CN112824470B - Organic binder based on phosphorus-containing polymer resin and preparation method and application thereof - Google Patents
Organic binder based on phosphorus-containing polymer resin and preparation method and application thereof Download PDFInfo
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- CN112824470B CN112824470B CN201911145283.8A CN201911145283A CN112824470B CN 112824470 B CN112824470 B CN 112824470B CN 201911145283 A CN201911145283 A CN 201911145283A CN 112824470 B CN112824470 B CN 112824470B
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- containing polymer
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 74
- 239000011574 phosphorus Substances 0.000 title claims abstract description 74
- 239000011230 binding agent Substances 0.000 title claims abstract description 50
- 239000002952 polymeric resin Substances 0.000 title claims abstract description 49
- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000003960 organic solvent Substances 0.000 claims description 97
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 88
- 229910052709 silver Inorganic materials 0.000 claims description 40
- 239000004332 silver Substances 0.000 claims description 40
- -1 aluminum compound Chemical class 0.000 claims description 18
- 238000009835 boiling Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 239000002002 slurry Substances 0.000 abstract description 30
- 238000000034 method Methods 0.000 abstract description 24
- 239000011521 glass Substances 0.000 abstract description 19
- 239000000843 powder Substances 0.000 abstract description 19
- 238000005245 sintering Methods 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 14
- 229920005989 resin Polymers 0.000 abstract description 13
- 239000011347 resin Substances 0.000 abstract description 13
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003063 flame retardant Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 5
- 230000003628 erosive effect Effects 0.000 abstract description 4
- 230000002045 lasting effect Effects 0.000 abstract description 4
- 230000003111 delayed effect Effects 0.000 abstract description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 description 12
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 10
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 8
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 8
- MXVMODFDROLTFD-UHFFFAOYSA-N 2-[2-[2-(2-butoxyethoxy)ethoxy]ethoxy]ethanol Chemical compound CCCCOCCOCCOCCOCCO MXVMODFDROLTFD-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 6
- OUWSNHWQZPEFEX-UHFFFAOYSA-N diethyl glutarate Chemical compound CCOC(=O)CCCC(=O)OCC OUWSNHWQZPEFEX-UHFFFAOYSA-N 0.000 description 6
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 6
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 6
- 238000003466 welding Methods 0.000 description 6
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 5
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 4
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 4
- 235000012431 wafers Nutrition 0.000 description 4
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 3
- 229940009827 aluminum acetate Drugs 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- BWZOPYPOZJBVLQ-UHFFFAOYSA-K aluminium glycinate Chemical compound O[Al+]O.NCC([O-])=O BWZOPYPOZJBVLQ-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000001934 delay Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229940067606 lecithin Drugs 0.000 description 2
- 235000010445 lecithin Nutrition 0.000 description 2
- 239000000787 lecithin Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XNRNVYYTHRPBDD-UHFFFAOYSA-N [Si][Ag] Chemical compound [Si][Ag] XNRNVYYTHRPBDD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940015826 dihydroxyaluminum aminoacetate Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/02—Homopolymers or copolymers of unsaturated alcohols
- C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
-
- 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
- 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
The invention discloses an organic binder based on phosphorus-containing polymer resin, a preparation method and application thereof. According to the invention, the partial performance of the organic binder carrier of the solar cell slurry is expanded, a proper phosphorus-containing resin is selected to be fused with the organic carrier, extra phosphorus is provided in the slurry sintering process, the probability of P-N junction burning-through is slowed down in the glass powder erosion process, the burning-out process of the organic binder carrier is delayed by utilizing the flame-retardant property of the phosphorus-containing material, the lasting supporting force is provided for the slurry to the maximum extent, and the height-width ratio after sintering is improved.
Description
Technical Field
The invention relates to a binder for a battery, in particular to an organic binder based on phosphorus-containing polymer resin, and a preparation method and application thereof, and belongs to the field of solar battery slurry.
Background
Solar cells are devices that convert light energy into electrical energy through the photoelectric effect. Radiation of a suitable wavelength incident on the P-N junction of a semiconductor acts as an external energy source that generates hole-electron pairs in the semiconductor. Due to the potential difference at the P-N junction, holes and electrons move across the junction in opposite directions. Electrons move to the negative contact and holes move to the positive contact, thereby generating a current that can deliver power to an external circuit. The electrode contacts of a solar cell are important for the performance of the cell.
