CN102708942A - Lead-free silver and aluminum slurry for solar photocell and preparation method of slurry - Google Patents
Lead-free silver and aluminum slurry for solar photocell and preparation method of slurry Download PDFInfo
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- 239000002002 slurry Substances 0.000 title claims abstract description 58
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims description 21
- 229910052709 silver Inorganic materials 0.000 title abstract description 9
- 239000004332 silver Substances 0.000 title abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 69
- 239000011521 glass Substances 0.000 claims abstract description 54
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 28
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 15
- 230000000996 additive effect Effects 0.000 claims abstract description 15
- 229910000410 antimony oxide Inorganic materials 0.000 claims abstract description 11
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 10
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 10
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004327 boric acid Substances 0.000 claims abstract description 9
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 9
- 239000004411 aluminium Substances 0.000 claims description 49
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 28
- -1 silver aluminum Chemical compound 0.000 claims description 19
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 4
- 239000000428 dust Substances 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 4
- 239000011241 protective layer Substances 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 239000010431 corundum Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 abstract 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 abstract 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 abstract 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract 1
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 13
- 239000010703 silicon Substances 0.000 description 13
- 238000005245 sintering Methods 0.000 description 10
- 238000007639 printing Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000006187 pill Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 238000007613 slurry method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007726 management method Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000010793 electronic waste Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
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Abstract
The invention discloses lead-free silver and aluminum slurry for a solar photocell. The slurry is prepared from raw materials in percent by mass as follows: 75-80% of silver powder, aluminum powder and copper powder, 15-20% of organic bond, 1-5% of inorganic glass powder, and 1-5% of additive; the purities of the silver powder, the aluminum powder and the copper powder are more than or equal to 99.9%; the organic bond is prepared from the following materials in percent by mass of: 0.5-2% of butyl carbitol, 1-2.5% of resin, 1-4% of rosin, 11-13% of ethylene glycol monomethyl ether, 5-9% of diethylene glycol monobutyl ether, 65-75% of cyclohexanone and 10-20% of n-butyl alcohol; the inorganic glass powder is prepared from the following materials in percent by mass of: 1-3% of titanium dioxide, 55-75% of boric acid, 3-5% of aluminium sesquioxide, 15-25% of antimony oxide and 2-5% of zirconium oxide; and the additive is prepared from the following materials in percent by mass of: 35-45% of span and 55-65% of pump oil. The lead-free silver and aluminum slurry prepared by the raw material has the advantages of good weldability and strong adhesion and meets the lead-free environmental friendless requirement.
Description
Technical field
The present invention relates to silicon solar cell and starch, be specifically related to a kind of solar photocell with lead-free silver aluminum slurry and preparation method thereof with electronics.
Background technology
Solar energy is inexhaustible, pollution-free, noiseless new forms of energy.Solar cell is the environmental type regenerative resource semiconductor device that directly solar energy is become electric energy.Its electric slurry preparation silver slurry, silver-colored aluminium paste, aluminium pastes of adopting are prepared more.Aluminium paste has low price, electric performance stablity.Aluminium and silicon are easy to form PN junction, have the long wave response characteristic, have the good Ohmic contact characteristic with silicon wafer or ceramic substrate, have good ageing resistance again.Therefore the aluminium electric slurry is selected as the material of the back surface field of silicon solar cell.
In order to reduce electronic product pollution to environment in making use, many countries all are that legislation is used in the harmful substance restriction.European Union had issued " electronic waste facture " in 2003, comprising two instructions, and one of which: " about the electronic and electrical equipment instruction "; Particularly second instruction " about in electronic and electrical equipment, banning use of some harmful material instruction " is RoHS; The electronic product that requirement exports to European Union market can not contain lead, mercury, cadmium, gathers bromo biphenyl and gather six kinds of harmful substances such as bromine hexichol; And the lead content in the regulation electrocondution slurry should be less than 100ppm, and Cd is less than 5ppm, and Cr is less than 100ppm; Hg is less than 2ppm, and PBBs/PBDEs (PBB/PBDE) is less than 5ppm.This instructs and comes into effect in July, 2006.China Ministry of Information Industry has issued " (electronics and IT products pollution control management way ", and content and RoHS are similar, and this management method was in enforcement on July 1 in 2006.
