CN114758812A - Back silver paste for crystalline silicon solar cell and preparation method thereof - Google Patents
Back silver paste for crystalline silicon solar cell and preparation method thereof Download PDFInfo
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- CN114758812A CN114758812A CN202210252893.3A CN202210252893A CN114758812A CN 114758812 A CN114758812 A CN 114758812A CN 202210252893 A CN202210252893 A CN 202210252893A CN 114758812 A CN114758812 A CN 114758812A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 55
- 239000004332 silver Substances 0.000 title claims abstract description 53
- 229910021419 crystalline silicon Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011521 glass Substances 0.000 claims abstract description 46
- 239000011230 binding agent Substances 0.000 claims abstract description 44
- 239000000843 powder Substances 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 36
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 15
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 11
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 229940116411 terpineol Drugs 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 239000001856 Ethyl cellulose Substances 0.000 claims description 7
- 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 7
- 238000000498 ball milling Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229920001249 ethyl cellulose Polymers 0.000 claims description 7
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000006060 molten glass Substances 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 6
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 229910000026 rubidium carbonate Inorganic materials 0.000 claims description 6
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 claims description 6
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims description 3
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 3
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 claims description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 3
- 229910002796 Si–Al Inorganic materials 0.000 claims description 3
- 229920002301 cellulose acetate Polymers 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- -1 silver-aluminum Chemical compound 0.000 abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 9
- 238000005245 sintering Methods 0.000 abstract description 7
- 229910000838 Al alloy Inorganic materials 0.000 abstract description 2
- 238000005303 weighing Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 11
- 238000003466 welding Methods 0.000 description 7
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 6
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 description 6
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010344 co-firing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
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
- H01B1/14—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
- 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
Abstract
The invention relates to a back silver paste for a crystalline silicon solar cell and a preparation method thereof, belonging to the technical field of conductive paste. The back silver paste for the crystalline silicon solar cell comprises: silver powder, organic binder, solvent A, glass powder and organic auxiliary agent; the mass ratio of the silver powder to the organic binder to the glass powder to the organic auxiliary agent is as follows: 35-75: 25-45: 0.1-5: 0.5-5; the organic auxiliary agent is tetrabutyl titanate; the addition amount of the solvent A is based on controlling the viscosity of the silver paste to be 30-60 Pa.s. The invention perfectly solves the problem of back silver-aluminum contact, reduces the generation of silver-aluminum alloy, and thereby prevents aluminum burs generated in the sintering process and silver-aluminum contact cracks and cavities caused by different expansion coefficients.
Description
Technical Field
The invention relates to a back silver paste for a crystalline silicon solar cell and a preparation method thereof, belonging to the technical field of conductive paste.
Background
The crystalline silicon solar cell is a cell device which converts solar energy into electric energy by using the photoelectric effect of semiconductor silicon. The internal current generated by the solar cell under the illumination condition outputs electric energy through the front electrode and the back electrode. In recent years, the battery piece is continuously upgraded, the slurry is continuously iterated, and the silver-aluminum contact is becoming a key point of the back silver slurry for the crystalline silicon solar battery, particularly at low solid content, however, related invention patents are rarely available in the market.
With the continuous improvement of the requirements of solar cells on the slurry, the silver content of the back silver slurry is reduced year by year at present, so that the sintering compactness is not enough, the lap joint of silver and aluminum is easy to have defects, the resistance of a cell is increased, even the cell is not conductive, and the EL test is completely black.
Disclosure of Invention
The first purpose of the invention is to provide a novel back silver paste for a crystalline silicon solar cell.
In order to achieve the first object of the present invention, the back silver paste for a crystalline silicon solar cell includes: silver powder, an organic binder, a solvent A, glass powder and an organic auxiliary agent; the mass ratio of the silver powder to the organic binder to the glass powder to the organic auxiliary agent is as follows: 35-75: 25-45: 0.1-5: 0.5-5; the organic auxiliary agent is tetrabutyl titanate; the addition amount of the solvent A is based on controlling the viscosity of the silver paste to be 30-60 Pa.s.