The front silver paste of the solar cell is an important basic material for manufacturing the photoelectric solar cell and is used for manufacturing a front electrode of the crystalline silicon solar cell. The front silver paste of the solar cell consists of glass powder, silver powder, an organic carrier, an inorganic additive and an organic additive; the glass powder mainly has the functions of burning through an insulating silicon nitride anti-reflection film, helping to form Ag/Si ohmic contact and providing adhesive force; the silver powder is mainly used for sintering and densifying the silver powder to form low grid line resistance and provide a good conductive electrode; the organic carrier mainly has the functions of wetting, printability, appearance and aspect ratio among the powder; the inorganic additive and the organic additive are mainly used for modification and improvement of slurry performance.
With the development of technology, in order to improve conversion efficiency and reduce surface recombination, various battery manufacturers have adopted shallow junction technology of low surface phosphorus concentration of battery pieces. The shallow junction means that the junction depth of the P-N junction of the solar cell is smaller than 0.2 mu m, and the minority carrier recombination velocity on the surface of the solar cell can be obviously reduced by using the shallow junction, so that the spectral response of a short wave band is improved. However, the P-N junction is shallow during sintering, so that the slurry is easy to burn through, and the slurry is required to have a wider sintering window and a proper corrosion rate.
Disclosure of Invention
Aiming at the defects of the prior art, the invention expands the partial performance of the solar cell slurry carrier, selects proper phosphorus-containing resin to be fused with an organic carrier, provides additional phosphorus in the slurry sintering process, slows down the probability of P-N junction burning-through in the glass powder erosion process, delays the burning-out process of an organic binder (carrier) by utilizing the flame retardant property of a phosphorus-containing material, furthest provides lasting supporting force for the slurry, and improves the height-width ratio after sintering.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
according to a first embodiment of the present invention, there is provided an organic binder based on a phosphorus-containing polymer resin, the binder being prepared by dissolving a phosphorus-containing polymer resin in an organic solvent system.
Preferably, the phosphorus-containing polymer resin is a phosphorus-containing flame-retardant polymer resin, and preferably a phosphorus-containing polymer polyvinyl alcohol resin (PVA) and/or a phosphorus-containing polymer epoxy resin.
Preferably, the organic solvent system refers to a mixed organic solvent system obtained by mixing organic solvents with different boiling points with each other.
Preferably, the organic solvent system comprises a first type of organic solvent, a second type of organic solvent, and a phase third type of organic solvent.
Preferably, the boiling point of the first class of organic solvents is 120-220 ℃, preferably 150-200 ℃.
Preferably, the second class of organic solvents has a boiling point of 200-300 ℃, preferably 220-270 ℃.
Preferably, the third class of organic solvents has a boiling point of greater than 270 ℃, preferably greater than 300 ℃.
Preferably, the mass ratio of the phosphorus-containing polymer resin to the organic solvent system is 5-20:80-95, preferably 7-18:82-93, and more preferably 10-15:85-90. And/or
Preferably, the mass ratio of the first organic solvent, the second organic solvent and the third organic solvent in the organic solvent system is 2-20:60-95:2-20, preferably 5-15:70-90:5-15.
Preferably, the first type of organic solvent is selected from one or more of gamma-butyrolactone, gamma-valerolactone, dimethyl glutarate, furfural, cyclohexanol, diethyl succinate, diethyl glutarate and tributyl phosphate. And/or
Preferably, the second organic solvent is selected from one or more of diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, alcohol ester twelve and tributyl citrate. And/or
Preferably, the third class of organic solvents is selected from one or more of tetraethylene glycol monobutyl ether, tetraethylene glycol, pentaerythritol triacrylate (PETA), and triethylene glycol.
According to a second embodiment of the present invention, there is provided a method for preparing the organic binder described in the first fact mode, the method comprising the steps of:
1) And uniformly mixing the first organic solvent, the second organic solvent and the third organic solvent to obtain an organic solvent system.
