CN102831955B - Silver paste with nanoscale mixed silver powder on front surface of solar cell and preparation method of silver paste - Google Patents
Silver paste with nanoscale mixed silver powder on front surface of solar cell and preparation method of silver paste Download PDFInfo
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- CN102831955B CN102831955B CN201210304674.1A CN201210304674A CN102831955B CN 102831955 B CN102831955 B CN 102831955B CN 201210304674 A CN201210304674 A CN 201210304674A CN 102831955 B CN102831955 B CN 102831955B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000004332 silver Substances 0.000 title claims abstract description 34
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 34
- 239000002002 slurry Substances 0.000 claims abstract description 58
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000000498 ball milling Methods 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011521 glass Substances 0.000 claims description 53
- 239000000428 dust Substances 0.000 claims description 49
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 36
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 32
- 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
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-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
- 238000009472 formulation Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- 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
- 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
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000006735 epoxidation reaction Methods 0.000 claims description 8
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 8
- 229920001249 ethyl cellulose Polymers 0.000 claims description 8
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 8
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 8
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 8
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- 229950000244 sulfanilic acid Drugs 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 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 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
- 239000001856 Ethyl cellulose Substances 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 claims description 6
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims description 6
- 229910006404 SnO 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 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- -1 isopropyl alcohols Chemical class 0.000 description 6
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- HDCUKDHYRMGLRT-UHFFFAOYSA-L [Ag+2].[O-]C(=O)C([O-])=O Chemical class [Ag+2].[O-]C(=O)C([O-])=O HDCUKDHYRMGLRT-UHFFFAOYSA-L 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
- 229910052802 copper Inorganic materials 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
- 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
- 150000003626 triacylglycerols Chemical class 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
Abstract
The invention discloses silver paste with nanoscale mixed silver powder on the front surface 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 aluminum powder and 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 solar cell front side silver paste containing nanoscale mixing silver powder 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 environmental-friendly conductive silver slurry 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 solar cell front side silver paste containing nanoscale mixing silver powder and preparation method thereof is provided, meeting under the prerequisite of solar cell electrical property, make solar cell meet the 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:
Solar cell front side silver paste containing nanoscale mixing silver powder 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 silver 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, ZnO5-10, Al
2o
35-8, Cu
2o2-5, ZrO
22-5, MgO1-3, described organic carrier A is made up of the raw material of following weight portion: isopropyl alcohol 30-40, cyclohexanone 15-20, ethylene glycol phenyl ether 10-20, ethyl cellulose 5-10, silver oxalate 2-5, oleamide 0.5-1, epoxidation triglyceride 2-5, phosphotriester 2-5;
B slurry:
30-60nm aluminium 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, Bi
2o
35-8, V
2o
52-5, BaO2-5, SnO
21-5, Ag
2o1-3, described organic carrier B is made up of the raw material of following weight portion: isopropyl alcohol 10-20, propylene glycol monobutyl ether 5-10, cyclohexanone 5-10, butyl carbitol acetate 2-5, hydroxypropyl cellulose 1-3, Isosorbide-5-Nitrae-dihydroxy sulfanilic acid 0.5-1, vinyl three ('beta '-methoxy ethyoxyl) silane 1-3.
The preparation method who contains the solar cell front side silver paste of nanoscale mixing silver powder 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, isopropyl alcohol, cyclohexanone, ethylene glycol phenyl ether are mixed, at 80-110 DEG C, add successively ethyl cellulose, silver oxalate, oleamide, epoxidation triglyceride, phosphotriester to dissolve, stir;
(4) preparation of organic carrier B
By formulation ratio, isopropyl alcohol, propylene glycol monobutyl ether, cyclohexanone are mixed, at 80-110 DEG C, add successively butyl carbitol acetate, hydroxypropyl cellulose, Isosorbide-5-Nitrae-dihydroxy sulfanilic acid, vinyl three ('beta '-methoxy ethyoxyl) silane 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 silver 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 30-60nm aluminium 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 the described solar cell front side silver paste containing nanoscale mixing silver powder.
