CN116759133B - Conductive silver-aluminum paste, preparation method, electrode and N-type Topcon battery - Google Patents
Conductive silver-aluminum paste, preparation method, electrode and N-type Topcon battery Download PDFInfo
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- CN116759133B CN116759133B CN202310481918.1A CN202310481918A CN116759133B CN 116759133 B CN116759133 B CN 116759133B CN 202310481918 A CN202310481918 A CN 202310481918A CN 116759133 B CN116759133 B CN 116759133B
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- -1 silver-aluminum Chemical compound 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000011521 glass Substances 0.000 claims abstract description 114
- 239000000843 powder Substances 0.000 claims abstract description 101
- 239000000654 additive Substances 0.000 claims abstract description 34
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000009826 distribution Methods 0.000 claims abstract description 30
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 29
- 230000000996 additive effect Effects 0.000 claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910006715 Li—O Inorganic materials 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 26
- 238000005245 sintering Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229920002545 silicone oil Polymers 0.000 claims description 5
- 229910052582 BN Inorganic materials 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-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
- 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 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 3
- 235000021314 Palmitic acid Nutrition 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- UGQCDGQZHSALDW-UHFFFAOYSA-N butyl benzoate;ethane-1,2-diol Chemical compound OCCO.CCCCOC(=O)C1=CC=CC=C1 UGQCDGQZHSALDW-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- 229920006217 cellulose acetate butyrate Polymers 0.000 claims description 3
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 3
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 3
- 229960001826 dimethylphthalate Drugs 0.000 claims description 3
- 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 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 3
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 claims description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 claims description 3
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 5
- 229910052709 silver Inorganic materials 0.000 description 15
- 239000004332 silver Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000005355 lead glass Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- RLAQMYBFAVTHSC-UHFFFAOYSA-M potassium;acetic acid;chloride Chemical compound [Cl-].[K+].CC(O)=O RLAQMYBFAVTHSC-UHFFFAOYSA-M 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910011763 Li2 O Inorganic materials 0.000 description 1
- 229910018162 SeO2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- H01B1/14—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 discloses a conductive silver-aluminum paste, a preparation method, an electrode and an N-type Topcon battery, wherein the conductive silver-aluminum paste comprises silver powder, aluminum powder, an inorganic powder additive, glass powder and an organic carrier, and the weight percentage of each component is as follows, based on the total weight of the conductive silver-aluminum paste being 100 percent: 80.0 to 90.0 percent of silver powder; 0.5 to 3.0 percent of aluminum powder; 0.0 to 1.0 percent of inorganic powder additive; 1.0 to 6.0 percent of glass powder; 7.0 to 13.0 percent of organic carrier; wherein the grain size distribution range of the silver powder is 0.1-4.5 mu m, and the D50 distribution range is 0.8-2.0 mu m; the grain size distribution range of the aluminum powder is 0.3-5.0 mu m, and the D50 distribution range is 0.8-2.0 mu m; the glass powder comprises a first glass powder and/or a second glass powder, wherein the first glass powder is one or more of Pb-Zn-Si-Ga-B-Li-O system, pb-Zn-Si-Al-B-Li-O system or Pb-Zn-Si-Ga-Al-B-Li-O system with a composite structure, the second glass powder is Pb-Si-Ti-B-Se-O system glass powder, the particle size distribution range of the glass powder is 0.1-8.0 mu m, and the D50 distribution range is 0.5-2.0 mu m. The invention realizes high reliability of the grid line of the N-type Topcon type silicon solar cell and strong acid resistance and corrosion resistance.
Description
Technical Field
The invention belongs to the field of silicon solar cells, and particularly relates to conductive silver-aluminum paste, a preparation method, an electrode and an N-type Topcon cell.
Background
Solar energy is the most widely distributed energy source with the greatest world reserves at present, and is the best choice for replacing fossil energy sources, so that the development and utilization of solar energy are hot spots for the development of various countries. It can be converted into heat energy, bioenergy, electric energy and the like for human use, so that numerous solar energy use projects are also developed, and the silicon solar cell power generation project is one of the most important development projects at present.