2) And (3) heating and preheating the organic solvent system prepared in the step (1).
3) And (3) adding the phosphorus-containing polymer resin into the organic solvent system after the preheating in the step (2) to be completely dissolved so as to obtain the target organic binder.
Preferably, in step 1), the boiling point of the first type of organic solvent is 120-220 ℃, preferably 150-200 ℃. The first organic solvent is selected from one or more of gamma-butyrolactone, gamma-valerolactone, dimethyl glutarate, furfural, cyclohexanol, diethyl succinate, diethyl glutarate and tributyl phosphate. And/or
Preferably, the second class of organic solvents has a boiling point of 200-300 ℃, preferably 220-270 ℃. The second organic solvent is selected from one or more of diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, alcohol ester twelve and tributyl citrate. And/or
Preferably, the third class of organic solvents has a boiling point of greater than 270 ℃, preferably greater than 300 ℃. The third class of organic solvents is selected from one or more of tetraethylene glycol monobutyl ether, tetraethylene glycol, pentaerythritol triacrylate (PETA), and triethylene glycol. And/or
Preferably, the mass ratio of the addition amount of the first organic solvent, the second organic solvent and the third organic solvent is 2-20:60-95:2-20, preferably 5-15:70-90:5-15.
Preferably, in step 2), the organic solvent system is preheated in a heating device to 45-90 ℃, preferably 50-80 ℃, more preferably 55-70 ℃.
Preferably, in step 3), the phosphorus-containing polymer resin is a phosphorus-containing flame retardant polymer resin, preferably a phosphorus-containing polymer polyvinyl alcohol resin (PVA) and/or a phosphorus-containing polymer epoxy resin. And/or
Preferably, the mass ratio of the phosphorus-containing polymer resin to the organic solvent system is 5-20:80-95, preferably 7-18:82-93, more preferably 10-15:85-90.
According to a third embodiment of the present invention, there is provided the use of the organic binder of a phosphorus-containing polymer resin as described in the first embodiment or the organic binder of a phosphorus-containing polymer resin prepared by the method as described in the second embodiment, for preparing a silver paste for a solar cell.
According to a fourth embodiment of the present invention, there is provided a silver paste for a solar cell, wherein the organic binder of the phosphorus-containing polymer resin according to the first embodiment or the organic binder of the phosphorus-containing polymer resin prepared by the method according to the second embodiment is uniformly mixed with silver powder, and then ground to a particle size of 15 μm or less (preferably 12 μm or less, more preferably 8 μm or less) to obtain the silver paste for a target solar cell.
Preferably, the mass ratio of the organic binder of the phosphorus-containing polymer resin to the silver powder is 1:5-12, preferably 1:8-10.
Preferably, the silver paste further comprises: an organoaluminum compound and an auxiliary agent; preferably, the organoaluminum compound is aluminum dihydroxyglycolate and/or aluminum acetate in an amount of 0.1 to 8%, preferably 0.5 to 5%, more preferably 0.8 to 3% of the amount of silver powder added. And/or
Preferably, the auxiliary agent is methyl silicone oil and/or lecithin, and the addition amount of the auxiliary agent is 0.1-10%, preferably 0.5-8%, more preferably 0.8-5% of the addition amount of silver powder.
In the invention, the silver powder is micron spherical silver powder and/or nanometer silver powder.
Preferably, the silver powder is a mixture of micron-sphere silver powder and nanometer silver powder.
More preferably, the silver powder is a mixture of 70-99% by weight of micron spherical silver powder and 1-30% by weight of nano silver powder.
In the invention, the glass powder is prepared from specific raw materials and has the following actions and effects that the glass powder with the particle size of 0.1-5 mu m (preferably 0.2-4 mu m) is adopted:
the softening temperature of the glass is reduced by controlling the components and the particle size of the glass, and the passivation layer is fully dissolved and corroded; optimizing the proportion of components with stronger corrosiveness, such as lead or bismuth, and the like, well corroding passivation layers, such as silicon nitride, silicon oxide or aluminum oxide, on the surface of the silicon battery, so that silver silicon is in good ohmic contact, an electron transfer channel is formed, and the effect of conducting electricity is achieved; meanwhile, other oxides (such as ZnO/V2O5/SiO 2) are introduced, so that the structure and expansion coefficient of the glass are controlled, the adhesion between the slurry and silicon is improved, and the reliability of the battery is improved.
