CN106098144A - A kind of glass dust and with its solar cell front side silver paste prepared and preparation method thereof - Google Patents
A kind of glass dust and with its solar cell front side silver paste prepared and preparation method thereof Download PDFInfo
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- CN106098144A CN106098144A CN201610431555.0A CN201610431555A CN106098144A CN 106098144 A CN106098144 A CN 106098144A CN 201610431555 A CN201610431555 A CN 201610431555A CN 106098144 A CN106098144 A CN 106098144A
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- China
- Prior art keywords
- front side
- solar cell
- silver paste
- cell front
- side silver
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000011521 glass Substances 0.000 title claims abstract description 71
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 68
- 239000004332 silver Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000428 dust Substances 0.000 title claims description 28
- 239000002002 slurry Substances 0.000 claims abstract description 53
- 239000000843 powder Substances 0.000 claims abstract description 40
- XHGGEBRKUWZHEK-UHFFFAOYSA-L tellurate Chemical compound [O-][Te]([O-])(=O)=O XHGGEBRKUWZHEK-UHFFFAOYSA-L 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 229910052681 coesite Inorganic materials 0.000 claims abstract 4
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract 4
- 229910052682 stishovite Inorganic materials 0.000 claims abstract 4
- 229910052905 tridymite Inorganic materials 0.000 claims abstract 4
- 238000003756 stirring Methods 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 11
- 239000004925 Acrylic resin Substances 0.000 claims description 7
- 229920000178 Acrylic resin Polymers 0.000 claims description 7
- 239000001856 Ethyl cellulose Substances 0.000 claims description 7
- 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 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 229920001249 ethyl cellulose Polymers 0.000 claims description 7
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 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 description 3
- 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 description 3
- 239000002245 particle Substances 0.000 claims description 3
- 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 description 3
- HBGPNLPABVUVKZ-POTXQNELSA-N (1r,3as,4s,5ar,5br,7r,7ar,11ar,11br,13as,13br)-4,7-dihydroxy-3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-2,3,4,5,6,7,7a,10,11,11b,12,13,13a,13b-tetradecahydro-1h-cyclopenta[a]chrysen-9-one Chemical compound C([C@@]12C)CC(=O)C(C)(C)[C@@H]1[C@H](O)C[C@]([C@]1(C)C[C@@H]3O)(C)[C@@H]2CC[C@H]1[C@@H]1[C@]3(C)CC[C@H]1C(=C)C HBGPNLPABVUVKZ-POTXQNELSA-N 0.000 claims description 2
- NBKXIQAGLFPJCA-UHFFFAOYSA-N 1-butoxypropyl acetate Chemical compound CCCCOC(CC)OC(C)=O NBKXIQAGLFPJCA-UHFFFAOYSA-N 0.000 claims description 2
- PFRGGOIBYLYVKM-UHFFFAOYSA-N 15alpha-hydroxylup-20(29)-en-3-one Natural products CC(=C)C1CCC2(C)CC(O)C3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 PFRGGOIBYLYVKM-UHFFFAOYSA-N 0.000 claims description 2
- SOKRNBGSNZXYIO-UHFFFAOYSA-N Resinone Natural products CC(=C)C1CCC2(C)C(O)CC3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 SOKRNBGSNZXYIO-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract description 9
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 9
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 239000010703 silicon Substances 0.000 description 12
- CGKQZIULZRXRRJ-UHFFFAOYSA-N Butylone Chemical compound CCC(NC)C(=O)C1=CC=C2OCOC2=C1 CGKQZIULZRXRRJ-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- YENIOYBTCIZCBJ-UHFFFAOYSA-N acetic acid;1-methoxypropan-2-ol Chemical compound CC(O)=O.COCC(C)O YENIOYBTCIZCBJ-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000005355 lead glass Substances 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 239000005365 phosphate glass Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- OGFYIDCVDSATDC-UHFFFAOYSA-N silver silver Chemical compound [Ag].[Ag] OGFYIDCVDSATDC-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 101100117236 Drosophila melanogaster speck gene Proteins 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000005331 crown glasses (windows) Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002498 deadly effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Energy (AREA)
- Electromagnetism (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Sustainable Development (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Photovoltaic Devices (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a kind of tellurate glass powder for preparing solar cell front side silver paste, it comprises each component of following percetage by weight: the SiO2 of the Al2O3 of the ZnO of the PbO of the Li2O of the Bi2O3 of TeO2,1%～20%, 1%～20%, 0.1%～5%, 0～10%, 0～5%, 0～10% of 55% 97.9%.Another aspect of the present invention discloses a kind of solar cell front side silver paste and preparation method thereof.The present invention is while ensureing environmental protection, and the efficiency of this solar cell front side silver paste can meet or exceed the level of commercial slurry.