The silicon solar cell mainly comprises a front electrode, an antireflection layer, a PN junction, a silicon substrate and a back field. When light irradiates the surface of the solar cell, photons enter the PN junction through the full absorption of the surface anti-reflection layer, the photons are absorbed through the PN junction, and a photoelectric effect occurs in the PN junction, so that electrons are emitted, and the electrons are exported by surface electrons to form current, namely, the light energy is converted into electric energy. With the development progress of silicon solar cell technology, high-efficiency N-type Topcon cells are becoming the mainstream of silicon solar cell development. In theory, the N-type semiconductor Topcon battery has the characteristics of longer minority carrier lifetime and weaker photoinduced attenuation, and the N-type Top-con battery has high open circuit voltage, high photoelectric conversion efficiency and high output power. In practice, two major problems to be solved in developing a high-efficiency N-Top-con battery are to design and process the battery sheet structure, and to develop silver-aluminum paste for metallizing the surface of the battery.
The silver-aluminum paste with metalized surfaces for developing the battery is the same as the silver paste for the P-type Se-Perc battery piece, and the service life and the ageing resistance effect of the battery assembly become important limiting conditions for restricting the use of the silver-aluminum paste. The silicon solar power generation equipment is an electronic device which is formed by combining a plurality of battery pieces in series or in parallel and then packaging the battery pieces. The current materials for solar cell packaging contain certain organic matters, such as EVA, which can generate acid matters, such as acetic acid, under long-term illumination, and can corrode the surface electrode of the silicon solar cell, so that the problems of electrode falling, poor contact and the like are caused, the photoelectric conversion efficiency of the silicon solar cell is reduced, and the service life of the silicon solar cell is seriously influenced.
Disclosure of Invention
The invention aims to provide conductive silver-aluminum paste, a preparation method, an electrode and an N-type Topcon battery, and the conductive silver-aluminum paste of a silicon solar battery and the N-type Top-con silicon solar battery front electrode prepared by using the conductive silver-aluminum paste are improved by improving the stability, the sintering assisting effect and the acid corrosion resistance of glass powder and controlling the corrosion effect of glass on a battery piece, and the electrode has good acid corrosion resistance, high voltage, low contact resistance, high photoelectric conversion efficiency and long service life. In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
The invention provides conductive silver-aluminum paste, which comprises silver powder, aluminum powder, inorganic powder additives, glass powder and an organic carrier, wherein the total weight of the conductive silver-aluminum paste is 100%, and the conductive silver-aluminum paste comprises the following components in percentage by weight:
Wherein the grain size distribution range of the silver powder is 0.1-4.5 mu m, and the D50 distribution range is 0.8-2.0 mu m; the grain size distribution range of the aluminum powder is 0.3-5.0 mu m, and the D50 distribution range is 0.8-2.0 mu m; the glass powder comprises a first glass powder and/or a second glass powder, wherein the first glass powder is one or more of Pb-Zn-Si-Ga-B-Li-O system, pb-Zn-Si-Al-B-Li-O system or Pb-Zn-Si-Ga-Al-B-Li-O system with a composite structure, the second glass powder is Pb-Si-Ti-B-Se-O system glass powder, the particle size distribution range of the glass powder is 0.1-8.0 mu m, and the D50 distribution range is 0.5-2.0 mu m.
Further, in the first glass frit, the mole percentages of the respective components are as follows, based on the total mole number of the components contained in the first glass frit being 100%:
Further, the first modifying additive is an oxide of one or more elements in Ca, sr, ba, na, ti, zr, sb, ge, sn, in, tl or a substance decomposed to obtain the oxide of the element in the process of preparing the first glass frit.
Further, in the second glass frit, the mole percentages of the respective components are as follows, based on the total mole number of the components contained in the second glass frit being 100%:
further, the second modifying additive is an oxide of one or more elements in Zn, ca, sr, ba, li, na, al, zr, sb, ge, sn, ga, in, tl or a substance that decomposes to obtain an oxide of the element during the process of making the second glass frit.
Further, the inorganic powder additive is one or more of boron powder, silicon nitride powder, boron nitride powder and silicon boride powder, the particle size distribution range of the inorganic powder additive is 0.1-8.0 mu m, and the D50 distribution range is 0.5-2.0 mu m.
