CN102831958B - Silver paste for environmental-friendly lead-free silicon solar cell front electrode and preparation method of silver paste - Google Patents
Silver paste for environmental-friendly lead-free silicon solar cell front electrode and preparation method of silver paste Download PDFInfo
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- CN102831958B CN102831958B CN201210304657.8A CN201210304657A CN102831958B CN 102831958 B CN102831958 B CN 102831958B CN 201210304657 A CN201210304657 A CN 201210304657A CN 102831958 B CN102831958 B CN 102831958B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 41
- 239000004332 silver Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 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
- 239000002002 slurry Substances 0.000 claims abstract description 58
- 238000002156 mixing Methods 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011521 glass Substances 0.000 claims description 53
- 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
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 28
- 239000002994 raw material Substances 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 16
- 238000009413 insulation Methods 0.000 claims description 16
- 238000010791 quenching Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 12
- 238000009472 formulation Methods 0.000 claims description 12
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 8
- 229910004298 SiO 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
- 125000006038 hexenyl group Chemical group 0.000 claims description 8
- 229920000058 polyacrylate Polymers 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 8
- 229920000120 polyethyl acrylate Polymers 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 6
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-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
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 abstract 2
- 230000008602 contraction Effects 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 238000012856 packing Methods 0.000 abstract 1
- 239000001993 wax Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- -1 butyl carbitol acetates Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 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
- 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
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- Conductive Materials (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a silver paste for an environmental-friendly lead-free silicon solar cell front electrode and a preparation method of the silver paste. The aluminum powder mixed silver paste is prepared from a slurry A and a slurry B through mixing and ball-grinding at an equal proportion. The silver paste prepared by adopting the preparation method does not contain lead, is little in damage to a human body and an environment, and completely accords with the requirement of environmental friendliness. According to the invention, silver powder with same particle diameter and other conductive particles are selected to be filled in gaps among the silver powder, thus the packing density of a membrane layer is increased, the contact area among the particles is increased, and the contraction force of the membrane layer is lowered, thus the conduction capacity of the silver paste is increased. According to the invention, copper powder and aluminum powder are added in the silver paste, thus the production cost of the silver paste is favorably lowered, and the conduction property of the silver paste is improved, therefore, the purpose of reducing manufacture cost of a solar cell is achieved, and a better economic benefit is obtained.
Description
Technical field
The present invention relates to a kind of leadless environment-friendly type crystal silicon solar energy battery front side silver paste and preparation method thereof, 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 in the time of 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 wrapped up uniformly, makes 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 popularized day by day, the use of leaded solar cell conductive silver slurry is restricted, will eliminate gradually soon, must develop the leadless environment-friendly type 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 leadless environment-friendly type crystal silicon solar energy battery front side silver paste and preparation method thereof is provided, meeting under the prerequisite of solar cell electrical property, make solar cell meet the leadless environment-friendly type 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:
Leadless environment-friendly type crystal silicon solar energy battery front side 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:
A slurry:
1-5 μ m silver powder 45-50,30-60nm aluminium powder 15-20, glass dust A10-15, organic carrier A15-20, described glass dust A is made up of the raw material of following weight portion: Bi
2o
320-30, SiO
210-20, B
2o
35-10, Al
2o
35-8, CaO2-5, Co
2o
32-5, Ag
2o1-3, described organic carrier A is made up of the raw material of following weight portion: dibutyl phthalate 30-40, methylisobutylketone 15-20, butyl carbitol acetate 10-20, carboxymethyl cellulose 5-10, acetylacetone,2,4-pentanedione silver 2-5, polyethyl acrylate 0.5-1, aminopropyl triethoxysilane 2-5, polyamide wax 2-5;
B slurry:
1-5 μ m silver powder 5-10,30-60nm copper powder 5-10, glass dust B3-6, organic carrier B5-10, described glass dust B is made up of the raw material of following weight portion: SiO
210-20, B
2o
35-10, TiO
25-8, V
2o
52-5, BaO2-5, Al
2o
31-5, Ag
2o1-3, described organic carrier B is made up of the raw material of following weight portion: terpinol 10-20, dibutyl phthalate 5-10, methylisobutylketone 5-10, polyacrylate 2-5, polyvinylpyrrolidone 1-3, hexenyl bis-stearamides 0.5-1, tricresyl phosphate 1-3.
