CN102831960B - Lead-free conducting silver paste used for silicon solar cell and preparation method thereof - Google Patents
Lead-free conducting silver paste used for silicon solar cell and preparation method thereof Download PDFInfo
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- CN102831960B CN102831960B CN201210304688.3A CN201210304688A CN102831960B CN 102831960 B CN102831960 B CN 102831960B CN 201210304688 A CN201210304688 A CN 201210304688A CN 102831960 B CN102831960 B CN 102831960B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000004332 silver Substances 0.000 title claims abstract description 27
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 11
- 239000010703 silicon Substances 0.000 title claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000011521 glass Substances 0.000 claims description 57
- 239000002002 slurry Substances 0.000 claims description 56
- 239000000428 dust Substances 0.000 claims description 53
- 239000002994 raw material Substances 0.000 claims description 29
- 239000000654 additive Substances 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 230000000996 additive effect Effects 0.000 claims description 17
- 238000010791 quenching Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- 238000009472 formulation Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 8
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 8
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 claims description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 8
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 241000779819 Syncarpia glomulifera Species 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000008240 homogeneous mixture Substances 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- 239000001739 pinus spp. Substances 0.000 claims description 8
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims description 8
- 229940036248 turpentine Drugs 0.000 claims description 8
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- KOEFSMLBFZGZLD-UHFFFAOYSA-L [bis(2-ethylhexoxy)-oxidophosphaniumyl] dihydrogen phosphate [bis(2-ethylhexoxy)-oxidophosphaniumyl] phosphate ethane-1,2-diolate titanium(4+) Chemical compound [Ti+4].[O-]CC[O-].CCCCC(CC)CO[P+]([O-])(OCC(CC)CCCC)OP(O)(O)=O.CCCCC(CC)CO[P+]([O-])(OCC(CC)CCCC)OP([O-])([O-])=O KOEFSMLBFZGZLD-UHFFFAOYSA-L 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 239000004359 castor oil Substances 0.000 claims description 4
- 235000019438 castor oil Nutrition 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
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 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 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000008602 contraction Effects 0.000 abstract 1
- -1 butyl carbitol acetates Chemical class 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 230000000171 quenching effect Effects 0.000 description 6
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007547 defect Effects 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
- 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
- QBUKAFSEUHGMMX-MTJSOVHGSA-N (5z)-5-[[3-(1-hydroxyethyl)thiophen-2-yl]methylidene]-10-methoxy-2,2,4-trimethyl-1h-chromeno[3,4-f]quinolin-9-ol Chemical group C1=CC=2NC(C)(C)C=C(C)C=2C2=C1C=1C(OC)=C(O)C=CC=1O\C2=C/C=1SC=CC=1C(C)O QBUKAFSEUHGMMX-MTJSOVHGSA-N 0.000 description 1
- 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
- 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
- 238000001556 precipitation Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
Abstract
The invention discloses a lead-free conducting silver paste used for a silicon solar cell and a preparation method thereof. The lead-free conducting silver paste is formed by mixing a part A paste material and a part B paste material in equal proportion through ball milling. The silver paste prepared in the invention does not contain lead, has small harm to human bodies and the environment and completely conforms to the environmental protection requirement. In the invention, silver powder with the same particle size is selected, other conducting particles are selected to fill gaps among the silver powder, the stacking density of a film is increased, the contact area among the particles is increased, the contraction force of the film is reduced, and the conductivity of the silver paste is increased. In the invention, aluminum powder and copper powder are added into the conducting paste materials, so that the production cost of the silver paste can be reduced, the conductivity of the silver paste is increased, the purpose of lowering the manufacturing cost of the solar cell is achieved, and good economic benefits are achieved.
Description
Technical field
The present invention relates to a kind of unleaded conductive silver paste and preparation method thereof for silicon solar cell, belong to solar cell conductive paste preparing technical field.
Background technology
the conductive silver paste of solar cell is prepared from by different proportionings by 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 the silver powder in conductive silver paste be not easy to produce precipitation and oxidation.
