CN109215829A - A kind of front electrode silver slurry used for solar batteries, silver powder and preparation method thereof - Google Patents
A kind of front electrode silver slurry used for solar batteries, silver powder and preparation method thereof Download PDFInfo
- Publication number
- CN109215829A CN109215829A CN201811021669.3A CN201811021669A CN109215829A CN 109215829 A CN109215829 A CN 109215829A CN 201811021669 A CN201811021669 A CN 201811021669A CN 109215829 A CN109215829 A CN 109215829A
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- China
- Prior art keywords
- silver
- silver powder
- weight
- preparation
- powder
- Prior art date
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Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 70
- 239000004332 silver Substances 0.000 title claims abstract description 70
- 239000002002 slurry Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- 239000011521 glass Substances 0.000 claims abstract description 47
- 239000000843 powder Substances 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 239000006185 dispersion Substances 0.000 claims abstract description 24
- 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 18
- 238000002203 pretreatment Methods 0.000 claims abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000007822 coupling agent Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 45
- 238000002156 mixing Methods 0.000 claims description 41
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 36
- 238000001914 filtration Methods 0.000 claims description 20
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 14
- 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 10
- 229920001249 ethyl cellulose Polymers 0.000 claims description 10
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 10
- -1 polyethylene Pyrrolidones Polymers 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 9
- 238000010907 mechanical stirring Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 8
- 239000004359 castor oil Substances 0.000 claims description 6
- 235000019438 castor oil Nutrition 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 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 6
- 150000003839 salts Chemical class 0.000 claims description 6
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 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
- 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 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
- 239000012266 salt solution Substances 0.000 claims description 4
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 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
- 239000000205 acacia gum Substances 0.000 claims description 2
- 235000010489 acacia gum Nutrition 0.000 claims description 2
- 150000001412 amines Chemical class 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
- 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
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 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
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 150000004668 long chain fatty acids Chemical class 0.000 claims 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 claims 1
- 229920000058 polyacrylate Polymers 0.000 claims 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 238000002525 ultrasonication Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 17
- 238000002604 ultrasonography Methods 0.000 abstract description 16
- 238000005245 sintering Methods 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 7
- 230000001788 irregular Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 description 21
- 238000003466 welding Methods 0.000 description 19
- 239000012071 phase Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 235000003891 ferrous sulphate Nutrition 0.000 description 7
- 239000011790 ferrous sulphate Substances 0.000 description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000000969 carrier Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 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
- 230000006872 improvement Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon 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
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000012216 bentonite Nutrition 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 2
- 229940005991 chloric acid Drugs 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 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 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 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 2
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 241000218195 Lauraceae Species 0.000 description 1
- 235000017858 Laurus nobilis Nutrition 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 235000005212 Terminalia tomentosa Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- SPBMDAHKYSRJFO-UHFFFAOYSA-N didodecyl hydrogen phosphite Chemical compound CCCCCCCCCCCCOP(O)OCCCCCCCCCCCC SPBMDAHKYSRJFO-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 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
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Conductive Materials (AREA)
- Powder Metallurgy (AREA)
Abstract
The present invention relates to a kind of front electrode silver slurries used for solar batteries, silver powder and preparation method thereof, silver powder the preparation method comprises the following steps: acid reducing agent solution is added in soluble silver salt dispersion liquid, it is stirred in adding procedure, after agent solution addition to be restored, 3-10min is stood, stirring then is applied to reaction solution and ultrasound is reacted, until silver powder is precipitated completely, reaction solution is post-processed, silver powder is obtained；Silver paste the preparation method comprises the following steps: silver powder, glass powder, which are separately added into organic solvent and coupling agent, carries out pre-treatment, modified silver powder and modified glass powder are added in organic carrier and are mixed, ground, filtered, front electrode silver slurry is obtained.The present invention prepares the simple process of silver powder used for solar batteries, and the silver powder of preparation is the irregular spherical shape of surface irregularity, and sintering activity is big；The front electrode silver slurry sintering temperature of preparation is low, and solderability is excellent, and can be effectively reduced sintered contact resistance, promotes electrical efficiency.
Description
Technical field
The present invention relates to a kind of front electrode silver slurries used for solar batteries, silver powder and preparation method thereof, belong to electronic material
Technical field.
Background technique
Crystal silicon solar energy battery is the highest solar battery of current utility ratio, and metallic electrode is crystal silicon solar
The critical material of battery, especially grid electrode front material, directly affect the incident photon-to-electron conversion efficiency of solar battery, fill factor,
The performance indexs such as series resistance.Electrode silver plasm as crystalline silicon solar battery electrode and the key material of grid line film,
Play the role of extraction electrode in solar cells and collect electric current, the superiority and inferiority of electrode silver plasm performance is by extreme influence solar energy
The incident photon-to-electron conversion efficiency of battery, and directly decide the service life and the dough softening of battery.
