CN116313214B - 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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- CN116313214B CN116313214B CN202310422402.XA CN202310422402A CN116313214B CN 116313214 B CN116313214 B CN 116313214B CN 202310422402 A CN202310422402 A CN 202310422402A CN 116313214 B CN116313214 B CN 116313214B
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- -1 silver-aluminum Chemical compound 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000011521 glass Substances 0.000 claims abstract description 79
- 239000000843 powder Substances 0.000 claims abstract description 77
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000009826 distribution Methods 0.000 claims abstract description 36
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 32
- 239000010703 silicon Substances 0.000 claims abstract description 32
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000654 additive Substances 0.000 claims abstract description 23
- 230000000996 additive effect Effects 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims description 45
- 239000011347 resin Substances 0.000 claims description 45
- 238000005245 sintering Methods 0.000 claims description 12
- 229910006715 Li—O Inorganic materials 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 8
- 239000013008 thixotropic agent Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 229920002545 silicone oil Polymers 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
- 239000002518 antifoaming agent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- YXTPWUNVHCYOSP-UHFFFAOYSA-N bis($l^{2}-silanylidene)molybdenum Chemical compound [Si]=[Mo]=[Si] YXTPWUNVHCYOSP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 5
- 229910021344 molybdenum silicide Inorganic materials 0.000 claims description 5
- 239000011863 silicon-based powder Substances 0.000 claims description 5
- WQJQOUPTWCFRMM-UHFFFAOYSA-N tungsten disilicide Chemical compound [Si]#[W]#[Si] WQJQOUPTWCFRMM-UHFFFAOYSA-N 0.000 claims description 5
- 229910021342 tungsten silicide Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 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
- FYEDNKVJQMKJTP-UHFFFAOYSA-N 2-(2-butoxyethoxycarbonyl)benzoic acid Chemical compound CCCCOCCOC(=O)C1=CC=CC=C1C(O)=O FYEDNKVJQMKJTP-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
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical class C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims description 3
- 239000001856 Ethyl cellulose Substances 0.000 claims description 3
- 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 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
- 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
- 239000002131 composite material Substances 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
- 229920001249 ethyl cellulose Polymers 0.000 claims description 3
- 235000019325 ethyl cellulose Nutrition 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
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 claims description 3
- 238000004519 manufacturing process Methods 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
- 239000000969 carrier Substances 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims 1
- YETXGSGCWODRAA-UHFFFAOYSA-N isopropyl palmitic acid Natural products CC(C)CCCCCCCCCCCCCCCC(O)=O YETXGSGCWODRAA-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000007639 printing Methods 0.000 description 8
- 238000011161 development Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052745 lead Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229920000896 Ethulose Polymers 0.000 description 2
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 239000012461 cellulose resin Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Sustainable Development (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Sustainable Energy (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Conductive Materials (AREA)
- Photovoltaic Devices (AREA)
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, zinc powder, silicon-containing element additive powder, 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: 82.0 to 88.0 percent of silver powder; 0.5 to 2.0 percent of aluminum powder; zinc powder 0.1-1.0%; 0.0 to 1.0 percent of additive powder containing silicon element; 1.0 to 5.0 percent of glass powder; 7.5% -12.5% of organic carrier, wherein the silver powder is spherical or spheroidic, the grain size distribution range is 0.1-6.0 μm, and the D50 distribution range is 1.0-2.0 μm; the aluminum powder is spherical or spheroidic, the grain size distribution range is 0.1-6.0 mu m, and the D50 distribution range is 0.8-2.0 mu m; the zinc powder is spherical or spheroidic, the distribution range of the particle size is 0.1-6.0 mu m, and the distribution range of the D50 is 0.5-2.0 mu m.
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
With the development progress of silicon solar cell technology, high-efficiency N-type Topcon cells are becoming the mainstream of development. In theory, the N-type semiconductor Topcon battery has the characteristics of long minority carrier lifetime and weak photoinduced attenuation, and the N-type Top-con battery has high open circuit voltage, high photoelectric conversion efficiency and high output power. In practice, to develop a high-efficiency N-Top-con battery, two major problems need to be solved, namely, the design and process of the battery piece structure and the development of silver-aluminum paste for surface metallization of the battery. The current cell structure design and process have been successful in stages, and the mass production of the N-type Topcon cell is realized, but the matched surface metalized silver-aluminum paste is still in a rapid development and change stage. The silver-aluminum paste with excellent performance for the N-type Topcon battery can further embody the efficiency advantage of the N-type Topcon battery, and can promote the rapid development of the N-type Topcon battery of a new generation.
