CN102831949A - Efficient lead-free silver paste on back of solar cell and preparation method of silver paste - Google Patents
Efficient lead-free silver paste on back of solar cell and preparation method of silver paste Download PDFInfo
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- CN102831949A CN102831949A CN2012103046188A CN201210304618A CN102831949A CN 102831949 A CN102831949 A CN 102831949A CN 2012103046188 A CN2012103046188 A CN 2012103046188A CN 201210304618 A CN201210304618 A CN 201210304618A CN 102831949 A CN102831949 A CN 102831949A
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- glass dust
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- silver
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 43
- 239000004332 silver Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000002002 slurry Substances 0.000 claims abstract description 58
- 238000000498 ball milling Methods 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000011521 glass Substances 0.000 claims description 61
- 239000000428 dust Substances 0.000 claims description 49
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 32
- 239000002994 raw material Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000654 additive Substances 0.000 claims description 20
- 230000000996 additive effect Effects 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 14
- 238000009472 formulation Methods 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 11
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 8
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 8
- 229920001249 ethyl cellulose Polymers 0.000 claims description 8
- 239000012467 final product Substances 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 8
- 238000010791 quenching Methods 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- 239000001856 Ethyl cellulose Substances 0.000 claims description 6
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- MUFTXXUPGWDJLU-UHFFFAOYSA-N 1-phenylprop-2-enylbenzene Chemical compound C=1C=CC=CC=1C(C=C)C1=CC=CC=C1 MUFTXXUPGWDJLU-UHFFFAOYSA-N 0.000 claims description 4
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 4
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 claims description 4
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 125000006038 hexenyl group Chemical group 0.000 claims description 4
- WQDGUYZIAJKLAB-UHFFFAOYSA-N octan-2-yl nitrite Chemical compound CCCCCCC(C)ON=O WQDGUYZIAJKLAB-UHFFFAOYSA-N 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 10
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- -1 glycol ethers Chemical class 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910006339 Si—Pb Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
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- Photovoltaic Devices (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses efficient lead-free silver paste on the back of a solar cell and a preparation method of the silver paste. The silver paste is obtained by mixing two parts of slurries including A and B according to equal proportion and subjecting the mixture to ball milling. The silver paste prepared is free of lead, less harmful to human body and environment, and completely in conformity with environmental requirements. By selecting silver power uniform in particle size for the silver paste and other conducting particles to fill gaps of the silver powder, stacking density of a film is improved, contact area between particles is enlarged, convergent force of the film is reduced, and conducting capability of the silver paste is improved. By adding copper powder into conductive slurry, reduction of preparation cost of the silver paste is facilitated, conductivity of the silver paste is improved, thus manufacturing cost of the solar cells is reduced, and good economic benefit is gained.
Description
Technical field
The present invention relates to a kind of efficient lead free solar cell back silver paste and preparation method thereof, belong to the solar cell conductive paste preparing technical field.
Background technology
The conductive silver paste of solar cell is prepared from by different proportionings raw material such as silver powder, glass glue, organic solvents, and wherein silver powder is as conducting medium; Glass glue melts when high temperature sintering, between silver powder and silicon base, forms ohmic contact; Organic solvent mainly plays a part to disperse and parcel, and silver powder particles is uniform
Wrap up, make that the silver powder in the conductive silver paste is not easy to produce deposition and oxidation.
The glass binder that present solar cell conductive silver slurry is adopted is a kind of Bi-Si-Pb glass mixed-powder; Though it is low that this glass dust has a softening temperature, advantages such as electric performance stablity, it is higher that this system contains proportion; Pollution to environment is bigger, does not meet environmental requirement.Under the situation that solar cell is popularized day by day, the use of leaded solar cell conductive silver slurry is restricted, will eliminate gradually soon, must develop the environmental protection conductive silver paste of high conduction performance, to satisfy large solar battery production demand.The content of the silver powder in the technology silver slurry is higher than more than 70% at present, and production cost is than higher, and reducing silver slurry cost is that the silver slurry is an important step that reduces the solar battery sheet cost, also can let solar cell have more the market advantage; In existing silver slurry, using the particle diameter of silver powder in addition is consistent basically; If the silver powder particle diameter is excessive, crackle appears in the silk screen printing meeting, and can increase contact resistance like this; If the silver powder particle diameter is too small; Agglomeration traits can appear in silver powder, influences the uniformity that silver powder distributes, and therefore is necessary the particle diameter of silver powder is effectively regulated and control.
