CN111524639B - Electrode silver paste, preparation method and N-type crystalline silicon solar cell - Google Patents
Electrode silver paste, preparation method and N-type crystalline silicon solar cell Download PDFInfo
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- CN111524639B CN111524639B CN202010489913.XA CN202010489913A CN111524639B CN 111524639 B CN111524639 B CN 111524639B CN 202010489913 A CN202010489913 A CN 202010489913A CN 111524639 B CN111524639 B CN 111524639B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 57
- 239000004332 silver Substances 0.000 title claims abstract description 57
- 229910021419 crystalline silicon Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011521 glass Substances 0.000 claims abstract description 78
- 239000000843 powder Substances 0.000 claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 34
- 238000009826 distribution Methods 0.000 claims abstract description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 17
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 15
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims description 25
- 239000000853 adhesive Substances 0.000 claims description 24
- 230000001070 adhesive effect Effects 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 239000002893 slag Substances 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000004744 fabric Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- 238000009736 wetting Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 239000013008 thixotropic agent Substances 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 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
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229920001249 ethyl cellulose Polymers 0.000 claims description 3
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 abstract description 8
- 229910052802 copper Inorganic materials 0.000 abstract description 7
- 229910052748 manganese Inorganic materials 0.000 abstract description 6
- 229910052719 titanium Inorganic materials 0.000 abstract description 6
- 239000010949 copper Substances 0.000 description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 7
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- -1 silver-aluminum Chemical compound 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical group CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 150000008431 aliphatic amides Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 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 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
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- 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
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- 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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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electromagnetism (AREA)
- Sustainable Development (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Energy (AREA)
- Inorganic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Conductive Materials (AREA)
Abstract
In the electrode silver paste, the particle size distribution D10, D50 and D90 and the specific surface area of spherical silver powder are limited; which in turn defines the plate-like silver powder particle size distributions D10, D50 and D90 and specific surface area; the glass powder is provided with oxide: pb, Si, Cu, Mn, B and Ti, and/or an alkali metal element, and/or an alkaline earth metal element. The preparation method comprises the steps of (1) to (3) preparing electrode silver paste; the N-type crystalline silicon solar cell is characterized in that a back aluminum electrode and the back silver electrode are printed on the back of a silicon wafer. The invention can improve the electric leakage problem, thereby improving the efficiency and the yield of the battery, enabling the leakage current of the battery piece manufactured by the scheme to be equivalent to that of the conventional P-type piece, reducing the influence of the back silver in the aluminum carry-over junction process in the prior art, and solving the problem of very serious electric leakage of the battery piece.
Description
Technical Field
The invention relates to the technical field of crystalline silicon solar cells, in particular to electrode silver paste, a preparation method and an N-type crystalline silicon solar cell.
Background
The existing market mainstream of the crystalline silicon solar cell is P type, N type crystalline silicon has the advantages of long minority carrier lifetime, no light attenuation and the like compared with the P type crystalline silicon solar cell, the N type crystalline silicon solar cell can be divided into an aluminum emitter, a boron emitter and a heterojunction cell according to the structural difference of a PN junction, the junction made by a boron diffusion substance needs high temperature, and the heterojunction completely adopts a new process and is not matched with the existing mainstream P type cell process.
The technology for manufacturing the N-type crystalline silicon battery by aluminum propelling still adopts the back silver of the P-type crystalline silicon battery to manufacture the back electrode, and because of the influence of the back silver in the process of manufacturing the knot by the aluminum propelling, the electric leakage of a battery piece is very serious, and the low-efficiency piece proportion is very high.
Disclosure of Invention
The invention aims to provide an electrode silver paste, which limits the particle size distribution and the specific surface area of spherical silver powder and flake silver powder, and then comprises the following oxides: pb, Si, Cu, Mn, B and Ti, and/or alkali metal elements, and/or alkaline earth metal elements.
The invention also provides a preparation method of the electrode silver paste, which prepares the electrode silver paste through the steps (1) to (3).
The invention also provides an N-type crystalline silicon solar cell, wherein a back aluminum electrode and the back silver electrode are printed on the back of the silicon wafer.