Disclosure of Invention
The invention aims to provide conductive silver-aluminum paste, a preparation method, an electrode and an N-type Topcon battery, and proper aluminum powder and zinc powder are introduced to promote the formation of aluminum thorns of the silver-aluminum paste and increase minority carrier diffusion capacity; by introducing a proper amount of silicon-containing element additive powder to balance window difference of aluminum powder and silver powder sintering, excessive corrosion of glass to the battery is prevented, the requirement of the current N-type Topcon battery on electrode material development is well met, and the method has the advantages of low contact resistance, high open circuit voltage, high photoelectric conversion efficiency and high output power. 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, zinc powder, silicon-containing element additive powder, 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 is 0.1-6.0 mu m, and the distribution range of the D50 is 1.0-2.0 mu m; the aluminum powder is spherical or spheroidic, the grain size distribution range is 0.1-6.0 mu m, and the D50 distribution range is 0.8-2.0 mu m; the zinc powder is spherical or spheroidic, the distribution range of the particle size is 0.1-6.0 mu m, and the distribution range of the D50 is 0.5-2.0 mu m.
Further, the particle size distribution range of the silicon-containing element additive powder is 0.1-6.0 mu m, and the D50 distribution range is 0.6-2.0 mu m.
Further, the silicon-containing element additive powder is one or more of silicon powder, molybdenum silicide, tungsten silicide and silicon boride.
Further, the glass powder is glass powder of a main element composition system, and comprises
One or more of Pb-Ba-Zn-Si-B-Li-O system, pb-Ba-Zn-Ge-B-Li-O system or Pb-Ba-Zn-Si-Ge-B-Li-O system glass powder with a composite structure, wherein the glass powder comprises the following components in percentage by mole based on 100% of the total mole number of the components:
wherein, the main element is introduced by oxide of the corresponding element or substances which are decomposed to obtain the oxide of the element in the process of preparing the glass powder; the particle size distribution range of the glass powder is 0.1-6.0 mu m, and the D50 distribution range is 0.5-2.0 mu m.
Further, the modifying additive is an oxide of one or more elements in Ca, sr, na, K, tl, ti, al, fe, ga, bi, sb, se or a substance decomposed to obtain the oxide of the element in the process of preparing the glass powder.
Further, the organic carrier comprises an organic solvent, organic resin, dimethyl silicone oil, an antifoaming agent and a thixotropic agent, and the contents of the components are as follows, based on the total weight of the organic carrier being 100 percent:
further, the organic resin comprises an elastic resin, and the elastic resin is one or more of SEPS resin, polyvinyl butyral resin, poly alpha-methyl styrene resin, SBS resin, SEBS resin, hydrogenated DCPD resin and acrylic resin.
Further, the organic resin further comprises a fiber resin, and the fiber resin is one or more of cellulose acetate butyrate, carboxymethyl cellulose, ethyl cellulose and hydroxyethyl cellulose.
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 ether phthalate, N-dimethyl decyl amide, tripropylene glycol monomethyl ether, diethylene glycol butyl ether and pentaerythritol triacrylate.
Further, the defoaming agent is one or more of isopropanol, palmitic acid and lithium stearate.
Further, the thixotropic agent is one or more of 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 by the organic carrier according to a set proportion, heating, stirring, mixing, high-speed centrifuging, dispersing uniformly, and filtering to obtain the organic carrier;
preparing conductive silver-aluminum paste: respectively adding silver powder, aluminum powder, zinc powder, silicon-containing element additive powder and prepared glass powder into prepared organic carriers according to mass ratio, mixing and stirring uniformly, and grinding, viscosity adjusting and filtering to obtain 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.