In one specific embodiment, the silver powder is silver powder A and silver powder B, the silver powder A is flake, needle or plate-shaped silver powder, and the average particle size is 1-1.5 μm; the silver powder B is spherical silver powder, and the average particle size is 0.5-2 mu m; the mass ratio of the silver powder A to the silver powder B is preferably 1-6: 6 to 12.
In one embodiment, the silver powder A has a specific surface area of 0.5-2 m 2(iv) g; the specific surface area of the silver powder B is 1-5 m2/g。
In a specific embodiment, the organic binder comprises a resin and a solvent B, wherein the resin is composed of one or more organic resins with different decomposition temperatures, and the resin preferably comprises one or more of rosin, cellulose acetate, ethyl cellulose, epoxy resin and acrylic resin;
the solvent A or the solvent B is one or more of ethyl acetate, terpineol, alcohol ester twelve, ethylene glycol butyl ether acetate, diethylene glycol butyl ether acetate and DBE.
In a specific embodiment, the mass ratio of the resin to the solvent B is 5-40: 60-95.
In one embodiment, the method of the organic binder is as follows: and mixing the resin and the solvent B, and dissolving at 50-100 ℃ for 1-3 hours to obtain the organic binder.
The resulting organic binder is transparent and uniform.
In one embodiment, the glass frit is composed of Bi2O3、PbO、B2O3、SiO2、CuO、MnO2、ZnO、ZrO2、Al2O3、As2O3、CaCO3、K2CO3、Li2CO3、Rb2CO3、GeO2、Ga2O3、Cr2O3、Co3O4NiO is prepared from the following components in percentage by mass: 3 to 10:6 to 12:20 to 35:20 to 30:3 to 10:0 to 8:5 to 15:0 to 5:0 to 0:0 to 30: 0 to 105: 0-5; the average particle size of the glass powder is preferably 1-3 μm.
In one embodiment, the silver paste has a fineness of less than 10 microns.
The second purpose of the invention is to provide a preparation method of the back silver paste for the crystalline silicon solar cell.
In order to achieve the purpose, the preparation method of the back silver paste for the crystalline silicon solar cell comprises the following steps: mixing and uniformly mixing silver powder, an organic binder, a solvent A, glass powder and an organic auxiliary agent, wherein the mass ratio of the silver powder to the organic binder to the glass powder to the organic auxiliary agent is as follows: 35-75: 25-45: 0.1-5: 0.5-5, and then grinding and rolling the slurry for 3-10 times to obtain the silver paste with the fineness of less than 10 micrometers and the addition of the solvent A so as to control the viscosity to be 30-60 Pa.s.
In one embodiment, the method further comprises the preparation of an organic binder: mixing the resin and the solvent B, and dissolving at 50-100 ℃ for 1-3 hours to obtain an organic binder;
preferably, the preparation of the glass powder comprises the following steps: the Bi is added2O3、PbO、B2O3、SiO2、CuO、MnO2、ZnO、ZrO2、Al2O3、As2O3、CaCO3、K2CO3、Li2CO3、Rb2CO3、GeO2、Ga2O3、Cr2O3、Co3O4And mixing NiO in proportion, melting for 4-7 hours at 1100-1400 ℃, introducing the molten glass material into deionized water, quenching in water, ball-milling, and drying to obtain glass powder with the average particle size of 1-3 mu m.
Has the advantages that:
1. the invention perfectly solves the problem of back silver-aluminum contact, reduces the generation of silver-aluminum alloy, and thereby prevents aluminum burs generated in the sintering process and silver-aluminum contact cracks and cavities caused by different expansion coefficients.