In order to achieve the purpose, the invention adopts the following technical scheme:
the electrode silver paste comprises the following components in percentage by weight: spherical silver powder, flake silver powder, glass powder and adhesive;
the particle size distribution of the spherical silver powder D10 is 0.5-1.5 μm, D50 is 1.0-2.0 μm, and D90 is 2.0-3.0 μm; the specific surface area is 1.0-2.0m2/g；
The particle size distribution of the flake silver powder D10 is 2.0-4.0 μm, D50 is 5.0-8.0 μm, and D90 is 10.0-15.0 μm; the specific surface area is 0.5-0.8m2/g；
The glass powder comprises oxides of the following elements: pb, Si, Cu, Mn, B and Ti, and/or an alkali metal element, and/or an alkaline earth metal element.
Preferably, the glass powder comprises the following oxides of elements in percentage by mass: 30-50% of Pb, 5-20% of Si, 10-30% of Cu, 5-15% of Mn, 2-10% of B, 3-10% of Ti, 0-3% of alkali metal element and 0-3% of alkaline earth metal element.
Preferably, the glass powder comprises the following components in percentage by mass: 30-50% of Pb, 5-20% of Si, 10-30% of Cu, 5-15% of Mn, 2-10% of B, 3-10% of Ti, and 0.5-3% of an oxide of an alkali metal element, and 0.5-3% of an oxide of an alkaline earth metal element;
the alkali metal element is at least one of Li, Na and K;
the alkaline earth metal element is at least one of Mg, Ba and Ga.
Preferably, the particle size D50 of the glass powder is 2.0-3.0 μm.
Preferably, the adhesive comprises: resins, dispersants, thixotropic agents and solvents;
the resin comprises: at least one of acrylic resin, ethyl cellulose, rosin resin, and polyurethane.
Preferably, the composition comprises the following components in percentage by weight: 40-55% of spherical silver powder, 5-15% of flake silver powder, 1.5-2.5% of glass powder and 35-50% of adhesive.
Preferably, the preparation method of the glass powder comprises the steps of weighing the components in proportion, and uniformly mixing by using a stirrer; smelting the mixed components in a muffle furnace until glass liquid is clear and transparent, taking out the glass liquid and quenching to obtain smelted glass slag; and ball-milling and drying the glass slag to obtain the glass powder.
The preparation method of the electrode silver paste comprises the following steps: the method comprises the following steps:
(1) weighing spherical silver powder, flake silver powder, glass powder and adhesive according to the electrode silver paste, and mixing; stirring until the mixed materials are uniform;
(2) wetting the materials, grinding the slurry by using a three-roller machine, and controlling the fineness of the slurry to be less than 12 mu m;
(3) and filtering the slurry by adopting a filter cloth.
Preferably, in the step (3), the slurry is filtered by using a filter cloth.
A back silver electrode and a back aluminum electrode are printed on the back of a silicon wafer; the back silver electrode is prepared from the electrode silver paste.
The invention has the beneficial effects that:
according to the invention, the problem of electric leakage can be improved by changing the appearance of the silver powder in the back silver paste and proportioning the silver powder and the components of the glass powder, so that the efficiency and the yield of the battery are improved, the leakage current of the battery piece manufactured by the scheme is equivalent to that of a conventional P-type piece, the influence of the back silver in the aluminum carry-over junction process in the prior art is reduced, and the problem of very serious electric leakage of the battery piece is solved. Meanwhile, the scheme can be used for manufacturing the back electrode silver paste of the N-type crystalline silicon battery by aluminum propulsion, can be completely matched with the existing battery production process, and is low in production cost.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
The electrode silver paste comprises the following components in percentage by weight: spherical silver powder, flake silver powder, glass powder and adhesive;
the particle size distribution of the spherical silver powder D10 is 0.5-1.5 μm, D50 is 1.0-2.0 μm, and D90 is 2.0-3.0 μm; the specific surface area is 1.0-2.0m2/g；
The particle size distribution of the flake silver powder D10 is 2.0-4.0 μm, D50 is 5.0-8.0 μm, and D90 is 10.0-15.0 μm; the specific surface area is 0.5-0.8m2(ii)/g; the large flake silver powder used in the scheme is favorable for blocking diffusion of aluminum paste to a silicon wafer in the sintering process, so that electric leakage of a silver-aluminum lap joint area is reduced, the leakage current can be remarkably reduced, and the welding tension is kept stable.