The conductive silver-aluminum paste disclosed by the invention can balance the sintering of aluminum powder, zinc powder, silver powder and glass powder with larger melting point difference by introducing a proper amount of silicon-containing element additive powder, so that local overburning of grid lines is prevented, a small amount of silicon-containing element additive powder enters the aluminum liquid, the aluminum thorn can be promoted to form a P++ channel, meanwhile, the damage degree of the aluminum liquid to PN junctions can be reduced, the contact resistance is improved, and meanwhile, the higher open-circuit voltage of a battery is also kept; through adding zinc powder, the melting point of the zinc powder is lower than that of silver powder and aluminum powder, and the addition of a proper amount of zinc powder can promote the sintering of the silver powder and the aluminum powder, prevent the oxidation of the silver powder, promote the conductive effect and the compactness of the grid line, reduce the bulk resistance of the grid line, simultaneously oxidize the zinc powder to form zinc oxide into glass, increase the viscosity of glass liquid, reduce the oxidability of the glass, prevent the glass liquid from corroding the PN junction of the battery deeply at high temperature, and further maintain the higher open-circuit voltage of the battery. The invention realizes the N-type Topcon monocrystalline silicon battery electrode with low contact resistance, high open circuit voltage, high photoelectric conversion efficiency and high output power.
Detailed Description
The invention provides a conductive silver-aluminum paste, which comprises silver powder, aluminum powder, zinc powder, silicon-containing element additive powder, 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 is 0.1-6.0 mu m, and the distribution range of the D50 is 1.0-2.0 mu m; the aluminum powder is spherical or spheroidic, the grain size distribution range is 0.1-6.0 mu m, and the D50 distribution range is 0.8-2.0 mu m; the zinc powder is spherical or spheroidic, the distribution range of the particle size is 0.1-6.0 mu m, and the distribution range of D50 is 0.5-2.0 mu m.
Further, the grain size distribution range of the silicon-containing element additive powder is 0.1-6.0 mu m, and the D50 distribution range is 0.6-2.0 mu m; the silicon-containing element additive powder is one or more of silicon powder, molybdenum silicide, tungsten silicide and silicon boride, on one hand, the substances can balance the sintering of aluminum powder, zinc powder, silver powder and glass powder with larger melting point difference, so that local overburning of a grid line is prevented, on the other hand, a small amount of silicon-containing element additive powder enters aluminum liquid, the aluminum thorn can be promoted to form a P++ channel, meanwhile, the damage degree of the aluminum liquid to PN junctions can be reduced, and the open-circuit voltage of a battery is also kept higher while the contact resistance is improved. Wherein, the dimension of the aluminum thorn is controlled in a proper range, and is not suitable to be too large or too small.
Furthermore, the glass powder is a glass powder of a system composed of main elements, and has good corrosion effect and low contact resistance. The main element comprises Pb, ba, zn, B, li, O, si, ge, and the formed glass powder is one or more of Pb-Ba-Zn-Si-B-Li-O system glass powder, pb-Ba-Zn-Ge-B-Li-O system glass powder or Pb-Ba-Zn-Si-Ge-B-Li-O system glass powder with a composite structure of the Pb-Ba-Zn-Si-Ge-B-Li-O system glass powder and the Pb-Ba-Zn-Ge-B-Li-O system glass powder. The glass powder comprises the following components in percentage by mole based on 100% of the total mole of the components:
wherein the main element is introduced from oxide of the corresponding element, or the oxide of the element is obtained by decomposition during glass powder preparation, and can be introduced from peroxide, carbonate or complex, such as BaO can be obtained from BaCO 3 Introduction. The distribution range of the particle size of the glass powder is 0.1-6.0 mu m, and the distribution range of the D50 is 0.5-2.0 mu m. According to the embodiment, the glass powder of the system consisting of the main element Pb, ba, zn, B, li, O, si, ge is introduced, so that the glass has moderate oxidizing property, low glass softening point and good liquid phase sintering assisting effect, and the molten glass has moderate viscosity and good fluidity, can well corrode an insulating anti-reflection film on the surface of the battery, forms excellent ohmic contact and keeps good open pressure; meanwhile, a small amount of Ba element is added into the glass powder, the Ba element is introduced through BaO, and BaO is alkali element oxide, so that the glass powder has better capability of cleaning aluminum oxide on the surface of aluminum powder at high temperature, which is beneficial to the formation of aluminum silicon silver thorn protrusions and the formation of P++ junction areas, and improves the contact resistance between the battery piece and the grid line. Wherein, the size of the aluminum silicon silver thorn convex is controlled in a proper range, and is not suitable to be too large or too small.
Further, modified addition ofThe substance being an oxide of one or more elements of Ca, sr, na, K, tl, ti, al, fe, ga, bi, sb, se, or a substance which decomposes during the production of the glass frit to give an oxide of the element, e.g. a carbonate or a complex, e.g. Li 2 CO 3 、CaCO 3 、SrCO 3 、Na 2 CO 3 、K 2 CO 3 An oxide of the corresponding element is introduced.
