CN109215829B - Front electrode silver paste and silver powder for solar cell and preparation method thereof - Google Patents
Front electrode silver paste and silver powder for solar cell and preparation method thereof Download PDFInfo
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- CN109215829B CN109215829B CN201811021669.3A CN201811021669A CN109215829B CN 109215829 B CN109215829 B CN 109215829B CN 201811021669 A CN201811021669 A CN 201811021669A CN 109215829 B CN109215829 B CN 109215829B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 191
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 75
- 239000004332 silver Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 238000003756 stirring Methods 0.000 claims abstract description 84
- 239000000843 powder Substances 0.000 claims abstract description 48
- 239000011521 glass Substances 0.000 claims abstract description 46
- 238000002156 mixing Methods 0.000 claims abstract description 35
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 24
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000007822 coupling agent Substances 0.000 claims abstract description 9
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 19
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 230000001376 precipitating effect Effects 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 13
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 239000001856 Ethyl cellulose Substances 0.000 claims description 10
- 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 10
- 229920001249 ethyl cellulose Polymers 0.000 claims description 10
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 10
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 8
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 8
- 239000004359 castor oil Substances 0.000 claims description 8
- 235000019438 castor oil Nutrition 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 8
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 8
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 8
- 229940116411 terpineol Drugs 0.000 claims description 8
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 229940096017 silver fluoride Drugs 0.000 claims description 6
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 239000004014 plasticizer Substances 0.000 claims description 5
- 239000013008 thixotropic agent Substances 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 229920000084 Gum arabic Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 241000978776 Senegalia senegal Species 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000205 acacia gum Substances 0.000 claims description 2
- 235000010489 acacia gum Nutrition 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 claims description 2
- 229940043264 dodecyl sulfate Drugs 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 150000004668 long chain fatty acids Chemical class 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 230000001788 irregular Effects 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 description 33
- 238000003466 welding Methods 0.000 description 16
- 239000012071 phase Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 235000003891 ferrous sulphate Nutrition 0.000 description 8
- 239000011790 ferrous sulphate Substances 0.000 description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- YQCFRFLCFGXQLH-UHFFFAOYSA-N C(CCCCCCCCCCCC)P(O)(O)O.C(CCCCCCCCCCCC)P(O)(O)O.C(CCCCCCC)O[Ti](OCCCCCCCC)(OCCCCCCCC)OCCCCCCCC Chemical compound C(CCCCCCCCCCCC)P(O)(O)O.C(CCCCCCCCCCCC)P(O)(O)O.C(CCCCCCC)O[Ti](OCCCCCCCC)(OCCCCCCCC)OCCCCCCCC YQCFRFLCFGXQLH-UHFFFAOYSA-N 0.000 description 2
- RQNFDKOLPIJOJC-UHFFFAOYSA-N CCCCCCCCCCCCP(O)(O)(O)CCCCCCCCCCCC.CCCCCCCCCCCCP(O)(O)(O)CCCCCCCCCCCC.CCCCCCCCO[Ti](OCCCCCCCC)(OCCCCCCCC)OCCCCCCCC Chemical compound CCCCCCCCCCCCP(O)(O)(O)CCCCCCCCCCCC.CCCCCCCCCCCCP(O)(O)(O)CCCCCCCCCCCC.CCCCCCCCO[Ti](OCCCCCCCC)(OCCCCCCCC)OCCCCCCCC RQNFDKOLPIJOJC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- -1 (dioctyl pyrophosphoryl oxy) isopropyl Chemical group 0.000 description 1
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 description 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 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
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- 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
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic 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
- 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
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
-
- 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 relates to front electrode silver paste and silver powder for a solar cell and a preparation method thereof, wherein the preparation method of the silver powder comprises the following steps: adding an acidic reducing agent solution into the soluble silver salt dispersion liquid, stirring in the adding process, standing for 3-10min after the reducing agent solution is added, stirring and ultrasonically reacting the reaction liquid until silver powder is completely separated out, and post-treating the reaction liquid to obtain the silver powder; the preparation method of the silver paste comprises the following steps: and adding the silver powder and the glass powder into an organic solvent and a coupling agent respectively for pretreatment, adding the modified silver powder and the modified glass powder into an organic carrier, mixing, grinding and filtering to obtain the front electrode silver paste. The process for preparing the silver powder for the solar cell is simple, the prepared silver powder is irregular spherical with uneven surfaces, and the sintering activity is high; the prepared front electrode silver paste is low in sintering temperature and excellent in weldability, and can effectively reduce contact resistance after sintering and improve the conductive efficiency.
Description
Technical Field
The invention relates to front electrode silver paste and silver powder for a solar cell and a preparation method thereof, belonging to the technical field of electronic materials.