Chinese patent, publication number CN1877864A, its invention has related to a kind of silicon solar cell back surface field aluminum conductive electric slurry and has formed and the preparation method, comprises lead oxide 40～50% by mass percentage in its slurry in the inorganic bond vitrifying agent metal powder.
The used unorganic glass powder of known solar silicon photovoltaic cell aluminium electric slurry is generally all leaded, and slurry is made in the use and can be polluted environment.
Summary of the invention
The objective of the invention is to overcome the defective that exists in the prior art, provide a kind of solar photocell with lead-free silver aluminum slurry and preparation method thereof, this leadless electronic slurry in silk screen printing, 830 ± 5 ℃ of scopes sintering on silicon chip; Silicon chip is not crooked, does not play the silver-colored pill of aluminium, does not blister; Do not have silver-colored aluminium ditch, can form the good ohmic contact, photoelectric conversion efficiency＞17.2%; Assembly bonds with EVA, and the EVA bonding can not peeled off grey peeling, reaches unleaded environmental requirement.
For realizing above-mentioned purpose; Technical scheme of the present invention is that a kind of solar photocell of design is used the lead-free silver aluminum slurry; It is characterized in that; Slurry is that 75～80% silver powder, aluminium powder and copper powder, 15～20% organic bond, 1～5% unorganic glass powder, 1～5% additive are formed gross mass 100% by mass percent; The purity of said silver powder, aluminium powder and copper powder is >=and 99.9%, average grain diameter is 1～3 μ m, and surface coverage has the sphere of nitrogenize protective layer and/or silver powder, aluminium powder and the copper powder of sheet shape; Said organic bond is formed gross mass 100% by 0.5～2% BC, 1～2.5% resin, 1～4% rosin, 11～13% diethylene glycol dimethyl ether, 5～9% diethylene glycol butyl ether, 65～75% cyclohexanone and 10～20% n-butanol by mass percentage; Said unorganic glass powder is 1～3% titanium dioxide by mass percent, 55～75% boric acid, and 3～5% alundum (Al, 15～25% antimony oxide, 2～5% zirconia is formed, gross mass 100%; Said additive is by 35～45% class of department by mass percentage, and 55～65% pump oil is formed gross mass 100%.
Wherein optimized technical scheme is, described organic bond is by being that 2% BC, 1.5% resin, 3% rosin, 7.5% diethylene glycol dimethyl ether, 3% diethylene glycol butyl ether, cyclohexanone 70% and 13% n-butanol are formed by mass percentage.
Optimized technical scheme also has, and described unorganic glass powder is a lead-free glass powder, by the titanium dioxide that is 3% by mass percentage, and 65% boric acid, 4% alundum (Al, 25% antimony oxide, 3% zirconia is formed.
A kind of solar photocell is characterized in that with the preparation method of lead-free silver aluminum slurry said preparation method accomplishes according to the following steps:
S1, the organic bond raw material of solid state is dissolved fully, obtain transparent organic bond;
After S2, the raw material that will form the unorganic glass powder fully mix, in the porcelain crucible of packing into, after putting into baking oven and drying by the fire some hrs at a certain temperature; Put into high temperature furnace again, high temperature melting 1～2h is dried after the shrend then; Reinstall in the crucible with high temperature melting 1.5～3h; Shrend oven dry back is broken, press zirconia ball: ultra-pure water: glass dust=3: 2: 1 ball milling is≤5 μ m extremely, dry the unorganic glass powder;
S3, said silver powder, aluminium powder, copper powder, organic bond, unorganic glass powder, additive mixed after, grind with three-roll grinder, the product leadless electronic slurry.
