CN112592068B - Glass powder, preparation method thereof and application of glass powder in TOPCon battery - Google Patents
Glass powder, preparation method thereof and application of glass powder in TOPCon battery Download PDFInfo
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- CN112592068B CN112592068B CN202011482245.4A CN202011482245A CN112592068B CN 112592068 B CN112592068 B CN 112592068B CN 202011482245 A CN202011482245 A CN 202011482245A CN 112592068 B CN112592068 B CN 112592068B
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- 239000011521 glass Substances 0.000 title claims abstract description 103
- 239000000843 powder Substances 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052709 silver Inorganic materials 0.000 claims abstract description 45
- 239000004332 silver Substances 0.000 claims abstract description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 20
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 11
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 11
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 11
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000464 lead oxide Inorganic materials 0.000 claims abstract description 11
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 10
- 229910052810 boron oxide Inorganic materials 0.000 claims abstract description 9
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 9
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 9
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003723 Smelting Methods 0.000 claims description 41
- 238000000498 ball milling Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- 239000012634 fragment Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008213 purified water Substances 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 239000002562 thickening agent Substances 0.000 claims description 3
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 239000013008 thixotropic agent Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 27
- 239000002184 metal Substances 0.000 abstract description 27
- 238000013329 compounding Methods 0.000 abstract description 4
- 239000002003 electrode paste Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 229910052710 silicon Inorganic materials 0.000 description 14
- 239000010703 silicon Substances 0.000 description 14
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 12
- 238000005215 recombination Methods 0.000 description 12
- 230000006798 recombination Effects 0.000 description 12
- 229920005591 polysilicon Polymers 0.000 description 8
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002905 metal composite material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 230000005641 tunneling Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- 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 description 1
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 description 1
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 235000020985 whole grains Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
-
- 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 glass powder, and relates to the field of silver electrode paste. The glass powder comprises the following components in parts by weight: 25-50 parts of lead oxide, 25-45 parts of tellurium oxide, 10-30 parts of bismuth oxide, 2-10 parts of molybdenum oxide, 0-6 parts of silicon dioxide, 0-6 parts of boron oxide, 0-4 parts of alkaline earth metal oxide, 0-6 parts of alkali metal oxide and 0-3 parts of rare earth metal oxide. The invention also provides TOPCon battery silver paste containing the glass powder, the TOPCon battery silver paste can balance the contact performance and metal compounding on thin Poly (60-100 nm), and the client-side efficiency is improved by more than 0.1%.
Description
Technical Field
The invention relates to the field of silver electrode paste, in particular to glass powder, a preparation method thereof and application thereof in TOPCon batteries.
Background
Compared with P-type monocrystalline silicon, N-type monocrystalline silicon has the advantages of long minority carrier lifetime, less boron-oxygen recombination, small photoinduced attenuation and the like, and has a higher efficiency-improving space. Meanwhile, the N-type component has the advantages of low temperature coefficient, good weak light response and the like. With new cell technology and technology, the market share of N-type silicon is expected to reach around 40% in 2035. The currently available N-type high-efficiency batteries mainly include N-PERT, N-TOPCon, HJT and IBC batteries, wherein the N-PERT and TOPCon batteries have high compatibility with the production line of PERC batteries, and TOPCon batteries are one of the future trends.
The TOPCon technology is that an ultra-thin tunneling oxidation layer and a highly doped polycrystalline silicon thin layer are prepared on the back of an N-type cell, and the ultra-thin tunneling oxidation layer and the highly doped polycrystalline silicon thin layer jointly form a passivation contact structure, the structure provides good surface passivation for the back of a silicon wafer, the ultra-thin oxidation layer can enable multi-electron tunneling to enter a polycrystalline silicon layer and simultaneously block minority hole recombination, and then electrons are laterally transmitted in the polycrystalline silicon layer and collected by metal, so that metal contact recombination current is greatly reduced, open-circuit voltage and short-circuit current of the cell are improved, and conversion efficiency can exceed 24%.