Further, the organic carrier comprises an organic solvent, organic resin, dimethyl silicone oil, an antifoaming agent and a thixotropic agent, and the contents of the components are as follows, based on the total weight of the organic carrier as 100 percent:
the organic resin comprises elastic resin, wherein the elastic resin is one or more of SEPS resin, polyvinyl butyral resin, poly alpha-methyl styrene resin, SBS resin, SEBS resin, hydrogenated DCPD resin and acrylic resin. The elastic resin can well tie up silver powder particles, prevent the grid lines from having obvious high and low points, well lock the organic solvent, prevent the grid lines from collapsing caused by separating out the solvent from two sides of the grid lines, and thus, the good printing linearity and the high-width ratio can be maintained. The organic resin also comprises fiber resin, wherein the fiber resin is one or more of cellulose acetate butyrate, carboxymethyl cellulose, ethyl cellulose and hydroxyethyl cellulose. The interaction of the elastic resin and the fiber resin not only improves the screen passing effect of silver-aluminum paste printing, but also ensures the better aspect ratio of the silver-aluminum paste after screen passing. 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 ether phthalate, N-dimethyl decyl amide, tripropylene glycol methyl ether, diethylene glycol butyl ether and pentaerythritol triacrylate. The defoamer is one or more of isopropanol, palmitic acid and lithium stearate. The thixotropic agent is one or more of polyamide wax and hydrogenated castor oil. The addition of the dimethyl silicone oil can improve the screen passing property of silver-aluminum paste and adapt to the printing requirement of narrower screen plates. According to the invention, the mixed solvents of different substances are used, so that the solvent volatilization temperature zone is differentiated, the continuous printability and stability of silver-aluminum paste and the molding effect of the grid line after printing are improved, the output power of the battery can be further improved, and the photoelectric conversion efficiency is improved.
The invention also provides a method for preparing the conductive silver-aluminum paste, which comprises the following steps:
preparing glass powder: the preparation method comprises the steps of weighing precursor raw materials used by glass powder according to a set proportion, ball milling or screening, uniformly mixing, placing the mixture in a crucible, placing the crucible in a high-temperature furnace, melting at 750-1100 ℃ for 10-60 min, pouring glass liquid into a constant-temperature pair roller at-5 ℃ after uniform melting, carrying out rapid cooling treatment to obtain glass blocks, drying the glass blocks, carrying out primary crushing, and carrying out fine crushing to obtain the required glass powder with proper particle size;
preparing an organic carrier: weighing raw materials of an organic carrier, such as an organic solvent, an elastic resin, a fiber resin, a defoaming agent, dimethyl silicone oil and a thixotropic agent 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;
preparing conductive silver-aluminum paste: the prepared silver powder, aluminum powder, zinc powder, silicon-containing element additive powder and prepared glass powder are respectively added into the prepared organic carrier according to the mass ratio, are uniformly mixed and stirred, are milled by three rollers, are subjected to viscosity adjustment, and are filtered 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:
(1) The silver-aluminum paste disclosed by the invention uses Pb, ba, zn, si, ge, B, li, O main element to form system glass, the oxidability of the glass is moderate, the softening point of the glass is low, the glass has a good liquid phase burning assisting effect, the viscosity of molten glass is moderate, the glass has good fluidity, an insulating anti-reflection film on the surface of a battery can be well corroded, excellent ohmic contact is formed, and the opening pressure is kept well;
(2) The glass powder is added with a small amount of Ba element, baO is a strong alkali element oxide, and has better capability of cleaning oxide aluminum oxide on the surface of aluminum powder at high temperature, which is beneficial to the formation of aluminum silicon silver thorn protrusions and P++ junction areas, and improves the contact resistance between a battery piece and a grid line;
(3) According to the invention, zinc powder is also added, the melting point of the zinc powder is lower than that of the aluminum powder of the silver powder, and the addition of a proper amount of zinc powder can promote the sintering of the silver powder and the aluminum powder, prevent the oxidation of the silver powder, and promote the conductive effect and the compactness of the grid line, so that the bulk resistance of the grid line can be reduced, meanwhile, zinc oxide formed by oxidation of the zinc powder enters the glass, the viscosity of glass liquid is increased, the oxidizing property of the glass is reduced, the PN junction of a battery is prevented from being corroded deeply by the glass liquid at high temperature, and the higher open-circuit voltage of the battery is maintained;
(4) The invention also adds silicon-containing element additive powder, including silicon powder, molybdenum silicide, tungsten silicide, silicon boride and other substances, which can balance the sintering of aluminum powder, zinc powder, silver powder and glass powder with larger melting point difference on one hand, prevent local overburning of grid lines, and on the other hand, a small amount of silicon-containing element powder enters aluminum liquid, so that P++ channels can be formed by aluminum thorns, and meanwhile, the damage degree of the aluminum liquid to PN junctions can be reduced, and the open-circuit voltage of the battery is kept higher while the contact resistance is improved.