The glass binder that solar cell conductive silver slurry adopts is at present a kind of Bi-Si-Pb glass mixed-powder, although it is low that this glass dust has softening temperature, the advantages such as electric performance stablity, this system is higher containing lead proportion, pollution to environment is larger, does not meet environmental requirement.In the situation that solar cell is day by day universal, 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 meet large solar battery production demand.The content of the silver powder in technology silver slurry is higher than more than 70% at present, and production cost is higher, and reducing silver slurry cost is that silver slurry is an important step that reduces solar battery sheet cost, also can allow solar cell have more the market advantage; In existing silver slurry, using the particle diameter of silver powder is in addition consistent substantially, if silver powder particle diameter is excessive like this, silk screen printing there will be crackle, and can increase contact resistance, if silver powder particle diameter is too small, silver powder there will be agglomeration traits, affects the uniformity that silver powder distributes, and is therefore necessary the particle diameter of silver powder to carry out Effective Regulation.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art; a kind of unleaded conductive silver paste and preparation method thereof for silicon solar cell is provided; meeting under the prerequisite of solar cell electrical property; make solar cell meet the environmental protection environmental requirement of international market to solar cell; reduce silver slurry production cost simultaneously, make solar cell have more the market advantage.
For achieving the above object, the technical solution used in the present invention is as follows:
Silicon solar cell is formed by A, B two parts slurry equal proportion mixing and ball milling with unleaded conductive silver paste, and the weight portion of its two parts constitutive material is:
A slurry:
1-5 μ m silver powder 40-50,30-60nm silver powder 10-15,1-5 μ m copper powder 10-15, glass dust A 8-12, organic carrier A 15-20, described glass dust A is made by the raw material of following weight portion: ZnO 20-40, SiO
210-20, B
2o
310-20, La
2o
32-8, TiO
22-5, SnO
21-5, Na
2o 1-5, described organic carrier A is made by the raw material of following weight portion: turpentine alcohol 30-40, butyl carbitol acetate 15-20, methylisobutylketone 10-20, epoxy resin 5-10, neodecanoic acid silver 2-5, additive 1-5;
B slurry:
1-5 μ m aluminium powder 5-10,61-90nm copper powder 5-10, glass dust B 3-6, organic carrier B 5-10, described glass dust B is made by the raw material of following weight portion: SiO
210-20, B
2o
35-10, Bi
2o
35-8, BaO 2-5, TiO
22-5, Y
2o
31-5, Co
2o
31-3, described organic carrier B is made by the raw material of following weight portion: butyl carbitol 10-20, butyl carbitol acetate 5-10, the rare glycol ether 5-10 of second, carboxymethyl cellulose 2-5, additive 0-3.
The preparation method of unleaded conductive silver paste for silicon solar cell, comprises the following steps:
(1) preparation of glass dust A
By formulation ratio, take each raw material, put into vibrations ball mill ball milling 1-2h, homogeneous mixture after ball milling, be put in 1000-1200 ℃ of high temperature sintering furnace and found 2-3 h, then with normal temperature, go dried up quenching, after 80-90 ℃ of oven dry, shake grinding, cross 200-300 mesh sieve, cooling, again at 600-700 ℃ of insulation 5-6 h, then, with deionized water, quench again, grind, cross the sieve of different meshes, collect and obtain 1-5 μ m glass dust respectively, 10-15 μ m glass dust and 20-25 μ m glass dust, use respectively again 20-30% salt acid soak 1-2 h, then with deionized water, clean to neutrality, dry for standby,
(2) preparation of glass dust B
By formulation ratio, take each raw material, put into vibrations ball mill ball milling 1-2h, homogeneous mixture after ball milling, be put in 1000-1200 ℃ of high temperature sintering furnace and found 2-3 h, then with normal temperature, go dried up quenching, after 80-90 ℃ of oven dry, shake grinding, cross 200-300 mesh sieve, cooling, again at 600-700 ℃ of insulation 5-6 h, then, with deionized water, quench again, grind, cross the sieve of different meshes, collect and obtain 1-5 μ m glass dust respectively, 10-15 μ m glass dust and 20-25 μ m glass dust, use respectively again 20-30% salt acid soak 1-2 h, then with deionized water, clean to neutrality, dry for standby,
(3) preparation of organic carrier A
By formulation ratio, turpentine alcohol, butyl carbitol acetate, methylisobutylketone are mixed, at 80-110 ℃, add successively epoxy resin, neodecanoic acid silver, additive to dissolve, stir;
(4) preparation of organic carrier B
By formulation ratio, butyl carbitol, butyl carbitol acetate, the rare glycol ether of second are mixed, at 80-110 ℃, add successively carboxymethyl cellulose, additive to dissolve, stir;
(5) preparation of A slurry
The glass dust A of the prepared different-grain diameter of step (1) is added in the prepared organic carrier A of step (3), stir mixed, every minor tick 30-40 minute adds 1-5 μ m silver powder, 30-60nm silver powder, 1-5 μ m copper powder successively again, and mixed 2-3 h, obtains A slurry;
(6) preparation of B slurry
The glass dust B of the prepared different-grain diameter of step (2) is added in the prepared organic carrier B of step (4), stir mixedly, more every minor tick 30-40 minute adds 1-5 μ m aluminium powder, 61-90nm copper powder successively, and mixed 2-3 h, obtains 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 slurry fineness and is less than 10 μ m, adjusts viscosity, and viscosity is 120-200Pas, obtains solar cell conductive silver slurry of the present invention.