In the invention, by expanding the performance of a solar cell slurry carrier part (organic binder), proper phosphorus-containing resin is selected to be fused with the organic carrier, extra phosphorus is provided in the slurry sintering process, the probability of P-N junction burning-through is slowed down in the glass powder erosion process, the burning-out process of the organic binder (carrier) is delayed by utilizing the flame retardant property of the phosphorus-containing material, the lasting supporting force is provided for the slurry to the maximum extent, and the height-width ratio after sintering is improved.
In the invention, by adding the silver paste into the P-type solar cell
Experimental study shows that the addition of the organic aluminum compound in the silver paste of the solar cell has the following actions and effects compared with the addition of the inorganic compound of aluminum:
the method has the main advantages that the method is more beneficial to dispersing in an organic carrier and uniformly dispersing in a slurry system, so that the problem that the silicon solar cell is compounded and increased due to excessive diffusion of silver into a silicon substrate in the sintering process is effectively reduced, and the open-circuit voltage of the cell is influenced; compared with conventional aluminum or aluminum compounds, the aluminum or aluminum compound is subjected to oxidative decomposition at a lower temperature to form a nano-scale oxide layer, which is favorable for reducing or relieving damage to PN junctions by silver powder and glass, reducing electronic recombination and improving the open-voltage effect.
Experiments prove that the dihydroxyaluminum aminoacetate and/or aluminum acetate are added into the silver paste of the P-type solar cell doped with the organic aluminum compound, so that the etching can be well slowed down, the corrosion depth can be controlled, and the opening pressure effect can be improved. The problem of compounding between slurry and silicon wafers in the process of preparing the solar cell is solved, the open-pressure of the solar cell is improved, and the photoelectric conversion efficiency is improved.
According to the invention, the organic aluminum compound is added into the silver paste of the P-type solar cell, so that the influence on VOC caused by the introduction of inorganic aluminum powder, aluminum-silicon alloy and other aluminum alloy substances into the silver paste of the P-type solar cell in the prior art is avoided. The addition of the organic aluminum compound does not damage the integrity of PN-junction, does not affect the structure of silicon on the surface of the cell, keeps higher open pressure and improves the efficiency of the solar cell.
In the invention, the silver powder is a mixture of micron spherical silver powder and nanometer silver powder. By adopting the mixture of silver powder with different particle sizes, the silver powder has the following actions and effects:
1. the nano silver powder has high surface activation energy and lower melting point, can be compacted and dissolved into glass at a lower temperature, so that the conductivity of the micron spherical silver powder is achieved at a lower sintering temperature; 2. meanwhile, as the nano silver powder particles are smaller, the nano silver powder particles are highly well filled into gaps of the micron spherical silver powder, the compactness of the grid line is improved, and the resistance of the grid line is reduced.
Compared with the prior art, the invention has the following beneficial technical effects:
1: the invention selects proper phosphorus-containing resin to be fused with the organic carrier, provides extra phosphorus in the slurry sintering process, greatly slows down the probability of P-N junction burning-through in the glass powder erosion process, delays the burning-out process of the organic binder (carrier) by utilizing the flame-retardant property of the phosphorus-containing material, provides lasting supporting force for the slurry to the maximum extent, and improves the height-width ratio after sintering.
2: the preparation method has the advantages of simple preparation process, easily obtained raw materials, low cost and improvement of economic benefit by about 10 percent.
Detailed Description
The following examples illustrate the technical aspects of the invention, and the scope of the invention claimed includes but is not limited to the following examples.
According to a first embodiment of the present invention, there is provided an organic binder based on a phosphorus-containing polymer resin, the binder being prepared by dissolving a phosphorus-containing polymer resin in an organic solvent system.
Preferably, the phosphorus-containing polymer resin is a phosphorus-containing flame-retardant polymer resin, and preferably a phosphorus-containing polymer polyvinyl alcohol resin (PVA) and/or a phosphorus-containing polymer epoxy resin.