Background
The crystalline silicon solar cell is the solar cell with the highest application rate at present, and the metallized electrode is a key material of the crystalline silicon solar cell, particularly a front grid material, and directly influences performance indexes of the solar cell, such as photoelectric conversion efficiency, filling factor, series resistance and the like. The electrode silver paste is used as a key material of the electrode and the grid line film of the crystalline silicon solar cell, plays a role in leading out the electrode and collecting current in the solar cell, greatly influences the photoelectric conversion efficiency of the solar cell by the quality of the electrode silver paste performance, and directly determines the service life and the attenuation degree of the cell.
The front electrode silver paste consists of three parts, namely a conductive phase, an organic phase and an inorganic phase. The conductive phase is metal powder with a conductive function, and the silver micro powder with the best conductive performance is generally adopted; the organic phase is an organic carrier suitable for the screen printing technology, and the organic carrier mainly comprises an organic solvent, a plasticizer, a thixotropic agent, a leveling agent, a surfactant and the like, so that the slurry has rheological properties such as viscosity, thixotropy and the like suitable for screen printing; the inorganic phase is mainly glass powder and metal oxide, and has the functions of burning through, reducing the reflection layer and binding.
The research on the front electrode silver paste in the prior art mainly focuses on the improvement of an inorganic phase, for example, in a patent with the patent document number of CN103559939A, a sintering accelerant is added into the paste, the generation of bypass knots is prevented, and the yield of battery pieces is improved; further, as disclosed in patent No. CN103559938A, by adding a compound containing indium and tin, the bonding strength between the electrode and the silicon substrate is enhanced, and the series resistance is reduced; there are also improvements in the prior art for conductive phase formulations, such as patent documents CN105118873B and CN107731346A for preparing front electrode silver pastes by designing the components of the conductive phase.
However, the prior art only relates to modification of inorganic phase design, conductive phase component design and the like of the front electrode silver paste, the performance of the front electrode silver paste is not improved from the perspective of the self structure of the conductive phase, the improvement of a front electrode silver paste system needs complex formula design, the process development route is complicated, and the sintering effect and the battery efficiency are difficult to control.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in order to solve the technical problems of the existing front electrode silver paste and the preparation method thereof, the invention provides the front electrode silver paste and silver powder for the solar cell and the preparation method thereof from the view point of the self structure of the conductive phase.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for preparing silver powder for a solar cell comprises the following steps:
adding a dispersing agent into a soluble silver salt solution, mixing, and adjusting the solution to be acidic to obtain a soluble silver salt dispersion solution;
under the condition of stirring, adding the acidic reducing agent solution into the soluble silver salt dispersion liquid at one time, and standing for 3-10min after the acidic reducing agent solution is added;
after standing, mechanically stirring and ultrasonically reacting the reaction liquid until the silver powder is completely separated out to obtain reaction liquid containing the silver powder;
and carrying out post-treatment on the reaction liquid containing the silver powder to obtain the silver powder for the solar cell.
The invention adds the acidic reducing agent solution into the soluble silver salt dispersion liquid, belongs to the excessive reaction of the soluble silver salt, and can instantly generate a large amount of silver crystal nuclei, so that the silver powder particles synchronously grow, and the particle size range is controllable; in addition, the acidic reducing agent solution is added into the soluble silver salt dispersion liquid under the stirring condition, so that the reducing agent can be uniformly dispersed at the first time, the phenomenon of local over-concentration is avoided, the stirring is stopped for 3-10min after the acidic reducing agent solution is added, time is provided for the irregular free growth of crystal nuclei, and then the reaction is continued under the stirring and ultrasonic conditions, so that the final silver powder is in an irregular spherical shape with uneven surfaces and small holes.
Preferably, the soluble silver salt is one of silver nitrate, silver fluoride, silver chlorate and silver perchlorate.
Preferably, the mass percentage of the dispersing agent to the mass of the soluble silver salt is 1-10 wt%, and the molar ratio of the soluble silver salt to the reducing agent is 1: 0.3-1.2.
Preferably, the concentration of the soluble silver salt solution is 0.1-1.5mol/L, and the concentration of the reducing agent solution is 0.1-1.1 mol/L.
Preferably, the pH of the soluble silver salt dispersion and the reducing agent solution is 1.5 to 4, and preferably the pH of the soluble silver salt dispersion and the pH of the reducing agent solution are the same.
Preferably, the reducing agent is at least one of ascorbic acid, hydrazine hydrate, ferrous salt, borohydride salt and hypophosphite.
Preferably, the dispersant is at least one of polyvinylpyrrolidone, polyvinyl alcohol, gelatin, carboxymethylcellulose, polyacrylate, gum arabic, long chain alkanolamine, lauryl sulfate, cetyltrimethylammonium bromide, polyethylene glycol, tween, long chain fatty acid.
Preferably, the reaction temperature is 20-35 ℃, the ultrasonic frequency is 5-40 KHZ, and the stirring speed is 500-2000 r/min.
The invention also provides the silver powder for the solar cell, which is prepared by the method, wherein the particle diameter of the silver powder for the solar cell is 0.8-2.5 mu m, and the tap density is 4-7.5g/cm3The specific surface area is 1-3 square meters per gram.
