CN109903885B - Conductive paste, application thereof, solar cell electrode and solar cell - Google Patents
Conductive paste, application thereof, solar cell electrode and solar cell Download PDFInfo
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- 239000000843 powder Substances 0.000 claims abstract description 38
- 229920000642 polymer Polymers 0.000 claims abstract description 34
- 239000011521 glass Substances 0.000 claims abstract description 32
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- -1 butylene glycol ester Chemical class 0.000 claims description 36
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 20
- 239000000654 additive Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 239000004952 Polyamide Substances 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 14
- 229920002678 cellulose Polymers 0.000 claims description 14
- 239000001913 cellulose Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 229920002647 polyamide Polymers 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 12
- 229910052714 tellurium Inorganic materials 0.000 claims description 12
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 12
- 229920001195 polyisoprene Polymers 0.000 claims description 11
- 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
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims description 10
- 229920002125 Sokalan® Polymers 0.000 claims description 10
- 229910052797 bismuth Inorganic materials 0.000 claims description 10
- 229920001249 ethyl cellulose Polymers 0.000 claims description 10
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 10
- 239000004584 polyacrylic acid Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 claims description 7
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- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 7
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- 229940086555 cyclomethicone Drugs 0.000 claims description 7
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 7
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 7
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 7
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 7
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 7
- 229920000609 methyl cellulose Polymers 0.000 claims description 7
- 239000001923 methylcellulose Substances 0.000 claims description 7
- 235000010981 methylcellulose Nutrition 0.000 claims description 7
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 claims description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 7
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 7
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- 229920002857 polybutadiene Polymers 0.000 claims description 7
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- 229920002635 polyurethane Polymers 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 7
- 239000012991 xanthate Substances 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 6
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- 229920000620 organic polymer Polymers 0.000 claims description 5
- 239000004014 plasticizer Substances 0.000 claims description 5
- 229920000212 poly(isobutyl acrylate) Polymers 0.000 claims description 5
- 239000013008 thixotropic agent Substances 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052810 boron oxide Inorganic materials 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 4
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 4
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 235000012431 wafers Nutrition 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
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- 229920006397 acrylic thermoplastic Polymers 0.000 description 4
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
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- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 2
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
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- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- IFPMZBBHBZQTOV-UHFFFAOYSA-N 1,3,5-trinitro-2-(2,4,6-trinitrophenyl)-4-[2,4,6-trinitro-3-(2,4,6-trinitrophenyl)phenyl]benzene Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C(C=2C(=C(C=3C(=CC(=CC=3[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)C(=CC=2[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)=C1[N+]([O-])=O IFPMZBBHBZQTOV-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
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- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- OHBRHBQMHLEELN-UHFFFAOYSA-N acetic acid;1-butoxybutane Chemical compound CC(O)=O.CCCCOCCCC OHBRHBQMHLEELN-UHFFFAOYSA-N 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
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- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
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- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- UFQXGXDIJMBKTC-UHFFFAOYSA-N oxostrontium Chemical compound [Sr]=O UFQXGXDIJMBKTC-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
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Abstract
The invention discloses a conductive paste, application thereof, a solar cell electrode and a solar cell. The conductive paste comprises conductive powder, glass powder and an organic carrier, wherein the organic carrier comprises an organic solvent and an organic low molecular/high molecular polymer containing a thermoplastic resin. By applying the solar conductive paste provided by the invention, a thin-line solar cell electrode can be manufactured, and the conversion efficiency and the mass production of the cell are effectively improved.
Description
Technical Field
The invention relates to the technical field of solar cell manufacturing, in particular to conductive paste and application thereof, a solar cell electrode and a solar cell.
Background
Since the conductive auxiliary gate electrode is formed on the front light receiving surface of the wafer silicon wafer of the solar cell, the light receiving area of the silicon wafer is reduced, and the efficiency is affected, so that a finer electrode is desirably formed on the front light receiving surface of the silicon wafer to increase the light receiving area, and further improve the photoelectric conversion efficiency of the cell.
In order to form a finer conductive sub-grid electrode, different screen technologies and/or parameter changes for controlling the thickness of printing screen sand, the thickness of film and the opening can be used to meet the requirement, but the current conductive paste is easy to cause unstable or reduced printability for a long time, thereby affecting the efficiency.