The preparation method of leadless environment-friendly type crystal silicon solar energy battery front side silver paste comprises the following steps:
(1) preparation of glass dust A
Take each raw material by formulation ratio, after mixing, be put in 1000-1300 DEG C of high temperature Ma Fulu and carry out sintering, insulation 30-50min, then after quenching with deionized water, grind, cross 200-300 mesh sieve, cooling, then at 600-700 DEG C of insulation 5-6 hour, then, quench with deionized water 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 hour, then clean to neutrality dry for standby with deionized water;
(2) preparation of glass dust B
Take each raw material by formulation ratio, after mixing, be put in 1000-1200 DEG C of high temperature Ma Fulu and carry out sintering, insulation 30-40min, then after quenching with deionized water, grind, cross 200-300 mesh sieve, cooling, at 600-700 DEG C of insulation 5-6 hour, then, then quench with deionized water again, grind, cross the sieve of different meshes, collect and obtain 1-5 μ m glass dust and 5-10 μ m glass dust respectively, then use respectively 20-30% salt acid soak 1-2 hour, then clean to neutrality dry for standby with deionized water;
(3) preparation of organic carrier A
By formulation ratio, dibutyl phthalate, methylisobutylketone, butyl carbitol acetate are mixed, at 80-110 DEG C, add successively carboxymethyl cellulose, acetylacetone,2,4-pentanedione silver, polyethyl acrylate, aminopropyl triethoxysilane, polyamide wax to dissolve, stir;
(4) preparation of organic carrier B
By formulation ratio, terpinol, dibutyl phthalate, methylisobutylketone are mixed, at 80-110 DEG C, add successively polyacrylate, polyvinylpyrrolidone, hexenyl bis-stearamides, tricresyl phosphate 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 mixedly, more every minor tick 30-40 minute adds 1-5 μ m silver powder, 30-60nm aluminium powder successively, and mixed 2-3 hour, 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 silver powder, 30-60nm copper powder successively, and mixed 2-3 hour, 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 front side silver paste of the present invention.
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 copper powder and aluminium 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 the raw material of following weight portion: Bi
2o
320 parts, SiO
215 parts, B
2o
310 parts, Al
2o
36 parts, CaO4 part, Co
2o
33 parts, Ag
2o2 part, is put in after mixing in 1100 DEG C of high temperature Ma Fulu and carries out sintering, insulation 40min, then after quenching with deionized water, grind, cross 250 mesh sieves, cooling, 700 DEG C of insulations 5 hours, then, then quench with deionized water again, grind, cross the sieve of different meshes, collect and obtain 3 μ m glass dust respectively, 10 μ m glass dust and 20 μ m glass dust, use respectively again 25% salt acid soak 2 hours, then clean to neutrality dry for standby with deionized water;
(2) preparation of glass dust B
Get the raw material of following weight portion: SiO
215 parts, B
2o
38 parts, TiO
26 parts, V
2o
54 parts, BaO4 part, Al
2o
33 parts, Ag
2o2 part, is put in after mixing in 1050 DEG C of high temperature Ma Fulu and carries out sintering, insulation 40min, then after quenching with deionized water, grind, cross 250 mesh sieves, cooling, 700 DEG C of insulations 5 hours, then, then quench with deionized water again, grind, cross the sieve of different meshes, collect and obtain 2 μ m glass dust and 8 μ m glass dust respectively, then use respectively 28% salt acid soak 2 hours, then clean to neutrality dry for standby with deionized water;
(3) preparation of organic carrier A