Front electrode silver slurry is made of conductive phase, organic phase and inorganic phase three parts.Conductive phase has been the gold of electric action
Belong to powder, the general micro silver powder best using electric conductivity；Organic phase is the organic carrier suitable for screen printing technique, organic
Carrier is mainly made of organic solvent, plasticizer, thixotropic agent, levelling agent and surfactant etc., is had slurry and is suitable for
The rheological properties such as viscosity, the thixotropy of silk-screen printing；Inorganic phase is mainly glass powder and metal oxide, plays and grills thoroughly anti-reflection layer
And cementation.
The prior art is concentrated mainly in the improvement to inorganic phase the research of front electrode silver slurry, as Patent document number is
The patent of CN103559939A, is added sintering aids in the slurry, and the generation for preventing bypass from tying improves the finished product of cell piece
Rate；For another example document number is the patent of CN103559938A, by adding the compound containing indium and tin, enhance electrode and silicon substrate it
Between adhesion strength, reduce series resistance；Also there is the improvement for conductive phase formula in the prior art, as Patent document number is
CN105118873B and CN107731346A is by the component of design conductive phase to prepare front electrode silver slurry.
But the prior art is all pertained only to the design of front electrode silver slurry inorganic phase, conductive phase component design etc.
It is modified, do not improve the performance of front electrode silver slurry from the point of view of conductive phase self structure, to front electrode silver slurry
The improvement of system needs complicated formula design, and process exploitation route is cumbersome, and sintering effect and battery efficiency are difficult to control.
Summary of the invention
The technical problem to be solved by the present invention is to solve technology existing for existing front electrode silver slurry and preparation method thereof
Problem, the present invention provide a kind of front electrode silver slurry used for solar batteries, silver powder from the point of view of conductive phase self structure
And preparation method thereof.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of preparation method of silver powder used for solar batteries, includes the following steps:
Dispersing agent is added in soluble silver salt solution and is mixed, solution is adjusted to acidity, obtains soluble silver salt dispersion liquid；
Under agitation, acid reducing agent solution is disposably added in soluble silver salt dispersion liquid, to acidity
Reducing agent solution addition after, stand 3-10min；
After the completion of standing, mechanical stirring is applied to reaction solution and ultrasound is reacted, until silver powder is precipitated completely, is contained
There is the reaction solution of silver powder；
Reaction solution containing silver powder is post-processed, silver powder used for solar batteries is obtained.
Acid reducing agent solution is added in soluble silver salt dispersion liquid by the present invention, is to belong to soluble silver salt excess
Reaction, moment can generate a large amount of silver-colored nucleus, make silver powder particles synchronous growth, particle size range is controllable；In addition, the present invention is stirring
Under the conditions of, acid reducing agent solution is added in soluble silver salt dispersion liquid, reducing agent can be made to disperse in first time
Uniformly, there is not the phenomenon that local over-concentration, after acid reducing agent solution addition, stop stirring 3-10min, be for crystalline substance
The irregular free growth of core provides the time, and then the reaction was continued under stirring and ultrasound condition, to realize final silver powder as surface
Rough irregular spherical shape, and have small pore size distribution.
Preferably, the soluble silver salt is one of silver nitrate, silver fluoride, silver chlorate, silver perchlorate.
Preferably, it is 1-10wt%, the silver soluble that the dispersing agent quality, which accounts for the percentage of silver soluble salt quality,
The molar ratio of salt and 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 reducing agent solution is 0.1-
1.1mol/L。
Preferably, the soluble silver salt dispersion liquid, reducing agent solution PH be 1.5-4, preferably silver soluble salinity
Dispersion liquid is identical as the pH of reducing agent solution.
Preferably, the reducing agent is ascorbic acid, hydrazine hydrate, ferrous salt, borohydride salts, at least one in hypophosphites
Kind.
Preferably, the dispersing agent is polyvinylpyrrolidone, polyvinyl alcohol, gelatin, carboxymethyl cellulose, polyacrylic acid
Salt, gum arabic, long chain alkanol amine, lauryl sulfate, cetyl trimethylammonium bromide, polyethylene glycol, tween, length
At least one of chain fatty acid.
Preferably, the reaction temperature is 20-35 DEG C, and supersonic frequency is 5~40KHZ, and speed of agitator is 500~2000r/
min。
The present invention also provides a kind of above method preparation silver powder used for solar batteries, the silver powder used for solar batteries
Partial size is 0.8-2.5 μm, tap density 4-7.5g/cm3, specific surface area is 1-3 ㎡/g.