The glass powder comprises oxides of the following elements: pb, Si, Cu, Mn, B and Ti, and/or an alkali metal element, and/or an alkaline earth metal element. The glass powder contains a certain amount of alkali metal and/or alkaline earth metal, and the glass powder is liquefied in the sintering process and combined with the flake silver powder to form a layer of blocking layer, so that the electric leakage of a silver-aluminum lap joint area is further reduced, and the electric leakage of a final product is the same as that of a conventional P-type battery.
According to the invention, the problem of electric leakage can be improved by changing the appearance of the silver powder in the back silver paste and proportioning the silver powder and the components of the glass powder, so that the efficiency and the yield of the battery are improved, the leakage current of the battery piece manufactured by the scheme is equivalent to that of a conventional P-type piece, the influence of the back silver in the aluminum carry-over junction process in the prior art is reduced, and the problem of very serious electric leakage of the battery piece is solved. Meanwhile, the scheme can be used for manufacturing the back electrode silver paste of the N-type crystalline silicon battery by aluminum propulsion, can be completely matched with the existing battery production process, and is low in production cost.
The scheme comprehensively limits the particle size distribution and the specific surface area of the spherical silver powder and the flake silver powder, and is matched with the glass powder mainly containing oxides Pb, Si, Cu, Mn, B and Ti, so that the reverse current is reduced, and the electric leakage of the product is small. The Pb-Si-Cu-Mn-B-Ti system in the scheme can improve the electric leakage resistance and the stripping force of a product by matching with the oxide of the alkali metal element and the alkaline earth metal element, and can provide a fluxing effect for the Pb-Si-Cu-Mn-B-Ti system.
Preferably, the glass powder comprises the following oxides of elements in percentage by mass: 30-50% of Pb, 5-20% of Si, 10-30% of Cu, 5-15% of Mn, 2-10% of B, 3-10% of Ti, 0-3% of alkali metal element and 0-3% of alkaline earth metal element.
Preferably, the glass powder comprises the following components in percentage by mass: 30-50% of Pb, 5-20% of Si, 10-30% of Cu, 5-15% of Mn, 2-10% of B, 3-10% of Ti, and 0.5-3% of an oxide of an alkali metal element, and 0.5-3% of an oxide of an alkaline earth metal element;
the alkali metal element is at least one of Li, Na and K;
the alkaline earth metal element is at least one of Mg, Ba and Ga.
Preferably, the particle size D50 of the glass powder is 2.0-3.0 μm.
In the scheme, the granularity of the glass powder can be other particle sizes, such as 1.0-10.0 μm or 1-20.0 μm; preferably, the particle size D50 of the glass powder is 2.0-3.0 μm, i.e. the particle size of the medium diameter is 2.0-3.0 μm, and in this range, the reverse current is lower and the performance is best.
Preferably, the adhesive comprises: resins, dispersants, thixotropic agents and solvents;
the resin comprises: at least one of acrylic resin, ethyl cellulose, rosin resin, and polyurethane.
The adhesive may be a known adhesive; and preferably, the system step of the adhesive can be that the resin, the solvent, the dispersant and the thixotropic agent are weighed according to the proportion and mixed, the mixture is heated in a water bath or an oil bath at the temperature of 60-80 ℃, and a stirring paddle is used for stirring and dissolving for 1-4 hours until the materials are completely mixed and dissolved, so that the clear transparent or semitransparent or opaque organic adhesive is obtained.
Preferably, the composition comprises the following components in percentage by weight: 40-55% of spherical silver powder, 5-15% of flake silver powder, 1.5-2.5% of glass powder and 35-50% of adhesive.
Preferably, the preparation method of the glass powder comprises the steps of weighing the components in proportion, and uniformly mixing by using a stirrer; smelting the mixed components in a muffle furnace until glass liquid is clear and transparent, taking out the glass liquid and quenching to obtain smelted glass slag; and ball-milling and drying the glass slag to obtain the glass powder.
The preparation method of the electrode silver paste comprises the following steps: the method comprises the following steps:
(1) weighing spherical silver powder, flake silver powder, glass powder and adhesive according to the electrode silver paste, and mixing; stirring until the mixed materials are uniform;
(2) wetting the materials, grinding the slurry by using a three-roller machine, and controlling the fineness of the slurry to be less than 12 mu m;
(3) and filtering the slurry by adopting a filter cloth.