Wherein optimized technical scheme is, said organic bond solution temperature is 90 ℃～130 ℃.
Optimized technical scheme also has, and said unorganic glass powder bake out temperature in baking oven is: 110 ℃～130 ℃.
Optimized technical scheme also has, and said unorganic glass powder drying time in baking oven is 1～3h.
Optimized technical scheme also has, and the temperature of said unorganic glass powder in high temperature furnace is 1000 ℃～1450 ℃.
Optimized technical scheme also has, and the temperature of said unorganic glass powder in crucible is 1000 ℃～1450 ℃.
Optimized technical scheme also has, and the fineness of using three-roll grinder to grind among the said step S3 is less than 5 μ m, and viscosity is 25000～30000mpa.s.
Advantage of the present invention and beneficial effect are:
1, among the present invention, the antimony oxide in the unorganic glass powder can improve the electric conductivity of slurry, the nanocrystalline structure that zirconia can refined pulp; The two mixes electrical property and the chemical stability that improves slurry altogether through antimony oxide and zirconia.In addition, purity is more than 99.9%, and particle diameter is for being sphere and/or sheet shape silver powder, aluminium powder and the copper powder of being protected by blanket of nitrogen less than 5 μ m and surface; Can make the slurry of preparation not only satisfy electrical property, can also make silicon chip sintering rear curved little, not play the silver-colored pill of aluminium; Do not have silver-colored aluminium ditch, silver-colored aluminium film is smooth.Thereby silver-colored aluminium film attaches firmly substrate after making the slurry sintering, forms good Ohmic contact, improves photoelectric conversion efficiency.
2, class of use department and diffusion pump oil are made the net performance excessively that additive can improve slurry.
3, the BC in the machine adhesive, resin, rosin, diethylene glycol dimethyl ether, diethylene glycol butyl ether, cyclohexanone and n-butanol play a part organic solvent and thickener respectively; Play the rheological behavior of control slurry; Regulate the viscosity of slurry; Make the solid particulate mixture of conductive phase, bonding phase and other effects of solid forms be dispersed into slurry, so that be transferred on the substrate with fluid behaviour.
4, the present invention carries out unorganic glass to found for twice in process of production, and its all inorganic raw materials are fully fused, and with after itself and silver powder, aluminium powder and the copper powder proportioning, obtains this electric slurry, in sintering process, the inorganic matter crystalline polamer do not occur.In addition, in this slurry, reduce the unorganic glass powder and increase aluminium powder, its effect is to be, this slurry is printed on silicon chip, behind oversintering, makes the silicon chip bending little, does not play the silver-colored pill of aluminium, does not have silver-colored aluminium ditch, and silver-colored aluminium film is smooth.Thereby silver-colored aluminium film attaches firmly substrate after making the slurry sintering, forms good Ohmic contact, improves photoelectric conversion efficiency.
In sum, the present invention is through different ratio proportionings, and sintering is on silicon chip in silk screen printing, 830 ± 5 ℃ of scopes for this leadless electronic slurry, and silicon chip is not crooked; Do not play the silver-colored pill of aluminium, do not blister, do not have silver-colored aluminium ditch; Can form the good ohmic contact, photoelectric conversion efficiency＞17.2%, assembly bonds with EVA; Do not play ash, do not have silver-colored aluminium and peel off phenomenon, reach unleaded environmental requirement.
Embodiment
Below in conjunction with embodiment, specific embodiments of the invention further describes.Following examples only are used for technical scheme of the present invention more clearly is described, and can not limit protection scope of the present invention with this.