Disclosure of Invention
The invention aims to provide conductive paste and application thereof, a solar cell electrode and a solar cell, and aims to solve the technical problem that the efficiency and the mass production are influenced due to the insufficient long-time mass production printability of electrode fine-line in the conventional conductive paste technology.
In order to achieve the above object, according to one aspect of the present invention, there is provided a conductive paste. The conductive paste comprises conductive powder, glass frit and an organic vehicle, wherein the organic vehicle comprises an organic solvent and an organic low molecular/high molecular polymer comprising a thermoplastic resin.
Further, the organic low molecular/high molecular polymer comprising the thermoplastic resin is selected from a plurality of kinds of the group consisting of cellulose acetate, cellulose xanthate, cellulose acetate butyrate, methyl cellulose, carboxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyamide cellulose, polyacrylic acid, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, isobutyl acrylate, polyacrylamide, polybutadiene butylene glycol ester, polyisoprene, polyurethane, polyvinyl butyral, polyamide, polydimethylsiloxane, polymethylphenylsiloxane, polyether polysiloxane copolymer, cyclomethicone, and aminosiloxane.
Further, the organic low molecular/high molecular polymer comprising a thermoplastic resin comprises a binder resin and an additive; preferably, the content of the binder resin in the conductive paste is 0.01-6 wt%; preferably, the content of the additive in the conductive paste is 0.01-6 wt%; preferably, the content of the thermoplastic resin in the organic low molecular/high molecular polymer containing the thermoplastic resin is 5-80 wt%; preferably, the mass ratio of the organic high molecular polymer to the organic low molecular polymer in the organic low molecular/high molecular polymer containing the thermoplastic resin is 1/4-1/1; preferably, the additives include a dispersant, a thixotropic agent and/or a plasticizer, more preferably, the additives are selected from one or more of the group consisting of polyvinyl butyral, polyurethane polyamide, polydimethylsiloxane, polymethylphenylsiloxane, polyether polysiloxane copolymer, cyclomethicone and aminosiloxane; preferably, the binder resin is one or more selected from the group consisting of cellulose acetate, cellulose xanthate, cellulose acetate butyrate, methyl cellulose, carboxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyamide cellulose, polyisoprene, polyacrylic acid, polymethyl acrylate, polyacrylamide, polybutadiene butylene glycol ester, and polyisoprene; preferably, the thermoplastic resin is one or more selected from the group consisting of polyacrylic acid, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate and polyisobutyl acrylate.
Further, the conductive paste comprises 75-95 wt% of conductive powder, 0.1-7 wt% of glass frit and 2.0-20 wt% of organic vehicle.
Further, the organic solvent accounts for 1-10 wt% of the conductive paste.
Furthermore, the composition of the binder resin and the additive accounts for 1-10 wt% of the conductive paste.
Further, the conductive powder comprises at least one inorganic powder having conductivity; preferably, the inorganic powder is silver powder.
Further, the silver powder has an average particle diameter D50 of 0.1 to 10 μm.
Furthermore, the glass powder material is composed of a body of lead oxide-bismuth oxide-tellurium oxide-tungsten oxide; preferably, the glass frit further comprises one or more selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide, phosphorus oxide, zinc oxide, silicon dioxide, boron oxide, titanium oxide and nickel oxide.
Further, the average particle diameter D50 of the glass frit is 0.1 to 10 μm.
According to another aspect of the invention, there is provided a use of the above conductive paste in the preparation of a solar cell.
According to yet another aspect of the present invention, a solar cell electrode is provided. The solar cell electrode is prepared from any one of the conductive pastes.
Further, the width of the solar cell electrode is 10 to 50 μm.
According to yet another aspect of the present invention, a solar cell is provided. The solar cell comprises an electrode, and the electrode is any one of the solar cell electrodes.