Preferably, the slurry is filtered using a filter cloth.
A back silver electrode and a back aluminum electrode are printed on the back of a silicon wafer; the back silver electrode is prepared from the electrode silver paste.
The N-type crystalline silicon solar cell is a known cell structure, a back silver electrode prepared by the electrode silver paste prepared by the scheme is preferably used for matching with a back aluminum electrode, the electric leakage problem is improved, and the leakage current of the cell slice manufactured by the technology of the patent is equivalent to that of a conventional P-type slice.
And (3) performance testing:
1. reverse current:
carrying out a verification experiment by adopting an N-type monocrystalline silicon wafer, printing back silver and back aluminum electrodes of each segmented embodiment on the back surface of the silicon wafer, simulating lap joint of the back silver and the back aluminum, drying and sintering, wherein a CT sintering furnace is adopted for sintering, and the peak temperature is 760 and 780 ℃; and (3) measuring the resistance between the two sections of electrodes by using a multimeter, wherein the larger the measured resistance value is, the smaller the electric leakage is.
2. Peel strength:
and (3) carrying out a tensile test on the N-type monocrystalline silicon wafer by using a peeling strength tester, welding a back silver electrode by using a lead-tin-plated copper strip (photovoltaic welding strip) with the thickness of 0.25mm and the width of 0.9mm, clamping the silicon wafer by using a clamp, peeling the welding strip at 180 degrees in the opposite direction, and testing the peeling strength of the silicon wafer.
Example A:
weighing the following raw materials in proportion of Pb according to Table 12O3、SiO2、CuO、MnO2、B2O3、TiO2And Li2O and MgO; uniformly mixing by using a stirrer; smelting the mixed components in a muffle furnace at 1000 ℃ for 2 hours until glass liquid is clear and transparent, taking out the glass liquid and quenching to obtain smelted glass slag; and ball-milling and drying the glass slag to obtain the glass powder.
The preparation method comprises the following steps: the method comprises the following steps:
(1) weighing 48% of spherical silver powder, 12% of flake silver powder, 2.0% of glass powder and 38% of adhesive (conventional adhesive on the market), and mixing to obtain different examples; stirring until the mixed materials are uniform;
wherein, the particle size distribution of the spherical silver powder D10 is 1.0 μm, D50 is 1.5 μm, and D90 is 2.5 μm; specific surface area of spherical silver powder 1.5m2/g；
The particle size distribution of the flaky silver powder is 3.0 mu m in D10, 7.0 mu m in D50 and 12.0 mu m in D90; specific surface area of the plate-like silver powder was 0.6m2/g。
The particle size of the glass frit is not limited.
(2) Wetting the materials, grinding the slurry by using a three-roller machine, and controlling the fineness of the slurry to be less than 12 mu m;
(3) and filtering the slurry by adopting 400-mesh filter cloth to obtain electrode silver paste.
TABLE 1 Components of example A
The electrode silver pastes prepared in examples A1-A9 were subjected to performance testing, as specified in Table 2.
Description of the drawings:
1. as can be seen from examples A1-A8, examples A1-A7 contain Pb in spite of2O3、SiO2、CuO、MnO2、B2O3、TiO2、Li2O and MgO are in the better mixture ratio, but the SiO is lacked in the embodiment2、CuO、MnO2、B2O3、TiO2、Li2Any one of O and MgO is not good in performance. As in examples A1-A5, each of the corresponding examples was insufficient in the reverse cell due to the absence of any of Si, Cu, Mn, B, Ti in the Pb-Si-Cu-Mn-B-Ti system; while example A8 has a Pb-Si-Cu-Mn-B-Ti system with the addition of Li to the Pb-Si-Cu-Mn-B-Ti system2The alkali metal element mainly containing O and the alkaline earth metal element mainly containing MgO greatly reduce the value of reverse current and improve the peel strength, wherein the reverse current is the lowest 0.43A, and the peel strength is the highest 5N; indicating that the final product has the least leakage and the greatest peel strength. Meanwhile, in the prior art, the reverse current of the P-type cell is between 0.2 and 0.5A under the normal condition, and the reverse current of the embodiment A8 is 0.43, which shows that the product prepared by the electrode silver paste of the N-type crystalline silicon can reach the level of the P-type cell and solves the problem of electric leakage of the cell.