(5) The organic carrier comprises an elastic resin, so that silver powder particles can be well bound, obvious high and low points of the grid line are prevented, meanwhile, an organic solvent can be well locked, the grid line is prevented from collapsing due to the fact that the solvent is separated out from the two sides of the grid line, and good printing linearity and high-width ratio can be maintained; the addition of the dimethyl silicone oil can improve the screen passing property of silver-aluminum paste and adapt to the printing requirement of narrower screen plates; the mixed solvents of different substances are used, so that the solvent volatilization temperature zone is differentiated, the continuous printability and stability of silver-aluminum paste and the molding effect of the printed grid line are improved, the output power of the battery can be further improved, and the photoelectric conversion efficiency 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 G01 to G06:
preparation of glass powder: the method comprises the steps of respectively calculating and weighing glass powder according to a set formula, ball milling or screening, uniformly mixing, placing the glass powder into a crucible, placing the crucible into a high-temperature furnace, melting at 750-1100 ℃ for 10-60 min, pouring glass liquid into a constant-temperature pair roller at-5 ℃ after uniform melting, carrying out rapid cooling treatment to obtain glass blocks, drying the glass blocks, carrying out primary crushing, carrying out fine crushing to obtain the required glass powder with proper particle size, and carrying out No. G01-G06 for later use, wherein the specific composition mole ratio of the glass powder is shown in a table 1.
TABLE 1 mole percent glass frit (at%)
Examples C01 to C06:
preparation of the organic carrier: the organic carrier is prepared by weighing raw materials of an organic solvent, an elastic resin, a cellulose resin, a defoaming agent, dimethyl silicone oil and a thixotropic agent according to a set proportion, heating in a water bath at 70-100 ℃, stirring and mixing uniformly, performing high-speed centrifugal dispersion uniformly, and filtering to obtain the required organic carrier, wherein the serial numbers C01-C06 are reserved, and the weight composition ratio of each organic carrier is shown in a table 2.
TABLE 2 weight component Table (wt%) of organic vehicle
Examples P01 to P12:
preparing conductive silver-aluminum paste: numbering silver powder as Ag1, aluminum powder as Al1 and zinc powder as Zn1; the silicon powder, molybdenum silicide, tungsten silicide and silicon boride powder in the silicon-containing element additive powder with proper particle size are numbered as S01, S02, S03 and S04 in sequence; according to the material combination selected in Table 3 and the mass percentages provided, the corresponding silver powder, aluminum powder, zinc powder, silicon-containing element additive powder and glass powder are respectively weighed, added into the organic carrier with the corresponding model and mass, mixed and stirred uniformly, and then the thick paste is obtained through filtration after pulp binding by using a three-roller mill, and the conductive silver-aluminum paste P01-P12 is obtained after pulp mixing, wherein the specific composition of the silver-aluminum paste is shown in Table 3.
TABLE 3 weight composition table (wt.%)
Test example:
and (3) screen printing the silver-aluminum paste prepared in the examples P01-P12 on the surface of the battery on an N-type Topcon battery piece, drying, sintering and cooling to obtain the battery containing the printed silver grid line electrode, and testing the electrical property of the battery. 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, and the printing sintering and testing electrical performance is compared with that of the silver-aluminum paste under the same condition, and the test results are shown in Table 4.