A preparation method of front electrode silver paste for a solar cell comprises the following steps:
silver powder pretreatment: mixing 100 parts by weight of the silver powder of claim 7, 40-70 parts by weight of an organic solvent, and 1-5 parts by weight of a coupling agent, precipitating, filtering, and drying a mixed solution containing the silver powder to obtain a modified silver powder;
pretreatment of glass powder: mixing 100 parts by weight of glass powder, 20-80 parts by weight of organic solvent and 0.2-3 parts by weight of coupling agent, precipitating, filtering and drying the mixed solution containing the glass powder to obtain modified glass powder;
preparing the front electrode silver paste of the solar cell: adding 70-90 parts by weight of modified silver powder and 0.5-4 parts by weight of modified glass powder into 9-21 parts by weight of organic carrier, mixing, grinding and filtering to obtain the front electrode silver paste of the solar cell; the organic carrier comprises 40-80 parts by weight of organic solvent, 1-3 parts by weight of thixotropic agent and 16-30 parts by weight of plasticizer.
Preferably, the organic solvent is at least one of terpineol, butyl carbitol, propylene glycol ether acetate and butyl carbitol acetate.
Preferably, the coupling agent is at least one of titanate coupling agent and silane coupling agent.
Preferably, the thixotropic agent is at least one of castor oil, hydrogenated castor oil, silica, organobentonite.
Preferably, the plasticizer is at least one of ethyl cellulose, butyl cellulose and hydroxy cellulose.
Preferably, the mixing and grinding conditions for adding the modified silver powder and the modified glass powder into the organic carrier are as follows: stirring and mixing for 10-60min at the stirring speed of 500-2000 r/min, and three-roll grinding until the fineness of the slurry is less than or equal to 5 mu m.
The invention also provides the front electrode silver paste for the solar cell, which is prepared by the method, wherein the solid content of the front electrode silver paste is 80-93%, the viscosity is 150-400pa.s, and the fineness of the paste is less than or equal to 5 mu m.
The invention has the beneficial effects that:
(1) the silver powder for the solar cell is simple in process and low in cost, the prepared silver powder is irregular spherical with uneven surfaces, and compared with the traditional silver powder, the silver powder has the characteristics of large specific surface area, uniform particle size distribution and small morphology difference, can be better contacted with an inorganic phase and an organic phase, is high in sintering activity, and can effectively reduce contact resistance after sintering.
(2) According to the invention, the irregular spherical silver powder with uneven surface is used as a conductive phase in the front electrode silver paste, and the silver powder and the glass powder are subjected to surface modification treatment, so that the silver powder and the glass powder are good in dispersing effect and not easy to settle, the prepared front electrode silver paste for the solar cell is low in sintering temperature, compact in sintered silver dissolution, good in ohmic contact, higher in sintering activity and excellent in weldability, can effectively reduce the contact resistance after sintering, improves the conductive efficiency, and can be applied to low-temperature sintered cells.
Detailed Description
The present invention will now be described in further detail.
Example 1
The embodiment provides a front electrode silver paste for a solar cell and a preparation method of the silver paste, wherein the preparation method of the silver powder comprises the following steps:
preparing 1L of silver fluoride aqueous solution with the concentration of 0.1mol/L, adding carboxymethyl cellulose into the aqueous solution, dropwise adding HF aqueous solution to adjust the pH value to 3.5, stirring and carrying out ultrasonic treatment for 30min, wherein the ultrasonic frequency is 5KHZ, and the stirring speed is 2000r/min, so as to obtain silver fluoride dispersion liquid, wherein the mass of the carboxymethyl cellulose accounts for 1 wt% of the mass of the silver fluoride;
preparing 1L ascorbic acid aqueous solution with the concentration of 0.11mol/L, and dropwise adding HF aqueous solution to adjust the pH value to 3.5;
adding the ascorbic acid aqueous solution into the silver fluoride dispersion liquid at one time at the temperature of 20 ℃, stirring (the stirring speed is 2000r/min) in the adding process, and stopping stirring for 3min after the ascorbic acid aqueous solution is added;
mechanically stirring and ultrasonically reacting the reaction liquid, wherein the ultrasonic frequency is 5KHz, and the stirring speed is 2000r/min until the reaction is finished to obtain the reaction liquid containing the silver powder;
carrying out suction filtration on the reaction liquid containing the silver powder, washing with deionized water and ethanol, drying and sieving to obtain the silver powder for the solar cell, wherein the particle diameter of the silver powder is 0.8-1.5 mu m, and the tap density is 4-5.5g/cm3The specific surface area is 1-3 square meters per gram.