By applying the solar conductive paste provided by the invention, a thin-line solar cell electrode can be manufactured, and the conversion efficiency and the mass production of the cell are effectively improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows a schematic view of a solar cell electrode manufactured using the conductive paste of the present invention in a method according to an embodiment of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
According to an exemplary embodiment of the present invention, a conductive paste is provided. The conductive paste comprises conductive powder, glass powder and an organic carrier, wherein the organic carrier comprises an organic solvent and an organic low molecular/high molecular polymer containing thermoplastic resin.
The "organic low molecular/high molecular polymer" in the present invention means an organic low molecular polymer and an organic high molecular polymer. The "organic low-molecular polymer" in the present invention means an organic polymer having a molecular weight of less than 2000; "organic high molecular polymer" means an organic polymer having a molecular weight of more than 3000.
The conductive paste can be used for preparing solar cell electrodes, can be used for manufacturing thin-line solar cell electrodes, and effectively improves the conversion efficiency and the mass production of cells.
Preferably, the organic low molecular/high molecular polymer is selected from a plurality of kinds selected from the group consisting of cellulose acetate, cellulose xanthate, cellulose acetate butyrate, methyl cellulose, carboxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyamide cellulose, polyacrylic acid, polymethyl acrylate, polyacrylamide, polybutadiene butylene glycol ester, polyisoprene, polyurethane, polyvinyl butyral, polyamide, polydimethylsiloxane, polymethylphenylsiloxane, polyether polysiloxane copolymer, cyclomethicone, and aminosiloxane.
The organic low molecular/high molecular polymer comprising a thermoplastic resin in the organic vehicle comprises a binder resin and an additive. Preferably, the content of the binder resin in the conductive paste is 0.01-6 wt%; the content of the additive in the conductive paste is 0.01-6 wt%.
Preferably, the content of the thermoplastic resin in the organic low molecular/high molecular polymer containing the thermoplastic resin is 5 to 80 wt%; the conductive paste has a wide sintering process window within the range, and can be matched with different screen printing plate specifications to produce a thin-line solar cell electrode. Preferably, the mass ratio of the organic high molecular polymer to the organic low molecular polymer in the organic low molecular/high molecular polymer containing the thermoplastic resin is 1/4-1/1; preferably, the additives include a dispersant, a thixotropic agent and/or a plasticizer, more preferably, the additives are selected from one or more of the group consisting of polyvinyl butyral, polyurethane polyamide, polydimethylsiloxane, polymethylphenylsiloxane, polyether polysiloxane copolymer, cyclomethicone and aminosiloxane; preferably, the binder resin is one or more selected from the group consisting of cellulose acetate, cellulose xanthate, cellulose acetate butyrate, methyl cellulose, carboxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyamide cellulose, polyisoprene, polyacrylic acid, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polyisobutyl acrylate, polyacrylamide, polybutadiene butylene glycol ester, and polyisoprene; preferably, the thermoplastic resin is one or more selected from the group consisting of polyacrylic acid, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate and polyisobutyl acrylate.
The thermoplastic resin has a coagulation effect on the conductive paste, can form cross connection with the silver powder surface dispersant and an organic carrier through interaction, avoids collapse or obvious flowing of powder under high-temperature sintering, and can effectively control the fine-line capability of the secondary grid.
According to a typical embodiment of the present invention, the conductive paste comprises 75 to 95 wt% of conductive powder, 0.1 to 7 wt% of glass frit, and 2.0 to 20 wt% of organic vehicle. Preferably, the organic solvent accounts for 1-10 wt% of the conductive paste, and the organic low/high molecular polymer containing the thermoplastic resin accounts for 1-10 wt% of the conductive paste.
According to an exemplary embodiment of the present invention, the conductive powder comprises at least one inorganic powder having conductivity; preferably, the inorganic powder is silver powder, and more preferably, the silver powder has an average particle diameter D50 of 0.1 to 10 μm.
According to a typical embodiment of the invention, the glass frit is composed of lead oxide-bismuth oxide-tellurium oxide-tungsten oxide as bulk; preferably, the glass frit contains one or more selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide, phosphorus oxide, zinc oxide, silicon dioxide, boron oxide, titanium oxide, and nickel oxide. More preferably, the average particle diameter D50 of the glass frit is 0.1 to 10 μm.