Get the raw material of following weight portion: 30 parts of dibutyl phthalates, 20 parts of methylisobutylketones, 15 parts of butyl carbitol acetates, 8 parts of carboxymethyl celluloses, 4 parts of acetylacetone,2,4-pentanedione silver, 0.8 part of polyethyl acrylate, 3 parts of aminopropyl triethoxysilanes, 4 parts of polyamide waxes
By formulation ratio, dibutyl phthalate, methylisobutylketone, butyl carbitol acetate are mixed, at 105 DEG C, add successively carboxymethyl cellulose, acetylacetone,2,4-pentanedione silver, polyethyl acrylate, aminopropyl triethoxysilane, polyamide wax to dissolve, stir;
(4) preparation of organic carrier B
Get the raw material of following weight portion: 15 parts of terpinols, 8 parts of dibutyl phthalates, 8 parts of methylisobutylketones, 4 parts of polyacrylate, 2 parts of polyvinylpyrrolidones, 0.6 part of hexenyl bis-stearamides, 2 parts of tricresyl phosphates,
By formulation ratio, terpinol, dibutyl phthalate, methylisobutylketone are mixed, at 90 DEG C, add successively polyacrylate, polyvinylpyrrolidone, hexenyl bis-stearamides, tricresyl phosphate to dissolve, stir;
(5) preparation of A slurry
Get the raw material of following weight portion: 3 45 parts, μ m silver powder, 20 parts of 44nm aluminium powders, glass dust A12 part, organic carrier A18 part,
Glass dust A is added in organic carrier A, stir mixedly, more every minor tick adds 3 μ m silver powder, 44nm aluminium powder for 40 minutes successively, mixed 3 hours, obtains A slurry;
(6) preparation of B slurry
Get the raw material of following weight portion: 28 parts, μ m silver powder, 8 parts of 56nm copper powders, glass dust B4 part, organic carrier B8 part,
Glass dust B is added in organic carrier B, stir mixedly, more every minor tick adds 2 μ m silver powder, 56nm copper powder for 40 minutes successively, mixed 3 hours, 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 150Pas, obtains solar cell front side silver paste of the present invention.
Adopt screen process press that silver slurry is printed on 125mm × 125mmSi substrate, then dry at 180 DEG C, carry out quick fired electrodes lead-in wire at 900 DEG C again, the contact conductor of making after high temperature sintering surface silvery white, smooth zero defect, peel strength 8N/cm, soldering is functional, sheet resistance < 10Siements/sq, and the solar cell photoelectric transformation efficiency of preparation is 18.4%,, tensile test result is adhesive force >10N/mm2.
Embodiment 2
(1) preparation of glass dust A
Get the raw material of following weight portion: Bi
2o
330 parts, SiO
215 parts, B
2o
38 parts, Al
2o
38 parts, CaO4 part, Co
2o
34 parts, Ag
2o
3part, after mixing, be put in 1200 DEG C of high temperature Ma Fulu and carry out sintering, insulation 50min, then after quenching with deionized water, grind, cross 250 mesh sieves, cooling, 700 DEG C of insulations 6 hours, then, then quench with deionized water again, grind, cross the sieve of different meshes, collect and obtain 4 μ m glass dust respectively, 12 μ m glass dust and 24 μ m glass dust, use respectively again 25% salt acid soak 2 hours, then clean to neutrality dry for standby with deionized water;
(2) preparation of glass dust B
Get the raw material of following weight portion: SiO
220 parts, B
2o
310 parts, TiO
25 parts, V
2o
55 parts, BaO5 part, Al
2o
33 parts, Ag
2o2 part, is put in after mixing in 1200 DEG C of high temperature Ma Fulu and carries out sintering, insulation 40min, then after quenching with deionized water, grind, cross 250 mesh sieves, cooling, 700 DEG C of insulations 6 hours, then, then quench with deionized water again, grind, cross the sieve of different meshes, collect and obtain 3 μ m glass dust and 9 μ m glass dust respectively, then use respectively 22% salt acid soak 2 hours, then clean to neutrality dry for standby with deionized water;