The preparation method of the front electrode silver paste for the solar cell comprises the following steps:
silver powder pretreatment: stirring and mixing 100 parts by weight of silver powder, 40 parts by weight of terpineol and 1.5 parts by weight of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane for 60min at a stirring speed of 500r/min, precipitating and filtering a mixed solution containing the silver powder, and drying for 1h at 80 ℃ to obtain modified silver powder;
pretreatment of glass powder: mixing 100 parts by weight of glass powder, 20 parts by weight of terpineol and 0.5 part by weight of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, precipitating and filtering a mixed solution containing the glass powder, and drying for 1h at 80 ℃ to obtain modified glass powder;
preparing the front electrode silver paste of the solar cell: adding 76 parts by weight of modified silver powder and 4 parts by weight of modified glass powder into 21 parts by weight of organic carrier, stirring and mixing for 60min at a stirring speed of 500r/min, transferring to a three-roll grinder, grinding for 3h, and filtering to obtain the front electrode silver paste of the solar cell;
the preparation method of the organic carrier comprises the following steps: taking 70 parts by weight of terpineol, adding 30 parts by weight of ethyl cellulose under the stirring condition, heating to 70-90 ℃, adding 3 parts by weight of castor oil after the ethyl cellulose is completely dissolved, and mixing to obtain the organic carrier.
The front electrode silver paste for the solar cell prepared in the embodiment has the solid content of 80%, the viscosity of 150pa · s, the fineness of the paste less than or equal to 5 μm, the sintering peak temperature of 720-2The cell efficiency was 20.16%.
The test conditions of the welding tension are as follows: a welding rod with the diameter of 1.2 multiplied by 0.25mm is selected, the welding rod is welded on the electrode by an electric iron (the set temperature is 350 ℃), a 180-degree tensile tester is used for testing the welding tension between the welding rod and the silver paste and between the welding rod and the silver paste, and stripping is carried out at the speed of 0.3cm/s during testing.
The test conditions of the series resistance and the battery efficiency are as follows: the front silver paste is printed on a monocrystalline silicon wafer to prepare a solar cell, a precision resistance meter is used for testing a series resistance, a solar simulation cell efficiency tester is used for testing the series resistance under standard conditions (the atmospheric quality AM1.5, the illumination intensity is 1000W/m)2And the test temperature is 25 ℃ to test the efficiency of the battery.
Example 2
The embodiment provides a front electrode silver paste for a solar cell and a preparation method of the silver paste, wherein the preparation method of the silver powder comprises the following steps:
preparing 1L of silver nitrate aqueous solution with the concentration of 0.3mol/L, adding polyvinylpyrrolidone into the aqueous solution, and dropwise adding HNO3Adjusting the pH value to 3, stirring and performing ultrasonic treatment for 20min at the ultrasonic frequency of 40KHZ and the stirring speed of 500r/min to obtain silver nitrate dispersion liquid, wherein the mass percent of polyvinylpyrrolidone in the mass of silver nitrate is 10 wt%;
1L ferrous sulfate aqueous solution with the concentration of 0.35mol/L is prepared, HNO is dripped3Adjusting the pH value to 3;
adding the ferrous sulfate aqueous solution into the silver nitrate dispersion liquid at 25 ℃, stirring (the stirring speed is 500r/min) in the adding process, and stopping stirring for 5min after the ferrous sulfate aqueous solution is added;
mechanically stirring and ultrasonically reacting the reaction liquid, wherein the ultrasonic frequency is 40KHZ, and the stirring speed is 500r/min until the reaction is finished to obtain the reaction liquid containing the silver powder;
carrying out suction filtration on the reaction liquid containing the silver powder, washing with deionized water and ethanol, drying and sieving to obtain the silver powder for the solar cell, wherein the particle diameter of the silver powder is 1-1.8 mu m, and the tap density is 4.3-5.8g/cm3The specific surface area is 1-3 square meters per gram.
The preparation method of the front electrode silver paste for the solar cell comprises the following steps:
silver powder pretreatment: stirring and mixing 100 parts by weight of silver powder, 50 parts by weight of butyl carbitol and 2 parts by weight of gamma-mercaptopropyl trimethoxy silane for 30min at the stirring speed of 1000r/min, precipitating and filtering a mixed solution containing the silver powder, and drying for 1h at 80 ℃ to obtain modified silver powder;
pretreatment of glass powder: mixing 100 parts by weight of glass powder, 40 parts by weight of butyl carbitol and 0.8 part by weight of tri (dioctyl pyrophosphoryl oxy) isopropyl titanate, precipitating and filtering mixed liquid containing the glass powder, and drying for 1h at 80 ℃ to obtain modified glass powder;
preparing the front electrode silver paste of the solar cell: adding 80 parts by weight of modified silver powder and 3 parts by weight of modified glass powder into 17 parts by weight of organic carrier, stirring and mixing for 10min at a stirring speed of 2000r/min, transferring to a three-roll grinder, grinding for 3h, and filtering to obtain the front electrode silver paste of the solar cell;
the preparation method of the organic carrier comprises the following steps: taking 70 parts by weight of butyl carbitol, adding 27 parts by weight of ethyl cellulose under the stirring condition, heating to 70-90 ℃, adding 3 parts by weight of hydrogenated castor oil after the ethyl cellulose is completely dissolved, and mixing to obtain the organic carrier.