According to an exemplary embodiment of the present invention, there is provided a use of the above conductive paste in the preparation of a solar cell. By applying the solar conductive paste provided by the invention, a thin-line solar cell electrode can be manufactured, and the conversion efficiency and the mass production of the cell are effectively improved.
According to an exemplary embodiment of the present invention, a solar cell electrode. The solar cell is prepared from any one of the conductive pastes, and preferably, the width of the solar cell electrode is 10-50 μm.
According to an exemplary embodiment of the present invention, a solar cell is provided, including an electrode. The electrode is a solar cell electrode prepared from the paste composition of the present invention.
According to an exemplary embodiment of the present invention, a solar cell electrode composition includes silver powder, lead oxide-bismuth oxide-tellurium oxide-tungsten oxide-based glass frit, and an organic vehicle. Now, the composition of the solar cell electrode of the present invention will be described in more detail.
(i) Silver powder
According to an exemplary embodiment of the present invention, the conductive paste for preparing the solar cell electrode includes silver powder as the conductive powder. The average particle size of the silver powder may be in the order of nanometers or micrometers. For example, the silver powder may have a particle size of several tens to several hundreds of nanometers or several to several tens of micrometers. Alternatively, it is a mixture of two or more silver powders which may have different particle diameters.
The silver powder may have a spherical, granular, flake, or amorphous shape.
The silver powder may preferably have an average particle size of D50 of about 0.1 to 10 microns, more preferably about 0.5 to 5 microns. The average particle size can be measured after three minutes by ultrasonic dispersion in isopropanol at room temperature 25 ℃ using Mastersize 2000(Malvern co., Ltd.). In this average particle size range, the conductive paste can provide lower line resistance and contact resistance.
The silver powder is added in an amount of about 60 to 95 wt% based on the weight of the conductive paste. Within this range, the conductive powder can prevent the conversion efficiency from deteriorating due to the increase in resistance. More preferably, the conductive powder is present at about 75 to 95 weight percent.
(ii) Glass powder
The glass frit serves to enhance adhesion between the conductive powder and the silicon wafer, and to reduce contact resistance by forming silver grains in the emitter region by etching the anti-reflection layer and melting the silver powder during high-temperature sintering of the conductive paste. In addition, during the sintering process, the glass powder softens and lowers the sintering temperature.
When the light absorption area of the cell is increased in order to improve the efficiency of the solar cell, there is a problem that the contact resistance may be increased. Therefore, there is a need to minimize the series resistance and the impact on the p-n junction. In addition, as the suitable sintering temperature varies over a range using various silicon wafers having different surface resistances, the glass powder needs to ensure sufficient thermal stability to withstand a large sintering temperature window.
The solar cell pieces are connected with each other through the solder strips to form the solar cell module. In this case, the low adhesive strength between the solar cell electrode and the solder ribbon may cause detachment of the cell sheet and decrease in reliability. In order to ensure better adhesive strength of the solar cell, the invention uses lead oxide-bismuth oxide-tellurium oxide-tungsten oxide (PbO-Bi)2O3-TeO2-WO3) Is the glass powder of the body.
In the present invention, the lead oxide-tellurium oxide-bismuth oxide-tungsten oxide based glass powder may comprise about 0.1 to 20 wt% of lead oxide, about 1 to 20 wt% of tellurium oxide, about 30 to 60 wt% of bismuth oxide, about 5 to 25 wt% of tungsten oxide, and a mass ratio of tellurium oxide to tungsten oxide is 0.5:1 to 1.75: 1. Within this range, the glass powder can ensure excellent adhesive strength and conversion efficiency.
According to an exemplary embodiment of the present invention, the lead oxide-tellurium oxide-bismuth oxide-tungsten oxide-based glass powder may further comprise at least one metal oxide selected from lithium oxide (Li) and the like2O), sodium oxide (Na)2O), potassium oxide (K)2O), magnesium oxide (MgO), calcium oxide (CaO), strontium oxide (SrO), barium oxide (BaO), phosphorus oxide (P)2O5) Zinc oxide (ZnO), silicon dioxide (SiO)2) Boron oxide (B)2O3) Titanium oxide (TiO)2) And nickel oxide (NiO).