Further, the organic carrier comprises an organic solvent, an organic resin and an additive, and the content of each component is as follows, based on the total weight of the organic carrier as 100 percent:
60.0 to 85.0 percent of organic solvent;
5.0 to 30.0 percent of organic resin;
2.0 to 15.0 percent of additive.
Further, the organic solvent is one or more of diethylene glycol butyl ether acetate, diethylene glycol diethyl ether acetate, alcohol ester twelve, dimethyl phthalate, ethylene glycol butyl benzoate, tripropylene glycol monomethyl ether, diethylene glycol butyl ether and pentaerythritol triacrylate.
Further, the organic resin is one or more of SEPS resin, SEBS resin, polyvinyl butyral resin, poly alpha-methyl styrene resin, petroleum resin, acrylic resin, cellulose acetate butyrate, carboxymethyl cellulose and hydroxyethyl cellulose.
Further, the additive is one or more of silicone oil, palmitic acid, lithium stearate, polyamide wax and hydrogenated castor oil.
The invention also provides a method for preparing the conductive silver-aluminum paste, which comprises the following steps:
Preparing glass powder: weighing raw materials used for the glass powder according to a set proportion, mixing, melting at high temperature, cooling, drying, and crushing to obtain the required glass powder;
Preparing an organic carrier: weighing raw materials used for the organic carrier according to a set proportion, heating, stirring, mixing, high-speed centrifuging, dispersing uniformly, and filtering to obtain the required organic carrier;
Preparing conductive silver-aluminum paste: adding silver powder, aluminum powder, inorganic powder additives and prepared glass powder into prepared organic carriers respectively according to mass ratio, mixing and stirring uniformly, and grinding, viscosity adjusting and filtering to obtain the required conductive silver-aluminum paste.
The invention also provides an electrode which is formed by sintering the conductive silver-aluminum paste on the surface of a battery silicon wafer.
The invention also provides an N-type Topcon battery, which comprises the electrode.
In summary, the conductive silver-aluminum paste provided by the invention uses the first glass powder and/or the second glass powder, both of which are high-lead glass, has the advantages of low glass softening point, good corrosiveness and good liquid phase sintering assisting effect, and the glass liquid can properly corrode an insulating film on the surface of a battery during sintering of the silver-aluminum paste, so that the conductive silver-aluminum paste has good open circuit voltage and contact resistance.
The first glass powder uses elements such as Si, ga, al and the like with higher content, reduces the content of B and alkali metal Li, improves the stability of a glass structure, and reduces the degree of hydrolysis of the glass, thereby reducing the degree of corrosion of the silver grid line and improving the anti-aging strength of the silver grid line; the second glass powder is introduced with Se elements to reduce the softening point of the glass, so that high-lead glass can still be melted into a large amount of Si and Ti element oxides under the condition of extremely low alkali metal content, the structures of Si, ti and other elements are stable, the oxides of the corresponding elements are introduced to be difficult to corrode and hydrolyze, the stability of the high-lead glass and the stability of precipitated crystals are improved, meanwhile, the better sintering assisting effect of the glass is maintained, the compactness of a silver grid line formed after sintering of silver-aluminum paste is effectively improved, the corrosion degree of the silver grid line formed after sintering of the silver-aluminum paste is reduced, and the ageing resistance of the silver grid line is improved.
Therefore, the silver-aluminum paste of the N-type Topcon type silicon solar cell, which has the advantages of high reliability of the grid line, good corrosion resistance, strong ageing resistance, high opening pressure, low contact resistance and high photoelectric conversion efficiency, is realized.