2. As can be seen from examples A6-A8, example A6 used only MgO and did not use Li2O; in a Pb-Si-Cu-Mn-B-Ti system, because alkali metal elements are lacked, the reverse current and the peel strength are reduced, the reverse current is only 0.50A, and the peel strength is 4.7N; while example A7 used only Li2O, and MgO is not used; in the Pb-Si-Cu-Mn-B-Ti system, because alkaline earth metal elements are lacked, the reverse current and the peel strength are reduced, the reverse current is only 0.49A, and the peel strength is 4.8N; while example A8 uses Li2O and MgO while optimizingThe Pb-Si-Cu-Mn-B-Ti system ensures that the product has the optimal reverse current of 0.43A and the optimal peel strength of 5.0N.
Example B:
weighing the starting material, Pb, as in example A82O3、SiO2、CuO、MnO2、B2O3、TiO2And Li2O and MgO; uniformly mixing by using a stirrer; smelting the mixed components in a muffle furnace at 1000 ℃ for 2 hours until glass liquid is clear and transparent, taking out the glass liquid and quenching to obtain smelted glass slag; and ball-milling and drying the glass slag to obtain the glass powder.
The preparation method comprises the following steps: the method comprises the following steps:
(1) weighing 48% of spherical silver powder, 12% of flake silver powder, 2.0% of glass powder and 38% of adhesive (conventional adhesive on the market), and mixing to obtain different examples; stirring until the mixed materials are uniform;
wherein, the selection indexes of the spherical silver powder and the flake silver powder are shown in Table 3;
wherein, the particle size distribution of the spherical silver powder D10 is 1.0 μm, D50 is 1.5 μm, and D90 is 2.5 μm;
the plate-like silver powder had a particle size distribution D10 of 3.0. mu.m, D50 of 7.0. mu.m, and D90 of 12.0. mu.m.
The particle size of the glass frit is not limited.
(2) Wetting the materials, grinding the slurry by using a three-roller machine, and controlling the fineness of the slurry to be less than 12 mu m;
(3) and filtering the slurry by adopting 400-mesh filter cloth to obtain electrode silver slurry of different embodiments.
TABLE 3 silver powder selection
The electrode silver pastes prepared in examples B1-B10 were subjected to performance testing, as specified in Table 4.
TABLE 4 Performance testing of example B
Description of the drawings:
as can be seen from the examples B1-B10, the following requirements are not simultaneously satisfied in each example: a specific surface area of spherical silver powder is 1.0-2.0m2(ii)/g; b specific surface area of flake silver powder 0.5-0.8m2(ii)/g; the parameters are the optimal particle distribution effect generated by the mutual particle size matching of the spherical silver powder and the flake silver powder so as to influence the performance of the sintered electrode silver paste; in the above embodiment, any value of the parameters of the spherical silver powder and the flake silver powder exceeds the optimal range, which results in poor distribution of the particles in the electrode silver paste and poor reverse current;
example B1 specific surface area 0.8m2In g, example B5 has a specific surface area of 2.2m2(g) the specific surface area of the football-shaped silver powder in the range of both examples is less than 1.0 to 2.0m2Therefore, its reverse current is not good, and the reverse currents are only 0.71A and 0.61A; the specific surface area of the plate-like silver powder was 0.6m2Based on the specific surface area of the spherical silver powder being 1.0 to 2.0m2The leakage current of the product of the embodiment is equivalent to that of the conventional P-type chip, and the reverse current of the embodiment B2 is 0.49A, the reverse current of the embodiment B3 is 0.43A, and the reverse current of the embodiment B4 is 0.45A.
As is clear from examples B6-B10, the specific surface area of the spherical silver powder was 1.5m2In example B6, the specific surface area of the plate-like silver powder was 0.3m2In example B10, the molar mass is 1.0m2In the range of 0.5 to 0.8m, each of which is not satisfactory in terms of specific surface area of the plate-like silver powder2The requirement of/g; thus, the leak resistance of examples B6 and B10 was insufficient, the reverse current of example B6 was 0.68A, and the reverse current of example B10 was 0.59A; in examples B7 to B9, the specific surface areas of the plate-like silver powders all corresponded to 0.5 to 0.8m2The reverse current of the embodiment B7 can reach 0.43A, the reverse current of the embodiment B8 is 0.44A, the reverse current of the embodiment B9 is 0.46A, and the leakage current of the product of the embodiment is equivalent to that of a conventional P type chip.