Preferably, the organic solvent system refers to a mixed organic solvent system obtained by mixing organic solvents with different boiling points with each other.
Preferably, the organic solvent system comprises a first type of organic solvent, a second type of organic solvent, and a phase third type of organic solvent.
Preferably, the boiling point of the first class of organic solvents is 120-220 ℃, preferably 150-200 ℃.
Preferably, the second class of organic solvents has a boiling point of 200-300 ℃, preferably 220-270 ℃.
Preferably, the third class of organic solvents has a boiling point of greater than 270 ℃, preferably greater than 300 ℃.
Preferably, the mass ratio of the phosphorus-containing polymer resin to the organic solvent system is 5-20:80-95, preferably 7-18:82-93, and more preferably 10-15:85-90. And/or
Preferably, the mass ratio of the first organic solvent, the second organic solvent and the third organic solvent in the organic solvent system is 2-20:60-95:2-20, preferably 5-15:70-90:5-15.
Preferably, the first type of organic solvent is selected from one or more of gamma-butyrolactone, gamma-valerolactone, dimethyl glutarate, furfural, cyclohexanol, diethyl succinate, diethyl glutarate and tributyl phosphate. And/or
Preferably, the second organic solvent is selected from one or more of diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, alcohol ester twelve and tributyl citrate. And/or
Preferably, the third class of organic solvents is selected from one or more of tetraethylene glycol monobutyl ether, tetraethylene glycol, pentaerythritol triacrylate (PETA), and triethylene glycol.
According to a second embodiment of the present invention, there is provided a method for preparing the organic binder described in the first fact mode, the method comprising the steps of:
1) And uniformly mixing the first organic solvent, the second organic solvent and the third organic solvent to obtain an organic solvent system.
2) And (3) heating and preheating the organic solvent system prepared in the step (1).
3) And (3) adding the phosphorus-containing polymer resin into the organic solvent system after the preheating in the step (2) to be completely dissolved so as to obtain the target organic binder.
Preferably, in step 1), the boiling point of the first type of organic solvent is 120-220 ℃, preferably 150-200 ℃. The first organic solvent is selected from one or more of gamma-butyrolactone, gamma-valerolactone, dimethyl glutarate, furfural, cyclohexanol, diethyl succinate, diethyl glutarate and tributyl phosphate. And/or
Preferably, the second class of organic solvents has a boiling point of 200-300 ℃, preferably 220-270 ℃. The second organic solvent is selected from one or more of diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, alcohol ester twelve and tributyl citrate. And/or
Preferably, the third class of organic solvents has a boiling point of greater than 270 ℃, preferably greater than 300 ℃. The third class of organic solvents is selected from one or more of tetraethylene glycol monobutyl ether, tetraethylene glycol, pentaerythritol triacrylate (PETA), and triethylene glycol. And/or
Preferably, the mass ratio of the addition amount of the first organic solvent, the second organic solvent and the third organic solvent is 2-20:60-95:2-20, preferably 5-15:70-90:5-15.
Preferably, in step 2), the organic solvent system is preheated in a heating device to 45-90 ℃, preferably 50-80 ℃, more preferably 55-70 ℃.
Preferably, in step 3), the phosphorus-containing polymer resin is a phosphorus-containing flame retardant polymer resin, preferably a phosphorus-containing polymer polyvinyl alcohol resin (PVA) and/or a phosphorus-containing polymer epoxy resin. And/or
Preferably, the mass ratio of the phosphorus-containing polymer resin to the organic solvent system is 5-20:80-95, preferably 7-18:82-93, more preferably 10-15:85-90.
According to a third embodiment of the present invention, there is provided the use of the organic binder of a phosphorus-containing polymer resin as described in the first embodiment or the organic binder of a phosphorus-containing polymer resin prepared by the method as described in the second embodiment, for preparing a silver paste for a solar cell.
According to a fourth embodiment of the present invention, there is provided a silver paste for a solar cell, wherein the organic binder of the phosphorus-containing polymer resin according to the first embodiment or the organic binder of the phosphorus-containing polymer resin prepared by the method according to the second embodiment is uniformly mixed with silver powder, and then ground to a particle size of 15 μm or less (preferably 12 μm or less, more preferably 8 μm or less) to obtain the silver paste for a target solar cell.