A kind of preparation method of front electrode silver slurry used for solar batteries, includes the following steps:
Silver powder pre-treatment: by 100 parts by weight silver powder as claimed in claim 7,40-70 weight parts organic solvent, 1-5 weight
Mixing liquid precipitate containing silver powder, filtering, drying are obtained modified silver powder by part coupling agent mixing；
Glass powder pre-treatment: by 100 parts by weight of glass powder, 20-80 weight parts organic solvent, 0.2-3 parts by weight coupling agent
Mixing, by the mixing liquid precipitate containing glass powder, filtering, drying, obtains modified glass powder；
Prepare front electrode of solar battery silver paste: by the part by weight modified silver powder of 70-90 and the part by weight modified glass of 0.5-4
Powder, which is added in 9-21 parts by weight organic carrier, to be mixed, grinds, filters, and front electrode of solar battery silver paste is obtained；It is described
Organic carrier includes the plasticizer of the organic solvent of 40-80 parts by weight, the thixotropic agent of 1-3 parts by weight and 16-30 parts by weight.
Preferably, the organic solvent is terpinol, butyl carbitol, propylene glycol man ether acetate, butyl carbitol vinegar
At least one of acid esters.
Preferably, the coupling agent is at least one of titanate coupling agent, silane coupling agent.
Preferably, the thixotropic agent is castor oil, rilanit special, silica, bentonite at least one.
Preferably, the plasticizer is at least one of ethyl cellulose, butyl cellulose, hydroxylated cellulose.
Preferably, it is specifically by the mixing in modified silver powder and modified glass powder addition organic carrier, grinding condition: stirring
10-60min is mixed, speed of agitator is 500~2000r/min, and three rollers are ground to slurry fineness≤5 μm.
The present invention also provides a kind of front electrode silver slurry used for solar batteries of above method preparation, the front electrode silvers
The solid content of slurry is 80-93%, viscosity 150-400pa.s, slurry fineness≤5 μm.
The beneficial effects of the present invention are:
(1) present invention prepare simple process and low cost of silver powder used for solar batteries, the silver powder of preparation for concave-convex surface not
Flat irregular spherical shape has large specific surface area compared with traditional silver powder, and particle diameter distribution is uniform, the small feature of varying topography,
Can preferably with inorganic phase and it is organic be in contact, sintering activity is big, can be effectively reduced sintering after contact resistance.
(2) present invention is using the silver powder of the irregular spherical shape of surface irregularity as the conductive phase in front electrode silver slurry,
And by carrying out surface modification treatment to silver powder, glass powder, keep silver powder, glass powder dispersion effect good, not easily settled, preparation is too
The sintering temperature of positive energy battery front side electrode silver paste is low, is sintered molten silver densification, Ohmic contact is good, and sintering with higher is lived
Property, solderability is excellent, and can be effectively reduced sintered contact resistance, promotes electrical efficiency, can be applied to low-temperature sintering electricity
Pond.
Specific embodiment
The present invention is described in further detail now.
Embodiment 1
The present embodiment provides a kind of front electrode silver slurry used for solar batteries, the preparation method of silver powder, the silver powder
The preparation method is as follows:
The silver fluoride aqueous solution that 1L concentration is 0.1mol/L is prepared, adds carboxymethyl cellulose thereto, and HF water is added dropwise
It is 3.5 that solution, which adjusts pH, and stirring, ultrasound 30min, supersonic frequency 5KHZ, speed of agitator 2000r/min obtain silver fluoride point
Dispersion liquid, the percentage that the carboxymethyl cellulose quality accounts for silver fluoride quality is 1wt%；
The aqueous ascorbic acid that 1L concentration is 0.11mol/L is prepared, it is 3.5 that HF aqueous solution, which is added dropwise, and adjusts pH；
Under the conditions of temperature is 20 DEG C, aqueous ascorbic acid is disposably added in silver fluoride dispersion liquid, is being added
It is stirred in the process (speed of agitator 2000r/min), and after aqueous ascorbic acid addition, stops stirring
3min；
Mechanical stirring is applied to reaction solution and ultrasound is reacted, supersonic frequency 5KHz, speed of agitator 2000r/
Min obtains the reaction solution containing silver powder until reaction terminates；
Reaction solution containing silver powder is filtered, is cleaned and is dried with deionized water, ethyl alcohol, after sieving processing, obtained
Silver powder used for solar batteries, the partial size of the silver powder are 0.8-1.5 μm, tap density 4-5.5g/cm3, specific surface area 1-3
㎡/g。
The preparation method of the front electrode silver slurry used for solar batteries, includes the following steps:
Silver powder pre-treatment: by 100 parts by weight of silver powder, 40 parts by weight terpinols, 1.5 parts by weight γ-(the third oxygen of 2,3- epoxy)
Propyl trimethoxy silicane is stirred 60min under the mixing speed of 500r/min, by the mixing liquid precipitate containing silver powder,
Filtering, 80 DEG C of drying 1h obtain modified silver powder；
Glass powder pre-treatment: by 100 parts by weight of glass powder, 20 parts by weight terpinols, 0.5 parts by weight γ-(2,3- epoxies third
Oxygen) propyl trimethoxy silicane mixing, by the mixing liquid precipitate containing glass powder, filtering, 80 DEG C of drying 1h obtain modified glass
Powder；
It prepares front electrode of solar battery silver paste: 76 part by weight modified silver powder and 4 part by weight modified glass powders is added
In 21 parts by weight organic carriers, it is stirred 60min under the mixing speed of 500r/min, goes to three-roll grinder grinding 3h,
Filtering, obtains front electrode of solar battery silver paste；
The organic carrier the preparation method is as follows: take 70 parts by weight terpinols, under agitation, 30 parts by weight are added
Ethyl cellulose, be warming up to 70-90 DEG C, after ethyl cellulose is completely dissolved, be added 3 parts by weight castor oil mixing, obtain
Organic carrier.