Detailed Description
The invention provides a conductive silver-aluminum paste, which comprises silver powder, aluminum powder, an inorganic powder additive, glass powder and an organic carrier, wherein the total weight of the conductive silver-aluminum paste is 100%, and the conductive silver-aluminum paste comprises the following components in percentage by weight:
Wherein, the silver powder is spherical or spheroidic, the distribution range of the particle size of the silver powder is 0.1-4.5 mu m, and the distribution range of D50 is 0.8-2.0 mu m; the aluminum powder is spherical or spheroidic, the grain size distribution range is 0.3-5.0 mu m, and the D50 distribution range is 0.8-2.0 mu m; the glass powder comprises a first glass powder and/or a second glass powder, wherein the first glass powder is one or more of Pb-Zn-Si-Ga-B-Li-O system, pb-Zn-Si-Al-B-Li-O system or Pb-Zn-Si-Ga-Al-B-Li-O glass powder with a composite structure of the Pb-Zn-Si-Al-B-Li-O system, the second glass powder is Pb-Si-Ti-B-Se-O system glass powder, the glass powder is spherical or spheroidic, the grain size distribution range is 0.1-8.0 mu m, and the D50 distribution range is 0.5-2.0 mu m.
Further, in the conductive silver aluminum paste, the first glass frit comprises a first modified additive, and the mole percentages of the components are as follows, based on 100% of the total mole number of the components contained in the first glass frit:
wherein the first modification additive is one or more oxides of elements in Ca, sr, ba, na, ti, zr, sb, ge, sn, in, tl or substances decomposed to obtain the oxides of the elements in the process of preparing the first glass powder. The substances decomposed to give the corresponding element oxides may be carbonates, peroxides or complexes.
Similarly, the components such as PbO, znO, siO 2、Ga2O3、Al2O3、B2O3、Li2 O in the first glass frit may be directly added oxides, or may be substances decomposed during the process of manufacturing the first glass frit to obtain the components, such as carbonates, peroxides, or composites.
Further, in the second glass frit, the mole percentages of the respective components are as follows, based on the total mole number of the components contained in the second glass frit being 100%:
Wherein the second modification additive is one or more oxides of elements in Zn, ca, sr, ba, li, na, al, zr, sb, ge, sn, ga, in, tl or substances decomposed to obtain the oxides of the elements in the process of preparing the second glass powder. The substances decomposed to give the corresponding element oxides may be carbonates, peroxides or complexes.
Similarly, the components of PbO, siO 2、TiO2、B2O3、SeO2 and the like in the second glass frit may be directly added oxides, or may be substances decomposed during the process of manufacturing the second glass frit to obtain the components, such as carbonate, peroxide or composite.
Further, the inorganic powder additive is one or more of boron powder, silicon nitride powder, boron nitride powder and silicon boride powder, the particle size distribution range of the inorganic powder additive is 0.1-8.0 mu m, and the D50 distribution range is 0.5-2.0 mu m.
Further, the organic carrier comprises an organic solvent, an organic resin and an additive, and the content of each component is as follows, based on 100% of the total weight of the organic carrier:
60.0 to 85.0 percent of organic solvent;
5.0 to 30.0 percent of organic resin;
2.0 to 15.0 percent of additive.
Wherein the organic solvent is one or more of diethylene glycol butyl ether acetate, diethylene glycol diethyl ether acetate, alcohol ester twelve, dimethyl phthalate, ethylene glycol butyl benzoate, tripropylene glycol monomethyl ether, diethylene glycol butyl ether and pentaerythritol triacrylate; the organic resin is one or more of SEPS resin, SEBS resin, polyvinyl butyral resin, poly alpha-methyl styrene resin, petroleum resin, acrylic resin, cellulose acetate butyrate, carboxymethyl cellulose and hydroxyethyl cellulose; the additive is one or more of silicone oil, palmitic acid, lithium stearate, polyamide wax and hydrogenated castor oil, and the silicone oil is preferably dimethyl silicone oil.
The invention also provides a method for preparing the conductive silver-aluminum paste, which comprises the following steps:
Preparing glass powder: weighing glass powder precursor raw materials according to a set proportion, ball milling or screening, uniformly mixing, placing into a crucible, placing the crucible into a high-temperature furnace, melting at 850-1100 ℃ for 10-60 min, pouring glass liquid into cold water at 5-20 ℃ after uniform melting, performing rapid cooling treatment to obtain glass particles, drying the glass particles, performing primary crushing, and performing fine crushing to obtain the required glass powder with proper particle size;
Preparing an organic carrier: weighing raw materials of an organic solvent, an organic resin and an additive for the organic carrier according to a set proportion, heating in a water bath at 70-100 ℃, stirring, mixing uniformly, and filtering after high-speed centrifugation dispersion uniformly to obtain the required organic carrier;
preparing conductive silver-aluminum paste: the prepared silver powder, aluminum powder, inorganic powder additive, glass powder and organic carrier are respectively added into the prepared organic carrier according to the mass ratio, mixed and stirred uniformly, then milled by three rollers, and finally subjected to viscosity adjustment and filtration to obtain the required conductive silver-aluminum paste.