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, ZnO5 part, Al
2o
38 parts, Cu
2o5 part, ZrO
23 parts, MgO3 part, be put in after mixing in 1050 DEG C of high temperature Ma Fulu and carry out sintering, insulation 40min, then after quenching with deionized water, grind, cross 300 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 5 μ m glass dust respectively, 15 μ m glass dust and 20 μ m glass dust, use respectively again 24% 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
310 parts, Bi
2o
36 parts, V
2o
54 parts, BaO5 part, SnO
25 parts, Ag
2o2 part, is put in after mixing in 1000 DEG C of high temperature Ma Fulu and carries out sintering, insulation 40min, then after quenching with deionized water, grind, cross 300 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 and 8 μ m glass dust respectively, then use respectively 25% 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 isopropyl alcohols, 20 parts of cyclohexanone, 20 parts of ethylene glycol phenyl ethers, 8 parts of ethyl celluloses, 4 parts of silver oxalates, 0.8 part of oleamide, 3 parts of epoxidation triglycerides, 3 parts of phosphotriesters,
By formulation ratio, isopropyl alcohol, cyclohexanone, ethylene glycol phenyl ether are mixed, at 95 DEG C, add successively ethyl cellulose, silver oxalate, oleamide, epoxidation triglyceride, phosphotriester to dissolve, stir;
(4) preparation of organic carrier B
Get the raw material of following weight portion: 2 parts of 10 parts of isopropyl alcohols, 10 parts of propylene glycol monobutyl ethers, 10 parts of cyclohexanone, 3 parts of butyl carbitol acetates, hydroxypropyl cellulose, 1,0.6 part of 4-dihydroxy sulfanilic acid, 2 parts, vinyl three ('beta '-methoxy ethyoxyl) silane
By formulation ratio, isopropyl alcohol, propylene glycol monobutyl ether, cyclohexanone are mixed, at 90 DEG C, add successively butyl carbitol acetate, hydroxypropyl cellulose, Isosorbide-5-Nitrae-dihydroxy sulfanilic acid, vinyl three ('beta '-methoxy ethyoxyl) silane to dissolve, stir;
(5) preparation of A slurry
Get the raw material of following weight portion: 2 45 parts, μ m silver powder, 20 parts, 50nm silver powder, glass dust A10 part, organic carrier A15 part,
Glass dust A is added in organic carrier A, stir mixedly, more every minor tick adds 2 μ m silver powder, 16 μ m silver powder for 30 minutes successively, mixed 3 hours, obtains A slurry;
(6) preparation of B slurry
Get the raw material of following weight portion: 8 parts of 45nm aluminium powders, 8 parts of 50nm copper powders, glass dust B5 part, organic carrier B7 part,
Glass dust B is added in organic carrier B, stir mixedly, more every minor tick adds 45nm aluminium powder, 50nm copper powder for 30 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 the described solar cell front side silver paste containing nanoscale mixing silver powder.
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 19.9%,, tensile test result is adhesive force >10N/mm
2.
Embodiment 2
(1) preparation of glass dust A
Get the raw material of following weight portion: Bi
2o
330 parts, SiO
220 parts, ZnO6 part, Al
2o
35 parts, Cu
2o4 part, ZrO
25 parts, MgO3 part, be put in after mixing in 1000 DEG C of high temperature Ma Fulu and carry out sintering, insulation 40min, then after quenching with deionized water, grind, cross 250 mesh sieves, cooling, 600 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 respectively, 14 μ m glass dust and 20 μ m glass dust, use respectively again 20% 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, Bi
2o
35 parts, V
2o
54 parts, BaO3 part, SnO
22 parts, Ag
2o3 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 5 μ m glass dust and 8 μ m glass dust respectively, then use respectively 30% 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 isopropyl alcohols, 15 parts of cyclohexanone, 15 parts of ethylene glycol phenyl ethers, 10 parts of ethyl celluloses, 5 parts of silver oxalates, 0.8 part of oleamide, 3 parts of epoxidation triglycerides, 5 parts of phosphotriesters,
By formulation ratio, isopropyl alcohol, cyclohexanone, ethylene glycol phenyl ether are mixed, at 106 DEG C, add successively ethyl cellulose, silver oxalate, oleamide, epoxidation triglyceride, phosphotriester to dissolve, stir;
(4) preparation of organic carrier B
Get the raw material of following weight portion: 2 parts of 20 parts of isopropyl alcohols, 8 parts of propylene glycol monobutyl ethers, 7 parts of cyclohexanone, 4 parts of butyl carbitol acetates, hydroxypropyl cellulose, 1,0.8 part of 4-dihydroxy sulfanilic acid, 1 part, vinyl three ('beta '-methoxy ethyoxyl) silane
By formulation ratio, isopropyl alcohol, propylene glycol monobutyl ether, cyclohexanone are mixed, at 98 DEG C, add successively butyl carbitol acetate, hydroxypropyl cellulose, Isosorbide-5-Nitrae-dihydroxy sulfanilic acid, vinyl three ('beta '-methoxy ethyoxyl) silane to dissolve, stir;
(5) preparation of A slurry
Get the raw material of following weight portion: 5 50 parts, μ m silver powder, 20 parts, 30nm silver powder, glass dust A15 part, organic carrier A20 part,
Glass dust A is added in organic carrier A, stir mixedly, more every minor tick adds 5 μ m silver powder, 18 μ m silver powder for 40 minutes successively, mixed 3 hours, obtains A slurry;
(6) preparation of B slurry
Get the raw material of following weight portion: 10 parts of 55nm aluminium powders, 10 parts of 32nm copper powders, glass dust B5 part, organic carrier B10 part,
Glass dust B is added in organic carrier B, stir mixedly, more every minor tick adds 55nm aluminium powder, 32nm 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 180Pas, obtains the described solar cell front side silver paste containing nanoscale mixing silver powder.