The glass powder may be prepared from lead oxide-tellurium oxide-bismuth oxide-tungsten oxide plus at least one metal oxide described above by any typical method. For example, the metal oxide and the lead oxide-tellurium oxide-bismuth oxide-tungsten oxide are mixed in a certain ratio by a ball mill or a planetary mill. The mixed composition is melted at about 900-1300 ℃ and then quenched to about 25 ℃. The resulting material is then pulverized using a disk mill, a planetary mill, or the like, to provide the desired glass powder.
The glass frit is added in an amount of about 0.1 to 7 wt% based on the weight of the conductive paste. Depending on the adhesion between the electrode and the substrate, the amount of the additive may be 0.1 to 4 wt% in one embodiment, 0.3 to 5 wt% in one embodiment, and 0.4 to 7 wt% in another embodiment.
(iii) Organic vehicle
The organic vehicle comprises an organic solvent and an organic low molecular/high molecular polymer containing a thermoplastic resin.
According to an exemplary embodiment of the present invention, wherein the organic solvent is one or more combinations selected from the group consisting of toluene, n-hexane, cyclohexanone, ethyl cellosolve, butyl cellosolve, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, monobutyl ether acetate, propylene glycol monomethyl ether, diethylene glycol butyl ether acetate, alcohol ester dodeca, tripropylene glycol monomethyl ether, and terpineol.
The organic solvent may be used in an amount of 2 to 10 wt% in one embodiment, 4 to 10 wt% in another embodiment, and 5 to 9 wt% in another embodiment, based on the weight of the conductive paste, and the amount of the organic solvent is sufficient to provide a suitable viscosity of the conductive paste for various printing requirements.
According to an exemplary embodiment of the present invention, the organic low molecular/high molecular polymer including the thermoplastic resin is a combination selected from a group consisting of a binder resin and an additive.
According to an exemplary embodiment of the present invention, the binder resin is one or more selected from the group consisting of cellulose acetate, cellulose xanthate, cellulose acetate butyrate, methyl cellulose, carboxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyamide cellulose, polyisoprene, polyacrylic acid, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polyacrylamide, polybutadiene butylene glycol ester, and polyisoprene.
According to an exemplary embodiment of the present invention, wherein the additives can increase the fluidity, processability and storage stability of the slurry, dispersants, thixotropic agents and plasticizers are included, selected from one or more combinations of polyvinyl butyral, polyurethane polyamide, polydimethylsiloxane, polymethylphenylsiloxane, polyether polysiloxane copolymer, cyclomethicone and aminosiloxane.
The organic vehicle, which includes an organic solvent and an organic low molecular/high molecular polymer including a thermoplastic resin, may be present in an amount of about 2 to 20% by weight, based on the total weight of the composition, and within this range, the organic vehicle may provide sufficient adhesive strength and excellent long-term printability to the conductive paste.
According to an exemplary embodiment of the present invention, a conductive paste is applied to the solar cell electrode and the solar cell. As shown in fig. 1, the back electrode 210 and the front electrode 230 may be formed by screen printing a cell electrode composition on a silicon wafer 100 including a P layer 101 and an n layer 102 serving as an emitter, and sintering at a high temperature. For example, a preliminary process for preparing a back electrode is performed by printing a back conductive paste on the back surface of a silicon wafer and drying the printed paste at 200 to 400 ℃ for 10 to 60 seconds. In addition, a preliminary process for preparing a front electrode may be performed by printing a front conductive paste on a light receiving surface of a silicon wafer and drying the printed paste at 200 to 400 ℃ for 5 to 10 seconds. Further, the front and back electrodes may be formed by sintering the wafer at about 400 to 950 ℃, preferably about 850 to 950 ℃, for about 30 to 50 seconds.
Next, the present invention will be described in more detail by referring to examples. It should be noted, however, that these examples are provided merely to illustrate the invention and should not be construed as limiting the invention in any way.
Detailed descriptions that are clear to those skilled in the art are omitted for the sake of clarity.
Example 1 and comparative example 1.
The conductive paste was made using the following materials. The weight% (also written as wt%) herein refers to a weight percentage calculated based on the total weight of the conductive paste.
Conductive powder: 89.3 wt% of spherical silver powder having a particle diameter (D50) of 1.3 to 2.1 μm.