Table 4 table of test data for conductive silver aluminum paste examples and comparative examples
As can be seen from Table 4, comparing the silver aluminum paste 995PFB silver aluminum paste produced by Shanghai silver paste technology Co Ltd with the silver aluminum paste of examples P01-P12 of the present invention, the silver aluminum paste of the present invention was found to have high printed line, narrow line width, high aspect ratio, and significantly improved printing linearity over the comparative examples, and the battery using the silver aluminum paste of the present invention had a higher open circuit voltage, a lower contact resistance, a superior photoelectric conversion efficiency, and a higher photoelectric conversion efficiency than the comparative examples, which indicates that the silver aluminum paste of the present invention provided good contact effect, a high open circuit voltage, and a high photoelectric conversion efficiency.
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 (13)
1. The conductive silver-aluminum paste is characterized by comprising silver powder, aluminum powder, zinc powder, silicon-containing element additive powder, 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 is 0.1-6.0 mu m, and the distribution range of the D50 is 1.0-2.0 mu m; the aluminum powder is spherical or spheroidic, the grain size distribution range is 0.1-6.0 mu m, and the D50 distribution range is 0.8-2.0 mu m; the zinc powder is spherical or spheroidic, the distribution range of the particle size is 0.1-6.0 mu m, and the distribution range of D50 is 0.5-2.0 mu m;
the glass powder is glass powder with a main element composition system, and comprises one or more of Pb-Ba-Zn-Si-B-Li-O system, pb-Ba-Zn-Ge-B-Li-O system or Pb-Ba-Zn-Si-Ge-B-Li-O system glass powder with a composite structure, wherein the glass powder comprises the following components in percentage by mole based on 100% of the total mole number of the components:
wherein, the main element is introduced by oxide of the corresponding element or substances which are decomposed to obtain the oxide of the element in the process of preparing the glass powder; the particle size distribution range of the glass powder is 0.1-6.0 mu m, and the D50 distribution range is 0.5-2.0 mu m.
2. The conductive silver-aluminum paste according to claim 1, wherein the silicon-containing element additive powder has a particle size distribution ranging from 0.1 to 6.0 μm and a D50 distribution ranging from 0.6 to 2.0 μm.
3. The conductive silver aluminum paste of claim 1, wherein the elemental silicon-containing additive powder is one or more of silicon powder, molybdenum silicide, tungsten silicide, silicon boride.
4. The conductive silver aluminum paste of claim 1, wherein the modifying additive is an oxide of one or more elements of Ca, sr, na, K, tl, ti, al, fe, ga, bi, sb, se or a substance that decomposes to obtain the oxide of the element during the glass frit manufacturing process.
5. The conductive silver-aluminum paste according to claim 1, wherein the organic carrier comprises an organic solvent, an organic resin, dimethyl silicone oil, a defoaming agent and a thixotropic agent, and the contents of the components are as follows, based on 100% of the total weight of the organic carrier:
6. the conductive silver aluminum paste of claim 5, wherein the organic resin comprises an elastomeric resin that is one or more of SEPS resin, polyvinyl butyral resin, poly-alpha-methylstyrene resin, SBS resin, SEBS resin, hydrogenated DCPD resin, acrylic resin.
7. The conductive silver aluminum paste of claim 6, wherein the organic resin further comprises a fiber resin, the fiber resin being one or more of cellulose acetate butyrate, carboxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose.
8. The conductive silver aluminum paste of claim 5, 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 ether phthalate, N-dimethyldecylamide, tripropylene glycol methyl ether, diethylene glycol butyl ether, pentaerythritol triacrylate.
9. The conductive silver aluminum paste of claim 5, wherein the defoamer is one or more of isopropyl alcohol, palmitic acid, and lithium stearate.
10. The conductive silver aluminum paste of claim 5, wherein the thixotropic agent is one or more of a polyamide wax and a hydrogenated castor oil.
11. A method for preparing the conductive silver-aluminum paste according to any of the preceding claims 1 to 10, 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 by the organic carrier according to a set proportion, heating, stirring, mixing, high-speed centrifuging, dispersing uniformly, and filtering to obtain the organic carrier;
preparing conductive silver-aluminum paste: respectively adding silver powder, aluminum powder, zinc powder, silicon-containing element additive powder and prepared glass powder into prepared organic carriers according to mass ratio, mixing and stirring uniformly, and grinding, viscosity adjusting and filtering to obtain conductive silver-aluminum paste.
12. An electrode, characterized in that the electrode is formed by sintering the conductive silver-aluminum paste according to any one of claims 1-10 on the surface of a battery silicon wafer.
13. An N-type Topcon cell comprising the electrode of claim 12.
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