The front electrode silver paste for the solar cell prepared in the embodiment has the solid content of 93%, the viscosity of 400pa · s, the slurry fineness of less than or equal to 5 μm, the sintering peak temperature of 680-820 ℃, the series resistance of 1.66m Ω, and the welding tension of 3.2N/mm2The cell efficiency was 20.32%.
The test conditions for the series resistance, the welding tension and the cell efficiency were the same as in example 1.
Example 3
The embodiment provides a front electrode silver paste for a solar cell and a preparation method of the silver paste, wherein the preparation method of the silver powder comprises the following steps:
preparing 1L of silver nitrate aqueous solution with the concentration of 0.5mol/L, adding cetyl trimethyl ammonium bromide into the aqueous solution, and dropwise adding HNO3Adjusting the pH value to 3, stirring and performing ultrasonic treatment for 30min at the ultrasonic frequency of 10KHZ and the stirring speed of 1000r/min to obtain silver nitrate dispersion liquid, wherein the mass percent of the cetyl trimethyl ammonium bromide in the silver nitrate is 8 wt%;
1L of hydrazine hydrate solution with the concentration of 0.55mol/L is prepared, and HNO is dripped3Adjusting the pH value to 3;
adding the hydrazine hydrate solution into the silver nitrate dispersion liquid at one time at the temperature of 25 ℃, stirring (the stirring speed is 1000r/min) in the adding process, and stopping stirring for 10min after the hydrazine hydrate solution is added;
mechanically stirring and ultrasonically reacting the reaction liquid, wherein the ultrasonic frequency is 10KHZ, and the stirring speed is 1000r/min until the reaction is finished to obtain the reaction liquid containing the silver powder;
carrying out suction filtration on the reaction liquid containing the silver powder, washing with deionized water and ethanol, drying and sieving to obtain the silver powder for the solar cell, wherein the particle diameter of the silver powder is 1.1-2 mu m, and the tap density is 4.6-6g/cm3The specific surface area is 1-3 square meters per gram.
The preparation method of the front electrode silver paste for the solar cell comprises the following steps:
silver powder pretreatment: stirring and mixing 100 parts by weight of silver powder, 50 parts by weight of propylene glycol diethyl ether acetate and 3 parts by weight of tri (dioctyl pyrophosphoryl acyloxy) isopropyl titanate for 10min at a stirring speed of 2000r/min, precipitating and filtering a mixed solution containing the silver powder, and drying for 1h at 80 ℃ to obtain modified silver powder;
pretreatment of glass powder: mixing 100 parts by weight of glass powder, 70 parts by weight of propylene glycol ether acetate and 1.2 parts by weight of tetraoctyloxy titanium [ bis (tridecyl phosphite) ], precipitating and filtering a mixed solution containing the glass powder, and drying at 80 ℃ for 1h to obtain modified glass powder;
preparing the front electrode silver paste of the solar cell: adding 85 parts by weight of modified silver powder and 2 parts by weight of modified glass powder into 13 parts by weight of organic carrier, stirring and mixing for 30min at a stirring speed of 1000r/min, transferring to a three-roll grinder, grinding for 3h, and filtering to obtain the front electrode silver paste of the solar cell;
the preparation method of the organic carrier comprises the following steps: taking 75 parts by weight of propylene glycol ether acetate, adding 23 parts by weight of ethyl cellulose under the stirring condition, heating to 70-90 ℃, adding 2 parts by weight of silicon dioxide after the ethyl cellulose is completely dissolved, and mixing to obtain the organic carrier.
The front electrode silver paste for the solar cell prepared in the embodiment has a solid content of 90%, a viscosity of 250pa · s, a paste fineness of less than or equal to 5 μm, a sintering peak temperature of 680-800 ℃, a series resistance of 1.62m Ω, and a welding tension of 3.4N/mm2The cell efficiency was 20.18%.
The test conditions for the series resistance, the welding tension and the cell efficiency were the same as in example 1.
Example 4
The embodiment provides a front electrode silver paste for a solar cell and a preparation method of the silver paste, wherein the preparation method of the silver powder comprises the following steps:
preparing 1L of silver chlorate aqueous solution with the concentration of 0.8mol/L, adding sodium polyacrylate into the silver chlorate aqueous solution, dropwise adding the sodium chlorate aqueous solution to adjust the pH value to 3, stirring and carrying out ultrasonic treatment for 30min, wherein the ultrasonic frequency is 20KHZ, and the stirring speed is 1500r/min, so as to obtain silver chlorate dispersion, wherein the mass percentage of the sodium polyacrylate in the mass of the silver chlorate is 5 wt%;
preparing 1L of 0.25mol/L aqueous solution of sodium hypophosphite, and dropwise adding aqueous solution of chloric acid to adjust the pH value to 3;
adding the sodium hypophosphite aqueous solution into the silver chlorate dispersion liquid at one time at the temperature of 28 ℃, stirring (the stirring speed is 1500r/min) in the adding process, and stopping stirring for 5min after the sodium hypophosphite aqueous solution is added;
mechanically stirring and ultrasonically reacting the reaction liquid, wherein the ultrasonic frequency is 20KHZ, and the stirring speed is 1500r/min until the reaction is finished to obtain the reaction liquid containing the silver powder;
carrying out suction filtration on the reaction liquid containing the silver powder, washing with deionized water and ethanol, drying and sieving to obtain the silver powder for the solar cell, wherein the particle diameter of the silver powder is 1.2-2.2 mu m, and the tap density is 4.9-6.5g/cm3The specific surface area is 1-3 square meters per gram.