Glass powder: 2.0% by weight of a lead oxide-tellurium oxide-bismuth oxide-tungsten oxide-based glass powder. The particle diameter (D50) is 1.8 to 2.0 μm. (refer to patent CN 201611271037.3).
The binder resin in the organic low/high molecular polymer may include acrylic thermoplastic resin and ethyl cellulose. The amounts added are shown in table 1.
Additive: a dispersant, a thixotropic agent and a plasticizer are included.
Organic solvent: the conductive paste comprises a mixture of propylene glycol monomethyl ether, diethylene glycol butyl ether acetate, alcohol ester twelve and tripropylene glycol monomethyl ether, and the weight of the conductive paste is 6-7.5%.
The conductive paste was prepared using the following procedure: mixing the organic polymer and the solvent, and stirring for 1 hour at 50-60 ℃. Glass powder and silver powder were added to the above mixture, and sufficiently stirred to form a paste composition. The paste composition was repeatedly rolled by a three-roll mill to obtain a conductive paste having a Fineness (FOG) of 15/10 μm or less.
The conductive paste obtained above was printed on the SiN layer (156 × 156mm) of the silicon wafer substrate by a screen printing technique. The used screen mesh specification is 400 meshes/16 mu m wire/total thickness 35-37 mu m/non-mesh screen plate with 24 mu m opening (narrow-face opening). The cell pieces were dried in an infrared drying oven and then passed through a belt firing oven and fired at 920 ℃ for 40 seconds. And cooling the baked conductive slurry to form the electrode.
The width of the formed electrodes was measured using an optical microscope and a microimager.
In the present invention, the compositions and the proportions of the glass frit used were kept the same in all the examples and comparative examples, as shown in Table 1.
TABLE 1
TABLE 1
In example 1-2 in which the conductive paste contains an acrylic thermoplastic resin, the line widths of the measurement electrodes were 35.4 μm and 35.1 μm, while the paste electrode using ethyl cellulose in comparative example 1 was 39.3 μm.
Examples 3 to 5 and comparative example 2
The amount of acrylic thermoplastic resin added was examined
A paste was prepared in the same manner as in example 1, and electrodes were formed using the same screen and printing techniques. The electrode widths measured in the same manner as described above are shown in table 1. The width of the printed electrodes in examples 3-6 was narrower than the width of the electrodes in comparative example 2.
Examples 7 to 9 and comparative example 3
Check optimized addition amount of acrylic thermoplastic resin
A slurry was prepared in the same manner as in example 1 except that the composition was as shown in table 1. The electrode width was measured in the same manner as described above, and the efficiency (EFF%) was measured. The formed solar cell was placed in a Berger solar cell tester under one light source condition for efficiency measurement. The xenon arc lamp in the solar cell tester simulates sunlight of known intensity and radiates to the light receiving front surface of the cell. The voltage (V) and current (I) were measured at a load resistance setting of about 400 using a four-point contact method to determine a voltage-current curve of the cell, from which the cell conversion Efficiency (EFF) was calculated.
As shown in table 1, the electrode width indicates that example 9 is the narrowest, and the electrode height slightly increases. Compared with comparative example 3, the efficiency of example 9 is obviously improved.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
by adopting thermoplastic resin such as acrylic resin and matching with ethyl cellulose, the method can realize fine-line grid line printing, improve the height and the height-width ratio of the electrode, improve the conversion efficiency of the battery, give consideration to good long-time printing performance and effectively improve the mass production performance of the solar cell.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (20)
1. An electroconductive paste comprising an electroconductive powder, a glass frit and an organic vehicle, wherein the organic vehicle comprises an organic solvent and organic low-molecular and high-molecular polymers comprising a thermoplastic resin, and the organic low-molecular polymer is an organic polymer having a molecular weight of less than 2000; the organic high molecular polymer is an organic polymer with a molecular weight of more than 3000; the organic low molecular and high molecular polymers comprising a thermoplastic resin are selected from a plurality of the group consisting of cellulose acetate, cellulose xanthate, cellulose acetate butyrate, methyl cellulose, carboxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyamide cellulose, polyacrylic acid, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polyisobutyl acrylate, polyacrylamide, polybutadiene butylene glycol ester, polyisoprene, polyurethane, polyvinyl butyral, polyamide, polydimethylsiloxane, polymethylphenylsiloxane, polyether polysiloxane copolymer, cyclomethicone, and aminosiloxane; the organic low-molecular and high-molecular polymers comprising thermoplastic resins comprise binder resins and additives; the mass ratio of the organic high molecular polymer to the organic low molecular polymer in the organic low molecular and high molecular polymers containing the thermoplastic resin is 1/4-1/1.