Summary of the invention
The objective of the invention is to deficiency to prior art; A kind of efficient lead free solar cell back silver paste and preparation method thereof is provided; Under the prerequisite that satisfies the solar cell electrical property; Make solar cell meet the environmental protection environmental requirement of international market, reduce silver slurry production cost simultaneously, make solar cell have more the market advantage solar cell.
For achieving the above object, the technical scheme that the present invention adopts is following:
Efficient lead free solar cell back silver paste is formed by A, B two parts slurry equal proportion mixing and ball milling, and the weight portion of its two parts constitutive material is:
The A slurry:
1-5 μ m silver powder 40-50,16-25 μ m silver powder 10-15,61-90nm silver powder 10-15, glass dust A 8-12, organic carrier A 15-20, described glass dust A is processed by the raw material of following weight portion: SiO
220-40, Bi
2O
310-20, NaF 5-10, Al
2O
32-8, TiO
22-5, Y
2O
31-5, Co
2O
31-5, described organic carrier A is processed by the raw material of following weight portion: ethylene glycol phenyl ether 30-40, dibutyl phthalate 15-20, the rare glycol ether 10-20 of second, polyvinyl butyral resin 5-10, acetylacetone,2,4-pentanedione silver 2-5, additive 1-5;
The B slurry:
6-10 μ m copper powder 5-10,30-60nm copper powder 5-10, glass dust B 3-6, organic carrier B 5-10, described glass dust B is processed by the raw material of following weight portion: SiO
210-20, B
2O
35-10, BaO5-8, BaO 2-5, Bi
2O
32-5, SnO
21-5, Na
2O 1-3, described organic carrier B is processed by the raw material of following weight portion: phenmethylol 10-20, BC acetate 5-10, propylene glycol monobutyl ether 5-10, ethyl cellulose 2-5, additive 0-3.
The preparation method of efficient lead free solar cell back silver paste may further comprise the steps:
(1) preparation of glass dust A
Taking by weighing each raw material by formulation ratio puts in the silica crucible; Put into 1100-1300 ℃ of electric furnace sintering after mixing; Insulation 20-30 min; Glass metal after the fusing is poured in the cold water; Ball milling is crossed the 200-300 mesh sieve then, cooling; Again 600-700 ℃ of insulation 5-6 hour; Then, quench ball milling again with deionized water; Cross the sieve of different meshes; Collect respectively and obtain 1-5 μ m glass dust, 10-15 μ m glass dust and 20-25 μ m glass dust are used 20-30% salt soak 1-2 hour more respectively; Clean to neutral dry for standby then with deionized water;
(2) preparation of glass dust B
Taking by weighing each raw material by formulation ratio puts in the silica crucible; Put into 1100-1300 ℃ of electric furnace sintering after mixing; Insulation 20-30 min; Glass metal after the fusing is poured in the cold water; Ball milling then; Cross the 200-300 mesh sieve, cooling is again 600-700 ℃ of insulation 5-6 hour; Then; Quench ball milling, the sieve of different meshes excessively again with deionized water; Collect respectively and obtain 10-15 μ m glass dust and 20-25 μ m glass dust; Use 20-30% salt soak 1-2 hour more respectively, clean to neutral dry for standby then with deionized water;
(3) preparation of organic carrier A
Press formulation ratio with ethylene glycol phenyl ether, dibutyl phthalate, the rare glycol ether mixing of second, under 80-110 ℃, add polyvinyl butyral resin, acetylacetone,2,4-pentanedione silver, additive dissolving successively, stirring gets final product;
(4) preparation of organic carrier B
Press formulation ratio with phenmethylol, BC acetate, propylene glycol monobutyl ether mixing, under 80-110 ℃, add ethyl cellulose, additive dissolving successively, stirring gets final product;
(5) preparation of A slurry
The glass dust A of the prepared different-grain diameter of step (1) is added in step (3) the prepared organic carrier A; Stir mixed; Each again 1-5 μ m silver powder, 16-25 μ m silver powder, 61-90nm silver powder of adding successively in 30-40 minute at interval mixed 2-3 hour, obtains the A slurry;
(6) preparation of B slurry
The glass dust B of the prepared different-grain diameter of step (2) is added in step (4) the prepared organic carrier B, and stirring is mixed, and each again 6-10 μ m copper powder, 30-60nm copper powder of adding successively in 30-40 minute at interval mixed 2-3 hour, obtains the B slurry;
(7) mixing and ball milling of A slurry and B slurry
A slurry and B slurry equal proportion are mixed, and ball milling is ground to the slurry fineness less than 10 μ m, transfers viscosity, and viscosity is 120-200Pas, promptly gets back silver paste of solar cell of the present invention.