Description
Technical field
The present invention relates to technical field of solar batteries, be specifically related to a kind of glass dust and the solaode prepared with it
Front side silver paste and preparation method thereof.
Background technology
Along with shortage and people's concern to CO2 emission of fossil energy, solar energy generation technology is jumped
The development of formula.And crystal silicon solar energy battery technology is as the main body of solar energy generation technology, enjoy the concern of people always, its
Photoelectric transformation efficiency constantly promotes.
The quality of solaode removes carrier concentration, distribution and the mobility depending in used crystal silicon material,
Also affected by battery plus-negative plate electrode performance.Wherein front electrode directly affects series resistance, shunt resistance, filling
The factor and photoelectric transformation efficiency, therefore the quality of front electrode silver slurry determines the performance of solaode.
Conductive silver paste mainly includes three ingredients, the argentum powder of major part (80～93%), the organic carrier of fraction
(5～15%) and glass dust (0.5～8%).In positive silver silver slurry, in addition to main body argentum powder, the composition of glass dust and content
The final efficiency of cell piece there is extremely crucial impact.Meanwhile, the silicon based cells to making of the glass frit component during silver is starched
The solderability of grid line and pulling force have conclusive impact.Grid line solderability is bad, can affect productivity and the yield of battery.And pulling force
Do not reach certain numerical value, then battery cannot encapsulate and make assembly, and can affect the service life of battery.
At present, mostly the glass dust of preparation silver slurry is business-like high pbo glass powder, by the lead corrosion silicon chip in glass dust
The SiN anti-reflection layer on surface, and assist argentum powder to form secondary crystallization at silicon face, form effective Ohmic contact.At this series glass
In glass powder, usual lead oxide content is higher than 50%.And lead oxide is severe toxicity heavy metal compound, six kinds clearly forbidden for RoHS
One of deadly poisonous compound.At present, in the slurry that solaode is used, silver slurry used by aluminium paste used by back surface field and back electrode is all
Having realized unleaded, only front side silver paste is still using leaded series silver slurry, and due to environmental protection, therefore positive silver paste is unleaded
Change the most positive silver developing direction.But in practice, it has been found that entirely without the front side silver paste prepared by lead glass in efficiency
The most barely satisfactory with in performance, accordingly, it would be desirable to exploitation one not only environmental protection but also high efficiency novel low lead crystal glass.
In the numerous patents (US20110308597, US20110232746, US20110308596) of Du Pont, profit is all proposed
Solaode just silver silver slurry is prepared with tellurate glass powder.Also mention with the interpolation of alkali metal Li.This tellurate P series glass,
Can effectively solve the silver-colored silicon contact problems under the square resistance of silicon chip height surface, improve battery efficiency.But, this tellurate
P series glass is high pbo glass, and content, more than 5%, is host element, irreplaceable, and the harm to environment is bigger.
The numerous patents (US20110094578A1, US20150122326A1) of clear flourish chemical industry proposes to use unleaded tellurium
Silicate glass powder prepares solar energy front side silver paste, though certain conversion efficiency can be arrived, but with commercial positive silver paste in conversion effect
Still there is gap in rate, do not possess practicality.Especially on the silicon chip that sheet resistance is higher, efficiency can drastically decline, and it is suitable for
The silicon chip sheet resistance rising space is limited, is not suitable with the developing direction of battery process.