The back electrode of the TOPCon battery is in contact with n + polysilicon, the polysilicon layer is amorphous silicon deposited in an LPCVD or PECVD mode, then is crystallized into polysilicon through annealing, and different from the polysilicon formed by ingot casting, the traditional silver paste is difficult to form good ohmic contact with the layer, and the traditional silver paste has the following defects: under the condition that the thickness of the polysilicon on the back surface of the TOPCon battery is more than 150nm, the contact performance and the metal composition of the common TOPCon back electrode on the market and the N + layer of the TOPCon battery can be balanced; when the thickness of the polysilicon is less than 120nm (especially less than 100 nm), under the condition of low sintering furnace temperature, the common TOPon silver paste is difficult to form good contact with the thin polysilicon layer, the sintering furnace temperature is increased, the contact performance can be improved, but the silicon dioxide layer is burnt through at high temperature, so that the metal composite is large, and the electrical performance is low; when the back surface of the TOPCon is polished, the adhesion of the dried slurry is affected, and the common TOPCon silver paste partially falls off after being dried, so that the sintered EL is poor, the appearance and the efficiency of the battery are affected, and the special TOPCon battery back electrode slurry needs to be developed.
Disclosure of Invention
Based on the above, the present invention aims to overcome the defects of the prior art and provide a glass frit which can make a silver paste and a thin polysilicon layer form good contact and has good adhesion when the back surface of a TOPCon battery is a polished surface.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: the glass powder comprises the following components in parts by weight: 25-50 parts of lead oxide, 25-45 parts of tellurium oxide, 10-30 parts of bismuth oxide, 2-10 parts of molybdenum oxide, 0-6 parts of silicon dioxide, 0-6 parts of boron oxide, 0-4 parts of alkaline earth metal oxide, 0-6 parts of alkali metal oxide and 0-3 parts of rare earth metal oxide.
The glass powder of the system provided by the invention can meet the balance of contact resistivity and metal compounding on thin POLY. The glass powder prepared by the system has moderate corrosivity on a thin POLY (POLY), namely does not cause great damage to the surface of the silicon wafer while promoting contact, and can balance the contact resistivity and metal recombination to a great extent, so that the recombination rate of electron hole pairs on the back surface of the silicon wafer is not too high, the current loss is reduced, and the conversion efficiency of a battery piece is improved.
Preferably, the glass powder comprises the following components in parts by weight: 38 parts of lead oxide, 30 parts of tellurium oxide, 17 parts of bismuth oxide, 4 parts of molybdenum oxide, 4 parts of silicon dioxide, 3.5 parts of boron oxide, 2 parts of alkaline earth metal oxide, 3.5 parts of alkali metal oxide and 1.5 parts of rare earth metal oxide.
Preferably, the alkali metal oxide is at least one of lithium oxide, potassium oxide and sodium oxide; the alkaline earth metal oxide is at least one of magnesium oxide, calcium oxide and barium oxide.
In addition, the invention also provides a preparation method of the glass powder, which comprises the following steps:
(1) Weighing and uniformly dispersing lead oxide, tellurium oxide, bismuth oxide, molybdenum oxide, silicon dioxide, boron oxide, alkaline earth metal oxide, alkali metal oxide and rare earth metal oxide, smelting in a high-temperature furnace, taking out purified water, quenching and cooling to obtain light yellow fragments A;
(2) And (2) performing ball milling treatment on the light yellow fragment A obtained in the step (1), sieving, standing, removing supernatant, drying and crushing to obtain the glass powder.
In the preparation method of the glass powder, the light yellow fragment A obtained in the step (1) is a light yellow glass slag fragment, the surface of the glass slag is bright, and the glass state is obvious.
Preferably, in the step (1), the smelting temperature is 900-1100 ℃, and the smelting time is 60-120min; in the step (2), the ball milling time is 6-18h, and the sieve after ball milling treatment is a 300-mesh sieve.
The inventor determines the manufacturing process of the glass powder by comparing the particle size and the softening point of the glass powder, the contact performance of the prepared slurry and the metal composition under different smelting temperatures, time and ball milling time.
The smelting temperature is 900-1100 ℃, when the smelting temperature is lower, the smelting state is poor due to the fact that the glass powder cannot reach the required temperature, complete glass is difficult to form, when the smelting temperature is higher, the stability of a container used for smelting is reduced, the container is broken, the smelting fails, and meanwhile, the energy waste is caused to a certain extent due to the fact that the temperature is higher.