(3) preparation of organic carrier A
Get the raw material of following weight portion: 40 parts of dibutyl phthalates, 15 parts of methylisobutylketones, 15 parts of butyl carbitol acetates, 8 parts of carboxymethyl celluloses, 5 parts of acetylacetone,2,4-pentanedione silver, 1 part of polyethyl acrylate, 3 parts of aminopropyl triethoxysilanes, 3 parts of polyamide waxes
By formulation ratio, dibutyl phthalate, methylisobutylketone, butyl carbitol acetate are mixed, at 108 DEG C, add successively carboxymethyl cellulose, acetylacetone,2,4-pentanedione silver, polyethyl acrylate, aminopropyl triethoxysilane, polyamide wax to dissolve, stir;
(4) preparation of organic carrier B
Get the raw material of following weight portion: 20 parts of terpinols, 10 parts of dibutyl phthalates, 5 parts of methylisobutylketones, 4 parts of polyacrylate, 2 parts of polyvinylpyrrolidones, 0.8 part of hexenyl bis-stearamides, 2 parts of tricresyl phosphates,
By formulation ratio, terpinol, dibutyl phthalate, methylisobutylketone are mixed, at 102 DEG C, add successively polyacrylate, polyvinylpyrrolidone, hexenyl bis-stearamides, tricresyl phosphate to dissolve, stir;
(5) preparation of A slurry
Get the raw material of following weight portion: 2 50 parts, μ m silver powder, 20 parts of 45nm aluminium powders, glass dust A15 part, organic carrier A20 part,
Glass dust A is added in organic carrier A, stir mixedly, more every minor tick adds 2 μ m silver powder, 45nm aluminium powder for 40 minutes successively, mixed 3 hours, obtains A slurry;
(6) preparation of B slurry
Get the raw material of following weight portion: 5 10 parts, μ m silver powder, 5 parts of 54nm copper powders, glass dust B5 part, organic carrier B8 part,
Glass dust B is added in organic carrier B, stir mixedly, more every minor tick adds 5 μ m silver powder, 54nm copper powder for 40 minutes successively, mixed 3 hours, 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 200Pas, obtains solar cell front side silver paste of the present invention.
Adopt screen process press that silver slurry is printed on 125mm × 125mmSi substrate, then dry at 180 DEG C, carry out quick fired electrodes lead-in wire at 900 DEG C again, the contact conductor of making after high temperature sintering surface silvery white, smooth zero defect, peel strength 10N/cm, soldering is functional, sheet resistance < 10Siements/sq, and the solar cell photoelectric transformation efficiency of preparation is 19.6%,, tensile test result is adhesive force >10N/mm2.
Claims (2)
1. a leadless environment-friendly crystal silicon solar energy battery front side 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:
A slurry:
1-5 μ m silver powder 45-50,30-60nm aluminium powder 15-20, glass dust A 10-15, organic carrier A 15-20, described glass dust A is made up of the raw material of following weight portion: Bi
2o
320-30, SiO
210-20, B
2o
35-10, Al
2o
35-8, CaO 2-5, Co
2o
32-5, Ag
2o 1-3, described organic carrier A is made up of the raw material of following weight portion: dibutyl phthalate 30-40, methylisobutylketone 15-20, butyl carbitol acetate 10-20, carboxymethyl cellulose 5-10, acetylacetone,2,4-pentanedione silver 2-5, polyethyl acrylate 0.5-1, aminopropyl triethoxysilane 2-5, polyamide wax 2-5;
B slurry:
1-5 μ m silver powder 5-10,30-60nm copper powder 5-10, glass dust B 3-6, organic carrier B 5-10, described glass dust B is made up of the raw material of following weight portion: SiO
210-20, B
2o
35-10, TiO
25-8, V
2o
52-5, BaO 2-5, Al
2o
31-5, Ag
2o 1-3, described organic carrier B is made up of the raw material of following weight portion: terpinol 10-20, dibutyl phthalate 5-10, methylisobutylketone 5-10, polyacrylate 2-5, polyvinylpyrrolidone 1-3, hexenyl bis-stearamides 0.5-1, tricresyl phosphate 1-3.