Example C:
example C is based on example A8, which differs from example A8 by: the granularity of the glass powder is D50 is 2.0-3.0 μm; while the particle size of the glass frit is not limited in example A8, a reverse current test was conducted for example C and example A8, as shown in Table 5.
TABLE 5 comparison of the Properties of example C with example A8
| Reverse current (A) | |
| Example A8 | 0.43 |
| Example C | 0.37 |
Description of the drawings:
while example C of the present embodiment is preferably 2.0 to 3.0 μm, and example A8 does not limit the particle size of the glass frit, when the particle size D50 of the glass frit in example C is limited to 2.0 to 3.0 μm, the reverse current can be reduced to only 0.37A, the leakage current can be effectively improved, and the performance is further superior to that of example A8.
Example D:
weighing the following raw materials in proportion of 30% of Pb2O315% of SiO225% of CuO, 10% of MnO27% of B2O37% of TiO2And 3% of Li2O and 3% MgO; uniformly mixing by using a stirrer; smelting the mixed components in a muffle furnace at 1000 ℃ for 3 hours until glass liquid is clear and transparent, taking out the glass liquid and quenching to obtain smelted glass slag; and ball-milling and drying the glass slag to obtain the glass powder.
The preparation method comprises the following steps: the method comprises the following steps:
(1) weighing 40% of spherical silver powder, 15% of flake silver powder, 2.5% of glass powder and 42.5% of adhesive (conventional adhesive on the market), and mixing to obtain different examples; stirring until the mixed materials are uniform;
wherein the particle size distribution of the spherical silver powder is D10 of 0.5 μm, D50 of 2.0 μm and D90 of 3.0 μm; specific surface area of spherical silver powder 2.0m2/g；
The particle size distribution of the flaky silver powder is 2.0 mu m in D10, 8.0 mu m in D50 and 15.0 mu m in D90; specific surface area of the plate-like silver powder was 0.8m2/g。
The particle size D50 of the glass powder was 2.0. mu.m.
(2) Wetting the materials, grinding the slurry by using a three-roller machine, and controlling the fineness of the slurry to be less than 12 mu m;
(3) and filtering the slurry by adopting 300-mesh filter cloth to obtain electrode silver paste.
Example E:
weighing the following raw materials in proportion of 50% of Pb2O35% of SiO230% of CuO and 5% of MnO24% of B2O34% of TiO21% of Na2O and Li2A combination of O, and a combination of 1% MgO and BaO; uniformly mixing by using a stirrer; smelting the mixed components in a muffle furnace at 1000 ℃ for 1.5 hours until glass liquid is clear and transparent, taking out the glass liquid and quenching to obtain smelted glass slag; and ball-milling and drying the glass slag to obtain the glass powder.
The preparation method comprises the following steps: the method comprises the following steps:
(1) weighing 55% of spherical silver powder, 5% of flake silver powder, 1.5% of glass powder and 38.5% of adhesive, and mixing to obtain different embodiments; stirring until the mixed materials are uniform;
(2) wetting the materials, grinding the slurry by using a three-roller machine, and controlling the fineness of the slurry to be less than 12 mu m;
(3) and filtering the slurry by adopting 300-mesh filter cloth to obtain electrode silver paste.
Wherein the particle size distribution D10 of the spherical silver powder is 0.5 μm,d50 is 1.0 μm, D90 is 3.0 μm; specific surface area of spherical silver powder 1.0m2/g；
The particle size distribution of the flaky silver powder is 4.0 mu m in D10, 5.0 mu m in D50 and 10.0 mu m in D90; specific surface area of the plate-like silver powder was 0.5m2/g。
The particle size D50 of the glass frit was 3.0. mu.m.
Preparation of the adhesive in this example: weighing the resin, the solvent, the dispersant and the thixotropic agent, heating in a water bath at 70 ℃, stirring and dissolving for 3 hours by a stirring paddle until the materials are completely mixed and dissolved to obtain the organic adhesive. Wherein the resin is polyurethane; the solvent is butyl carbitol acetate; the dispersant is an aliphatic amide dispersant; the thixotropic agent is hydrogenated castor oil.
The properties of examples D and E are shown in Table 6.