Currently existing crown glass series, is traditional silicic-boric acid or series of phosphate glass, when silicon chip surface side
Hinder low in the case of, these glass or applicable, but inefficient.But at present, in order to pursue higher photoelectric transformation efficiency, silicon
Based solar battery all uses high sheet resistivity technique to prepare, and therefore, traditional silicic-boric acid or series of phosphate glass are high at this
Can not be suitable under sheet resistance technique.Even unleaded tellurate glass, use its prepared slurry in the high square resistance suitability
The most restricted, especially in high square resistance single crystal battery, it may appear that loose contact, under EL (electroluminescent), present the feelings of black speck
Condition.
At present, only tellurate glass can be suitable on high square resistance, obtains high efficiency, but as mentioned above, it is known that uses
In tellurate glass series, or it is that lead tolerance is higher, is unfavorable for environmental protection, although or the most leaded, but performance is the most silver-colored with commercialization
There is the biggest gap.
Summary of the invention
The technical problem to be solved in the present invention is the defect overcoming prior art, it is provided that a kind of glass dust and preparing with it
Solar cell front side silver paste and preparation method thereof, while ensureing environmental protection, the efficiency of this solar cell front side silver paste is permissible
Meet or exceed the level of commercial slurry.
In order to solve above-mentioned technical problem, the invention provides following technical scheme:
The first aspect of the invention is to provide a kind of tellurate glass powder for preparing solar cell front side silver paste,
It comprises each component of following percetage by weight: the TeO of 55%-97.9%2, 1%～the Bi of 20%2O3, 1%～20%
Li2The Al of the ZnO of the PbO of O, 0.1%～5%, 0～10%, 0～5%2O3, 0～the SiO of 10%2；Each component sum more than and
For absolutely.
Further, each component of following percetage by weight is comprised: the TeO of 90%2, the Bi of 5%2O3, the Li of 2.5%2O、
The PbO of 2%, the SiO of 0.5%2。
Further, each component of following percetage by weight is comprised: the TeO of 84.5%2, the Bi of 6.5%2O3, 2.5%
Li2O, the PbO of 2.5%, the ZnO of 4%.
Further, each component of following percetage by weight is comprised: the TeO of 78.5%2, the Bi of 6%2O3, the Li of 3%2O、
The PbO of 4.8%, the SiO of 2.8%2, the ZnO of 2.5%, the Al of 2.4%2O3。
Further, each component of following percetage by weight is comprised: the TeO of 71.6%2, the Bi of 15%2O3, 2.8%
Li2O, the PbO of 4.5%, the ZnO of 5.1%, the Al of 1%2O3。
Further, each component of following percetage by weight is comprised: the TeO of 63.8%2, the Bi of 10%2O3, 14.6%
Li2O, the PbO of 3.6%, the SiO of 8%2。
The tellurate glass of present invention design, a kind of particular situation is: these compositions can be glass phase；Another kind of feelings
Condition is, these compositions can be crystal, partial crystals, and noncrystal, part is noncrystal, or combinations thereof.Wherein, term
' glass ' or ' glass phase ' here refers mainly to the combination of any above-mentioned noncrystal and crystal.
Raw material used in the present invention, is not limited only to oxide, other the carbonate comprising above cation, phosphoric acid
Salt, fluoride, and all can be changed into the material of oxide, all in this scope after high-temperature process.
An additional aspect of the present invention is to provide a kind of solar cell front side silver paste using tellurate glass powder to prepare,
It comprises each component of following percetage by weight: argentum powder 80%～93%, organic carrier 5%～15%, tellurate glass powder
0.5%～6%.
Further, described argentum powder be purity be 99.9%～99.999%, described argentum powder be particle mean size at 0.5um～
Spherical or flakey body between 10um.It is furthermore preferred that the particle mean size of argentum powder is between 0.5um～3um, pattern should be spherical
Or subglobular.
Further, described organic carrier includes that organic resin and organic solvent, described organic resin include ethyl cellulose
Element resin, rosin resin, acrylic resin one or more；Described organic solvent includes propandiol butyl ether acetate, butyl
One or more in carbitol, ethylene glycol monomethyl ether acetate, petroleum ether, ether solvent.
