CN106409379B - A kind of rear electrode for crystal silicon solar battery hinders silver paste and preparation method thereof with low string - Google Patents
A kind of rear electrode for crystal silicon solar battery hinders silver paste and preparation method thereof with low string Download PDFInfo
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- CN106409379B CN106409379B CN201610578117.7A CN201610578117A CN106409379B CN 106409379 B CN106409379 B CN 106409379B CN 201610578117 A CN201610578117 A CN 201610578117A CN 106409379 B CN106409379 B CN 106409379B
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- silver paste
- silver powder
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- crystal silicon
- solar battery
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 61
- 239000004332 silver Substances 0.000 title claims abstract description 59
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 32
- 239000010703 silicon Substances 0.000 title claims abstract description 32
- 239000013078 crystal Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 12
- 239000000654 additive Substances 0.000 claims abstract description 48
- 230000000996 additive effect Effects 0.000 claims abstract description 37
- 239000011521 glass Substances 0.000 claims abstract description 28
- 239000000428 dust Substances 0.000 claims abstract description 25
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000002562 thickening agent Substances 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000080 wetting agent Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 239000013530 defoamer Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 239000013008 thixotropic agent Substances 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 abstract description 29
- 230000000694 effects Effects 0.000 abstract description 10
- 230000009467 reduction Effects 0.000 abstract description 4
- 230000009466 transformation Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 13
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 11
- 239000000470 constituent Substances 0.000 description 9
- 238000003466 welding Methods 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 8
- 239000013074 reference sample Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000000034 method Methods 0.000 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 description 5
- 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 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
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- 239000000843 powder Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 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 description 5
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 5
- 239000001856 Ethyl cellulose Substances 0.000 description 4
- 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 description 4
- 229910000676 Si alloy Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 229920001249 ethyl cellulose Polymers 0.000 description 4
- 235000019325 ethyl cellulose Nutrition 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 229910003069 TeO2 Inorganic materials 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- -1 NC Nitroncellulose Chemical compound 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- VPJOGDPLXNTKAZ-UHFFFAOYSA-N 2-methylpropanoic acid;2,2,4-trimethylpentane-1,3-diol Chemical class CC(C)C(O)=O.CC(C)C(O)C(C)(C)CO VPJOGDPLXNTKAZ-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000001293 FEMA 3089 Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000005308 flint glass Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- 230000008719 thickening Effects 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
-
- 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
Abstract
Silver paste is hindered with low string the invention discloses a kind of rear electrode for crystal silicon solar battery, its formula includes：Ball shape silver powder, glass dust, organic solvent and auxiliary agent, anti-shrink additive comprising thickener and network structure in auxiliary agent, the percentage by weight of silver paste moderate resistance shrink additives is 0.05~5%, the fusing point of anti-shrink additive is higher than 700 DEG C and mesh aperture is not less than the average grain diameter of silver powder, and the porosity of anti-shrink additive is 40 ~ 80%.Anti-shrink additive of the invention by adding appropriate network structure, allow it as the effect of support frame, the sintering stress that can aid in produced by reduction silver paste sintering, reduce shrinkage factor during back side silver paste sintering, so as to reach the uniformity of backplate silver film, further reduce the series resistance of solar cell and improve its photoelectric transformation efficiency.
Description
Technical field
The present invention relates to crystal silicon solar battery back face electrode paste, and in particular to a kind of crystal silicon solar energy battery
Back electrode hinders silver paste and preparation method thereof with low string.
Background technology
Crystal silicon solar energy battery is a kind of semiconductor devices converted solar energy into electrical energy.By back side silver paste organizine net
The backplate that printing, sintering are formed is the important component of solar battery sheet, and backplate has to provide excellent
Adhesive force and solderability, while having lower contact resistance and high electricity conversion, to ensure the stabilization of cell piece component
Reliability.
Crystal silicon solar battery back face silver paste on the market has the following disadvantages at present：
1. poor adhesive force between silver electrode and silicon chip, cell piece service life is short；
2. silver electrode solderability, soldering resistance are poor, there is rosin joint and cross the phenomenons such as weldering, cell piece scrappage is high.
3. the silver powder used in slurry is ball shape silver powder, shrink big in sintering, cause film layer compactness after sintering poor, sheet resistance
Higher, electrical property is poor.