2. The back silver paste with good silver-aluminum contact for the crystalline silicon solar cell mainly comprises four major parts, namely a conductive functional phase, an organic carrier, an inorganic binder and other auxiliaries, is printed on a silicon wafer and is in compact contact with the aluminum paste in the sintering process, and the function of collecting current is achieved. The good contact between the back electrode and the aluminum paste is the key of the back silver paste for the crystalline silicon solar cell.
3. The silver electrode material adopts the flake, needle or plate silver powder and the spherical silver powder, so that the compactness of the sintered silver layer is effectively improved, and the resistance of the silver electrode wire and the contact resistance of silver and aluminum are reduced.
4. The self-made glass powder well infiltrates the silver powder in the sintering, makes the silver electrode compact, has reduced silver electrode resistance, and simultaneously, the glass powder can effectual lag the erosion of soldering tin to silver after the welding, has increased ageing resistance, provides ageing adhesion.
Drawings
FIG. 1 is a PL test chart of example 1 and comparative example 1, wherein the lower left and upper right light squares in FIG. 1 are Experimental example 1 and the lower right and upper left dark squares are comparative example 1;
FIG. 2 is a topographical view of the electrode microscope of example 1;
FIG. 3 is a topographical view under a comparative example 3 electrode microscope.
Detailed Description
In order to achieve the first object of the present invention, the back silver paste for a crystalline silicon solar cell includes: silver powder, an organic binder, a solvent A, glass powder and an organic auxiliary agent; the mass ratio of the silver powder to the organic binder to the glass powder to the organic auxiliary agent is as follows: 35-75: 25-45: 0.1-5: 0.5-5; the organic auxiliary agent is tetrabutyl titanate; the addition amount of the solvent A is based on controlling the viscosity of the silver paste to be 30-60 Pa.s.
In one specific embodiment, the silver powder is silver powder A and silver powder B, the silver powder A is flake, needle or plate-shaped silver powder, and the average particle size is 1-1.5 μm; the silver powder B is spherical silver powder, and the average particle size is 0.5-2 mu m; the mass ratio of the silver powder A to the silver powder B is preferably 1-6: 6 to 12.
In one embodiment, the silver powder A has a specific surface area of 0.5-2 m2(ii)/g; the specific surface area of the silver powder B is 1 to5m2/g。
In a specific embodiment, the organic binder comprises a resin and a solvent B, wherein the resin is composed of one or more organic resins with different decomposition temperatures, and the resin preferably comprises one or more of rosin, cellulose acetate, ethyl cellulose, epoxy resin and acrylic resin;
The solvent A or the solvent B is one or more of ethyl acetate, terpineol, alcohol ester dodeca, ethylene glycol butyl ether acetate, diethylene glycol butyl ether acetate and DBE.
In a specific embodiment, the mass ratio of the resin to the solvent is 5-40: 60 to 95.
In one embodiment, the method of the organic binder is as follows: and mixing the resin and the solvent B, and dissolving at 50-100 ℃ for 1-3 hours to obtain the organic binder.
The resulting organic binder is transparent and uniform.
In one embodiment, the glass frit is a Bi-Pb-B-Si-Al system, and the glass frit is preferably composed of Bi2O3、PbO、B2O3、SiO2、CuO、MnO2、ZnO、ZrO2、Al2O3、As2O3、CaCO3、K2CO3、Li2CO3、Rb2CO3、GeO2、Ga2O3、Cr2O3、Co3O4NiO is prepared from the following components in percentage by mass: 3-10: 6-12: 20-35: 20-30: 3-10: 0-8: 5-15: 0-5: 5; the average particle size of the glass powder is preferably 1-3 μm.
In one embodiment, the silver paste has a fineness of less than 10 microns.
In order to achieve the second object, the preparation method of the back silver paste for the crystalline silicon solar cell comprises the following steps: mixing and uniformly mixing silver powder, an organic binder, a solvent A, glass powder and an organic auxiliary agent, wherein the mass ratio of the silver powder to the organic binder to the glass powder to the organic auxiliary agent is as follows: mixing and uniformly mixing the components 35-75: 25-45: 0.1-5: 0.5-5, and then grinding and rolling the slurry for 3-10 times to obtain the silver slurry with the fineness of less than 10 micrometers and the addition of the solvent A so as to control the viscosity to be 30-60 Pa.s.