Preferably, the mass ratio of the organic binder of the phosphorus-containing polymer resin to the silver powder is 1:5-12, preferably 1:8-10.
Preferably, the organoaluminum compound is aluminum dihydroxyglycolate and/or aluminum acetate in an amount of 0.1 to 8%, preferably 0.5 to 5%, more preferably 0.8 to 3% of the amount of silver powder added. And/or
Preferably, the auxiliary agent is methyl silicone oil and/or lecithin, and the addition amount of the auxiliary agent is 0.1-10%, preferably 0.5-8%, more preferably 0.8-5% of the addition amount of silver powder.
Example 1
1) Preparation of organic binder of phosphorus-containing high polymer resin:
15.0g of diethyl glutarate (first type organic solvent), 65.0g of tributyl citrate (second type organic solvent) and 20.0g of tetraethylene glycol monobutyl ether (third type organic solvent) are added into a container, stirred for 10min, and an organic solvent system is obtained after uniform mixing. Then heating the container with the organic solvent system to raise the temperature and preheat to 60 ℃. Finally, adding 5.5g of phosphorus-containing high polymer polyvinyl alcohol resin (PVA) flame retardant into the preheated organic solvent system, and stirring for 20min until the resin is completely dissolved in the organic solvent system (no visible fixation and impurities exist), thus obtaining the organic binder of the phosphorus-containing high polymer resin.
2) Preparing silver paste of a solar cell:
3.0g of glass powder, 9.0g of the organic binder of the prepared phosphorus-containing polymer resin, 88.0g of silver powder, 4.4g of aluminum dihydroxyaminoacetate and 0.4g of methyl silicone oil are weighed according to the mass parts and added into a reactor; then stirring for 30min by using a dispersing machine, uniformly mixing, and grinding for 1.5h by using a three-roller grinder (until the fineness is below 8 mu m) to obtain the solar cell silver paste.
Reference slurry: the raw materials of SBR series organic binders purchased in the market are selected. Similarly, 88g of silver powder, 3.0g of glass powder, 9.0g of SBR organic binder and 0.4g of methyl silicone oil are weighed according to the mass parts, and are uniformly mixed by using a dispersing machine, and then are ground into silver paste with the fineness of less than 8 mu m by using a three-roller grinder.
The prepared solar cell silver paste sample is printed on a P-type silicon wafer (square resistor 120-140 omega) with the specification of 156mm multiplied by 156mm through a 430-mesh screen to form an electrode film, the main grid width is 0.65 micrometers, and the electrode film is sintered in a despatich sintering furnace, and the actual peak temperature is 700-780 ℃.
Example 1 the electrical data after sintering were tested as follows: the short-circuit current 9.856A, the open-circuit voltage 679.5mv and the photoelectric conversion efficiency of 21.89% are tested, and the welding tension is 1.9N.
The electrical data of the sintered reference slurry are as follows: the short-circuit current 9.839A, the open-circuit voltage 677mv and the photoelectric conversion efficiency 21.51% are tested, and the welding tension is 1.6N.
Compared with the existing slurry, the short-circuit current of the slurry in the example is 0.017A, the efficiency is 0.38% and the tensile force is 0.3N.
Example 2
1) Preparation of organic binder of phosphorus-containing high polymer resin:
5.0g of diethyl glutarate, 12.0g of furfural (first organic solvent), 23.0g of diethylene glycol monobutyl ether, 42.0g of diethylene glycol monobutyl ether acetate (second organic solvent) and 13.0g of tetraethylene glycol monobutyl ether (third organic solvent) are added into a container, stirred for 10min, and an organic solvent system is obtained after uniform mixing. Then heating the container with the organic solvent system to raise the temperature and preheat to 60 ℃. Finally, 10.6g of the phosphorus-containing polymer epoxy resin is added into the preheated organic solvent system, and the mixture is stirred for 20 minutes until the resin is completely dissolved in the organic solvent system (no visible fixation and impurities exist), so that the organic binder of the phosphorus-containing polymer resin is obtained.