Described additive is formed by the raw materials mix of following weight portion: glycerine glycerinate 2-5, hexenyl bis-stearamides 0.5-1, polyvinylpyrrolidone 2-5, vinyl diphenyl-methane 0.5-1, diethylene glycol monobutyl ether acetate 2-5, N-(β one aminoethyl)-γ-aminopropyl front three (second) TMOS 1-3,2-Octyl Nitrite 2-4.
Beneficial effect of the present invention is following:
1, not leaded in the silver slurry that the present invention prepares, little to human body and environmental hazard, complete compliance with environmental protection requirements;
2, the present invention has selected for use in the silver slurry with silver powder and other conducting particles of particle diameter and has filled the gap between silver powder, has improved the bulk density of rete, increases interparticle contact area, has reduced the convergent force of rete, thereby has improved the conductive capability of silver-colored slurry;
3, the silver slurry and the silicon chip coefficient of expansion matching that prepare of the present invention is good, shrinks little, the rate of finished products height, resistance is little, can not form pore, can not form crackle;
4, the present invention has added copper powder and can help to reduce silver slurry production cost in electrocondution slurry, improves the electric conductivity of silver slurry simultaneously, thereby has reached the purpose that reduces the solar cell manufacturing cost, has obtained good economic benefit.
Embodiment
Below in conjunction with embodiment the present invention is explained further details.
Embodiment 1
(1) preparation of glass dust A
Get the raw material of following weight portion: SiO
230 parts, Bi
2O
320 parts, 10 parts of NaF, Al
2O
36 parts, TiO
25 parts, Y
2O
35 parts, Co
2O
33 parts, put in the silica crucible, put into 1150 ℃ of electric furnace sintering after mixing, be incubated 30 min, the glass metal after the fusing is poured in the cold water; Ball milling is crossed 200 mesh sieves then, and cooling is again 650 ℃ of insulations 6 hours, then; Quench with deionized water again, ball milling, the sieve of different meshes is collected respectively and is obtained 2 μ m glass dust excessively; 12 μ m glass dust and 25 μ m glass dust are used 25% salt soak 2 hours more respectively, clean to neutral dry for standby then with deionized water;
(2) preparation of glass dust B
Get the raw material of following weight portion: SiO
215 parts, B
2O
310 parts, 6 parts of BaO, 3 parts of BaO, Bi
2O
35 parts, SnO
25 parts, Na
22 parts of O put in the silica crucible, put into 1100 ℃ of electric furnace sintering after mixing, and are incubated 30 min, and the glass metal after the fusing is poured in the cold water; Ball milling is crossed 200 mesh sieves then, and cooling is again 700 ℃ of insulations 5 hours; Then, quench ball milling, the sieve of different meshes excessively again with deionized water; Collect respectively and obtain 12 μ m glass dust and 24 μ m glass dust, use 20% salt soak 2 hours more respectively, clean to neutral dry for standby then with deionized water;
(3) preparation of organic carrier A
Get the raw material of following weight portion: 30 parts of ethylene glycol phenyl ethers, 20 parts of dibutyl phthalates, 20 parts of the rare glycol ethers of second, 7 parts of polyvinyl butyral resins, 3 parts of acetylacetone,2,4-pentanedione silver, 3 parts of additives,
Press formulation ratio with ethylene glycol phenyl ether, dibutyl phthalate, the rare glycol ether mixing of second, under 100 ℃, add polyvinyl butyral resin, acetylacetone,2,4-pentanedione silver, additive dissolving successively, stirring gets final product;
(4) preparation of organic carrier B
Get the raw material of following weight portion: 10 parts of phenmethylols, 10 parts of BC acetates, 10 parts of propylene glycol monobutyl ethers, 4 parts of ethyl celluloses, 1 part of additive,