In one embodiment, the method further comprises the preparation of an organic binder: mixing the resin and the solvent B, and dissolving for 1-3 hours at 50-100 ℃ to obtain an organic binder;
preferably, the preparation of the glass powder comprises the following steps: the Bi is added2O3、PbO、B2O3、SiO2、CuO、MnO2、ZnO、ZrO2、Al2O3、As2O3、CaCO3、K2CO3、Li2CO3、Rb2CO3、GeO2、Ga2O3、Cr2O3、Co3O4And mixing NiO in proportion, melting for 4-7 hours at 1100-1400 ℃, introducing the molten glass material into deionized water, quenching in water, ball-milling, and drying to obtain glass powder with the average particle size of 1-3 mu m.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
The viscosity of the invention is measured by using an Antopa rheometer under the conditions of a shear rate of 15/s, a gap of 0.1mm and a temperature of 25 ℃.
Preparation of organic binder: weighing ethyl cellulose with the mass fraction of 8% according to the formula proportion; weighing terpineol with the mass fraction of 92%; then dissolving for 3 hours at the temperature of 80 ℃ to obtain a transparent and uniform organic binder;
preparing glass powder: weighing 6 parts of Bi according to a certain mass fraction according to the formula2O310 parts of PbO and 10 parts of B2O327 parts of SiO224 parts of CuO and 5 parts of MnO22 parts of ZnO and 3 parts of ZrO 210 parts of Al2O33 parts of Cr2O3Mixing, preparing glass material, melting for 6 hours at 1250 ℃, introducing the molten glass material into deionized water for water quenching, ball milling, and drying to obtain a glass powder finished product with the average particle size of 1.73 micrometers;
weighing the following components in parts by weight according to the formula proportion: an average particle diameter of 1.21 μm and an average specific surface area of 1.21m215 parts/g of a plate-like, needle-like or plate-like silver powder having an average particle diameter of 0.91 μm and an average specific surface area of 1.41m244.8 parts of spherical silver powder/g; 1.2 parts of glass powder; 30 parts of organic binder; 7 parts of terpineol solvent and 1 part of tetrabutyl titanate, uniformly mixing, and then rolling the mixture for 8 times by using a three-roll grinder, wherein the fineness is less than 10 micrometers, and the viscosity is 31.36Pa.s, so that the back silver paste with good silver-aluminum contact for the crystalline silicon solar cell is prepared.
Example 2
Preparation of organic binder: weighing ethyl cellulose with the mass fraction of 8% according to the formula proportion; weighing terpineol with the mass fraction of 92%; then dissolving for 3 hours at the temperature of 80 ℃ to obtain a transparent and uniform organic binder;
preparing glass powder: weighing 6 parts of Bi according to a certain mass fraction according to the formula2O310 parts of PbO and 10 parts of B2O327 parts of SiO224 parts of CuO and 5 parts of MnO 22 parts of ZnO and 3 parts of ZrO210 parts of Al2O33 parts of Cr2O3Mixing, preparing glass material, melting for 6 hours at 1250 ℃, introducing the molten glass material into deionized water for water quenching, ball milling, and drying to obtain a glass powder finished product with the average particle size of 1.73 micrometers;
weighing the following components in parts by weight according to the formula proportion: an average particle diameter of 1.21 μm and an average specific surface area of 1.21m215 parts/g of a plate-like, needle-like or plate-like silver powder having an average particle diameter of 0.91 μm and an average specific surface area of 1.41m244.8 parts of spherical silver powder/g; 1.2 parts of glass powder; 28 parts of organic binder; 7 parts of terpineol solvent and 3 parts of tetrabutyl titanate, uniformly mixing, then rolling for 8 times by using a three-roll grinder, and enabling the fineness to be less than 10 micrometers and the viscosity to be 30.76Pa.s to obtain the productThe back silver paste for the crystalline silicon solar cell with good silver-aluminum contact.