2) Preparing silver paste of a solar cell:
3.0g of glass powder, 8.5g of the organic binder of the prepared phosphorus-containing polymer resin, 88.5g of silver powder, 4.43g of aluminum dihydroxyglycine and 0.4g of methyl silicone oil are weighed according to the mass parts and added into a reactor; then stirring for 30min by using a dispersing machine, uniformly mixing, and grinding for 1.5h by using a three-roller grinder (until the fineness is below 8 mu m) to obtain the solar cell silver paste.
Reference slurry: the raw materials of SBR series organic binders purchased in the market are selected. Similarly, 88.5g of silver powder, 3.0g of glass powder, 8.5g of SBR organic binder and 0.4g of methyl silicone oil are weighed according to the mass parts, and are uniformly mixed by using a dispersing machine, and then are ground into silver paste with the fineness of less than 8 mu m by using a three-roller grinder.
The prepared solar cell silver paste sample is printed on a P-type silicon wafer (square resistor 120-140 omega) with the specification of 156mm multiplied by 156mm through a 430-mesh screen to form an electrode film, the main grid width is 0.65 micrometers, and the electrode film is sintered in a despatich sintering furnace, and the actual peak temperature is 700-780 ℃.
The electrical data after sintering are: the short-circuit current 9.866A, the open-circuit voltage 680.5mv and the photoelectric conversion efficiency 21.71% are tested, and the welding tension is 1.75N.
The electrical data of the sintered reference slurry are as follows: the short-circuit current 9.839A, the open-circuit voltage 677mv and the photoelectric conversion efficiency 21.51% are tested, and the welding tension is 1.6N.
Compared with the existing slurry, the short-circuit current of the slurry of the example is 0.027A, the efficiency is 0.2% and the tensile force is 0.15N.
Example 3
1) Preparation of organic binder of phosphorus-containing high polymer resin:
10.0g of tributyl phosphate, 8.0g of cyclohexanol (first type of organic solvent), 27.0g of diethylene glycol monobutyl ether, 38.0g of diethylene glycol monobutyl ether acetate (second type of organic solvent) and 17.0g of tetraethylene glycol monobutyl ether (third type of organic solvent) are added into a container, stirred for 10min, and an organic solvent system is obtained after uniform mixing. Then heating the container with the organic solvent system to raise the temperature and preheat to 60 ℃. And finally, adding 17.6g of phosphorus-containing high polymer polyvinyl alcohol resin (PVA) flame retardant into the preheated organic solvent system, and stirring for 20min until the resin is completely dissolved in the organic solvent system (no visible fixation and impurities exist), thus obtaining the organic binder of the phosphorus-containing high polymer resin.
2) Preparing silver paste of a solar cell:
3.0g of glass powder, 8.0g of the organic binder of the prepared phosphorus-containing polymer resin, 89.0g of silver powder, 4.45g of aluminum dihydroxyglycine and 0.4g of methyl silicone oil are weighed according to the mass parts and added into a reactor; then stirring for 30min by using a dispersing machine, uniformly mixing, and grinding for 1.5h by using a three-roller grinder (until the fineness is below 8 mu m) to obtain the solar cell silver paste.
Reference slurry: the raw materials of SBR series organic binders purchased in the market are selected. In the same way, 89g of positive silver powder, 3.0g of glass powder, 8.0g of SBR organic binder and 0.4g of methyl silicone oil are weighed according to the mass parts, and are uniformly mixed by using a dispersing machine, and then are ground into silver paste with the fineness of less than 8 mu m by using a three-roller grinder.
Electrode films were formed on P-type silicon wafers (sheet resistance 120-140. OMEGA.) of 156mm by 156mm in specification by 430 mesh screen printing using the solar cell silver paste sample prepared in example 3, with a main gate width of 0.65 μm, and sintered in a despatich sintering furnace at a peak actual temperature of 700-780 ℃.
The electrical data after sintering are: short-circuit current 9.861A, open-circuit voltage 683.4mv and photoelectric conversion efficiency 22.31%, and the welding tension is 2.3N.