The solid content of front electrode silver slurry used for solar batteries manufactured in the present embodiment is 80%, viscosity 150pa.s, slurry
Expect fineness≤5 μm, sintering peak temperature is 720-840 DEG C, and series resistance is 1.72m Ω, and welding pulling force is 3.5N/mm2, battery
Efficiency is 20.16%.
The test condition of the welding pulling force are as follows: select 1.2 × 0.25mm welding rod, (setting temperature is 350 with electric iron
DEG C) by welding rod welding on the electrode, with 180 ° of measurer for pulling force test welding rods and silver paste and interelectrode welding pulling force, when test
It is removed with the speed of 0.3cm/s.
The series resistance, the test condition of battery efficiency are as follows: be printed on monocrystalline silicon piece, prepared with above-mentioned positive silver paste
Sunny energy battery, tests series resistance using precision resistance instrument, using solar energy simulated battery efficiency tester, in standard bar
(air quality AM1.5, intensity of illumination 1000W/m under part2, 25 DEG C of test temperature) and test battery efficiency.
Embodiment 2
The present embodiment provides a kind of front electrode silver slurry used for solar batteries, the preparation method of silver powder, the silver powder
The preparation method is as follows:
The silver nitrate aqueous solution that 1L concentration is 0.3mol/L is prepared, adds polyvinylpyrrolidone thereto, and be added dropwise
HNO3Adjusting pH is 3, stirring, ultrasound 20min, supersonic frequency 40KHZ, speed of agitator 500r/min, obtains silver nitrate dispersion
Liquid, the percentage that the polyvinylpyrrolidone quality accounts for silver nitrate quality is 10wt%；
The ferrous sulfate aqueous solution that 1L concentration is 0.35mol/L is prepared, HNO is added dropwise3Adjusting PH is 3；
In the case where temperature is 25 DEG C, ferrous sulfate aqueous solution is disposably added in silver nitrate dispersion liquid, in adding procedure
In be stirred (speed of agitator 500r/min), and ferrous sulfate aqueous solution addition after, stop stirring 5min；
Mechanical stirring is applied to reaction solution and ultrasound is reacted, supersonic frequency 40KHZ, speed of agitator 500r/
Min obtains the reaction solution containing silver powder until reaction terminates；
Reaction solution containing silver powder is filtered, is cleaned and is dried with deionized water, ethyl alcohol, after sieving processing, obtained
Silver powder used for solar batteries, the partial size of the silver powder are 1-1.8 μm, tap density 4.3-5.8g/cm3, specific surface area 1-3
㎡/g。
The preparation method of the front electrode silver slurry used for solar batteries, includes the following steps:
Silver powder pre-treatment: by 100 parts by weight of silver powder, 50 parts by weight butyl carbitols, 2 parts by weight γ-mercapto propyl trimethoxy
Base silane is stirred 30min under the mixing speed of 1000r/min, by the mixing liquid precipitate containing silver powder, filters, 80 DEG C
1h is dried, modified silver powder is obtained；
Glass powder pre-treatment: by 100 parts by weight of glass powder, 40 parts by weight butyl carbitols, 0.8 parts by weight, three (dioctyl
Pyrophosphoryl oxygroup) isopropyl titanate mixing, by the mixing liquid precipitate containing glass powder, filtering, 80 DEG C of drying 1h obtain modified glass
Powder；
It prepares front electrode of solar battery silver paste: 80 part by weight modified silver powder and 3 part by weight modified glass powders is added
In 17 parts by weight organic carriers, it is stirred 10min under the mixing speed of 2000r/min, goes to three-roll grinder grinding 3h,
Filtering, obtains front electrode of solar battery silver paste；
The organic carrier the preparation method is as follows: take 70 parts by weight butyl carbitols, under agitation, 27 weights are added
The ethyl cellulose for measuring part, is warming up to 70-90 DEG C, and after ethyl cellulose is completely dissolved, it is mixed that 3 parts by weight of hydrogenated castor oil are added
It closes, obtains organic carrier.