The preparation method of the front electrode silver paste for the solar cell comprises the following steps:
silver powder pretreatment: stirring and mixing 100 parts by weight of silver powder, 60 parts by weight of butyl carbitol acetate and 2 parts by weight of tetraoctyloxy titanium [ bis (tridecyl phosphite) ] at a stirring speed of 1000r/min for 30min, precipitating and filtering a mixed solution containing the silver powder, and drying for 1h at 80 ℃ to obtain modified silver powder;
pretreatment of glass powder: mixing 100 parts by weight of glass powder, 80 parts by weight of butyl carbitol acetate and 1.6 parts by weight of tetraoctyloxy titanium [ di (dilauryl phosphite) ], precipitating and filtering a mixed solution containing the glass powder, and drying for 1h at 80 ℃ to obtain modified glass powder;
preparing the front electrode silver paste of the solar cell: adding 85 parts by weight of modified silver powder and 1 part by weight of modified glass powder into 14 parts by weight of organic carrier, stirring and mixing for 30min at a stirring speed of 1000r/min, transferring to a three-roll grinder, grinding for 3h, and filtering to obtain the front electrode silver paste of the solar cell;
the preparation method of the organic carrier comprises the following steps: taking 75 parts by weight of butyl carbitol acetate, adding 23 parts by weight of hydroxy cellulose under the stirring condition, heating to 70-90 ℃, adding 2 parts by weight of organic bentonite after the hydroxy cellulose is completely dissolved, and mixing to obtain the organic carrier.
The front electrode silver paste for the solar cell prepared in the embodiment has the solid content of 86%, the viscosity of 290pa.s, the fineness of the paste less than or equal to 5 μm, the sintering peak temperature of 700-2The battery efficiency is20.26％。
The test conditions for the series resistance, the welding tension and the cell efficiency were the same as in example 1.
Example 5
The embodiment provides a front electrode silver paste for a solar cell and a preparation method of the silver paste, wherein the preparation method of the silver powder comprises the following steps:
preparing 1L of silver nitrate aqueous solution with the concentration of 1mol/L, adding sodium dodecyl sulfate into the aqueous solution, and dropwise adding HNO3Adjusting the pH value to 2.5, stirring and performing ultrasonic treatment for 30min at the ultrasonic frequency of 30KHZ and the stirring speed of 1000r/min to obtain silver nitrate dispersion liquid, wherein the mass percent of the sodium dodecyl sulfate in the silver nitrate is 4 wt%;
1L of sodium borohydride aqueous solution with the concentration of 1.1mol/L is prepared, and HNO is dripped3Adjusting the pH value to 2.5;
adding the sodium borohydride aqueous solution into the silver nitrate dispersion liquid at one time at the temperature of 30 ℃, stirring (the stirring speed is 1000r/min) in the adding process, and stopping stirring for 5min after the sodium borohydride aqueous solution is added;
mechanically stirring and ultrasonically reacting the reaction liquid, wherein the ultrasonic frequency is 30KHz, and the stirring speed is 1000r/min until the reaction is finished to obtain the reaction liquid containing the silver powder;
carrying out suction filtration on the reaction liquid containing the silver powder, washing with deionized water and ethanol, drying and sieving to obtain the silver powder for the solar cell, wherein the particle diameter of the silver powder is 1.2-2.5 mu m, and the tap density is 4.8-7g/cm3The specific surface area is 1-3 square meters per gram.
The preparation method of the front electrode silver paste for the solar cell comprises the following steps:
silver powder pretreatment: stirring and mixing 100 parts by weight of silver powder, 50 parts by weight of terpineol and 3 parts by weight of tetraoctyloxy titanium [ di (dilauryl phosphite) ] at the stirring speed of 1000r/min for 30min, precipitating and filtering a mixed solution containing the silver powder, and drying for 1h at 80 ℃ to obtain modified silver powder;
pretreatment of glass powder: mixing 100 parts by weight of glass powder, 70 parts by weight of terpineol and 2 parts by weight of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, precipitating and filtering a mixed solution containing the glass powder, and drying for 1h at 80 ℃ to obtain modified glass powder;
preparing the front electrode silver paste of the solar cell: adding 88 parts by weight of modified silver powder and 0.8 part by weight of modified glass powder into 11.5 parts by weight of organic carrier, stirring and mixing for 30min at a stirring speed of 1000r/min, transferring to a three-roll grinder for grinding for 3h, and filtering to obtain the front electrode silver paste of the solar cell;
the preparation method of the organic carrier comprises the following steps: taking 80 parts by weight of terpineol, adding 19 parts by weight of butyl cellulose under the stirring condition, heating to 70-90 ℃, adding 1 part by weight of hydrogenated castor oil after the butyl cellulose is completely dissolved, and mixing to obtain the organic carrier.