Another aspect of the present invention is to provide the preparation method of a kind of solar cell front side silver paste, and it includes following step
Rapid:
(1) preparing organic carrier: take the organic resin that mass percent is 10%～40%, adding mass percent is
The organic solvent of 60%～90% stirs 1～2 hour at 80～150 DEG C, obtains the organic carrier of homogeneous transparent after dissolving；
(2) preparing glass dust: by load weighted above-mentioned glass dust raw material at 800 DEG C～1400 DEG C, insulation 0.5～1 is little
Time fusing, after the glass molten slurry quenching after fusing, be milled to 0.5～2um, then sieve through 325～400 eye mesh screens, the most available
The glass powder being suitable for is standby；
(3) silver slurry mixing: take argentum powder that mass percent is 80%～93%, 10%～15% the having of step (1) gained
Airborne body, 0.5%～the 5% glass dust mixing and stirring described in step (2)；
(4) silver slurry dispersion: combined silver slurry step (3) prepared is put into three-roll grinder and is fully ground 8～10 times, extremely
Slurry fineness is less than 10 μm, thus obtains silver slurry slurry.
Compared with prior art, the present invention is reached to provide the benefit that:
(1) solar cell front side silver paste that the present invention provides, uses tellurate glass powder body system, and this glass dust system is adopted
Combine with low lead compound；In this glass dust component, lead is not main component, and its mass percent is less than 5%, is properly added
Lead can regulate high temperature viscosity and the softening point of glass, reduces contact resistance, extends the slurry suitability to silicon chip sheet resistance；
But lead content is relatively low, non-main constituent, both reached ecological requirements, and achieved again the suitability of high square resistance technique, effectively solve
The problem of positive silver paste environmental protection；
(2) present invention is by controlling the addition of alkali metal Li, effectively extends sintering temperature, it is ensured that the performance of product is steady
Qualitative, the effective photoelectric transformation efficiency improving silicon based cells, improves solderability and the pulling force of grid line simultaneously, uses this tellurate
The cell piece of the positive silver prepared by glass dust, while ensureing environmental protection, its efficiency can meet or exceed the water of commercial slurry
Flat.
Detailed description of the invention
Hereinafter the preferred embodiments of the present invention are illustrated, it will be appreciated that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1
A kind of preparation method of solar cell front side silver paste, it comprises the following steps:
(1) organic carrier is prepared: taking mass percent is 15% ethyl cellulose resin, and mass percent is 8% Colophonium
Resin, mass percent is 10% acrylic resin, adds organic solvent (the propylene glycol monomethyl ether acetic acid that mass percent is 67%
Ester, ethylene glycol monomethyl ether acetate, butyl carbitol, one or more mixture of petroleum ether), the temperature of 80～150 DEG C
Under dissolve in the way of heating while stirring, the organic carrier of homogeneous transparent can be obtained after 2 hours；
(2) glass dust is prepared: take each raw material of following percetage by weight: the TeO of 90%2, the Bi of 5%2O3, 2.5%
Li2O, the PbO of 2%, the SiO of 0.5%2, by load weighted above-mentioned raw materials after batch mixer mix homogeneously, it is placed in high temperature Muffle furnace
In, temperature controls, at 800 DEG C～1400 DEG C, to be incubated 1 hour；Glass after fusing is melted slurry and pours in deionized water after shrend,
It is milled to 1um standby through the 325～400 eye mesh screens glass powder that i.e. can obtain being suitable for that sieves again；
(3) silver slurry mixing: take argentum powder that mass percent is 89%, mass percent is having of preparing of 8.5% step (1)
Airborne body, mass percent are the glass dust mixing and stirring that 2.5% step (2) prepares；
(4) silver slurry dispersion: the raw material after stirring described in step (3) is put into three-roll grinder and is fully ground 10
Secondary, it is ground to outward appearance fine and smooth, uniformly without obvious granule, < 10um i.e. can be made into silica-based solar to measure fineness with Hegman fineness grind agent
The silver slurry slurry of battery.