The smelting time is 60-120min, when the smelting time is short, the glass material is not fully contacted, so that complete glass is difficult to form, and when the smelting time is too long, the stability of a smelting container is also reduced, so that the risk of failure is increased; in the step (2), the ball milling time is 6-18h, when the ball milling time is short, the formed glass powder has a large span, namely the size difference of the glass powder is large, and the silver paste prepared by using the glass powder is not uniformly corroded on the back surface of the silicon wafer, so that the stability of the silver paste is poor; when the ball milling time is longer, the whole grain size of the formed glass powder is smaller, although the contact performance is helped to a certain extent, the combination rate is too high due to the higher corrosivity, and the balance between the contact resistivity and the metal combination cannot be well realized.
More preferably, in the step (1), the smelting temperature is 1050 ℃, and the smelting time is 90min; in the step (2), the ball milling time is 15h.
In addition, the invention also provides application of the glass powder in TOPCon battery silver paste.
Meanwhile, the invention also provides TOPCon battery silver paste containing the glass powder.
Preferably, the TOPCon battery silver paste comprises the following components in parts by weight: 81-91 parts of silver powder, 0.3-1.5 parts of metal oxide, 0.7-2.5 parts of nano silver powder, 1-4 parts of glass powder and 7-11 parts of organic adhesive.
The above silver paste formula is preferred according to the requirements of the battery structure of the client on the performance of the paste.
Preferably, the silver powder is sphere-like silver powder and/or nano silver powder, and the average grain diameter of the silver powder is 0.8-2.8 μm; the metal oxide is at least one of bismuth oxide, lead oxide, antimony oxide and molybdenum oxide, and the particle size D50 of the metal oxide is 0.6-1.0 mu m; the average grain diameter of the nano silver powder is between 300 and 700nm; the organic binder includes a solvent, a thickener, a plasticizer, and a thixotropic agent.
The solvent is an organic solvent and comprises at least one of dioctyl phthalate, mixed dibasic acid ester, terpineol, butyl carbitol acetate, benzyl alcohol, methyl glycol monomethyl ether and diethylene glycol dibutyl ether; the thickening agent comprises at least one of ethyl cellulose, nitrocellulose, solid acrylic resin and ABS resin.
The invention also provides a preparation method of the TOPCon battery silver paste, which comprises the following steps: and weighing silver powder, metal oxide, nano silver powder, glass powder and an organic adhesive, and grinding to obtain the TOPCon battery silver paste.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, by optimizing the proportion of oxides in the glass powder and optimizing the manufacturing process, the contact performance and metal composition of the prepared TOPCon battery silver paste on thin Poly (60-100 nm) can be balanced, and the effect of a client is improved by more than 0.1%.
(2) According to the invention, the preparation process of the glass powder is optimized, the particle size and the softening point of the glass powder are adjusted, the adhesive force of the dried silver paste is improved, the electrical property is not influenced, and the adhesive force of the dried TOPCon battery is good when the back surface of the TOPCon battery is of a polished structure.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Examples 1 to 3 were set up and the components and parts by weight of examples 1 to 3 are shown in Table 1, while comparative examples 1 to 12 were set up and the components and parts by weight of comparative examples 1 to 6 are shown in Table 2, the preparation method was exactly the same as example 2, and comparative examples 7 to 12 were exactly the same as the components of example 2, except that the preparation method was different:
TABLE 1 selection of Components and parts by weight of examples 1-3
TABLE 2 selection of Components and parts by weight of comparative examples 1-6
Example 1
After selecting the components and the parts by weight according to example 1 described in table 1, the preparation method of the glass frit comprises the following steps:
(1) Weighing lead oxide, tellurium oxide, bismuth oxide, molybdenum oxide, silicon dioxide, boron oxide, alkaline earth metal oxide, alkali metal oxide and rare earth metal oxide, uniformly dispersing, smelting in a high-temperature furnace at 900 ℃ for 60min, taking out, and quenching and cooling with purified water to obtain A;
(2) And (2) performing ball milling treatment on the A obtained in the step (1), wherein the ball milling time is 6 hours, the sieve subjected to ball milling treatment is a 300-mesh sieve, standing after sieving, removing supernatant, and drying and crushing to obtain the glass powder.