Example 3
Preparation of organic binder: weighing ethyl cellulose with the mass fraction of 8% according to the formula proportion; weighing terpineol with the mass fraction of 92%; then dissolving for 3 hours at the temperature of 80 ℃ to obtain a transparent and uniform organic binder;
preparing glass powder: weighing 6 parts of Bi according to a certain mass fraction according to the formula2O312 parts of PbO and 10 parts of B 2O325 parts of SiO221 parts of CuO and 8 parts of MnO24 parts of ZnO and 3 parts of ZrO28 parts of Al2O33 parts of Cr2O3Mixing, preparing glass material, melting for 6 hours at 1250 ℃, introducing the molten glass material into deionized water for water quenching, ball milling, and drying to obtain a glass powder finished product with the average particle size of 1.53 microns;
weighing the following components in parts by weight according to the formula proportion: an average particle diameter of 1.21 μm and a specific surface area of 1.21m215 parts/g of a plate-like, needle-like or plate-like silver powder having an average particle diameter of 0.91 μm and a specific surface area of 1.41m244.8 parts of spherical silver powder/g; 1.2 parts of glass powder; 30 parts of organic binder; 7 parts of terpineol solvent and 1 part of tetrabutyl titanate, uniformly mixing, and then rolling the mixture for 8 times by using a three-roll grinder, wherein the fineness is less than 10 micrometers, and the viscosity is 31.59Pa.s, so that the back silver paste with good silver-aluminum contact for the crystalline silicon solar cell is prepared.
Comparative example 1
Preparation of organic binder: weighing ethyl cellulose with the mass fraction of 8% according to the formula proportion; weighing terpineol with the mass fraction of 92%; then dissolving for 3 hours at the temperature of 80 ℃ to obtain a transparent and uniform organic binder;
preparing glass powder: weighing 6 parts of Bi according to a certain mass fraction according to the formula 2O310 parts of PbO and 10 parts of B2O327 parts of SiO224 parts of CuO and 5 parts of MnO22 parts of ZnO and 3 parts of ZrO 210 parts of Al2O33 parts of Cr2O3Mixing, preparing a glass material,melting for 6 hours at 1250 ℃, then introducing the molten glass material into deionized water for water quenching, ball milling, and drying to obtain a glass powder finished product with the average particle size of 1.73 micrometers;
weighing the following components in parts by weight according to the formula proportion: an average particle diameter of 1.21 μm and a specific surface area of 1.21m215 parts/g of a plate-like, needle-like or plate-like silver powder having an average particle diameter of 0.91 μm and a specific surface area of 1.41m244.8 parts of spherical silver powder/g; 1.2 parts of glass powder; 30 parts of organic binder; 8 parts of terpineol serving as a solvent is uniformly mixed and then is milled for 8 times by a three-roll grinder, the fineness is less than 10 micrometers, and the viscosity is 28.65Pa.s, so that the back silver paste with good silver-aluminum contact for the crystalline silicon solar cell is prepared.
Comparative example 2
The commercially available PERC backside silver paste, Confuchsin technologies, Inc. RX63600A7-5-8, is commonly available in Guangzhou.
Comparative example 3
Common commercial low-solid PERC back silver paste, Changsha New Material Industrial research institute Co., Ltd HT3612
The specific test method is as follows:
tension force: a fixed pattern (rectangular pattern 20cm in length and 0.8mm in width) was printed, and the welding tension was measured by welding at 350 ℃.
Tension force during high-temperature welding: a fixed pattern (rectangular pattern with a length of 20cm and a width of 0.8 mm) was printed, and the welding tension was measured by welding at 450 ℃.