Embodiment 2
A kind of preparation method of solar cell front side silver paste, it comprises the following steps:
(1) organic carrier is prepared: taking mass percent is 15% ethyl cellulose resin, and mass percent is 5% Colophonium
Resin, mass percent is 10% acrylic resin, adds organic solvent (the propylene glycol monomethyl ether acetic acid that mass percent is 70%
Ester, ethylene glycol monomethyl ether acetate, butyl carbitol, one or more mixture of petroleum ether), the temperature of 80～150 DEG C
Under dissolve in the way of heating while stirring, the organic carrier of homogeneous transparent can be obtained after 2 hours；
(2) glass dust is prepared: take each raw material of following percetage by weight: the TeO of 84.5%2, the Bi of 6.5%2O3, 2.5%
Li2O, the PbO of 2.5%, the ZnO of 4%, by load weighted above-mentioned raw materials after batch mixer mix homogeneously, be placed in high temperature Muffle
In stove, temperature controls, at 800 DEG C～1400 DEG C, to be incubated 1 hour；Glass after fusing is melted slurry and pours shrend in deionized water into
After, it is milled to 1um standby through the 325～400 eye mesh screens glass powder that i.e. can obtain being suitable for that sieves again；
(3) silver slurry mixing: take argentum powder that mass percent is 89.5%, mass percent is that 7.8% step (1) prepares
Organic carrier, mass percent are the glass dust mixing and stirring that 2.7% step (2) prepares；
(4) silver slurry dispersion: the raw material after stirring described in step (3) is put into three-roll grinder and is fully ground 10
Secondary, it is ground to outward appearance fine and smooth, uniformly without obvious granule, < 10um i.e. can be made into silica-based solar to measure fineness with Hegman fineness grind agent
The silver slurry slurry of battery.
Embodiment 3
A kind of preparation method of solar cell front side silver paste, it comprises the following steps:
(1) organic carrier is prepared: taking mass percent is 7% ethyl cellulose resin, and mass percent is 5% rosin tree
Fat, mass percent is 15% acrylic resin, adds organic solvent (the propylene glycol monomethyl ether acetic acid that mass percent is 73%
Ester, ethylene glycol monomethyl ether acetate, butyl carbitol, one or more mixture of petroleum ether), the temperature of 80～150 DEG C
Under dissolve in the way of heating while stirring, the organic carrier of homogeneous transparent can be obtained after 2 hours；
(2) glass dust is prepared: take each raw material of following percetage by weight: the TeO of 78.5%2, the Bi of 6%2O3, 3%
Li2O, the PbO of 4.8%, the SiO of 2.8%2, the ZnO of 2.5%, the Al of 2.4%2O3, by load weighted above-mentioned raw materials through batch mixer
After mix homogeneously, being placed in high temperature Muffle furnace, temperature controls, at 800 DEG C～1400 DEG C, to be incubated 1 hour；By the glass after fusing
Molten slurry is poured in deionized water after shrend, is milled to 1um and sieves the glass dust that i.e. can obtain being suitable for through 325～400 eye mesh screens
Expect standby；
(3) silver slurry mixing: take argentum powder that mass percent is 89.6%, mass percent is that 7.9% step (1) prepares
Organic carrier, mass percent are the glass dust mixing and stirring that 2.5% step (2) prepares；
(4) silver slurry dispersion: the raw material after stirring described in step (3) is put into three-roll grinder and is fully ground 10
Secondary, it is ground to outward appearance fine and smooth, uniformly without obvious granule, < 10um i.e. can be made into silica-based solar to measure fineness with Hegman fineness grind agent
The silver slurry slurry of battery.
Embodiment 4
A kind of preparation method of solar cell front side silver paste, it comprises the following steps:
(1) organic carrier is prepared: taking mass percent is 13% ethyl cellulose resin, and mass percent is 5% Colophonium
Resin, mass percent is 8% acrylic resin, adds organic solvent (the propylene glycol monomethyl ether acetic acid that mass percent is 75%
Ester, ethylene glycol monomethyl ether acetate, butyl carbitol, one or more mixture of petroleum ether), the temperature of 80～150 DEG C
Under dissolve in the way of heating while stirring, the organic carrier of homogeneous transparent can be obtained after 2 hours；
(2) glass dust is prepared: take each raw material of following percetage by weight: the TeO of 71.6%2, the Bi of 15%2O3, 2.8%
Li2O, the PbO of 4.5%, the ZnO of 5.1%, the Al of 1%2O3, by load weighted above-mentioned raw materials after batch mixer mix homogeneously,
Being placed in high temperature Muffle furnace, temperature controls, at 800 DEG C～1400 DEG C, to be incubated 1 hour；Will fusing after glass melt slurry pour into from
In sub-water after shrend, it is milled to 1um standby through the 325～400 eye mesh screens glass powder that i.e. can obtain being suitable for that sieves again；
(3) silver slurry mixing: take argentum powder that mass percent is 89.6%, mass percent is that 8.1% step (1) prepares
Organic carrier, mass percent are the glass dust mixing and stirring that 2.3% step (2) prepares；
(4) silver slurry dispersion: the raw material after stirring described in step (3) is put into three-roll grinder and is fully ground 10
Secondary, it is ground to outward appearance fine and smooth, uniformly without obvious granule, < 10um i.e. can be made into silica-based solar to measure fineness with Hegman fineness grind agent
The silver slurry slurry of battery.