Described additive is mixed by the raw material of following weight portion: castor oil 2-5, glyceryl tristearate 0.5-1, polyvinylpyrrolidone 2-5, dodecyl sodium sulfate 0.5-1, polyvinyl alcohol 2-5, Di(dioctylpyrophosphato) ethylene titanate 1-3, butyl polyacrylate 2-4.
Beneficial effect of the present invention is as follows:
1, not leaded in the silver slurry that the present invention prepares, little to human body and environmental hazard, meet environmental requirement completely;
2, the present invention has selected with silver powder and other conducting particles of particle diameter and has filled the gap between silver powder in silver slurry, 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 present invention prepares silver slurry and silicon chip coefficient of expansion matching are good, shrink littlely, and rate of finished products is high, and resistance is little, can not form pore, can not form crackle;
4, the present invention has added aluminium powder and copper powder and can contribute to reduce silver slurry production cost in electrocondution slurry, improves the electric conductivity of silver slurry simultaneously, thereby has reached the object that reduces solar cell manufacturing cost, has obtained good economic benefit.
Embodiment
Below in conjunction with embodiment, the present invention is described in further details.
Embodiment 1
(1) preparation of glass dust A
Get 20 parts of the raw material of following weight portion: ZnO, SiO
220 parts, B
2o
315 parts, La
2o
34 parts, TiO
23 parts, SnO
23 parts, Na
22 parts of O, put into vibrations ball mill ball milling 2h, homogeneous mixture after ball milling, be put in 1000 ℃ of high temperature sintering furnaces and found 3 h, then with normal temperature, go dried up quenching, after 90 ℃ of oven dry, shake grinding, cross 300 mesh sieves, cooling, then at 650 ℃ of insulation 6 h, then, then quench with deionized water, grind, cross the sieve of different meshes, collect and obtain 3 μ m glass dust, 15 μ m glass dust and 22 μ m glass dust respectively, use respectively again 25% salt acid soak 2 h, then with deionized water, clean to neutrality dry for standby;
(2) preparation of glass dust B
Get the raw material of following weight portion: SiO
216 parts, B
2o
38 parts, Bi
2o
36 parts, 4 parts of BaO, TiO
25 parts, Y
2o
33 parts, Co
2o
32 parts, put into vibrations ball mill ball milling 1h, homogeneous mixture after ball milling, be put in 1000-1200 ℃ of high temperature sintering furnace and found 2 h, then with normal temperature, go dried up quenching, after 90 ℃ of oven dry, shake grinding, cross 300 mesh sieves, cooling, then at 600 ℃ of insulation 6 h, then, then quench with deionized water, grind, cross the sieve of different meshes, collect and obtain 2 μ m glass dust, 10 μ m glass dust and 23 μ m glass dust respectively, use respectively again 20% salt acid soak 2 h, then with deionized water, clean to neutrality dry for standby;
(3) preparation of organic carrier A
Get the raw material of following weight portion: 30 parts of turpentine alcohol, 20 parts of butyl carbitol acetates, 20 parts of methylisobutylketones, 8 parts of epoxy resin, 3 parts of neodecanoic acid silver, 3 parts of additives,
By formulation ratio, turpentine alcohol, butyl carbitol acetate, methylisobutylketone are mixed, at 96 ℃, add successively epoxy resin, neodecanoic acid silver, additive to dissolve, stir;
(4) preparation of organic carrier B
Get the raw material of following weight portion: 15 parts of butyl carbitol, 8 parts of butyl carbitol acetates, 7 parts of the rare glycol ethers of second, 3 parts of carboxymethyl celluloses, 1 part of additive,
By formulation ratio, butyl carbitol, butyl carbitol acetate, the rare glycol ether of second are mixed, at 92 ℃, add successively carboxymethyl cellulose, additive to dissolve, stir;