The solid content of front electrode silver slurry used for solar batteries manufactured in the present embodiment is 93%, viscosity 400pa.s, slurry
Expect fineness≤5 μm, sintering peak temperature is 680-820 DEG C, and series resistance is 1.66m Ω, and welding pulling force is 3.2N/mm2, battery
Efficiency is 20.32%.
The test condition of the series resistance, welding pulling force and battery efficiency is the same as embodiment 1.
Embodiment 3
The present embodiment provides a kind of front electrode silver slurry used for solar batteries, the preparation method of silver powder, the silver powder
The preparation method is as follows:
The silver nitrate aqueous solution that 1L concentration is 0.5mol/L is prepared, adds cetyl trimethylammonium bromide thereto, and
HNO is added dropwise3Adjusting PH is 3, and stirring, ultrasound 30min, supersonic frequency 10KHZ, speed of agitator 1000r/min obtain silver nitrate
Dispersion liquid, the percentage that the cetyl trimethylammonium bromide quality accounts for silver nitrate quality is 8wt%；
The hydrazine hydrate solution that 1L concentration is 0.55mol/L is prepared, HNO is added dropwise3Adjusting PH is 3；
Under the conditions of temperature is 25 DEG C, hydrazine hydrate solution is disposably added in silver nitrate dispersion liquid, in adding procedure
In be stirred (speed of agitator 1000r/min), and hydrazine hydrate solution addition after, stop stirring 10min；
Mechanical stirring is applied to reaction solution and ultrasound is reacted, supersonic frequency 10KHZ, speed of agitator 1000r/
Min obtains the reaction solution containing silver powder until reaction terminates；
Reaction solution containing silver powder is filtered, is cleaned and is dried with deionized water, ethyl alcohol, after sieving processing, obtained
Silver powder used for solar batteries, the partial size of the silver powder are 1.1-2 μm, tap density 4.6-6g/cm3, specific surface area be 1-3 ㎡/
g。
The preparation method of the front electrode silver slurry used for solar batteries, includes the following steps:
Silver powder pre-treatment: by 100 parts by weight of silver powder, 50 parts by weight of propylene glycol man ether acetates, 3 parts by weight, three (dioctyl
Pyrophosphoryl oxygroup) isopropyl titanate under the mixing speed of 2000r/min, is stirred 10min, by the mixed liquor containing silver powder
Precipitating, filtering, 80 DEG C of drying 1h obtain modified silver powder；
Glass powder pre-treatment: by 100 parts by weight of glass powder, 70 parts by weight of propylene glycol person's ether acetates, 1.2 parts by weight four are pungent
Oxygroup titanium [two (tridecyl phosphite)] mixing, by the mixing liquid precipitate containing glass powder, filtering, 80 DEG C of drying 1h are obtained
Modified glass powder；
It prepares front electrode of solar battery silver paste: 85 part by weight modified silver powder and 2 part by weight modified glass powders is added
In 13 parts by weight organic carriers, it is stirred 30min under the mixing speed of 1000r/min, goes to three-roll grinder grinding 3h,
Filtering, obtains front electrode of solar battery silver paste；
The organic carrier the preparation method is as follows: 75 parts by weight of propylene glycol person's ether acetates is taken to add under agitation
The ethyl cellulose for entering 23 parts by weight, is warming up to 70-90 DEG C, and after ethyl cellulose is completely dissolved, the dioxy of 2 parts by weight is added
SiClx mixing, obtains organic carrier.
The solid content of front electrode silver slurry used for solar batteries manufactured in the present embodiment is 90%, viscosity 250pa.s, slurry
Expect fineness≤5 μm, sintering peak temperature is 680-800 DEG C, and series resistance is 1.62m Ω, and welding pulling force is 3.4N/mm2, battery
Efficiency is 20.18%.
The test condition of the series resistance, welding pulling force and battery efficiency is the same as embodiment 1.