Shrink big for silver powder in sintering mentioned above, the silver powder having from high-crystallinity makees the conduction of back silver paste
Phase, but the sintering temperature of the silver powder needs of high-crystallinity is high, is unfavorable for the development trend of green energy conservation.In the prior art, for
The compactness of electrode film layer arranges in pairs or groups to realize by the optimization of the silver powder of different-shape, different-grain diameter or different preparation methods mostly
(A of CN 103854719 A, CN 103956197) and from gap between silver powder and copper powder the filling silver powder with particle diameter, to carry
The bulk density of high film layer, increases particle contact area, film layer convergent force is reduced, so as to improve conductive capability (CN
The A of 102831949 A, CN 102831954), and the characteristic easily shunk during for silver powder in the silver paste of the back side through high temperature sintering, this hair
Bright to provide a kind of rear electrode for crystal silicon solar battery low string resistance silver paste and preparation method thereof, the back side silver paste is through high temperature sintering
When, silver powder shrinkage degree is small, can ensure the uniformity of electrode film layer well.
The content of the invention
The present invention is for above-mentioned the deficiencies in the prior art there is provided a kind of rear electrode for crystal silicon solar battery with low
String resistance silver paste and preparation method thereof, the electrode silver film cause that the back silver paste is formed after printing-sintering is dense and uniform, with silicon substrate
The welding pulling force of plate is excellent, at the same time it can also reduce the series resistance of back electrode, so as to improve electricity conversion.
To achieve the above object, the technical solution adopted by the present invention is as follows：A kind of rear electrode for crystal silicon solar battery is used
Low string resistance silver paste, it is characterised in that its formula includes：Increasing is included in ball shape silver powder, glass dust, organic solvent and auxiliary agent, auxiliary agent
Thick dose and the anti-shrink additive of network structure, the percentage by weight of silver paste moderate resistance shrink additives is 0.05~5%, anti-shrink
The fusing point of additive is not less than the average grain diameter of silver powder higher than 700 DEG C and mesh aperture, the porosity of anti-shrink additive for 40~
80%.
The fusing point of anti-shrink additive is preferably above 700 DEG C, to ensure in the sintering process of slurry, anti-shrink addition
Agent can not be melted or the melting of fraction is to retain the structure that its is netted, and the network structure that the anti-shrink additive has makes
It can help to reduce the sintering stress produced by the silver paste sintering process of the back side, further as the skeleton for supporting silverskin
Shrinkage factor during back side silver paste sintering is reduced, so as to improve the uniformity of backplate silver film, solar energy can be finally reduced
The series resistance of battery and its photoelectric transformation efficiency of raising.The consumption of anti-shrink additive is too small, then anti-shrink ability is poor, its
Consumption is excessive, then can influence the electrical property of slurry.The porosity of anti-shrink additive is too small, and anti-shrink effect is not substantially or in sintering
Big barrier is formed mutually so as to influence electrical property, its porosity is too big, the adhesive force of back of the body silver is adversely affected.
It is preferred that technical scheme be that the anti-shrink additive is made up of the combination of component A or component B or component A, B, group
It is that, selected from least one of Au, Ag, Cu, Ni, CNT, component B is selected from ZnO, WO to divide A3、NiO、Al2O3、CuO、
SnO2、TiO2、SiO2At least one of.The network structure that component A and component B have can reduce back silver paste high temperature burning
Shrinkage factor during knot, meanwhile, component A addition is to the holding of back silver paste electrical property or improves favourable, and component B is conducive to carrying
The welding pulling force of high back silver paste, therefore above two component is compounded by a certain percentage, back silver paste can be made with low
Sintering shrinkage on the premise of, while have concurrently good electric conductivity and welding pulling force；In addition, above-mentioned anti-shrink additive
Species is the conventional constituents of conductive silver paste, and not only the compatibility with back silver paste is preferable, and avoids new impurities phase
Introduce.
It is preferred that technical scheme be that the size of the anti-shrink additive is 0.1~5 μm, 0.1~3 μm of mesh aperture.Net
During 0.1 μm of hole aperture ＜, it is impossible to the most silver powder not melted and glass dust is passed through mesh, so that in slurry sintering
When, glass dust is helped that to burn the formation of effect and glass dust to the adhesion strength of silicon substrate, silver-colored silicon alloy equal to the fluxing of silver powder
It is adversely affected, that is, is unfavorable for the holding or raising of back silver paste electrical property and welding pulling force；During 3 μm of mesh aperture ＞,
Each just it can only be unfavorable for the equal of anti-shrink effect comprising a mesh in the particle of the anti-shrink additive with above-mentioned size
Even property, so as to be unfavorable for the homogeneity of electrode film layer.