Example 2
After selecting the components and the parts by weight according to the example 2 described in table 1, the preparation method of the glass powder comprises the following steps:
(1) Weighing lead oxide, tellurium oxide, bismuth oxide, molybdenum oxide, silicon dioxide, boron oxide, alkaline earth metal oxide, alkali metal oxide and rare earth metal oxide, uniformly dispersing, smelting in a high-temperature furnace at 1050 ℃, wherein the smelting time is 90min, and taking out purified water for quenching and cooling to obtain A;
(2) And (2) performing ball milling treatment on the A obtained in the step (1), wherein the ball milling time is 15 hours, the sieve subjected to ball milling treatment is a 300-mesh sieve, standing after sieving, removing supernatant, and drying and crushing to obtain the glass powder.
Example 3
After selecting the components and the parts by weight according to the example 3 described in table 1, the preparation method of the glass powder comprises the following steps:
(1) Weighing lead oxide, tellurium oxide, bismuth oxide, molybdenum oxide, silicon dioxide, boron oxide, alkaline earth metal oxide, alkali metal oxide and rare earth metal oxide, uniformly dispersing, smelting in a high-temperature furnace at 1100 ℃ for 120min, taking out purified water, quenching and cooling to obtain A;
(2) And (2) performing ball milling treatment on the A obtained in the step (1), wherein the ball milling time is 18h, the sieve subjected to ball milling treatment is a 300-mesh sieve, standing after sieving, removing supernatant, and drying and crushing to obtain the glass powder.
Compared with the example 2, the temperature of the smelting is different, and the smelting temperature is 1250 ℃; compared with the example 2, the temperature of the smelting is only different, and the smelting temperature is 850 ℃; compared with the example 2, the smelting time is different, and is 150min; compared with the example 2, the smelting time is different, and is 30min in the comparative example 10; compared with the example 2, the ball milling time is different in the comparative example 11 and is 20h; comparative example 12 compared with example 2, the ball milling time was 4h, which was different from that of example 2.
The glass powder prepared in the examples and the comparative examples is applied to silver paste of a TOPCon battery, and the TOPCon battery silver paste comprises the following components in parts by weight: 81 parts of silver powder, 1 part of metal oxide, 2 parts of nano silver powder, 2 parts of glass powder and 10 parts of organic adhesive.
Test example 1
The effects of examples and comparative examples on the electrical properties of the batteries are shown in table 3:
TABLE 3 influence of examples and comparative examples on the electrical properties of batteries
It can be seen from the table that, in the examples 1 to 3, compared with the comparative examples 1 to 3, as the content of lead is reduced, the contact resistivity is increased, the metal recombination is reduced, and when the content of lead is 25% to 50%, the contact resistivity and the metal recombination reach a better balance, because PbO itself has a better silver melting capability, it is beneficial to improve the contact when the content is increased, but the etching level of the glass powder to the passivation layer on the back surface of the silicon wafer is increased while the content of lead is increased, the silicon wafer is excessively corroded, and the efficiency is reduced.
Although it is theoretically better that the metal composition and the contact resistivity are smaller, the corrosion degree is smaller while the metal composition is reduced, that is, the contact resistivity is larger, so that the balance between the metal composition and the contact resistivity can only be considered, that is, the contact lift caused by corrosion is larger than the loss of the metal composition.
Compared with comparative examples 4 to 6, in examples 1 to 3, when the content of molybdenum oxide is 0% to 10%, the contact resistivity is substantially flat, and when the content of molybdenum oxide is 12%, the contact resistivity is obviously increased; when the content of molybdenum oxide is 2-10%, the metal composition is small, and when the content of molybdenum oxide is 0-1.5%, the metal composition is obviously increased, namely when the content of molybdenum oxide is 2-10%, the contact resistivity and the metal composition reach a good balance, because molybdenum oxide can improve the softening point of glass powder and improve the wetting capacity of glass liquid, silver microcrystals are separated on a silicon wafer by driving silver sol, so that the contact is promoted by increasing the content of molybdenum oxide, but when the content of molybdenum oxide is more than 10%, the fluidity of glass is too large, the damage caused by corrosion to the silicon wafer is lower than the gain caused by contact promotion of the silicon wafer, and therefore the content of molybdenum oxide is preferably 2-10%.