The invention also provides an electrode which is formed by sintering the conductive silver-aluminum paste on the surface of a battery silicon wafer. Specifically, the prepared conductive silver aluminum paste is printed in a screen printing mode to form grid lines required by the surface of the N-type Topcon battery, and then sintered to form the conductive silver grid line electrode. For other technical features of the electrode, please refer to the prior art, and a detailed description thereof is omitted herein.
The invention also provides an N-type Topcon battery, which comprises the electrode, and other technical characteristics of the N-type Topcon battery are referred to in the prior art and are not repeated herein.
The beneficial effects of the invention are as follows:
The conductive silver-aluminum paste uses the first glass powder and/or the second glass powder, which are both high-lead glass, has the advantages of low glass softening point, good corrosiveness, good liquid phase sintering assisting effect, and good open circuit voltage and contact resistance, and the glass liquid can properly corrode an insulating film on the surface of a battery during sintering of the silver-aluminum paste. The first glass powder uses elements such as Si, ga, al and the like with higher content, reduces the content of B and alkali metal Li, improves the stability of a glass structure, and reduces the degree of hydrolysis of the glass, thereby reducing the degree of corrosion of the silver grid line and improving the anti-aging strength of the silver grid line; the second glass powder is introduced with Se elements to reduce the softening point of the glass, so that high-lead glass can still be melted into a large amount of Si and Ti element oxides under the condition of extremely low alkali metal content, the structures of Si, ti and other elements are stable, the oxides of the corresponding elements are introduced to be difficult to corrode and hydrolyze, the stability of the high-lead glass and the stability of precipitated crystals are improved, meanwhile, the better sintering assisting effect of the glass is maintained, the compactness of a silver grid line formed after sintering of silver-aluminum paste is effectively improved, the corrosion degree of the silver grid line formed after sintering of the silver-aluminum paste is reduced, and the ageing resistance of the silver grid line is improved.
The present invention will be described in further detail with reference to test examples and specific embodiments. It should not be construed that the scope of the above subject matter of the present invention is limited to the following embodiments, and all techniques realized based on the present invention are within the scope of the present invention.
The following description is made in connection with specific embodiments:
examples BG1 to BG6:
Preparation of a first glass frit: the method comprises the steps of respectively calculating and weighing raw materials for the first glass powder according to a set formula, ball milling or screening, uniformly mixing, placing the raw materials in a crucible, placing the crucible in a high-temperature furnace, melting at 850-1100 ℃ for 10-60 min, pouring glass liquid into cold water at 5-20 ℃ after uniform melting, carrying out rapid cooling treatment to obtain glass particles, drying the glass particles, carrying out primary crushing, and carrying out fine crushing to obtain the required glass powder with proper particle size, wherein the number of the first glass powder is BG1-BG6, and the specific composition molar ratio of the first glass powder is shown in a table 1.
TABLE 1 first glass frit mole percent Table (at%)
Examples BS1-BS6:
Preparing a second glass powder: the method comprises the steps of respectively calculating and weighing raw materials for the second glass powder according to a set formula, ball milling or screening, uniformly mixing, placing the mixture in a crucible, placing the crucible in a high-temperature furnace, melting at 850-1100 ℃ for 10-60 min, pouring glass liquid into cold water at 5-20 ℃ after uniform melting, carrying out rapid cooling treatment to obtain glass particles, drying the glass particles, carrying out primary crushing, and carrying out fine crushing to obtain the required glass powder with proper particle size, wherein the number of the second glass powder is BS1-BS6, and the specific composition mole ratio of the second glass powder is shown in a table 2.