It is preferred that technical scheme be that the formula of silver paste includes：First ball shape silver powder 25~40%, the second ball shape silver powder 10~
20%th, flake silver powder 7~15%, glass dust 1~4%, organic solvent 18~44%, thickener 4~12%, anti-shrink additive
1~3% and other auxiliary agents 0.5~2%；The average grain diameter of second ball shape silver powder is less than the average grain diameter of the first ball shape silver powder.Ball
Shape silver powder is small due to granularity, and closs packing is good, and sintering activity is high, is conducive to sintering；Flake silver powder not only makes sintering disposed slurry and silicon
Contact resistance between substrate is low, advantageously reduces series resistance, and with the characteristics of shrinkage factor is low when sintering.By spherical silver
Powder is used with flake silver powder collocation, is conducive to while playing the above-mentioned advantage of the two.Further to be preferably, described first is spherical
1~3 μm of the average grain diameter of silver powder, 1 μm of the average grain diameter ＜ of the second ball shape silver powder, tap density >=4.0g/cm3；Sheet silver
The average grain diameter of powder is 1~5 μm, 2.8~4.0g/cm of tap density3。
Component in the glass dust includes：Bi2O340~60%, B2O36~20%, SiO28~15%, ZnO 10
~20%, Al2O30.5~5%, BaO 0.1~4%, TeO210~25%, Na2O 0.3~2%, ZrO20~3% He
P2O51~5%；Its softening point is 450~600 DEG C, 0.2~3 μm of average grain diameter.
In back silver paste, lead-free glass powder as inorganic binder, its 450~600 DEG C through preferably having it is soft
Change point in order to back silver paste be calcined at 600~900 DEG C when, ensure that have between back electrode and silicon substrate it is enough viscous
Close intensity and ensure the formation of silver-colored silicon alloy.If the softening point of selected glass dust is too low, sintering degree can be excessive；And
Softening point is too high, enough melt-flows can not occur during baking, it is impossible to realize liquid-phase sintering with silver particles, so that electric
The adhesion strength of pole and silicon substrate is relatively low.
The preferred anti-shrink additive and the silver powder and glass dust of selection with above-mentioned mesh aperture size in the present invention
Particle size match, melting and the silver powder that does not melt and glass dust is passed freely through mesh, when slurry is sintered,
Glass dust is not influenceed to burn effect on fluxing help of silver powder and do not influence glass dust to the adhesion strength of silicon substrate, silver-colored silicon alloy
Formed, i.e., do not influence the welding pulling force and electrical property of backplate.
It is preferred that technical scheme be, thickener be ethyl cellulose, hydroxymethyl cellulose, NC Nitroncellulose, acrylic acid tree
Fat, phenolic resin, alkyd resin, epoxy resin, polyvinyl butyral resin, polyamide, rosin resin, rosin modified phenolic
At least one of resin and Abietyl modified glyceride.
It is preferred that technical scheme be, other auxiliary agents include thixotropic agent, dispersant, levelling agent, defoamer and wetting agent
At least one of.
It is preferred that technical scheme be, organic solvent be terpinol, turpentine oil, ethylene glycol ethyl ether, butyl glycol ether, ethylene glycol
Ethyl ether acetate ester, ethylene glycol phenyl ether, diethylene glycol dimethyl ether, diethylene glycol ether, butyl, diethylene glycol dibutyl
Ether, butyl acetate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, 2,2,4- trimethyl -1,3- pentanediol isobutyls
In acid esters, tributyl phosphate, 3- hydroxyl -3- carboxyl glutaric acids tributyl, dibutyl phthalate, tributyl phthalate
At least two mixture.
In order to reach in reduction back side silver paste sintering shrinkage, so as to while reducing the series resistance of back electrode, make too
Positive the energy electricity conversion of battery and the welding pulling force of electrode also obtain a certain degree of raising, further add anti-shrink
Agent component A and component B are compounded, and technical scheme preferably is that the anti-shrink additive is by Ag and selected from SnO2, in CuO
One kind combine, weight ratio is 1：(1~2).
It is preferred that technical scheme can also be that the anti-shrink additive is by Cu, Ni and TiO2Combine, weight ratio
For 1：(1~1.5)：(2~3).