(5) preparation of A slurry
Get the raw material of following weight portion: 2 40 parts, μ m silver powder, 15 parts, 56nm silver powder, 5 15 parts of μ m copper powders, 10 parts of glass dust A, 18 parts of organic carrier A,
Glass dust A is added in organic carrier A, stir mixedly, more every minor tick adds 2 μ m silver powder, 56nm silver powder, 5 μ m copper powders for 30 minutes successively, and mixed 3 h, obtain A slurry;
(6) preparation of B slurry
Get the raw material of following weight portion: 5 10 parts of μ m aluminium powders, 6 parts of 85nm copper powders, 4 parts of glass dust B, 8 parts of organic carrier B,
Glass dust B is added in organic carrier B, stir mixedly, more every minor tick adds 5 μ m aluminium powders, 85nm copper powder for 30 minutes successively, and mixed 3 h, obtain 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 slurry fineness and is less than 10 μ m, adjusts viscosity, and viscosity is 150Pas, obtains solar cell conductive silver slurry of the present invention.
Described additive is mixed by the raw material of following weight portion: 3 parts of castor oil, 0.6 part of glyceryl tristearate, 2 parts of polyvinylpyrrolidones, 0.8 part of dodecyl sodium sulfate, 3 parts of polyvinyl alcohol, 2 parts of Di(dioctylpyrophosphato) ethylene titanate, 3 parts of butyl polyacrylates.
Adopt screen process press that silver slurry is printed on 125mm * 125mm Si substrate, then dry at 180 ℃, at 800 ℃, carry out quick fired electrodes lead-in wire again, the contact conductor of making after high temperature sintering surface silvery white, smooth zero defect, peel strength 8 N/cm, soldering is functional, sheet resistance < 8 Siements/sq, and the solar cell photoelectric transformation efficiency of preparation is 19.3%,, tensile test result is adhesive force >12N/mm
2.
Embodiment 2
(1) preparation of glass dust A
Get 40 parts of the raw material of following weight portion: ZnO, SiO
215 parts, B
2o
315 parts, La
2o
38 parts, TiO
25 parts, SnO
22 parts, Na
23 parts of O, put into vibrations ball mill ball milling 2h, homogeneous mixture after ball milling, be put in 1200 ℃ of high temperature sintering furnaces and found 3 h, then with normal temperature, go dried up quenching, after 90 ℃ of oven dry, shake grinding, cross 200 mesh sieves, cooling, then at 700 ℃ of insulation 6 h, then, then quench with deionized water, grind, cross the sieve of different meshes, collect and obtain 5 μ m glass dust, 15 μ m glass dust and 25 μ m glass dust respectively, use respectively again 30% salt acid soak 2 h, then with deionized water, clean to neutrality dry for standby;
(2) preparation of glass dust B
Get the raw material of following weight portion: SiO
220 parts, B
2o
310 parts, Bi
2o
36 parts, 3 parts of BaO, TiO
24 parts, Y
2o
34 parts, Co
2o
32 parts, put into vibrations ball mill ball milling 1h, homogeneous mixture after ball milling, be put in 1100 ℃ of high temperature sintering furnaces and found 2 h, then with normal temperature, go dried up quenching, after 90 ℃ of oven dry, shake grinding, cross 200 mesh sieves, cooling, then 650 ℃ of insulations 6 hours, then, with deionized water, quench again, grind, cross the sieve of different meshes, collect and obtain 2 μ m glass dust respectively, 12 μ m glass dust and 24 μ m glass dust, use respectively again 20-30% salt acid soak 1-2 hour, then with deionized water, clean to neutrality dry for standby;
(3) preparation of organic carrier A
Get the raw material of following weight portion: 40 parts of turpentine alcohol, 15 parts of butyl carbitol acetates, 20 parts of methylisobutylketones, 10 parts of epoxy resin, 5 parts of neodecanoic acid silver, 3 parts of additives,