TABLE 2 second glass frit composition table (at%)
Examples ZT1-ZT6:
Preparation of the organic carrier: the organic carrier is prepared by weighing raw materials of organic solvent, organic resin and additive according to a set proportion, heating in a water bath at 70-100 ℃, stirring and mixing uniformly, and filtering after high-speed centrifugal dispersion uniformly to obtain the required organic carrier, wherein the number ZT1-ZT6 is reserved, and the weight composition ratio of each organic carrier is shown in a table 3.
TABLE 3 weight component Table (wt%) of organic vehicle
Examples AA01 to AA15:
preparing conductive silver-aluminum paste: the silver powder is AG1, the aluminum powder is AL1, the inorganic powder additives with proper particle sizes, namely boron powder, silicon nitride powder, boron nitride powder and silicon boride powder are sequentially numbered as TJ1, TJ2, TJ3, TJ4 and TJ5, the corresponding silver powder, aluminum powder, inorganic powder additives and glass powder are respectively weighed according to the material combination selected in the table 4 and the provided mass percentage, and are added into the organic carrier with the corresponding model and mass, the mixture is uniformly mixed and stirred, the slurry is pricked by a three-roller mill, the slurry is filtered to obtain coarse slurry, and the conductive silver aluminum slurry AA01-AA15 is obtained after the slurry is mixed, wherein the specific weight composition of the silver aluminum slurry is shown in the table 4.
TABLE 4 silver aluminum paste weight composition table (wt%)
Table 4 weight composition table (wt.%)
Test example:
and (3) screen printing the silver-aluminum paste prepared in the examples AA01-AA15 on the surface of a battery on an N-type Topcon battery piece, drying, sintering and cooling to obtain a battery containing a printed silver grid electrode, testing the efficiency of the battery, exposing the prepared silicon solar battery piece to a sealing environment of a 3% potassium chloride saturated solution environment, driving a fan at 85 ℃ to enable air in the sealing environment to circularly flow for 10 hours, closing the fan to cool the sealing environment to room temperature, taking the silicon solar battery piece, testing the photoelectric conversion efficiency of the battery piece, comparing the photoelectric conversion efficiency difference of the battery pieces before and after the test, and calculating the photoelectric conversion efficiency attenuation percentage of the battery pieces. In order to conveniently observe the electrical performance characteristics of the silver-aluminum paste, the silver-aluminum paste 995PFB produced by Shanghai silver paste technology Co., ltd is specially selected, the printing sintering and testing electrical performance is compared with the silver-aluminum paste under the same condition, and the test results are shown in Table 5.
Table 5 table of data for testing silver-aluminum paste of the present invention
As can be seen from Table 5, comparing the silver aluminum paste 995PFB silver aluminum paste produced by Shanghai silver paste technology Co., ltd. With the silver aluminum paste of examples AA01-AA15 of the present invention, the silver aluminum paste battery of the present invention was found to have a higher open circuit voltage, a lower contact resistance, a higher photoelectric conversion efficiency, and a lower attenuation rate of the photoelectric conversion efficiency in the potassium acetate-chloride experiment. As can be seen from Table 5, the open-circuit voltage of each embodiment of the invention is not less than 0.7181V, the series resistance is not more than 0.261mΩ, the photoelectric conversion efficiency is not less than 25.13%, the photoelectric conversion efficiency attenuation rate of the potassium acetate-chloride experiment is not more than 13.02%, and is far less than 58.03% of the comparative example, which indicates that the silver-aluminum paste provided by the invention has good contact effect, high open-circuit voltage, high photoelectric conversion efficiency, low photoelectric conversion efficiency attenuation rate of the potassium acetate-chloride experiment, good acid resistance and corrosion resistance and strong ageing resistance.
It should be noted that, in the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described as different from other embodiments, and identical and similar parts between the embodiments are all enough to be referred to each other.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the present invention. Accordingly, the scope of the invention should be assessed as that of the appended claims.