Embodiment 1
A kind of solar photocell is used the lead-free silver aluminum slurry, it is characterized in that, slurry is that 80% silver powder, aluminium powder and copper powder, 15% organic bond, 2% unorganic glass powder, 3% additive are formed gross mass 100% by mass percent; The purity of said silver powder, aluminium powder and copper powder is >=and 99.9%, average grain diameter is silver powder, aluminium powder and the copper powder that 3 μ m and surface coverage have the sphere of nitrogenize protective layer; Said organic bond is formed gross mass 100% by 0.5% BC, 1.5% resin, 1% rosin, 11% diethylene glycol dimethyl ether, 6% diethylene glycol butyl ether, 65% cyclohexanone and 15% n-butanol by mass percentage; Said unorganic glass powder is 3% titanium dioxide by mass percent, 70% boric acid, and 5% alundum (Al, 20% antimony oxide, 2% zirconia is formed, gross mass 100%; Said additive is by 45% class of department by mass percentage, and 55% pump oil is formed gross mass 100%.
Embodiment preferred is in the present invention, and described organic bond is by being that 2% BC, 1.5% resin, 3% rosin, 7.5% diethylene glycol dimethyl ether, 3% diethylene glycol butyl ether, cyclohexanone 70% and 13% n-butanol are formed by mass percentage.
Optimized technical scheme also has in the present invention, and described unorganic glass powder is a lead-free glass powder, by the titanium dioxide that is 3% by mass percentage, and 65% boric acid, 4% alundum (Al, 25% antimony oxide, 3% zirconia is formed.
A kind of solar photocell is with the preparation method of lead-free silver aluminum slurry, and this preparation method accomplishes according to the following steps:
The first step, the organic bond raw material of solid state is dissolved fully, obtain transparent organic bond;
After second step, the raw material that will form the unorganic glass powder fully mix, in the porcelain crucible of packing into, after putting into baking oven and drying by the fire some hrs at a certain temperature; Put into high temperature furnace again, high temperature melting 2h is dried after the shrend then; Reinstall and use high temperature melting 3h in the crucible; Shrend oven dry back is broken, press zirconia ball: ultra-pure water: glass dust=3: 2: 1 ball millings are extremely less than 5 μ m, dry the unorganic glass powder;
The 3rd step, said silver powder, aluminium powder, copper powder, organic bond, unorganic glass powder, additive mixed after, grind with three-roll grinder, the product leadless electronic slurry.
Embodiment preferred is in the present invention, and said organic bond solution temperature is 120 ℃.
Embodiment preferred also has in the present invention, and said unorganic glass powder bake out temperature in baking oven is 120 ℃.
Embodiment preferred also has in the present invention, and said unorganic glass powder drying time in baking oven is 3h.
Optimized technical scheme also has in the present invention, and the temperature of said unorganic glass powder in high temperature furnace is 1250 ℃.
Optimized technical scheme also has in the present invention, and the temperature of said unorganic glass powder in crucible is 1100 ℃.
Optimized technical scheme also has in the present invention, and the fineness of in said third step, using three-roll grinder to grind is 250nm, and viscosity is 30000mpa.s.
Above-mentioned gained leadless electronic slurry is on probation at production line: before the corrosion, and monocrystalline silicon specification 125 * 125mm, thickness 200 μ m, thickness is 180 μ m before the printing; Printing screen 280 orders, the automatic press printing, print thickness be every with the slurry 0.7g; About 3 minutes of 200 ℃ of bake out temperatures, oven dry aluminium film does not have obscission, changes another side and prints positive silver-colored aluminium paste; Dry laggard continuous tunnel furnace sintering, 830 ± 5 ℃ of sintering temperatures, 1.5 minutes cycles; About 20 seconds of peak temperature time, electrical property (mean value), photoelectric conversion efficiency＞18% are surveyed in the back of coming out of the stove.
Measure between crooked 0.50～0.80mm with vernier caliper.Silver aluminium film grey, smooth, do not have the silver-colored pill of aluminium, nothing silver aluminium ditch, do not blister, do not fall ash, assembly does not have the phenomenon of peeling off with the EVA silver-colored aluminium film that bonds, and reaches the leadless environment-friendly requirement fully.