The preparation of silver paste is hindered with low string another object of the present invention is to provide a kind of rear electrode for crystal silicon solar battery
Method, comprises the steps：
S1：The preparation of organic carrier, is first added organic solvent in container by formula rate, then adds thickening under agitation
Agent, is warming up to 50~100 DEG C, is incubated 0.5~3h, cools to add at 40~50 DEG C after other auxiliary agents, filtering and has obtained airborne
Body；
S2：The preparation of back silver paste, anti-shrink additive is added in organic carrier made from S1, and ultrasonic disperse 10~
30min, then sequentially adds the first ball shape silver powder, the second ball shape silver powder, flake silver powder and glass dust, through high-speed stirred in proportion
Mixing and three-roll grinder grinding distribution, obtain rear electrode for crystal silicon solar battery and hinder silver paste with low string.
Advantages of the present invention and having the beneficial effect that for obtaining：
(1) present invention adds appropriate anti-shrink additive in traditional back side silver paste, and anti-shrink additive is had
Network structure, allow it as the effect of support frame, the sintering for helping to reduce produced by silver paste sintering process should
Power, further shrinkage factor during reduction back side silver paste sintering, so as to improve the uniformity of backplate silver film, is finally reduced too
The series resistance of positive energy battery and its photoelectric transformation efficiency of raising.
(2) the anti-shrink additive with specific mesh pore size preferred in the present invention, with being selected in the present invention
The particle size of silver powder and glass dust matches, and the silver powder and glass dust for making melting and not melting can pass freely through mesh,
When slurry is sintered, glass dust is not influenceed to help burning effect and not influence glass dust strong to the bonding of silicon substrate the fluxing of silver powder
The formation of degree, silver-colored silicon alloy, i.e., do not influence the welding pulling force and electrical property of back electrode.
Embodiment
With reference to embodiment, the embodiment to the present invention is further described.Following examples are only used for more
Plus technical scheme is clearly demonstrated, and can not be limited the scope of the invention with this.
Embodiment 1~5 and the rear electrode for crystal silicon solar battery of comparative example 1~2 hinder the weight of each component of silver paste with low string
Measure percentage composition as shown in table 1 below.
Silver powder：In embodiment 1, silver powder is the mixture of the first ball shape silver powder and the second ball shape silver powder；In embodiment 2~5,
Silver powder is the mixture of the first ball shape silver powder, the second ball shape silver powder and flake silver powder, in above-described embodiment 1~5, the specification of silver powder
It is as follows：1~3 μm of the average grain diameter of first ball shape silver powder, 1 μm of the average grain diameter ＜ of the second ball shape silver powder, tap density >=
4.0g/cm3；The average grain diameter of flake silver powder is 1~5 μm, and tap density is 2.8~4.0g/cm3。
Glass dust：In embodiment 1~5, the softening point of selected glass dust system is 500~600 DEG C, and average grain diameter is
1-3μm.Its concrete component and weight percentage are：Bi2O340~60%, B2O36~20%, SiO28~15%, ZnO
10~20%, Al2O30.5~5%, BaO 0.1~4%, TeO210~25%, Na2O 0.3~2%, ZrO20~3% He
P2O51~5%；Further preferably：Bi2O343%th, B2O315%th, SiO210%th, ZnO 12%, Al2O33%th, BaO 1%,
TeO212%th, Na2O 1%, ZrO22% and P2O51%.Glass dust can be using known to art technology workman in the present invention
Prepared by method, can also directly select commercially available prod, it is desirable to meet the requirement of softening temperature and particle diameter distribution.Adopted in embodiment
Glass dust is lead-free glass powder, and above-mentioned lead-free glass powder can also be replaced with flint glass powder system.
Table 1：
Anti-shrink additive：The percentage by weight of the moderate resistance shrink additives of embodiment 1 is 4%, specifically chosen netted SiO2；
It is netted ZnO in embodiment 2；It is netted Al in embodiment 32O3And NiO, the two mass ratio 1:1；It is carbon nanometer in embodiment 4
Pipe, CNT is multi-walled carbon nanotube, 1~5 μm of length, external diameter ＞ 50nm, purity ＞ 98%；It is netted WO in embodiment 53
And Au, the mass ratio 2 of the two:1, in above-described embodiment 1~5, the size of anti-shrink additive is 0.1~5 μm, mesh aperture
It it is 0.1~3 μm, porosity is 40~80%.
Thickener：It is ethyl cellulose in embodiment 1, is rosin resin and ethyl cellulose, the matter of the two in embodiment 2
Amount compares 1:1；It is epoxy resin, polyvinyl butyral resin and NC Nitroncellulose, the mass ratio 2 of three in embodiment 3:1:1；Implement
It is rosin modified phenolic resin in example 4；It is ethyl cellulose and phenolic resin, mass ratio 4 in embodiment 5:1.