Embodiment 5
A kind of preparation method of solar cell front side silver paste, it comprises the following steps:
(1) organic carrier is prepared: taking mass percent is 15% ethyl cellulose resin, and mass percent is 8% Colophonium
Resin, mass percent is 10% acrylic resin, adds organic solvent (the propylene glycol monomethyl ether acetic acid that mass percent is 67%
Ester, ethylene glycol monomethyl ether acetate, butyl carbitol, one or more mixture of petroleum ether), the temperature of 80～150 DEG C
Under dissolve in the way of heating while stirring, the organic carrier of homogeneous transparent can be obtained after 2 hours；
(2) glass dust is prepared: take each raw material of following percetage by weight: the TeO of 63.8%2, the Bi of 10%2O3, 14.6%
Li2O, the PbO of 3.6%, the SiO of 8%2, by load weighted above-mentioned raw materials after batch mixer mix homogeneously, it is placed in high temperature Muffle
In stove, temperature controls, at 800 DEG C～1400 DEG C, to be incubated 1 hour；Glass after fusing is melted slurry and pours shrend in deionized water into
After, it is milled to 1um standby through the 325～400 eye mesh screens glass powder that i.e. can obtain being suitable for that sieves again；
(3) silver slurry mixing: take argentum powder that mass percent is 90%, mass percent be 8% step (1) prepare organic
Carrier, mass percent are the glass dust mixing and stirring that 2% step (2) prepares；
(4) silver slurry dispersion: the raw material after stirring described in step (3) is put into three-roll grinder and is fully ground 10
Secondary, it is ground to outward appearance fine and smooth, uniformly without obvious granule, < 10um i.e. can be made into silica-based solar to measure fineness with Hegman fineness grind agent
The silver slurry slurry of battery.
Using above-mentioned silver slurry as positive silver paste with 400 mesh silk screen printings on 156X156 polysilicon chip (thickness 180 ±
5um), back side Al back surface field and back electrode silver paste all use commercialization slurry, and after drying, sintering, the electrical property average of test is such as
Following table:
Control sample is commercially available commercial product；By the commercial control sample of contrast, it can be seen that in multiple components, the present invention's
Positive silver paste all can reach even to surmount commercially available prod, it is possible to achieve substituting completely, it is right to decrease in instant component formula
The lead element usage amount of bad environmental, it is achieved that environmental protection purpose, and effectively promote cell piece efficiency, improve photoelectric transformation efficiency
Thus improve the technical merit of existing unleaded positive silver paste.
Finally it is noted that the foregoing is only the preferred embodiments of the present invention, it is not limited to the present invention,
Although being described in detail the present invention with reference to previous embodiment, for a person skilled in the art, it still may be used
So that the technical scheme described in foregoing embodiments to be modified, or wherein portion of techniques feature is carried out equivalent.
All within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. made, should be included in the present invention's
Within protection domain.
Claims (10)
1. the tellurate glass powder being used for preparing solar cell front side silver paste, it is characterised in that comprise following weight hundred
Each component of mark: the TeO of 55%-97.9%2, 1%～the Bi of 20%2O3, 1%～the Li of 20%2O, 0.1%～5%
The Al of the ZnO of PbO, 0～10%, 0～5%2O3, 0～the SiO of 10%2；More than and, each component sum is absolutely.