By formulation ratio, turpentine alcohol, butyl carbitol acetate, methylisobutylketone are mixed, at 105 ℃, add successively epoxy resin, neodecanoic acid silver, additive to dissolve, stir;
(4) preparation of organic carrier B
Get the raw material of following weight portion: 20 parts of butyl carbitol, 10 parts of butyl carbitol acetates, 8 parts of the rare glycol ethers of second, 5 parts of carboxymethyl celluloses, 2 parts of additives,
By formulation ratio, butyl carbitol, butyl carbitol acetate, the rare glycol ether of second are mixed, at 100 ℃, add successively carboxymethyl cellulose, additive to dissolve, stir;
(5) preparation of A slurry
Get the raw material of following weight portion: 5 50 parts, μ m silver powder, 10 parts, 55nm silver powder, 3 10 parts of μ m copper powders, 12 parts of glass dust A, 20 parts of organic carrier A,
Glass dust A is added in organic carrier A, stir mixedly, more every minor tick adds 5 μ m silver powder, 55nm silver powder, 3 μ m copper powders for 40 minutes successively, and mixed 3 h, obtain A slurry;
(6) preparation of B slurry
Get the raw material of following weight portion: 4 10 parts of μ m aluminium powders, 10 parts of 65nm copper powders, 5 parts of glass dust B, 10 parts of organic carrier B,
Glass dust B is added in organic carrier B, stir mixedly, more every minor tick adds 4 μ m aluminium powders, 65nm copper powder for 40 minutes successively, and mixed 3 h, obtain 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 slurry fineness and is less than 10 μ m, adjusts viscosity, and viscosity is 150Pas, obtains solar cell conductive silver slurry of the present invention.
Described additive is mixed by the raw material of following weight portion: 3 parts of castor oil, 0.8 part of glyceryl tristearate, 4 parts of polyvinylpyrrolidones, 0.6 part of dodecyl sodium sulfate, 3 parts of polyvinyl alcohol, 2 parts of Di(dioctylpyrophosphato) ethylene titanate, 3 parts of butyl polyacrylates.
Adopt screen process press that silver slurry is printed on 125mm * 125mm Si substrate, then dry at 180 ℃, at 800 ℃, carry out quick fired electrodes lead-in wire again, the contact conductor of making after high temperature sintering surface silvery white, smooth zero defect, peel strength 10 N/cm, soldering is functional, sheet resistance < 9 Siements/sq, and the solar cell photoelectric transformation efficiency of preparation is 19.6%,, tensile test result is adhesive force >10N/mm
2.
Claims (2)
1. the unleaded conductive silver paste of silicon solar cell, 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:
A slurry:
1-5 μ m silver powder 40-50,30-60nm silver powder 10-15,1-5 μ m copper powder 10-15, glass dust A 8-12, organic carrier A 15-20, described glass dust A is made by the raw material of following weight portion: ZnO 20-40, SiO
210-20, B
2o
310-20, La
2o
32-8, TiO
22-5, SnO
21-5, Na
2o 1-5, described organic carrier A is made by the raw material of following weight portion: turpentine alcohol 30-40, butyl carbitol acetate 15-20, methylisobutylketone 10-20, epoxy resin 5-10, neodecanoic acid silver 2-5, additive 1-5;
B slurry:
1-5 μ m aluminium powder 5-10,61-90nm copper powder 5-10, glass dust B 3-6, organic carrier B 5-10, described glass dust B is made by the raw material of following weight portion: SiO
210-20, B
2o
35-10, Bi
2o
35-8, BaO 2-5, TiO
22-5, Y
2o
31-5, Co
2o
31-3, described organic carrier B is made by the raw material of following weight portion: butyl carbitol 10-20, butyl carbitol acetate 5-10, the rare glycol ether 5-10 of second, carboxymethyl cellulose 2-5, additive 0-3;
Described additive is mixed by the raw material of following weight portion: castor oil 2-5, glyceryl tristearate 0.5-1, polyvinylpyrrolidone 2-5, dodecyl sodium sulfate 0.5-1, polyvinyl alcohol 2-5, Di(dioctylpyrophosphato) ethylene titanate 1-3, butyl polyacrylate 2-4.