TABLE 6 Performance testing of examples D and E
| Reverse current (A) | Peel strength (N) | |
| Example D | 0.40 | 5.0 |
| Example E | 0.41 | 4.9 |
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (9)
1. The electrode silver paste is characterized by comprising the following components in percentage by weight: spherical silver powder, flake silver powder, glass powder and adhesive;
the particle size distribution of the spherical silver powder D10 is 0.5-1.5 μm, D50 is 1.0-2.0 μm, and D90 is 2.0-3.0 μm; the specific surface area is 1.0-2.0m2/g；
The particle size distribution of the flake silver powder D10 is 2.0-4.0 μm, D50 is 5.0-8.0 μm, and D90 is 10.0-15.0 μm; the specific surface area is 0.5-0.8m2/g；
The glass powder comprises the following oxides of elements in percentage by mass: 30-50% of Pb, 5-20% of Si, 10-30% of Cu, 5-15% of Mn, 2-10% of B, 3-10% of Ti, 0-3% of alkali metal element and 0-3% of alkaline earth metal element.
2. The electrode silver paste of claim 1, wherein the glass frit comprises, by mass: 30-50% of Pb, 5-20% of Si, 10-30% of Cu, 5-15% of Mn, 2-10% of B, 3-10% of Ti, and 0.5-3% of an oxide of an alkali metal element, and 0.5-3% of an oxide of an alkaline earth metal element;
the alkali metal element is at least one of Li, Na and K;
the alkaline earth metal element is at least one of Mg, Ba and Ga.
3. The electrode silver paste of claim 1, wherein the glass frit has a particle size D50 of 2.0-3.0 μm.
4. The electrode silver paste of claim 1, wherein the binder comprises: resins, dispersants, thixotropic agents and solvents;
the resin comprises: at least one of acrylic resin, ethyl cellulose, rosin resin, and polyurethane.
5. The electrode silver paste of claim 1, which comprises, by weight: 40-55% of spherical silver powder, 5-15% of flake silver powder, 1.5-2.5% of glass powder and 35-50% of adhesive.
6. The electrode silver paste according to any one of claims 1 to 5, wherein the glass powder is prepared by weighing the components in proportion and uniformly mixing the components by using a stirrer; smelting the mixed components in a muffle furnace until glass liquid is clear and transparent, taking out the glass liquid and quenching to obtain smelted glass slag; and ball-milling and drying the glass slag to obtain the glass powder.
7. The preparation method of the electrode silver paste is characterized by comprising the following steps: the method comprises the following steps:
(1) the electrode silver paste according to any one of claims 1 to 5, wherein spherical silver powder, flake silver powder, glass powder and an adhesive are weighed and mixed; stirring until the mixed materials are uniform;
(2) wetting the materials, grinding the slurry by using a three-roller machine, and controlling the fineness of the slurry to be less than 12 mu m;
(3) and filtering the slurry by adopting a filter cloth.
8. The method according to claim 7, wherein in the step (3), the slurry is filtered using a filter cloth.
9. An N-type crystalline silicon solar cell is characterized in that a back silver electrode and a back aluminum electrode are printed on the back of a silicon wafer; the back silver electrode is prepared from the electrode silver paste of any one of claims 1-6.
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| CN103531266A (en) * | 2012-07-03 | 2014-01-22 | 苏州柏特瑞新材料有限公司 | Wafer solar battery back electrode silver paste and preparing method thereof |
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| CN105764168A (en) * | 2016-01-12 | 2016-07-13 | 昆明理工大学 | Car rear windshield heating wire silver paste and preparation method thereof |
| CN105825913B (en) * | 2016-05-16 | 2017-11-24 | 南通天盛新能源股份有限公司 | A kind of ageing-resistant crystal silicon solar energy battery back silver paste and preparation method thereof |
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| CN103426495A (en) * | 2012-05-17 | 2013-12-04 | 比亚迪股份有限公司 | Electrical conductive slurry for solar cell and preparation method thereof and manufacture process of solar cell piece |
| CN103531266A (en) * | 2012-07-03 | 2014-01-22 | 苏州柏特瑞新材料有限公司 | Wafer solar battery back electrode silver paste and preparing method thereof |
| CN103915131A (en) * | 2013-01-04 | 2014-07-09 | 硕禾电子材料股份有限公司 | Conductive composition for solar cell |
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