Press formulation ratio with phenmethylol, BC acetate, propylene glycol monobutyl ether mixing, under 90 ℃, add ethyl cellulose, additive dissolving successively, stirring gets final product;
(5) preparation of A slurry
Get the raw material of following weight portion: 40 parts in 2 μ m silver powder, 18 15 parts in μ m silver powder, 15 parts in 85nm silver powder, 10 parts of glass dust A, 16 parts of organic carrier A,
Glass dust A is added among the organic carrier A, and stirring is mixed, and each again 2 μ m silver powder, 18 μ m silver powder, 85nm silver powder of adding successively in 40 minutes at interval mixed 3 hours, obtains the A slurry;
(6) preparation of B slurry
Get the raw material of following weight portion: 86 parts of μ m copper powders, 10 parts of 50nm copper powders, 4 parts of glass dust B, 8 parts of organic carrier B,
Glass dust B is added among the organic carrier B, and stirring is mixed, and each again 8 μ m copper powders, 50nm copper powder of adding successively in 30 minutes at interval mixed 3 hours, obtains the B slurry;
(7) mixing and ball milling of A slurry and B slurry
A slurry and B slurry equal proportion are mixed, and ball milling is ground to the slurry fineness less than 10 μ m, transfers viscosity, and viscosity is 150Pas, promptly gets back silver paste of solar cell of the present invention.
Described additive is formed by the raw materials mix of following weight portion: 3 parts of glycerine glycerinate, 0.8 part of hexenyl bis-stearamides, 3 parts of polyvinylpyrrolidones, 0.6 part of vinyl diphenyl-methane, 4 parts of diethylene glycol monobutyl ether acetates, N-(β one aminoethyl)-γ-2 parts of aminopropyl front three (second) TMOSs, 3 parts of 2-Octyl Nitrites.
Adopt screen process press that the silver slurry is printed on 125mm * 125mm Si substrate,, carry out quick fired electrodes lead-in wire at 880 ℃ more then 180 ℃ of dryings; The contact conductor surface silvery white of processing behind the high temperature sintering, smooth zero defect, peel strength 10 N/cm; Soldering is functional, side's resistance＜10 Siements/sq, and the solar cell photoelectric transformation efficiency of preparation is 19.7%;, the tensile test result is Fu Zheli>10N/mm
2
Embodiment 2
(1) preparation of glass dust A
Get the raw material of following weight portion: SiO
240 parts, Bi
2O
315 parts, 8 parts of NaF, Al
2O
36 parts, TiO
24 parts, Y
2O
32 parts, Co
2O
33 parts, put in the silica crucible, put into 1250 ℃ of electric furnace sintering after mixing, be incubated 30 min, the glass metal after the fusing is poured in the cold water; Ball milling is crossed 300 mesh sieves then, and cooling is again 700 ℃ of insulations 6 hours, then; Quench with deionized water again, ball milling, the sieve of different meshes is collected respectively and is obtained 3 μ m glass dust excessively; 12 μ m glass dust and 24 μ m glass dust are used 30% salt soak 2 hours more respectively, clean to neutral dry for standby then with deionized water;
(2) preparation of glass dust B
Get the raw material of following weight portion: SiO
220 parts, B
2O
310 parts, 5 parts of BaO, 3 parts of BaO, Bi
2O
32 parts, SnO
24 parts, Na
22 parts of O put in the silica crucible, put into 1100 ℃ of electric furnace sintering after mixing, and are incubated 30 min, and the glass metal after the fusing is poured in the cold water; Ball milling is crossed 300 mesh sieves then, and cooling is again 650 ℃ of insulations 6 hours; Then, quench ball milling, the sieve of different meshes excessively again with deionized water; Collect respectively and obtain 15 μ m glass dust and 25 μ m glass dust, use 25% salt soak 2 hours more respectively, clean to neutral dry for standby then with deionized water;
(3) preparation of organic carrier A
Get the raw material of following weight portion: 40 parts of ethylene glycol phenyl ethers, 15 parts of dibutyl phthalates, 18 parts of the rare glycol ethers of second, 10 parts of polyvinyl butyral resins, 5 parts of acetylacetone,2,4-pentanedione silver, 5 parts of additives,