Other auxiliary agents：Dispersant 0.15%, defoamer 0.2%, levelling agent 0.25% and wetting agent are added in embodiment 1
0.2%；Thixotropic agent 0.2%, wetting agent 0.2%, defoamer 0.1% are added in embodiment 2；Thixotropic agent is added in embodiment 3
0.2%th, defoamer 0.2%, dispersant 0.3%, levelling agent 0.2% and wetting agent 0.1%；Thixotropic agent is added in embodiment 4
0.3%th, defoamer 0.5%, dispersant 0.3%, levelling agent 0.6% and wetting agent 0.3%；Thixotropic agent is added in embodiment 5
0.25%th, dispersant 0.25%, levelling agent 0.4% and wetting agent 0.6%.
Organic solvent：Organic solvent is that terpinol and butyl glycol ether are mixed in embodiment 1, the mass ratio 3 of the two:
2；It is butyl acetate and 2 in embodiment 2,2,4- trimethyl -1,3- pentanediol isobutyrates are mixed, the two
Mass ratio 2:1；It is that 3- hydroxyl -3- carboxyl glutaric acid tributyls and terpinol are mixed in embodiment 3, the mass ratio of the two
3:1；Mixed in embodiment 4 for tributyl phosphate, diethylene glycol dimethyl ether and terpinol, the mass ratio 1 of three:2:1；Implement
Mixed in example 5 for terpinol, butyl and butyl acetate, three's mass ratio 8:1:1.
Embodiment 6：It is reference sample with embodiment 3, the moderate resistance shrink additives of embodiment 6 are Ag and CuO, the quality of the two
Than 1:2, remaining constituent content and physical property are same as Example 3.
Embodiment 7：It is reference sample with embodiment 3, the moderate resistance shrink additives of embodiment 7 are Ag and SnO2, the matter of the two
Amount compares 1:1, remaining constituent content and physical property are same as Example 3.
Embodiment 8：It is reference sample with embodiment 3, the moderate resistance shrink additives of embodiment 8 are Cu, Ni and TiO2, three's
Mass ratio 1:1:2, remaining constituent content and physical property are same as Example 3.
Embodiment 9：It is reference sample with embodiment 3, the moderate resistance shrink additives of embodiment 9 are Cu, Ni and TiO2, three's
Mass ratio 2:3:6, remaining constituent content and physical property are same as Example 3.
Comparative example 1：It is without anti-shrink additive A l in reference sample, comparative example 1 with embodiment 32O3And NiO, accordingly
Increase the percentage composition of organic solvent, remaining constituent content and physical property are same as Example 3.
Comparative example 2：Take embodiment 3 as the netted Al of anti-shrink additive added in reference sample, comparative example 22O3And NiO
0.1 μm of the equal ＜ of mesh aperture, remaining constituent content and physical property are same as Example 3.
Comparative example 3：It is that anti-shrink additive netted Al (fusing points 660 are added in reference sample, comparative example 3 with embodiment 3
DEG C), remaining constituent content and physical property are same as Example 3.
Comparative example 4：Take embodiment 3 as the anti-shrink additive A l added in reference sample, comparative example 42O3And NiO, its hole
Rate is all higher than 80%, and remaining constituent content and physical property are same as Example 3.
Crystal silicon solar batteries back side silver paste prepared by above-described embodiment 1~9 and comparative example 1~4 carry out electrical property and
The test of pulling force is welded, its method of testing is this area conventional method.Test result is listed in the table below in 2.
Table 2：
By adding appropriate anti-shrink additive (embodiment 3 and contrast it can be seen from the test result listed by table 2
Example 1) series resistance of back electrode can be reduced, improve the electricity conversion of solar cell；And with the addition of with it is preferred
Anti-shrink additive A l2O3The Al different with NiO specifications parameters2O3With (embodiment 3 with comparative example 2) after NiO, due to its mesh
Aperture is too small, have impact on passing through for silver powder and glass dust, so as to have impact on the holding of electrical property and welding pulling force；In comparative example 3
After netted Al of the fusing point less than 700 DEG C is selected as anti-shrink additive, because its melting temperature is low, in the sintering process of slurry
In its network structure destroyed, so its anti-shrink effect also receive adverse effect；And the selection porosity of comparative example 4 ＞ 80%
Netted Al2O3After NiO, welding pulling force reduction.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, some improvements and modifications can also be made, these improvements and modifications
Also it should be regarded as protection scope of the present invention.