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 21.6%,, tensile test result is adhesive force >10N/mm
2.
Claims (2)
1. containing a solar cell front side silver paste for nanoscale mixing silver powder, it 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 silver 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, ZnO 5-10, Al
2o
35-8, Cu
2o 2-5, ZrO
22-5, MgO 1-3, described organic carrier A is made up of the raw material of following weight portion: isopropyl alcohol 30-40, cyclohexanone 15-20, ethylene glycol phenyl ether 10-20, ethyl cellulose 5-10, silver oxalate 2-5, oleamide 0.5-1, epoxidation triglyceride 2-5, phosphotriester 2-5;
B slurry:
30-60nm aluminium 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, Bi
2o
35-8, V
2o
52-5, BaO 2-5, SnO
21-5, Ag
2o 1-3, described organic carrier B is made up of the raw material of following weight portion: isopropyl alcohol 10-20, propylene glycol monobutyl ether 5-10, cyclohexanone 5-10, butyl carbitol acetate 2-5, hydroxypropyl cellulose 1-3, Isosorbide-5-Nitrae-dihydroxy sulfanilic acid 0.5-1, vinyl three ('beta '-methoxy ethyoxyl) silane 1-3.
2. a preparation method for the solar cell front side silver paste containing nanoscale mixing silver powder 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, isopropyl alcohol, cyclohexanone, ethylene glycol phenyl ether are mixed, at 80-110 DEG C, add successively ethyl cellulose, silver oxalate, oleamide, epoxidation triglyceride, phosphotriester to dissolve, stir;
(4) preparation of organic carrier B
By formulation ratio, isopropyl alcohol, propylene glycol monobutyl ether, cyclohexanone are mixed, at 80-110 DEG C, add successively butyl carbitol acetate, hydroxypropyl cellulose, Isosorbide-5-Nitrae-dihydroxy sulfanilic acid, vinyl three ('beta '-methoxy ethyoxyl) silane 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 silver 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 30-60nm aluminium 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 the described solar cell front side silver paste containing nanoscale mixing silver powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| JP2002362942A (en) * | 2001-06-07 | 2002-12-18 | Asahi Glass Co Ltd | Glass frit and method of coating aluminum electrode |
| CN101094818A (en) * | 2004-05-29 | 2007-12-26 | 肖特股份公司 | Nano glass powder and use thereof, particularly multicomponent glass powder with a mean particle size of less than 1 [mu]m |
| CN101931014A (en) * | 2009-06-26 | 2010-12-29 | 比亚迪股份有限公司 | Conductive slurry for solar battery and preparation method |
| CN102629496A (en) * | 2012-04-27 | 2012-08-08 | 西安银泰新能源材料科技有限公司 | Crystalline silicon solar battery front side electrode lead-free conductive lead slurry and preparation method of crystalline silicon solar battery front side electrode lead-free conductive lead slurry |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002362942A (en) * | 2001-06-07 | 2002-12-18 | Asahi Glass Co Ltd | Glass frit and method of coating aluminum electrode |
| CN101094818A (en) * | 2004-05-29 | 2007-12-26 | 肖特股份公司 | Nano glass powder and use thereof, particularly multicomponent glass powder with a mean particle size of less than 1 [mu]m |
| CN101931014A (en) * | 2009-06-26 | 2010-12-29 | 比亚迪股份有限公司 | Conductive slurry for solar battery and preparation method |
| CN102629496A (en) * | 2012-04-27 | 2012-08-08 | 西安银泰新能源材料科技有限公司 | Crystalline silicon solar battery front side electrode lead-free conductive lead slurry and preparation method of crystalline silicon solar battery front side electrode lead-free conductive lead slurry |
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Denomination of invention: Silver paste with nanoscale mixed silver powder on front surface of solar cell and preparation method of silver paste Effective date of registration: 20181204 Granted publication date: 20140820 Pledgee: Feidong SME financing Company limited by guarantee Pledgor: CHINALAND SOLAR ENERGY Co.,Ltd. Registration number: 2018340000704 |
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Denomination of invention: Silver paste on the front of solar cells containing nanoscale mixed silver powder and its preparation method Effective date of registration: 20231213 Granted publication date: 20140820 Pledgee: China Construction Bank Corporation Feidong sub branch Pledgor: CHINALAND SOLAR ENERGY Co.,Ltd. Registration number: Y2023980071321 |