Press formulation ratio with ethylene glycol phenyl ether, dibutyl phthalate, the rare glycol ether mixing of second, under 108 ℃, add polyvinyl butyral resin, acetylacetone,2,4-pentanedione silver, additive dissolving successively, stirring gets final product;
(4) preparation of organic carrier B
Get the raw material of following weight portion: 20 parts of phenmethylols, 8 parts of BC acetates, 8 parts of propylene glycol monobutyl ethers, 4 parts of ethyl celluloses, 2 parts of additives,
Press formulation ratio with phenmethylol, BC acetate, propylene glycol monobutyl ether mixing, under 102 ℃, add ethyl cellulose, additive dissolving successively, stirring gets final product;
(5) preparation of A slurry
Get the raw material of following weight portion: 50 parts in 5 μ m silver powder, 18 15 parts in μ m silver powder, 15 parts in 78nm silver powder, 12 parts of glass dust A, 20 parts of organic carrier A,
Glass dust A is added among the organic carrier A, and stirring is mixed, and each again 5 μ m silver powder, 18 μ m silver powder, 78nm silver powder of adding successively in 40 minutes at interval mixed 3 hours, obtains the A slurry;
(6) preparation of B slurry
Get the raw material of following weight portion: 7 10 parts of μ m copper powders, 8 parts of 54nm copper powders, 5 parts of glass dust B, 8 parts of organic carrier B,
Glass dust B is added among the organic carrier B, and stirring is mixed, and is at interval each again, adds 7 μ m copper powders, 54nm copper powder successively, and mixed 3 hours, obtains the B slurry in 35 minutes;
(7) mixing and ball milling of A slurry and B slurry
A slurry and B slurry equal proportion are mixed, and ball milling is ground to the slurry fineness less than 10 μ m, transfers viscosity, and viscosity is 180Pas, promptly gets back silver paste of solar cell of the present invention.
Described additive is formed by the raw materials mix of following weight portion: 5 parts of glycerine glycerinate, 0.8 part of hexenyl bis-stearamides, 3 parts of polyvinylpyrrolidones, 0.8 part of vinyl diphenyl-methane, 4 parts of diethylene glycol monobutyl ether acetates, N-(β one aminoethyl)-γ-2 parts of aminopropyl front three (second) TMOSs, 3 parts of 2-Octyl Nitrites.
Adopt screen process press that the silver slurry is printed on 125mm * 125mm Si substrate,, carry out quick fired electrodes lead-in wire at 880 ℃ more then 180 ℃ of dryings; The contact conductor surface silvery white of processing behind the high temperature sintering, smooth zero defect, peel strength 12 N/cm; Soldering is functional, side's resistance＜10 Siements/sq, and the solar cell photoelectric transformation efficiency of preparation is 20.2%;, the tensile test result is Fu Zheli>12N/mm
2
Claims (3)
1. an efficient lead free solar cell back silver paste is characterized in that, it is formed by A, B two parts slurry equal proportion mixing and ball milling, and the weight portion of its two parts constitutive material is:
The A slurry:
1-5 μ m silver powder 40-50,16-25 μ m silver powder 10-15,61-90nm silver powder 10-15, glass dust A 8-12, organic carrier A 15-20, described glass dust A is processed by the raw material of following weight portion: SiO
220-40, Bi
2O
310-20, NaF 5-10, Al
2O
32-8, TiO
22-5, Y
2O
31-5, Co
2O
31-5, described organic carrier A is processed by the raw material of following weight portion: ethylene glycol phenyl ether 30-40, dibutyl phthalate 15-20, the rare glycol ether 10-20 of second, polyvinyl butyral resin 5-10, acetylacetone,2,4-pentanedione silver 2-5, additive 1-5;
The B slurry:
6-10 μ m copper powder 5-10,30-60nm copper powder 5-10, glass dust B 3-6, organic carrier B 5-10, described glass dust B is processed by the raw material of following weight portion: SiO
210-20, B
2O
35-10, BaO5-8, BaO 2-5, Bi
2O
32-5, SnO
21-5, Na
2O 1-3, described organic carrier B is processed by the raw material of following weight portion: phenmethylol 10-20, BC acetate 5-10, propylene glycol monobutyl ether 5-10, ethyl cellulose 2-5, additive 0-3.