2. a preparation method for unleaded conductive silver paste for silicon solar cell as claimed in claim 1, is characterized in that comprising the following steps:
(1) preparation of glass dust A
By formulation ratio, take each raw material, put into vibrations ball mill ball milling 1-2h, homogeneous mixture after ball milling, be put in 1000-1200 ℃ of high temperature sintering furnace and found 2-3 h, then by deionized water at normal temperature, quench, after 80-90 ℃ of oven dry, shake grinding, cross 200-300 mesh sieve, cooling, again at 600-700 ℃ of insulation 5-6 h, then, with deionized water, quench again, grind, cross the sieve of different meshes, collect and obtain 1-5 μ m glass dust respectively, 10-15 μ m glass dust and 20-25 μ m glass dust, use respectively again 20-30% salt acid soak 1-2 h, then with deionized water, clean to neutrality, dry for standby,
(2) preparation of glass dust B
By formulation ratio, take each raw material, put into vibrations ball mill ball milling 1-2h, homogeneous mixture after ball milling, be put in 1000-1200 ℃ of high temperature sintering furnace and found 2-3 h, then by deionized water at normal temperature, quench, after 80-90 ℃ of oven dry, shake grinding, cross 200-300 mesh sieve, cooling, again at 600-700 ℃ of insulation 5-6 h, then, with deionized water, quench again, grind, cross the sieve of different meshes, collect and obtain 1-5 μ m glass dust respectively, 10-15 μ m glass dust and 20-25 μ m glass dust, use respectively again 20-30% salt acid soak 1-2 h, then with deionized water, clean to neutrality, dry for standby,
(3) preparation of organic carrier A
By formulation ratio, turpentine alcohol, butyl carbitol acetate, methylisobutylketone are mixed, at 80-110 ℃, add successively epoxy resin, neodecanoic acid silver, additive to dissolve, stir;
(4) preparation of organic carrier B
By formulation ratio, butyl carbitol, butyl carbitol acetate, the rare glycol ether of second are mixed, at 80-110 ℃, add successively carboxymethyl cellulose, additive to dissolve, stir;
(5) preparation of A slurry
The glass dust A of the prepared different-grain diameter of step (1) is added in the prepared organic carrier A of step (3), stir mixed, every minor tick 30-40 minute adds 1-5 μ m silver powder, 30-60nm silver powder, 1-5 μ m copper powder successively again, and mixed 2-3 h, obtains A slurry;
(6) preparation of B slurry
The glass dust B of the prepared different-grain diameter of step (2) is added in the prepared organic carrier B of step (4), stir mixedly, more every minor tick 30-40 minute adds 1-5 μ m aluminium powder, 61-90nm copper powder successively, and mixed 2-3 h, obtains 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 slurry fineness and is less than 10 μ m, adjusts viscosity, and viscosity is 120-200Pas, obtains solar cell conductive silver slurry of the present invention.
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| CN101770829A (en) * | 2010-03-16 | 2010-07-07 | 彩虹集团公司 | Special silver electrode paste for touch screen and preparation method thereof |
| CN102324263A (en) * | 2011-07-04 | 2012-01-18 | 江苏瑞德新能源科技有限公司 | Silver paste for solar cells and preparation method thereof |
| CN102522140A (en) * | 2011-12-27 | 2012-06-27 | 彩虹集团公司 | Aluminum paste for silicon-based solar cell and preparation method for aluminum paste |
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| US8987586B2 (en) * | 2010-08-13 | 2015-03-24 | Samsung Electronics Co., Ltd. | Conductive paste and electronic device and solar cell including an electrode formed using the conductive paste |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101770829A (en) * | 2010-03-16 | 2010-07-07 | 彩虹集团公司 | Special silver electrode paste for touch screen and preparation method thereof |
| CN102324263A (en) * | 2011-07-04 | 2012-01-18 | 江苏瑞德新能源科技有限公司 | Silver paste for solar cells and preparation method thereof |
| CN102522140A (en) * | 2011-12-27 | 2012-06-27 | 彩虹集团公司 | Aluminum paste for silicon-based solar cell and preparation method for aluminum paste |
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Denomination of invention: Lead free conductive silver paste and its preparation method for silicon solar cells Effective date of registration: 20231213 Granted publication date: 20140730 Pledgee: China Construction Bank Corporation Feidong sub branch Pledgor: CHINALAND SOLAR ENERGY Co.,Ltd. Registration number: Y2023980071321 |