Embodiment 4
The present embodiment provides a kind of front electrode silver slurry used for solar batteries, the preparation method of silver powder, the silver powder
The preparation method is as follows:
The silver chlorate aqueous solution that 1L concentration is 0.8mol/L is prepared, adds Sodium Polyacrylate thereto, and chloric acid water is added dropwise
It is 3 that solution, which adjusts PH, stirring, ultrasound 30min, supersonic frequency 20KHZ, speed of agitator 1500r/min, obtains silver chlorate dispersion
Liquid, the percentage that the Sodium Polyacrylate quality accounts for silver chlorate quality is 5wt%；
The sodium hypophosphite aqueous solution that 1L concentration is 0.25mol/L is prepared, it is 3 that chloric acid aqueous solution, which is added dropwise, and adjusts PH；
Under the conditions of temperature is 28 DEG C, sodium hypophosphite aqueous solution is disposably added in silver chlorate dispersion liquid, is being added
It is stirred in the process (speed of agitator 1500r/min), and after the addition of sodium hypophosphite aqueous solution, stops stirring
5min；
Mechanical stirring is applied to reaction solution and ultrasound is reacted, supersonic frequency 20KHZ, speed of agitator 1500r/
Min obtains the reaction solution containing silver powder until reaction terminates；
Reaction solution containing silver powder is filtered, is cleaned and is dried with deionized water, ethyl alcohol, after sieving processing, obtained
Silver powder used for solar batteries, the partial size of the silver powder are 1.2-2.2 μm, tap density 4.9-6.5g/cm3, specific surface area 1-3
㎡/g。
The preparation method of the front electrode silver slurry used for solar batteries, includes the following steps:
Silver powder pre-treatment: by 100 parts by weight of silver powder, 60 parts by weight butyl carbitol acetates, 2 parts by weight, four octyloxy titanium
[two (tridecyl phosphite)] is stirred 30min under the mixing speed of 1000r/min, by the mixing containing silver powder
Liquid precipitate, filtering, 80 DEG C of drying 1h, obtain modified silver powder；
Glass powder pre-treatment: by 100 parts by weight of glass powder, 80 parts by weight butyl carbitol acetates, 1.6 parts by weight four are pungent
Oxygroup titanium [two (dilauryl phosphorite)] mixing, by the mixing liquid precipitate containing glass powder, filtering, 80 DEG C of drying 1h are obtained
Modified glass powder；
It prepares front electrode of solar battery silver paste: 85 part by weight modified silver powder and 1 part by weight modified glass powder is added
In 14 parts by weight organic carriers, it is stirred 30min under the mixing speed of 1000r/min, goes to three-roll grinder grinding 3h,
Filtering, obtains front electrode of solar battery silver paste；
The organic carrier the preparation method is as follows: 75 parts by weight butyl carbitol acetates is taken to add under agitation
The hydroxylated cellulose for entering 23 parts by weight, is warming up to 70-90 DEG C, and after hydroxylated cellulose is completely dissolved, 2 parts by weight organic bentonites are added
Profit soil mixing, obtains organic carrier.
The solid content of front electrode silver slurry used for solar batteries manufactured in the present embodiment is 86%, viscosity 290pa.s, slurry
Expect fineness≤5 μm, sintering peak temperature is 700-820 DEG C, and series resistance is 1.65m Ω, and welding pulling force is 3.6N/mm2, battery
Efficiency is 20.26%.
The test condition of the series resistance, welding pulling force and battery efficiency is the same as embodiment 1.
Embodiment 5
The present embodiment provides a kind of front electrode silver slurry used for solar batteries, the preparation method of silver powder, the silver powder
The preparation method is as follows:
The silver nitrate aqueous solution that 1L concentration is 1mol/L is prepared, adds lauryl sodium sulfate thereto, and HNO is added dropwise3
Adjusting PH is 2.5, stirring, ultrasound 30min, supersonic frequency 30KHZ, speed of agitator 1000r/min, obtains silver nitrate dispersion
Liquid, the percentage that the lauryl sodium sulfate quality accounts for silver nitrate quality is 4wt%；
The sodium borohydride aqueous solution that 1L concentration is 1.1mol/L is prepared, HNO is added dropwise3Adjusting PH is 2.5；
Under the conditions of temperature is 30 DEG C, sodium borohydride aqueous solution is disposably added in silver nitrate dispersion liquid, is being added
It is stirred in the process (speed of agitator 1000r/min), and after sodium borohydride aqueous solution addition, stops stirring
5min；
Mechanical stirring is applied to reaction solution and ultrasound is reacted, supersonic frequency 30KHz, speed of agitator 1000r/
Min obtains the reaction solution containing silver powder until reaction terminates；
Reaction solution containing silver powder is filtered, is cleaned and is dried with deionized water, ethyl alcohol, after sieving processing, obtained
Silver powder used for solar batteries, the partial size of the silver powder are 1.2-2.5 μm, tap density 4.8-7g/cm3, specific surface area 1-3
㎡/g。
The preparation method of the front electrode silver slurry used for solar batteries, includes the following steps:
Silver powder pre-treatment: by 100 parts by weight of silver powder, 50 parts by weight terpinols, 3 parts by weight, four octyloxy titaniums [two (two laurels
Base phosphite ester)] under the mixing speed of 1000r/min, it is stirred 30min, by the mixing liquid precipitate containing silver powder, mistake
Filter, 80 DEG C of drying 1h obtain modified silver powder；
Glass powder pre-treatment: by 100 parts by weight of glass powder, 70 parts by weight terpinols, 2 parts by weight γ-(2,3- epoxies third
Oxygen) propyl trimethoxy silicane mixing, by the mixing liquid precipitate containing glass powder, filtering, 80 DEG C of drying 1h obtain modified glass
Powder；
It prepares front electrode of solar battery silver paste: 88 part by weight modified silver powder and 0.8 part by weight modified glass powder is added
Enter in 11.5 parts by weight organic carriers, be stirred 30min under the mixing speed of 1000r/min, goes to three-roll grinder and grind
3h is ground, filtering obtains front electrode of solar battery silver paste；
The organic carrier the preparation method is as follows: take 80 parts by weight terpinols, under agitation, 19 parts by weight are added
Butyl cellulose, be warming up to 70-90 DEG C, after butyl cellulose is completely dissolved, 1 parts by weight of hydrogenated castor oil mixing be added,
Obtain organic carrier.