Claims (11)
1. The conductive silver-aluminum paste is characterized by comprising silver powder, aluminum powder, inorganic powder additives, glass powder and an organic carrier, wherein the total weight of the conductive silver-aluminum paste is 100%, and the conductive silver-aluminum paste comprises the following components in percentage by weight:
Wherein the grain size distribution range of the silver powder is 0.1-4.5 mu m, and the D50 distribution range is 0.8-2.0 mu m; the grain size distribution range of the aluminum powder is 0.3-5.0 mu m, and the D50 distribution range is 0.8-2.0 mu m; the glass powder comprises a first glass powder and/or a second glass powder, wherein the first glass powder is Pb-Zn-Si-Ga-B-Li-O system glass powder and/or Pb-Zn-Si-Ga-Al-B-Li-O system glass powder, the second glass powder is Pb-Si-Ti-B-Se-O system glass powder, the particle size distribution range of the glass powder is 0.1-8.0 mu m, and the D50 distribution range is 0.5-2.0 mu m;
In the first glass powder, the mole percentages of the components are as follows, based on 100% of the total mole number of the components contained in the first glass powder:
in the second glass powder, the mole percentages of the components are as follows, based on the total mole number of the components contained in the second glass powder being 100 percent:
2. The conductive silver aluminum paste of claim 1, wherein the first modifying additive is an oxide of one or more elements of Ca, sr, ba, na, ti, zr, sb, ge, sn, in, tl or a material that decomposes to obtain the oxide of the element during the formation of the first glass frit.
3. The conductive silver aluminum paste of claim 1, wherein the second modifying additive is an oxide of one or more elements of Zn, ca, sr, ba, li, na, al, zr, sb, ge, sn, ga, in, tl or a material that decomposes to provide an oxide of the element during the formation of the second glass frit.
4. The conductive silver-aluminum paste according to claim 1, wherein the inorganic powder additive is one or more of boron powder, silicon nitride powder, boron nitride powder and silicon boride powder, the particle size distribution range of the inorganic powder additive is 0.1-8.0 μm, and the D50 distribution range is 0.5-2.0 μm.
5. The conductive silver-aluminum paste according to claim 1, wherein the organic carrier comprises an organic solvent, an organic resin and an additive, and the contents of the components are as follows, based on the total weight of the organic carrier as 100 percent:
60.0 to 85.0 percent of organic solvent;
5.0 to 30.0 percent of organic resin;
2.0 to 15.0 percent of additive.
6. The conductive silver aluminum paste of claim 1, wherein the organic solvent is one or more of diethylene glycol butyl ether acetate, diethylene glycol diethyl ether acetate, alcohol ester twelve, dimethyl phthalate, ethylene glycol butyl benzoate, tripropylene glycol monomethyl ether, diethylene glycol butyl ether, pentaerythritol triacrylate.
7. The conductive silver aluminum paste of claim 1, wherein the organic resin is one or more of SEPS resin, SEBS resin, polyvinyl butyral resin, poly-alpha-methyl styrene resin, petroleum resin, acrylic resin, cellulose acetate butyrate, carboxymethyl cellulose, hydroxyethyl cellulose.
8. The conductive silver aluminum paste of claim 1, wherein the additive is one or more of silicone oil, palmitic acid, lithium stearate, polyamide wax, hydrogenated castor oil.
9. A method for preparing the conductive silver-aluminum paste according to any of the preceding claims 1 to 8, characterized by comprising the following steps:
Preparing glass powder: weighing raw materials used for the glass powder according to a set proportion, mixing, melting at high temperature, cooling, drying, and crushing to obtain the required glass powder;
Preparing an organic carrier: weighing raw materials used for the organic carrier according to a set proportion, heating, stirring, mixing, high-speed centrifuging, dispersing uniformly, and filtering to obtain the required organic carrier;
Preparing conductive silver-aluminum paste: adding silver powder, aluminum powder, inorganic powder additives and prepared glass powder into prepared organic carriers respectively according to mass ratio, mixing and stirring uniformly, and grinding, viscosity adjusting and filtering to obtain the required conductive silver-aluminum paste.
10. An electrode, characterized in that the electrode is formed by sintering the conductive silver-aluminum paste according to any one of claims 1-8 on the surface of a battery silicon wafer.
11. An N-type Topcon cell comprising the electrode of claim 10.
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