2. the preparation method of an efficient lead free solar cell back silver paste as claimed in claim 1 is characterized in that may further comprise the steps:
(1) preparation of glass dust A
Taking by weighing each raw material by formulation ratio puts in the silica crucible; Put into 1100-1300 ℃ of electric furnace sintering after mixing; Insulation 20-30 min; Glass metal after the fusing is poured in the cold water; Ball milling is crossed the 200-300 mesh sieve then, cooling; Again 600-700 ℃ of insulation 5-6 hour; Then, quench ball milling again with deionized water; Cross the sieve of different meshes; Collect respectively and obtain 1-5 μ m glass dust, 10-15 μ m glass dust and 20-25 μ m glass dust are used 20-30% salt soak 1-2 hour more respectively; Clean to neutral dry for standby then with deionized water;
(2) preparation of glass dust B
Taking by weighing each raw material by formulation ratio puts in the silica crucible; Put into 1100-1300 ℃ of electric furnace sintering after mixing; Insulation 20-30 min; Glass metal after the fusing is poured in the cold water; Ball milling then; Cross the 200-300 mesh sieve, cooling is again 600-700 ℃ of insulation 5-6 hour; Then; Quench ball milling, the sieve of different meshes excessively again with deionized water; Collect respectively and obtain 10-15 μ m glass dust and 20-25 μ m glass dust; Use 20-30% salt soak 1-2 hour more respectively, clean to neutral dry for standby then with deionized water;
(3) preparation of organic carrier A
Press formulation ratio with ethylene glycol phenyl ether, dibutyl phthalate, the rare glycol ether mixing of second, under 80-110 ℃, add polyvinyl butyral resin, acetylacetone,2,4-pentanedione silver, additive dissolving successively, stirring gets final product;
(4) preparation of organic carrier B
Press formulation ratio with phenmethylol, BC acetate, propylene glycol monobutyl ether mixing, under 80-110 ℃, add ethyl cellulose, additive dissolving successively, stirring gets final product;
(5) preparation of A slurry
The glass dust A of the prepared different-grain diameter of step (1) is added in step (3) the prepared organic carrier A; Stir mixed; Each again 1-5 μ m silver powder, 16-25 μ m silver powder, 61-90nm silver powder of adding successively in 30-40 minute at interval mixed 2-3 hour, obtains the A slurry;
(6) preparation of B slurry
The glass dust B of the prepared different-grain diameter of step (2) is added in step (4) the prepared organic carrier B, and stirring is mixed, and each again 6-10 μ m copper powder, 30-60nm copper powder of adding successively in 30-40 minute at interval mixed 2-3 hour, obtains the B slurry;
(7) mixing and ball milling of A slurry and B slurry
A slurry and B slurry equal proportion are mixed, and ball milling is ground to the slurry fineness less than 10 μ m, transfers viscosity, and viscosity is 120-200Pas, promptly gets back silver paste of solar cell of the present invention.
3. efficient lead free solar cell back silver paste according to claim 1 and 2; It is characterized in that described additive is formed by the raw materials mix of following weight portion: glycerine glycerinate 2-5, hexenyl bis-stearamides 0.5-1, polyvinylpyrrolidone 2-5, vinyl diphenyl-methane 0.5-1, diethylene glycol monobutyl ether acetate 2-5, N-(β one aminoethyl)-γ-aminopropyl front three (second) TMOS 1-3,2-Octyl Nitrite 2-4.
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| CN104037621A (en) * | 2014-05-12 | 2014-09-10 | 铜陵市超远精密电子科技有限公司 | High-conductive performance printed circuit board silver paste and preparation method thereof |
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| CN104037621A (en) * | 2014-05-12 | 2014-09-10 | 铜陵市超远精密电子科技有限公司 | High-conductive performance printed circuit board silver paste and preparation method thereof |
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| CN105006267A (en) * | 2015-08-10 | 2015-10-28 | 浙江凯盈新材料有限公司 | Silver powder based on processing of aminosilane coupling agent, preparation method and application thereof |
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| CN115073005A (en) * | 2022-07-21 | 2022-09-20 | 西安宏星电子浆料科技股份有限公司 | Anti-precipitation LTCC insulating medium slurry |
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