g, D10 are 1.0-1.5 μm, D50 is 2.0-
3.0 μm and D90 are 3.0-5.0 μm, and the dispersion on described second argentum powder surface is selected from Oleic acid, linoleic acid, linoleic acid sodium, Hard Fat
At least one in acid, lauric acid, lecithin and phosphorous surfactant；
B, frit：It is made up of the frit of 2-4 kind difference Tg, different-grain diameter and different system, described frit is starched whole
Mass percent in material system is 1%-5%；
C, organic carrier：Be made up of organic solvent, thickening agent, organic thixotropic agents and wetting dispersing agent and these four compositions matter
Amount ratio is (70-90)：(2-15)：(2-10)：(1-5), mass percent in whole slurry system for the described organic carrier
For 5%-10%；
D, inorganic additive：Oxide containing U, Th, Ru, Pt, Rh, Cr, Ca, Zn, W, Fe, Co, Ni, Te, Mo or Mn, fluorination
At least one in thing, carbonation, simple substance and alloy, mass percent in whole slurry system for the described inorganic additive is
0.002%-0.5%.
2. as claimed in claim 1 low lead high square resistance silicon solar cell front silver electrode paste it is characterised in that described glass
Glass material includes following components and weight percentage：TeO2:30-80%, PbO:0-5%, Bi2O3:1-20%, ZnO:0-50%.
3. as claimed in claim 1 low lead high square resistance silicon solar cell front silver electrode paste it is characterised in that described have
The selection of airborne body is as follows：
Described organic solvent is selected from dipropylene glycol dibenzoate, lauryl alcohol ester, butyl carbitol, terpineol, phthalic acid
At least one in diethylester and dimethyl phthalate；
Described thickening agent is selected from rosin glyceride, maleic rosin ester, cerinic acid cellulose butyrate, poly- methacrylate ester and alcohol
At least one in acid resin；
Described organic thixotropic agents are selected from least one in castor oil hydrogenated and polyolefin-wax；
Described wetting dispersing agent is selected from least one in lecithin and tributyl citrate.
4. as claimed in claim 2 low lead high square resistance silicon solar cell front silver electrode paste it is characterised in that described glass
Glass material is using the hybrid glass powder being made up of with Te-Bi-Zn system Te-Bi-Pb-Zn system.
5. a kind of low lead high square resistance silicon solar cell front silver electrode paste as any one of Claims 1-4
Preparation method is it is characterised in that comprise the steps：
First, argentum powder preparation：Argentum powder is made up of with the second argentum powder the first argentum powder, and the first argentum powder and the second argentum powder are respectively provided with spherical
Grain, the blending ratio of the first argentum powder and the second argentum powder is 1-6；The tap density of the first argentum powder is 3.5-4.5g/cm3, specific surface
For 0.6-0.8m2/ g, D10 are 1.0-1.5 μm, D50 is 2.0-2.5 μm and D90 and is 4.0-8.0 μm, the first argentum powder surface
Dispersion is selected from least one in Oleic acid, linoleic acid, linoleic acid sodium, stearic acid and phosphorous surfactant；Second silver medal
The tap density of powder is 5g/cm3Above, specific surface is 0.5-0.8m2/ g, D10 be 1.0-1.5 μm, D50 be 2.0-3.0 μm and
D90 is 3.0-5.0 μm, the dispersion on the second argentum powder surface be selected from Oleic acid, linoleic acid, linoleic acid sodium, stearic acid, lauric acid,
At least one in lecithin and phosphorous surfactant；
First argentum powder and the second argentum powder carry out dispensing according to above blending ratio scope with controlling requirement, and according to below scheme
Preparation：Dispensing → addition surface modifier → the first argentum powder mixs homogeneously → ball milling → drying → screening with the second argentum powder；
2nd, frit preparation:Frit includes following components and its percentage by weight：TeO2:30-80%, PbO:0-5%,
Bi2O3:1-20%, ZnO:0-50%；
3rd, organic carrier preparation:Organic carrier be made up of organic solvent, thickening agent, organic thixotropic agents and wetting dispersing agent and
The mass ratio of these four compositions is (70-90)：(2-15)：(2-10)：(1-5)；
Described organic solvent is selected from dipropylene glycol dibenzoate, lauryl alcohol ester, butyl carbitol, terpineol, phthalic acid