Oven aging tension: printing a fixed pattern (a rectangular pattern with the length of 20cm and the width of 0.8 mm), welding at 350 ℃, putting into an oven, heating to 150 ℃, taking out after 1 hour, and testing the tensile force.
PL (photoluminescence) test: the printed fixed block diagram (as shown in the experimental example and the comparative example of fig. 1 below) is printed on the same cell, and the common aluminum paste on the market is printed on the upper part, and the PL is tested, wherein the brighter the PL indicates that the cell has higher minority carrier lifetime and the etching of the passivation layer by the paste is less.
Electrical properties: and printing the PERC back silver paste on the solar PERC cell, drying, co-firing with the PERC aluminum paste and the PERC positive silver, and forming a back electrode at the peak temperature of 750-.
The electrode appearance is as follows: the electrode silver aluminum contact morphology was observed under a microscope as shown in fig. 2 and 3.
The specific data of the examples and comparative examples are as follows:
TABLE 1 test results of examples 1 to 3 and comparative examples 1 to 3
Fig. 1 shows PL test conditions of example 1 and comparative example 1, with example 1 being significantly brighter, which relies on the fact that a film is formed on the electrode surface during the sintering process by the method of the present invention, which prevents the aluminum paste from immersing the silver electrode, and also reduces the etching of the passivation layer of the cell by the paste, thereby improving the minority carrier lifetime.
FIG. 2 shows the electrode morphology of example 1 with Ag and Al contacts and with regular contact shape without defects, and FIG. 3 shows the electrode morphology of comparative example 3 with Ag and Al contacts having a plurality of black spots due to the different expansion coefficients of the components at the Ag-Al interface during sintering, which results in dishing and defects during temperature rise and drop.
Claims (10)
1. The back silver paste for the crystalline silicon solar cell is characterized by comprising the following components in percentage by weight: silver powder, an organic binder, a solvent A, glass powder and an organic auxiliary agent; the mass ratio of the silver powder to the organic binder to the glass powder to the organic auxiliary agent is as follows: 35-75: 25-45: 0.1-5: 0.5-5; the organic auxiliary agent is tetrabutyl titanate; the addition amount of the solvent A is based on controlling the viscosity of the silver paste to be 30-60 Pa.s.
2. The back silver paste for a crystalline silicon solar cell according to claim 1, wherein the silver powder is silver powder A and silver powder B, the silver powder A is a plate-like, needle-like or plate-like silver powder, and the average particle diameter is 1 to 1.5 μm; the silver powder B is spherical silver powder, and the average particle size is 0.5-2 mu m; the mass ratio of the silver powder A to the silver powder B is preferably 1-6: 6 to 12.
3. The back silver paste for crystalline silicon solar cells according to claim 1 or 2, wherein the silver powder A has a specific surface area of 0.5 to 2m 2(iv) g; the specific surface area of the silver powder B is 1-5 m2/g。
4. The back silver paste for the crystalline silicon solar cell according to claim 1 or 2, wherein the organic binder comprises a resin and a solvent B, the resin is composed of one or more organic resins with different decomposition temperatures, and the resin preferably comprises one or more of rosin, cellulose acetate, ethyl cellulose, epoxy resin and acrylic resin;
the solvent A or the solvent B is one or more of ethyl acetate, terpineol, alcohol ester dodeca, ethylene glycol butyl ether acetate, diethylene glycol butyl ether acetate and DBE.
5. The back silver paste for the crystalline silicon solar cell according to claim 4, wherein the mass ratio of the resin to the solvent B is 5-40: 60-95.
6. The back silver paste for crystalline silicon solar cells according to claim 4, wherein the method of the organic binder is as follows: and mixing the resin and the solvent B, and dissolving for 1-3 hours at 50-100 ℃ to obtain the organic binder.