The solid content of front electrode silver slurry used for solar batteries manufactured in the present embodiment is 93%, viscosity 350pa.s, slurry
Expect fineness≤5 μm, sintering peak temperature is 630-750 DEG C, and series resistance is 1.56m Ω, and welding pulling force is 3.9N/mm2, battery
Efficiency is 20.35%.
The test condition of the series resistance, welding pulling force and battery efficiency is the same as embodiment 1.
Embodiment 6
The present embodiment provides a kind of front electrode silver slurry used for solar batteries, silver powder and preparation method thereof, the silver powder
The preparation method is as follows:
The silver nitrate aqueous solution that 1L concentration is 1.5mol/L is prepared, adds lauryl sodium sulfate thereto, and be added dropwise
HNO3Adjusting PH is 1.5, and stirring, ultrasound 30min, supersonic frequency 20KHZ, speed of agitator 1000r/min obtain silver nitrate point
Dispersion liquid, the percentage that the lauryl sodium sulfate quality accounts for silver nitrate quality is 6wt%；
The ferrous sulfate aqueous solution that 1L concentration is 0.55mol/L is prepared, HNO is added dropwise3Adjusting PH is 1.5；
Under the conditions of temperature is 35 DEG C, ferrous sulfate aqueous solution is disposably added in silver nitrate dispersion liquid, is being added
It is stirred in the process (speed of agitator 1000r/min), and after ferrous sulfate aqueous solution addition, stops stirring
5min；
Mechanical stirring is applied to reaction solution and ultrasound is reacted, supersonic frequency 20KHZ, speed of agitator 1000r/
Min obtains the reaction solution containing silver powder until reaction terminates；
Reaction solution containing silver powder is filtered, is cleaned and is dried with deionized water, ethyl alcohol, after sieving processing, obtained
Silver powder used for solar batteries, the partial size of the silver powder are 1.2-2.5 μm, tap density 5-7.5g/cm3, specific surface area 1-3
㎡/g。
The preparation method of the front electrode silver slurry used for solar batteries, includes the following steps:
Silver powder pre-treatment: by 100 parts by weight of silver powder, 70 parts by weight butyl carbitols, 5 parts by weight γ-(2,3- epoxy third
Oxygen) propyl trimethoxy silicane under the mixing speed of 2000r/min, is stirred 20min, the mixed liquor containing silver powder sunk
It forms sediment, filtering, 80 DEG C of drying 1h obtain modified silver powder；
Glass powder pre-treatment: by 100 parts by weight of glass powder, 70 parts by weight butyl carbitols, 2.5 parts by weight γ-(2,3- rings
The third oxygen of oxygen) propyl trimethoxy silicane mixing, by the mixing liquid precipitate containing glass powder, filtering, 80 DEG C of drying 1h obtain modified glass
Glass powder；
It prepares front electrode of solar battery silver paste: 90 part by weight modified silver powder and 0.8 part by weight modified glass powder is added
Enter in 9.2 parts by weight organic carriers, be stirred 30min under the mixing speed of 1000r/min, goes to three-roll grinder grinding
4h, filtering, obtains front electrode of solar battery silver paste；
The organic carrier the preparation method is as follows: take 40 parts by weight butyl carbitols, under agitation, 16 weights are added
The ethyl cellulose for measuring part, is warming up to 70-90 DEG C, and after ethyl cellulose is completely dissolved, the mixing of 1 parts by weight castor oil is added,
Obtain organic carrier.
The solid content of front electrode silver slurry used for solar batteries manufactured in the present embodiment is 90%, viscosity 350pa.s, slurry
Expect fineness≤5 μm, sintering peak temperature is 650-780 DEG C, and series resistance is 1.51m Ω, and welding pulling force is 3.7N/mm2, battery
Efficiency is 20.46%.
The test condition of the series resistance, welding pulling force and battery efficiency is the same as embodiment 1.