At least one in diethylester and dimethyl phthalate；
Described thickening agent is selected from rosin glyceride, maleic rosin ester, cerinic acid cellulose butyrate, poly- methacrylate ester and alcohol
At least one in acid resin；
Described organic thixotropic agents are selected from least one in castor oil hydrogenated and polyolefin-wax；
Described wetting dispersing agent is selected from least one in lecithin and tributyl citrate；
Organic carrier carries out dispensing according to above mass ratio and material, and according to below scheme preparation：Dispensing → dissolving → point
Dissipate → dry preparation；
Organic carrier through above method preparation presents milky；
4th, slurry preparation：Slurry is made up of the mass percent scope of following material：Quality of cathode silver hundred ratio is 85%-93%,
Frit quality hundred ratio is 1%-5%, and than being 5%-10%, inorganic additive quality hundred ratio is 0.002- to organic carrier quality hundred
0.5%, wherein inorganic additive be selected from U, Th, Ru, Pt, Rh, Cr, Ca, Zn, W, Fe, Co, Ni, Te, Mo or Mn oxide,
At least one in fluoride, carbonation, simple substance and alloy；
Slurry preparation carries out dispensing according to the mass percent scope of each material above with material, and enters with reference to following preparation flow
Row makes：Dispensing → mixing dispersion → three-roller rolling → filter → test.
6. the preparation method of low lead high square resistance silicon solar cell front silver electrode paste as claimed in claim 5, its feature
It is, the granularity of described slurry is less than 8 μm, under conditions of shear rate is for 20/s, the viscosity of slurry is 150 ± 5Pa s.
Priority Applications (2)
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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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| CN104867537B true CN104867537B (en) | 2017-03-01 |
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| 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 |
| EP3583612A1 (en) * | 2017-02-15 | 2019-12-25 | Basf Se | Glass frit, conductive paste and use of the conductive paste |
| 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 |
| KR102263618B1 (en) * | 2019-03-29 | 2021-06-10 | 대주전자재료 주식회사 | Mixed silver powder and conductive paste comprising same |
| CN110217992A (en) * | 2019-05-24 | 2019-09-10 | 江苏大学 | A kind of preparation method of environment-friendly glass frit |
| CN111564508B (en) * | 2020-05-20 | 2021-12-28 | 浙江晶科能源有限公司 | Slurry and damp-heat attenuation resistant photovoltaic cell |
| CN112164488B (en) * | 2020-09-25 | 2022-04-26 | 广东羚光新材料股份有限公司 | Silver paste for ceramic filter and preparation method thereof |
| CN113314249A (en) * | 2021-05-26 | 2021-08-27 | 福建溥昱电子科技有限公司 | Silver paste for 5G ceramic dielectric filter and preparation method thereof |
| CN113628780B (en) * | 2021-10-12 | 2021-12-21 | 西安宏星电子浆料科技股份有限公司 | Low-cost low-resistance thick film resistor paste |
| CN114203337A (en) * | 2021-12-13 | 2022-03-18 | 江苏聚盈新材料科技有限公司 | High-recovery solar cell front silver paste and preparation method thereof |
| CN114315159B (en) * | 2021-12-16 | 2023-10-31 | 浙江光达电子科技有限公司 | Glass powder for TOPCON battery main gate electrode silver paste, and preparation method and application thereof |
| CN117809882A (en) * | 2024-03-01 | 2024-04-02 | 浙江晶科新材料有限公司 | Conductive paste, preparation method thereof and solar cell |
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| JP2965815B2 (en) * | 1993-04-05 | 1999-10-18 | アルプス電気株式会社 | Solderable conductive paste for film formation |
| 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 |
| 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 |
| KR101587683B1 (en) * | 2013-02-15 | 2016-01-21 | 제일모직주식회사 | The composition for forming solar cell electrode comprising the same, and electrode prepared using the same |
| CN103440897B (en) * | 2013-08-06 | 2017-03-01 | 浙江光达电子科技有限公司 | A kind of high square resistance silicon solar cell front silver electrode paste and preparation method thereof |
| 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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| CN104867537A (en) | 2015-08-26 |
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