The front electrode silver paste for the solar cell prepared in the embodiment has the solid content of 93%, the viscosity of 350pa.s, the fineness of the paste less than or equal to 5 μm, the sintering peak temperature of 630-750 ℃, the series resistance of 1.56m omega, and the welding tension of 3.9N/mm2The cell efficiency was 20.35%.
The test conditions for the series resistance, the welding tension and the cell efficiency were the same as in example 1.
Example 6
The embodiment provides a front electrode silver paste for a solar cell, silver powder and a preparation method of the silver powder, wherein the preparation method of the silver powder comprises the following steps:
preparing 1L of silver nitrate aqueous solution with the concentration of 1.5mol/L, adding sodium dodecyl sulfate into the aqueous solution, and dropwise adding HNO3Adjusting the pH value to 1.5, stirring and performing ultrasonic treatment for 30min at the ultrasonic frequency of 20KHZ and the stirring speed of 1000r/min to obtain silver nitrate dispersion liquid, wherein the mass percent of the sodium dodecyl sulfate in the silver nitrate is 6 wt%;
1L ferrous sulfate aqueous solution with the concentration of 0.55mol/L is prepared, HNO is dripped3Adjusting the pH value to 1.5;
under the condition that the temperature is 35 ℃, adding the ferrous sulfate aqueous solution into the silver nitrate dispersion liquid at one time, stirring (the stirring speed is 1000r/min) in the adding process, and stopping stirring for 5min after the ferrous sulfate aqueous solution is added;
mechanically stirring and ultrasonically reacting the reaction liquid, wherein the ultrasonic frequency is 20KHZ, and the stirring speed is 1000r/min until the reaction is finished to obtain the reaction liquid containing the silver powder;
carrying out suction filtration on the reaction liquid containing the silver powder, washing with deionized water and ethanol, drying and sieving to obtain the silver powder for the solar cell, wherein the particle diameter of the silver powder is 1.2-2.5 mu m, and the tap density is 5-7.5g/cm3The specific surface area is 1-3 square meters per gram.
The preparation method of the front electrode silver paste for the solar cell comprises the following steps:
silver powder pretreatment: stirring and mixing 100 parts by weight of silver powder, 70 parts by weight of butyl carbitol and 5 parts by weight of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane at the stirring speed of 2000r/min for 20min, precipitating and filtering a mixed solution containing the silver powder, and drying for 1h at the temperature of 80 ℃ to obtain modified silver powder;
pretreatment of glass powder: mixing 100 parts by weight of glass powder, 70 parts by weight of butyl carbitol and 2.5 parts by weight of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, precipitating and filtering a mixed solution containing the glass powder, and drying for 1h at 80 ℃ to obtain modified glass powder;
preparing the front electrode silver paste of the solar cell: adding 90 parts by weight of modified silver powder and 0.8 part by weight of modified glass powder into 9.2 parts by weight of organic carrier, stirring and mixing for 30min at a stirring speed of 1000r/min, transferring to a three-roll grinder for grinding for 4h, and filtering to obtain the front electrode silver paste of the solar cell;
the preparation method of the organic carrier comprises the following steps: taking 40 parts by weight of butyl carbitol, adding 16 parts by weight of ethyl cellulose under the stirring condition, heating to 70-90 ℃, adding 1 part by weight of castor oil after the ethyl cellulose is completely dissolved, and mixing to obtain the organic carrier.
The front electrode silver paste for the solar cell prepared in the embodiment has a solid content of 90%, a viscosity of 350pa · s, a paste fineness of less than or equal to 5 μm, a sintering peak temperature of 650-2The cell efficiency was 20.46%.
The test conditions for the series resistance, the welding tension and the cell efficiency were the same as in example 1.