The most according to claim 1 for preparing the tellurate glass powder of solar cell front side silver paste, it is characterised in that bag
Each component containing following percetage by weight: the TeO of 90%2, the Bi of 5%2O3, the Li of 2.5%2O, the PbO of 2%, 0.5%
SiO2。
The most according to claim 1 for preparing the tellurate glass powder of solar cell front side silver paste, it is characterised in that bag
Each component containing following percetage by weight: the TeO of 84.5%2, the Bi of 6.5%2O3, the Li of 2.5%2O, the PbO of 2.5%, 4%
ZnO.
The most according to claim 1 for preparing the tellurate glass powder of solar cell front side silver paste, it is characterised in that bag
Each component containing following percetage by weight: the TeO of 78.5%2, the Bi of 6%2O3, the Li of 3%2O, the PbO of 4.8%, 2.8%
SiO2, the ZnO of 2.5%, the Al of 2.4%2O3。
The most according to claim 1 for preparing the tellurate glass powder of solar cell front side silver paste, it is characterised in that bag
Each component containing following percetage by weight: the TeO of 71.6%2, the Bi of 15%2O3, the Li of 2.8%2O, the PbO of 4.5%, 5.1%
ZnO, the Al of 1%2O3。
The most according to claim 1 for preparing the tellurate glass powder of solar cell front side silver paste, it is characterised in that bag
Each component containing following percetage by weight: the TeO of 63.8%2, the Bi of 10%2O3, the Li of 14.6%2O, the PbO of 3.6%, 8%
SiO2。
7. use a solar cell front side silver paste prepared by the arbitrary described tellurate glass powder of claim 1～6, its feature
It is, comprises each component of following percetage by weight: argentum powder 80%～93%, organic carrier 5%～15%, tellurate glass powder
0.5%～6%.
Solar cell front side silver paste the most according to claim 7, it is characterised in that described argentum powder be purity be 99.9%
～99.999%, described argentum powder is the particle mean size spherical or flakey body between 0.5um～10um.
Solar cell front side silver paste the most according to claim 7, it is characterised in that described organic carrier includes organic tree
Fat and organic solvent, described organic resin include ethyl cellulose resin, rosin resin, acrylic resin one or more；Institute
The organic solvent stated includes that propandiol butyl ether acetate, butyl carbitol, ethylene glycol monomethyl ether acetate, petroleum ether, ethers are molten
One or more in agent.
10. the preparation method of solar cell front side silver paste described in a claim 7, it is characterised in that comprise the following steps:
(1) prepare organic carrier: take the organic resin that mass percent is 10%～40%, add mass percent be 60%～
The organic solvent of 90% stirs 1～2 hour at 80～150 DEG C, obtains the organic carrier of homogeneous transparent after dissolving；
(2) prepare glass dust: by load weighted above-mentioned glass dust raw material at 800 DEG C～1400 DEG C, be incubated 0.5～1 hour and melt
Change, after molten for the glass after fusing slurry quenching, be milled to 0.5～2um, then sieve through 325～400 eye mesh screens, i.e. can be suitable for
Glass powder standby；
(3) silver slurry mixing: take argentum powder that mass percent is 80%～93%, 10%～15% step (1) gained have airborne
Body, 0.5%～the 5% glass dust mixing and stirring described in step (2)；
(4) silver slurry dispersion: combined silver slurry step (3) prepared is put into three-roll grinder and is fully ground 8-10 time, to slurry
Fineness is less than 10 μm, thus obtains silver slurry slurry.
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| CN107285637A (en) * | 2017-05-08 | 2017-10-24 | 江苏东昇光伏科技有限公司 | It is a kind of to be used to prepare glass dust of solar cell front side silver paste and preparation method thereof |
| CN107346671A (en) * | 2017-01-23 | 2017-11-14 | 上海匡宇科技股份有限公司 | Low light attenuation solar cell front side silver paste and preparation method thereof |
| CN107746184A (en) * | 2017-10-20 | 2018-03-02 | 苏州晶银新材料股份有限公司 | A kind of glass frit composition and the conductive silver paste and preparation method containing it |
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| CN114394754A (en) * | 2021-12-31 | 2022-04-26 | 广州市儒兴科技股份有限公司 | Glass powder with wide application window and high-performance conductive silver paste |
| CN114394754B (en) * | 2021-12-31 | 2023-05-23 | 广州市儒兴科技股份有限公司 | Glass powder with wide application window and high-performance conductive silver paste |
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