Comparative example
This comparative example provides a kind of front electrode silver slurry used for solar batteries, silver powder and preparation method thereof, the present embodiment with
The difference of embodiment 6 is only that: directly right without standing after ferrous sulfate aqueous solution addition in the preparation of silver powder
Reaction solution applies mechanical stirring and ultrasound is reacted；The partial size of gained silver powder is 0.9-3.5 μm, tap density 4.1-6.5g/
cm3, specific surface area is 0.9-2.5 ㎡/g, and the solid content of gained front electrode silver slurry is 90%, viscosity 350pa.s, and slurry is thin
≤ 5 μm of degree, sintering peak temperature are 650-780 DEG C, and series resistance is 1.74m Ω, and welding pulling force is 2.7N/mm2, battery efficiency
It is 20.21%.It has been found by contrast that silver powder particle size distribution range manufactured in the present embodiment is larger, specific surface area is smaller, gained front
The series resistance of electrode silver plasm is larger, and welding pulling force is smaller, and battery efficiency is lower.As it can be seen that in the preparation of silver powder, in sulfuric acid Asia
After water solution adds, standing the performance boost to front electrode silver slurry has biggish beneficial effect.
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (10)
1. a kind of preparation method of silver powder used for solar batteries, which comprises the steps of:
Dispersing agent is added in soluble silver salt solution and is mixed, solution is adjusted to acidity, obtains soluble silver salt dispersion liquid；
Under agitation, acid reducing agent solution is disposably added in soluble silver salt dispersion liquid, is gone back to acid
After former agent solution addition, 3-10min is stood；
After the completion of standing, to soluble silver salt dispersion liquid application mechanical stirring and ultrasonication until silver powder is precipitated completely, obtain
Reaction solution containing silver powder；
Reaction solution containing silver powder is post-processed, silver powder used for solar batteries is obtained.
2. the preparation method of silver powder used for solar batteries according to claim 1, which is characterized in that the soluble silver salt
For one of silver nitrate, silver fluoride, silver chlorate, silver perchlorate.
3. the preparation method of silver powder used for solar batteries according to claim 1 or 2, which is characterized in that the dispersing agent
Quality accounts for the percentage of silver soluble salt quality as 1-10wt%, and the molar ratio of the soluble silver salt and 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 reducing agent solution is 0.1-1.1mol/L.
4. the preparation method of silver powder used for solar batteries according to claim 1-3, which is characterized in that it is described can
Soluble silver salt dispersion liquid, reducing agent solution pH be 1.5-4.
5. the preparation method of silver powder used for solar batteries according to claim 1-4, which is characterized in that described to go back
Former agent is at least one of ascorbic acid, hydrazine hydrate, ferrous salt, borohydride salts, hypophosphites, and the dispersing agent is polyethylene
Pyrrolidones, polyvinyl alcohol, gelatin, carboxymethyl cellulose, polyacrylate, gum arabic, long chain alkanol amine, dodecyl
At least one of sulfate, cetyl trimethylammonium bromide, polyethylene glycol, tween, long chain fatty acids.
6. the preparation method of silver powder used for solar batteries according to claim 1-5, which is characterized in that described anti-
Answering temperature is 20-35 DEG C, and supersonic frequency is 5~40KHz, and speed of agitator is 500~2000r/min.
7. a kind of silver powder used for solar batteries prepared by the method using claim 1-6, which is characterized in that the solar-electricity
The partial size of pond silver powder is 0.8-2.5 μm, tap density 4-7.5g/cm3, specific surface area is 1-3 ㎡/g.
8. a kind of preparation method of front electrode silver slurry used for solar batteries, which comprises the steps of:
Silver powder pre-treatment: 100 parts by weight silver powder as claimed in claim 7,40-70 weight parts organic solvent, 1-5 parts by weight are even
Join agent mixing, by the mixing liquid precipitate containing silver powder, filtering, drying, obtains modified silver powder；
Glass powder pre-treatment: by 100 parts by weight of glass powder, 20-80 weight parts organic solvent, 0.2-3 parts by weight coupling agent is mixed,
By the mixing liquid precipitate containing glass powder, filtering, drying, modified glass powder is obtained；
It prepares front electrode of solar battery silver paste: the part by weight modified silver powder of 70-90 and the part by weight modified glass powder of 0.5-4 is added
Enter and mixed, ground in 9-21 parts by weight organic carrier, obtains front electrode of solar battery silver paste；The organic carrier packet
Include the plasticizer of the organic solvent of 40-80 parts by weight, the thixotropic agent of 1-3 parts by weight and 16-30 parts by weight.
9. the preparation method of front electrode silver slurry used for solar batteries according to claim 8, which is characterized in that described to have
Solvent is at least one of terpinol, butyl carbitol, propylene glycol methyl ether acetate, butyl carbitol acetate, the idol
Connection agent is at least one of titanate coupling agent, silane coupling agent, and the thixotropic agent is castor oil, rilanit special, titanium dioxide
Silicon, bentonite are at least one, the plasticizer be ethyl cellulose, butyl cellulose, hydroxylated cellulose at least one
Kind.
10. a kind of front electrode silver slurry used for solar batteries of the method preparation using claim 8 or 9, which is characterized in that institute
The solid content for stating front electrode silver slurry is 80-93%, viscosity 150-400pa.s, slurry fineness≤5 μm.
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