Claims (9)
1. a kind of rear electrode for crystal silicon solar battery hinders silver paste with low string, it is characterised in that its formula includes：Ball shape silver powder,
Anti-shrink adds in the anti-shrink additive comprising thickener and network structure, silver paste in glass dust, organic solvent and auxiliary agent, auxiliary agent
Plus the percentage by weight of agent is 0.05~5%, the fusing point of anti-shrink additive is higher than 700 DEG C and mesh aperture is not less than silver powder
Average grain diameter, the porosity of anti-shrink additive is 40 ~ 80%.
2. rear electrode for crystal silicon solar battery according to claim 1 hinders silver paste with low string, it is characterised in that described anti-
Shrink additives are made up of the combination of component A or component B or component A, B, and component A is selected from Au, Ag, Cu, Ni, CNT
At least one of, component B is selected from ZnO, WO3、NiO、Al2O3、CuO、SnO2、TiO2、SiO2At least one of.
3. rear electrode for crystal silicon solar battery according to claim 1 hinders silver paste with low string, it is characterised in that described anti-
The size of shrink additives is 0.1 ~ 5 μm, and mesh aperture is 0.1 ~ 3 μm.
4. rear electrode for crystal silicon solar battery according to claim 1 hinders silver paste with low string, it is characterised in that by weight
Percentages, the formula of silver paste includes：First ball shape silver powder 25~40%, the second ball shape silver powder 10~20%, flake silver powder 7~
15%th, glass dust 1~4%, organic solvent 18~44%, thickener 4~12%, anti-shrink additive 1~3% and other auxiliary agents 0.5~
2%；The average grain diameter of second ball shape silver powder is less than the average grain diameter of the first ball shape silver powder.
5. rear electrode for crystal silicon solar battery according to claim 4 hinders silver paste with low string, it is characterised in that described the
1 ~ 3 μm of the average grain diameter of one ball shape silver powder, 1 μm of the average grain diameter ＜ of the second ball shape silver powder, tap density >=4.0 g/cm3；
The average grain diameter of flake silver powder is 1 ~ 5 μm, the g/cm of tap density 2.8 ~ 4.03。
6. rear electrode for crystal silicon solar battery according to claim 4 with it is low string hinder silver paste, it is characterised in that it is described its
Its auxiliary agent includes at least one of thixotropic agent, dispersant, levelling agent, defoamer and wetting agent.
7. rear electrode for crystal silicon solar battery according to claim 2 hinders silver paste with low string, it is characterised in that described anti-
Shrink additives are by Ag and selected from SnO2, one kind in CuO combine, weight ratio is 1：（1~2）.
8. rear electrode for crystal silicon solar battery according to claim 2 hinders silver paste with low string, it is characterised in that described anti-
Shrink additives are by Cu, Ni and TiO2Combine, weight ratio is 1：（1~1.5）：（2~3）.
9. a kind of rear electrode for crystal silicon solar battery hinders the preparation method of silver paste with low string, comprise the steps：
S1：The preparation of organic carrier, is first added organic solvent in container by formula rate, then adds thickener under agitation,
50 ~ 100 DEG C are warming up to, 0.5 ~ 3h is incubated, cools to after other auxiliary agents, filtering are added at 40 ~ 50 DEG C and obtain organic carrier；
S2：The preparation of back silver paste, anti-shrink additive is added in organic carrier made from S1, and ultrasonic disperse 10 ~
30min, then sequentially adds the first ball shape silver powder, the second ball shape silver powder, flake silver powder and glass dust, through high-speed stirred in proportion
Mixing and three-roll grinder grinding distribution, obtain rear electrode for crystal silicon solar battery and hinder silver paste with low string.
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| CN109659067A (en) * | 2018-12-06 | 2019-04-19 | 中国科学院山西煤炭化学研究所 | Positive silver paste and preparation method for perc crystal silicon solar energy battery |
| CN113299423A (en) * | 2021-05-09 | 2021-08-24 | 江西师范大学 | Organic carrier for crystalline silicon solar cell front silver paste and preparation method thereof |
| CN113903495A (en) * | 2021-09-17 | 2022-01-07 | 江苏国瓷泓源光电科技有限公司 | Copper slurry for dielectric ceramic filter and preparation and spraying film forming methods thereof |
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