2. The conductive paste according to claim 1, wherein the content of the binder resin in the conductive paste is 0.01 to 6 wt%.
3. The conductive paste according to claim 1, wherein the additive is contained in the conductive paste in an amount of 0.01 to 6 wt%.
4. The conductive paste according to claim 1, wherein the content of the thermoplastic resin in the organic low-molecular and high-molecular polymers containing a thermoplastic resin is 5 to 80 wt%.
5. The conductive paste according to claim 1, wherein the additive comprises a dispersant, a thixotropic agent and/or a plasticizer, and the additive is one or more selected from the group consisting of polyvinyl butyral, polyurethane polyamide, polydimethylsiloxane, polymethylphenylsiloxane, polyether polysiloxane copolymer, cyclomethicone and aminosiloxane.
6. The conductive paste as claimed in claim 1, wherein the binder resin is one or more selected from the group consisting of cellulose acetate, cellulose xanthate, cellulose acetate butyrate, methyl cellulose, carboxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyamide cellulose, polyisoprene, polyacrylic acid, polymethyl acrylate, polyacrylamide, polybutadiene butylene glycol ester, and polyisoprene.
7. The electroconductive paste according to claim 1, wherein said thermoplastic resin is one or more selected from the group consisting of polyacrylic acid, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate and polyisobutyl acrylate.
8. The conductive paste according to claim 1, wherein the conductive paste comprises 75 to 95 wt% of the conductive powder, 0.1 to 7 wt% of the glass frit, and 2.0 to 20 wt% of the organic vehicle.
9. The conductive paste according to claim 8, wherein the organic solvent is 1 to 10 wt% of the conductive paste.
10. The conductive paste according to claim 2, wherein the composition of the binder resin and the additive accounts for 1 to 10 wt% of the conductive paste.
11. The electroconductive paste according to claim 1, wherein said electroconductive powder comprises at least one inorganic powder having electroconductivity.
12. The electroconductive paste according to claim 11, wherein said inorganic powder is silver powder.
13. The conductive paste according to claim 12, wherein the silver powder has an average particle diameter D50 of 0.1 to 10 μm.
14. The conductive paste according to claim 1, wherein the glass frit is composed of lead oxide-bismuth oxide-tellurium oxide-tungsten oxide as a bulk.
15. The conductive paste according to claim 1, wherein the glass frit contains one or more selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide, phosphorus oxide, zinc oxide, silica, boron oxide, titanium oxide, and nickel oxide.
16. The conductive paste according to claim 1, wherein the average particle diameter D50 of the glass frit is 0.1 to 10 μm.
17. Use of the conductive paste according to any of claims 1 to 16 for the preparation of a solar cell.
18. A solar cell electrode prepared from the electroconductive paste according to any one of claims 1 to 16.
19. The solar cell electrode according to claim 18, wherein the width of the solar cell electrode is 10 to 50 μm.
20. A solar cell comprising an electrode, wherein the electrode is the solar cell electrode of claim 19.
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| CN111261322A (en) * | 2020-02-13 | 2020-06-09 | 轻工业部南京电光源材料科学研究所 | Silk-screen conductive silver paste for touch screen and preparation method thereof |
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| CN114038608B (en) * | 2021-12-24 | 2022-04-19 | 西安宏星电子浆料科技股份有限公司 | Low-resistivity solar cell conductive paste |
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| WO2015046096A1 (en) * | 2013-09-30 | 2015-04-02 | 東洋紡株式会社 | Electro-conductive paste, electro-conductive film, electro-conductive circuit, electro-conductive laminate, and touch panel |
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