7. The back silver paste for crystalline silicon solar cell according to claim 1 or 2, wherein the glass frit is Bi-Pb-B-Si-Al system, and the glass frit is Bi-Pb-B-Si-Al system 2O3、PbO、B2O3、SiO2、CuO、MnO2、ZnO、ZrO2、Al2O3、As2O3、CaCO3、K2CO3、Li2CO3、Rb2CO3、GeO2、Ga2O3、Cr2O3、Co3O4、NiOAccording to the following mass ratio: 3-10: 6-12: 20-35: 20-30: 3-10: 0-8: 5-15: 0-5: 0-5: 5; the average particle size of the glass powder is preferably 1-3 μm.
8. The back silver paste for the crystalline silicon solar cell according to claim 1 or 2, wherein the silver paste fineness is less than 10 microns.
9. The method for preparing the back silver paste for the crystalline silicon solar cell according to any one of claims 1 to 8, wherein the method comprises the following steps: mixing and uniformly mixing silver powder, an organic binder, a solvent A, glass powder and an organic auxiliary agent, wherein the mass ratio of the silver powder to the organic binder to the glass powder to the organic auxiliary agent is as follows: 35-75: 25-45: 0.1-5: 0.5-5, and then grinding and rolling the slurry for 3-10 times to obtain the silver paste with the fineness of less than 10 micrometers and the addition of the solvent A so as to control the viscosity to be 30-60 Pa.s.
10. The method for preparing the back silver paste for the crystalline silicon solar cell according to claim 9, further comprising the preparation of an organic binder: mixing the resin and the solvent B, and dissolving at 50-100 ℃ for 1-3 hours to obtain an organic binder;
preferably, the preparation of the glass powder comprises the following steps: the Bi is added 2O3、PbO、B2O3、SiO2、CuO、MnO2、ZnO、ZrO2、Al2O3、As2O3、CaCO3、K2CO3、Li2CO3、Rb2CO3、GeO2、Ga2O3、Cr2O3、Co3O4And melting NiO for 4-7 hours at 1100-1400 ℃ after mixing in proportion, then introducing the molten glass material into deionized water for water quenching, ball milling, and drying to obtain glass powder with the average particle size of 1-3 mu m.
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| CN117727488A (en) * | 2024-02-18 | 2024-03-19 | 浙江晶科新材料有限公司 | Conductive paste for N-type TOPCON solar cell, preparation method and solar cell |
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| CN105825913A (en) * | 2016-05-16 | 2016-08-03 | 南通天盛新能源股份有限公司 | Anti-aging back silver pulp used in crystalline silicon solar cell and preparation method for same |
| CN106128552A (en) * | 2016-08-31 | 2016-11-16 | 海宁市瑞银科技有限公司 | A kind of crystal silicon solar batteries silver aluminum overlap joint ungauged regions back silver paste |
| CN111403077A (en) * | 2019-09-04 | 2020-07-10 | 杭州正银电子材料有限公司 | General back electrode silver paste for PERC single-sided double-sided battery and preparation method |
| CN114155993A (en) * | 2021-12-03 | 2022-03-08 | 华东理工大学 | Composite glass powder for crystalline silicon solar cell back electrode silver paste and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105825913A (en) * | 2016-05-16 | 2016-08-03 | 南通天盛新能源股份有限公司 | Anti-aging back silver pulp used in crystalline silicon solar cell and preparation method for same |
| CN106128552A (en) * | 2016-08-31 | 2016-11-16 | 海宁市瑞银科技有限公司 | A kind of crystal silicon solar batteries silver aluminum overlap joint ungauged regions back silver paste |
| CN111403077A (en) * | 2019-09-04 | 2020-07-10 | 杭州正银电子材料有限公司 | General back electrode silver paste for PERC single-sided double-sided battery and preparation method |
| CN114155993A (en) * | 2021-12-03 | 2022-03-08 | 华东理工大学 | Composite glass powder for crystalline silicon solar cell back electrode silver paste and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117727488A (en) * | 2024-02-18 | 2024-03-19 | 浙江晶科新材料有限公司 | Conductive paste for N-type TOPCON solar cell, preparation method and solar cell |
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