Embodiment 2
The present invention is that a kind of solar photocell is used the lead-free silver aluminum slurry, and this slurry is that 75% silver powder, aluminium powder and copper powder, 18% organic bond, 5% unorganic glass powder, 2% additive are formed gross mass 100% by mass percent; The purity of said silver powder, aluminium powder and copper powder is >=and 99.9%, average grain diameter is 3 μ m and surface coverage has the sphere of nitrogenize protective layer and/or silver powder, aluminium powder and the copper powder of sheet shape; Said organic bond is formed gross mass 100% by 1% BC, 2% resin, 3% rosin, 11% diethylene glycol dimethyl ether, 9% diethylene glycol butyl ether, 60% cyclohexanone and 14% n-butanol by mass percentage; Said unorganic glass powder is 1% titanium dioxide by mass percent, 75% boric acid, and 3% alundum (Al, 19% antimony oxide, 2% zirconia is formed, gross mass 100%; Said additive is by 35% class of department by mass percentage, and 65% pump oil is formed gross mass 100%.
Embodiment preferred is in the present invention, and described organic bond is by being that 2% BC, 1.5% resin, 3% rosin, 7.5% diethylene glycol dimethyl ether, 3% diethylene glycol butyl ether, cyclohexanone 70% and 13% n-butanol are formed by mass percentage.
Embodiment preferred also has in the present invention, and described unorganic glass powder is a lead-free glass powder, by the titanium dioxide that is 3% by mass percentage, and 65% boric acid, 4% alundum (Al, 25% antimony oxide, 3% zirconia is formed.
A kind of solar photocell is with the preparation method of lead-free silver aluminum slurry, and this preparation method accomplishes according to the following steps:
The first step, the organic bond raw material of solid state is dissolved fully, obtain transparent organic bond;
After second step, the raw material that will form the unorganic glass powder fully mix, in the porcelain crucible of packing into, after putting into baking oven and drying by the fire some hrs at a certain temperature; Put into high temperature furnace again, high temperature melting 1h is dried after the shrend then; Reinstall and use high temperature melting 3h in the crucible; Shrend oven dry back is broken, press zirconia ball: ultra-pure water: glass dust=3: 2: 1 ball milling is≤5 μ m extremely, dry the unorganic glass powder;
S3, said silver powder, aluminium powder, copper powder, organic bond, unorganic glass powder, additive mixed after, grind with three-roll grinder, the product leadless electronic slurry.
Optimized technical scheme is in the present invention, and said organic bond solution temperature is 100 ℃.
Embodiment preferred also has in the present invention, and said unorganic glass powder bake out temperature in baking oven is: 110 ℃.
Embodiment preferred also has in the present invention, and said unorganic glass powder drying time in baking oven is 1h.
Embodiment preferred also has in the present invention, and the temperature of said unorganic glass powder in high temperature furnace is 1300 ℃.
Embodiment preferred also has in the present invention, and the temperature of said unorganic glass powder in crucible is 1300 ℃.
Embodiment preferred also has in the present invention, and the fineness of in said third step, using three-roll grinder to grind is less than 5 μ m, and viscosity is 25000mpa.s.
Above-mentioned gained leadless electronic slurry is on probation at production line: monocrystalline silicon specification 125 * 125mm, and thickness 200 μ m (before the corrosion), thickness is 180 μ m before the printing; Printing screen 320 orders, the automatic press printing, print thickness be every with the slurry 0.7g; About 3 minutes of 280 ℃ of bake out temperatures, drying silver-colored aluminium film does not have obscission, changes another side printing front side silver paste; Dry laggard continuous tunnel furnace sintering, 830 ± 5 ℃ of sintering temperatures, 1.9 minutes cycles; About 18 seconds of peak temperature time, electrical property (mean value), photoelectric conversion efficiency＞18.2% are surveyed in the back of coming out of the stove.