The electrical data of the sintered reference slurry are as follows: the short-circuit current 9.839A, the open-circuit voltage 677mv and the photoelectric conversion efficiency 21.51% are tested, and the welding tension is 1.6N.
The slurry of the example is 0.022A higher than the short-circuit current of the existing slurry, 0.8% higher in efficiency and 0.7N higher in tensile force.
Claims (7)
1. The solar cell silver paste is characterized in that: uniformly mixing an organic binder of the phosphorus-containing polymer resin with silver powder, and grinding until the granularity is less than or equal to 15 mu m to obtain target solar cell silver paste;
wherein: the organic binder of the phosphorus-containing polymer resin is prepared by dissolving the phosphorus-containing polymer resin in an organic solvent system; the phosphorus-containing polymer resin is phosphorus-containing polymer epoxy resin; the organic solvent system refers to a mixed organic solvent system obtained by mutually mixing organic solvents with different boiling points;
wherein: the mass ratio of the organic binder of the phosphorus-containing polymer resin to the silver powder is 1:5-12;
the silver paste also comprises: an organoaluminum compound and an auxiliary agent; the organic aluminum compound is aluminum dihydroxyglycolate, and the addition amount of the organic aluminum compound is 0.1-8% of that of silver powder; the addition agent is methyl silicone oil, and the addition amount of the addition agent is 0.1-10% of the addition amount of silver powder.
2. The solar cell silver paste of claim 1, wherein: uniformly mixing an organic binder of the phosphorus-containing polymer resin with silver powder, and grinding until the granularity is less than or equal to 12 mu m to obtain target solar cell silver paste;
wherein: the mass ratio of the organic binder of the phosphorus-containing polymer resin to the silver powder is 1:8-10.
3. The solar cell silver paste of claim 1, wherein: and (3) uniformly mixing the organic binder of the phosphorus-containing polymer resin with silver powder, and grinding the mixture until the granularity is less than or equal to 8 mu m to obtain the target solar cell silver paste.
4. The solar cell silver paste of claim 1, wherein: the silver paste also comprises: the addition amount of the organic aluminum compound is 0.5-5% of the addition amount of the silver powder.
5. The solar cell silver paste of claim 4, wherein: the silver paste also comprises: the addition amount of the organic aluminum compound is 0.8-3% of the addition amount of the silver powder.
6. The solar cell silver paste of claim 1, wherein: the addition amount of the auxiliary agent is 0.5-8% of the addition amount of the silver powder.
7. The solar cell silver paste of claim 6, wherein: the addition amount of the auxiliary agent is 0.8-5% of the addition amount of the silver powder.
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| CN101165076A (en) * | 2006-10-17 | 2008-04-23 | 比亚迪股份有限公司 | Anti-flaming phosphorus-containing epoxy resin, preparation method thereof and composition containing the same |
| CN102439770A (en) * | 2010-06-30 | 2012-05-02 | 大金工业株式会社 | Binder composition for electrode |
| CN104403603A (en) * | 2014-10-22 | 2015-03-11 | 上海大学 | Flame-retardant cross-linked polyvinyl alcohol binder and preparation method thereof |
| CN106876003A (en) * | 2017-03-09 | 2017-06-20 | 江苏欧耐尔新型材料股份有限公司 | Match solar battery front side conductive silver paste and preparation method without net netting version |
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| KR101631711B1 (en) * | 2008-03-21 | 2016-06-17 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Phosphorus paste for diffusion and method for preparing solar cell by using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101165076A (en) * | 2006-10-17 | 2008-04-23 | 比亚迪股份有限公司 | Anti-flaming phosphorus-containing epoxy resin, preparation method thereof and composition containing the same |
| CN102439770A (en) * | 2010-06-30 | 2012-05-02 | 大金工业株式会社 | Binder composition for electrode |
| CN104403603A (en) * | 2014-10-22 | 2015-03-11 | 上海大学 | Flame-retardant cross-linked polyvinyl alcohol binder and preparation method thereof |
| CN106876003A (en) * | 2017-03-09 | 2017-06-20 | 江苏欧耐尔新型材料股份有限公司 | Match solar battery front side conductive silver paste and preparation method without net netting version |
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