2. a preparation method for leadless environment-friendly crystal silicon solar energy battery front side silver paste as claimed in claim 1, is characterized in that comprising the following steps:
(1) preparation of glass dust A
Take each raw material by formulation ratio, after mixing, be put in 1000-1300 DEG C of high temperature Ma Fulu and carry out sintering, insulation 30-50 min, then after quenching with deionized water, grind, cross 200-300 mesh sieve, cooling, then at 600-700 DEG C of insulation 5-6 hour, then, quench with deionized water 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 hour, then clean to neutrality dry for standby with deionized water;
(2) preparation of glass dust B
Take each raw material by formulation ratio, after mixing, be put in 1000-1200 DEG C of high temperature Ma Fulu and carry out sintering, insulation 30-40 min, then after quenching with deionized water, grind, cross 200-300 mesh sieve, cooling, at 600-700 DEG C of insulation 5-6 hour, then, then quench with deionized water again, grind, cross the sieve of different meshes, collect and obtain 1-5 μ m glass dust and 5-10 μ m glass dust respectively, then use respectively 20-30% salt acid soak 1-2 hour, then clean to neutrality dry for standby with deionized water;
(3) preparation of organic carrier A
By formulation ratio, dibutyl phthalate, methylisobutylketone, butyl carbitol acetate are mixed, at 80-110 DEG C, add successively carboxymethyl cellulose, acetylacetone,2,4-pentanedione silver, polyethyl acrylate, aminopropyl triethoxysilane, polyamide wax to dissolve, stir;
(4) preparation of organic carrier B
By formulation ratio, terpinol, dibutyl phthalate, methylisobutylketone are mixed, at 80-110 DEG C, add successively polyacrylate, polyvinylpyrrolidone, hexenyl bis-stearamides, tricresyl phosphate 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 mixedly, more every minor tick 30-40 minute adds 1-5 μ m silver powder, 30-60nm aluminium powder successively, and mixed 2-3 hour, 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 silver powder, 30-60nm copper powder successively, and mixed 2-3 hour, 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 front side silver paste.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN105825913B (en) * | 2016-05-16 | 2017-11-24 | 南通天盛新能源股份有限公司 | A kind of ageing-resistant crystal silicon solar energy battery back silver paste and preparation method thereof |
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| CN101377966A (en) * | 2008-09-27 | 2009-03-04 | 彩虹集团公司 | Method for preparing leadless silver electrode slurry for glass substrates |
| CN102139368A (en) * | 2011-03-18 | 2011-08-03 | 中科院广州化学有限公司 | High-dispersion silver powder and solar battery electrode conductive silver paste |
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| CN101816045A (en) * | 2007-10-18 | 2010-08-25 | E.I.内穆尔杜邦公司 | Lead-free conductive compositions and processes for use in the manufacture of semiconductor devices: Mg-containing additive |
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| CN101377966A (en) * | 2008-09-27 | 2009-03-04 | 彩虹集团公司 | Method for preparing leadless silver electrode slurry for glass substrates |
| CN102139368A (en) * | 2011-03-18 | 2011-08-03 | 中科院广州化学有限公司 | High-dispersion silver powder and solar battery electrode conductive silver paste |
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Denomination of invention: Silver paste for environmental-friendly lead-free silicon solar cell front electrode and preparation method of silver paste Effective date of registration: 20180207 Granted publication date: 20140910 Pledgee: Hefei state control construction finance Company limited by guarantee Pledgor: CHINALAND SOLAR ENERGY Co.,Ltd. Registration number: 2018340000047 |
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Denomination of invention: Silver paste for environmental-friendly lead-free silicon solar cell front electrode and preparation method of silver paste Effective date of registration: 20191115 Granted publication date: 20140910 Pledgee: Feidong SME financing Company limited by guarantee Pledgor: CHINALAND SOLAR ENERGY Co.,Ltd. Registration number: Y2019980000607 |
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