Comparative example
This comparative example provides a front electrode silver paste and silver powder for a solar cell and a method for preparing the same, and the present example is different from example 6 only in that: during the preparation of the silver powder, after the ferrous sulfate aqueous solution is added, the reaction solution is directly subjected to mechanical stirring and ultrasonic reaction without standing; the obtained silver powder has particle diameter of 0.9-3.5 μm and tap density of 4.1-6.5g/cm3The specific surface area is 0.9-2.5 square meters per gram, the solid content of the obtained front electrode silver paste is 90 percent, the viscosity is 350pa.s, the fineness of the paste is less than or equal to 5 mu m, the sintering peak temperature is 650 plus 780 ℃, the series resistance is 1.74m omega, and the welding tension is 2.7N/mm2The cell efficiency was 20.21%. The comparison shows that the silver powder prepared by the embodiment has a large particle size distribution range and a small specific surface area, and the obtained front electrode silver paste has large series resistance, small welding tension and low battery efficiency. Therefore, during the preparation of the silver powder, after the ferrous sulfate aqueous solution is added, the standing has a great beneficial effect on the performance improvement of the front electrode silver paste.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (8)
1. The preparation method of the silver powder for the solar cell is characterized by comprising the following steps of:
adding a dispersing agent into the soluble silver salt solution, mixing, and adjusting the pH value of the solution to 1.5-4 to obtain a soluble silver salt dispersion liquid;
under the condition of stirring, adding a reducing agent solution with the pH of 1.5-4 into the soluble silver salt dispersion liquid for reaction at one time, and standing for 3-10min after the addition of the acidic reducing agent solution is finished to obtain a mixed solution;
after standing, applying mechanical stirring and ultrasonic action to the mixed solution until the silver powder is completely separated out to obtain a reaction solution containing the silver powder;
carrying out post-treatment on the reaction liquid containing the silver powder to obtain silver powder for the solar cell;
the mass percentage of the dispersing agent in the soluble silver salt is 1-10 wt%, the molar ratio of the soluble silver salt to the reducing agent is 1:0.3-1.2, the concentration of the soluble silver salt solution is 0.1-1.5mol/L, and the concentration of the reducing agent solution is 0.1-1.1 mol/L.
2. The method for preparing silver powder for a solar cell according to claim 1, wherein the soluble silver salt is one of silver nitrate, silver fluoride, silver chlorate and silver perchlorate.
3. The method for producing silver powder for solar cells according to claim 1 or 2, wherein the reducing agent is at least one of ascorbic acid, hydrazine hydrate, ferrous salt, borohydride salt, and hypophosphite, and the dispersing agent is at least one of polyvinylpyrrolidone, polyvinyl alcohol, gelatin, carboxymethyl cellulose, polyacrylate, gum arabic, long-chain alkanolamine, lauryl sulfate, cetyltrimethylammonium bromide, polyethylene glycol, tween, and long-chain fatty acid.
4. The method for preparing silver powder for solar cells according to claim 1 or 2, wherein the reaction temperature is 20 to 35 ℃, the ultrasonic frequency is 5 to 40KHz, and the stirring speed is 500 to 2000 r/min.
5. A silver powder for solar cells produced by the method according to any one of claims 1 to 4, characterized in that the silver powder for solar cells has a particle diameter of 0.8 to 2.5 μm and a tap density of 4 to 7.5g/cm3The specific surface area is 1-3 square meters per gram.
6. The preparation method of the front electrode silver paste for the solar cell is characterized by comprising the following steps:
silver powder pretreatment: mixing 100 parts by weight of the silver powder of claim 5, 40-70 parts by weight of an organic solvent, and 1-5 parts by weight of a coupling agent, precipitating, filtering, and drying a mixed solution containing the silver powder to obtain a modified silver powder;
pretreatment of glass powder: mixing 100 parts by weight of glass powder, 20-80 parts by weight of organic solvent and 0.2-3 parts by weight of coupling agent, precipitating, filtering and drying the mixed solution containing the glass powder to obtain modified glass powder;
preparing the front electrode silver paste of the solar cell: adding 70-90 parts by weight of modified silver powder and 0.5-4 parts by weight of modified glass powder into 9-21 parts by weight of organic carrier, mixing and grinding to obtain the front electrode silver paste of the solar cell; the organic carrier comprises 40-80 parts by weight of organic solvent, 1-3 parts by weight of thixotropic agent and 16-30 parts by weight of plasticizer.
7. The method for preparing the front electrode silver paste for the solar cell according to claim 6, wherein the organic solvent is at least one of terpineol, butyl carbitol, propylene glycol methyl ether acetate and butyl carbitol acetate, the coupling agent is at least one of titanate coupling agent and silane coupling agent, the thixotropic agent is at least one of castor oil, hydrogenated castor oil, silicon dioxide and organic bentonite, and the plasticizer is at least one of ethyl cellulose, butyl cellulose and hydroxy cellulose.
8. The front electrode silver paste for the solar cell, which is prepared by the method of claim 6 or 7, is characterized in that the solid content of the front electrode silver paste is 80-93%, the viscosity is 150-400pa.s, and the fineness of the paste is less than or equal to 5 μm.
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| CN114939668A (en) * | 2021-06-16 | 2022-08-26 | 河南金渠银通金属材料有限公司 | Preparation method of superfine silver powder and silver conductive paste thereof |
| CN113880435A (en) * | 2021-07-16 | 2022-01-04 | 杭州正银电子材料有限公司 | Modified glass powder for PERC back silver paste and preparation method and application thereof |
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