Measure between crooked 0.50～0.80mm with vernier caliper.Silver aluminium film grey, smooth, do not have the silver-colored pill of aluminium, nothing silver aluminium ditch, do not blister, do not fall ash, assembly does not have the phenomenon of peeling off with EVA bonding aluminium film, reaches the leadless environment-friendly requirement fully.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from know-why of the present invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (10)
1. a solar photocell is used the lead-free silver aluminum slurry; It is characterized in that; Slurry is that 75～80% silver powder, aluminium powder and copper powder, 15～20% organic bond, 1～5% unorganic glass powder, 1～5% additive are formed gross mass 100% by mass percent; The purity of said silver powder, aluminium powder and copper powder is >=and 99.9%, average grain diameter is 1～3 μ m and surface coverage has the sphere of nitrogenize protective layer and/or silver powder, aluminium powder and the copper powder of sheet shape; Said organic bond is formed gross mass 100% by 0.5～2% BC, 1～2.5% resin, 1～4% rosin, 11～13% diethylene glycol dimethyl ether, 5～9% diethylene glycol butyl ether, 65～75% cyclohexanone and 10～20% n-butanol by mass percentage; Said unorganic glass powder is 1～3% titanium dioxide by mass percent, 55～75% boric acid, and 3～5% alundum (Al, 15～25% antimony oxide, 2～5% zirconia is formed, gross mass 100%; Said additive is by 35～45% class of department by mass percentage, and 55～65% pump oil is formed gross mass 100%.
2. solar photocell as claimed in claim 1 is used the lead-free silver aluminum slurry; It is characterized in that described organic bond is by being that 2% BC, 1.5% resin, 3% rosin, 7.5% diethylene glycol dimethyl ether, 3% diethylene glycol butyl ether, cyclohexanone 70% and 13% n-butanol are formed by mass percentage.
3. solar photocell as claimed in claim 1 is used the lead-free silver aluminum slurry, it is characterized in that, described unorganic glass powder is a lead-free glass powder; By the titanium dioxide that is 3% by mass percentage, 65% boric acid, 4% alundum (Al; 25% antimony oxide, 3% zirconia is formed.
One kind by the described solar photocell of claim 1 with the preparation method of lead-free silver aluminum slurry, it is characterized in that said preparation method accomplishes according to the following steps:
S1, the organic bond raw material of solid state is dissolved fully, obtain transparent organic bond;
After S2, the raw material that will form the unorganic glass powder fully mix, in the high-purity corundum crucible of packing into, after putting into baking oven and drying by the fire some hrs at a certain temperature; Put into high temperature furnace again, high temperature melting 1～2h is dried after the shrend then; Reinstall in the crucible with high temperature melting 1.5～3h; Shrend oven dry back is broken, press zirconia ball: ultra-pure water: glass dust=3: 2: 1 ball milling is≤5 μ m extremely, dry the unorganic glass powder;
S3, said silver powder, aluminium powder, copper powder, organic bond, unorganic glass powder, additive mixed after, grind with three-roll grinder, the product leadless electronic slurry.
5. solar photocell as claimed in claim 4 is characterized in that with the preparation method of lead-free silver aluminum slurry said organic bond solution temperature is 90 ℃～130 ℃.
6. solar photocell as claimed in claim 4 is characterized in that with the preparation method of lead-free silver aluminum slurry said unorganic glass powder bake out temperature in baking oven is: 110 ℃～130 ℃.
7. solar photocell as claimed in claim 4 is characterized in that with the preparation method of lead-free silver aluminum slurry said unorganic glass powder drying time in baking oven is 1～3h.
8. solar photocell as claimed in claim 4 is characterized in that with the preparation method of lead-free silver aluminum slurry the temperature of said unorganic glass powder in high temperature furnace is 1000 ℃～1450 ℃.
9. solar photocell as claimed in claim 4 is characterized in that with the preparation method of lead-free silver aluminum slurry the temperature of said unorganic glass powder in crucible is 1000 ℃～1450 ℃.
10. solar photocell as claimed in claim 4 is characterized in that with the preparation method of lead-free silver aluminum slurry the fineness of using three-roll grinder to grind among the said step S3 is less than 5 μ m, and viscosity is 25000～30000mpa.s.
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