Test example 2
The results of the glass frit property tests are shown in table 4, and the effects of the examples and comparative examples on the electrical properties of the battery are shown in table 5:
TABLE 4 glass powder Performance test results
As can be seen from Table 4, in examples 1 to 3, the softening points within the selected process range are all 550 ℃, the D50 is between 0.8 and 1.0, the powder does not fall off after drying, and the EL is qualified after sintering.
Compared with the comparative examples 7 and 8, the comparative example 7 shows that the softening point of the glass powder is reduced and the powder falling phenomenon is obvious after drying when the temperature of the smelting furnace is increased and is higher than 1100 ℃, because when the temperature of the smelting furnace is too high, a formed glass system is fragile, the softening point of the finished glass powder is reduced, the thermal stability of the glass powder is reduced, the thermal expansion coefficient is increased, and the powder falling phenomenon occurs during drying; as can be seen from the comparative example 8, when the melting time is 850 ℃, the glass powder cannot be completely fused together to form a complete glass system due to the excessively low melting temperature, and the problem of powder falling occurs when the glass powder is applied to TOPCon back surface silver paste and is in poor contact with the back surface of a silicon wafer; therefore, the furnace temperature is preferably 900 to 1100 ℃.
Compared with comparative examples 9 and 10, the comparative example 9 shows that when the melting time is 150min, the softening point of the glass powder is reduced along with the increase of the melting time, and the powder falling phenomenon after drying is obvious, because the stability of a glass system is reduced and a glass network becomes fragile when the glass liquid is kept at a high temperature for a long time, loose and porous glass slag fragments are obtained after the glass liquid is poured out and subjected to cold quenching, the softening point of the glass powder is lower after the glass powder is prepared into a finished product, the thermal stability is poor, and the powder falling phenomenon is easy to occur after the glass powder is applied to silver paste and dried; when the smelting time is 30min, the glass powder is not fused together for enough time, so that the glass system is incomplete, the performance of the formed finished glass powder is poor, and the problem of powder falling occurs when the glass powder is applied to TOPCon back silver paste; therefore, the melting time is preferably 60 to 120min.
Compared with the embodiments 11 and 12, as can be seen from the comparative example 11, along with the increase of the ball milling time, the softening point of the glass powder is reduced, the diameter of the glass powder particles is reduced, and the powder falling phenomenon occurs when the ball milling time is 20 hours, because the too long ball milling time can cause the particle diameter of the finished glass powder to be too small, when the glass powder is applied to the silver paste, the filling compactness is high, the space left for the organic binder is reduced, the fluidity is poor, the flowing of the slurry before sintering and the adhesion of the silver grid lines after drying are determined to a large extent by the organic binder, the organic binder is not easy to flow, and the drying of the slurry is not uniform, so that the silver grid lines are partially dropped, and the EL is unqualified; as can be seen from comparative example 12, when the ball milling time was 4 hours, the large-particle glass powder in the formed finished glass powder was more, resulting in poor filling when applied to TOPCon backside silver paste, and voids were easily formed in the gate lines during drying, resulting in powder dropping; therefore, the ball milling time is preferably 6 to 18 hours.
TABLE 5 influence of examples and comparative examples on the electrical properties of batteries
| Contact resistivity (m omega cm) 2 ) | Metal composite (fA/cm 2) | |
| Example 1 | 0.45 | 105 |
| Example 2 | 0.39 | 115 |
| Example 3 | 0.36 | 124 |
| Comparative example 7 | 0.42 | 158 |
| Comparative example 8 | 0.58 | 168 |
| Comparative example 9 | 0.37 | 155 |
| Comparative example 10 | 0.65 | 185 |
| Comparative example 11 | 0.55 | 165 |
| Comparative example 12 | 0.85 | 165 |
As can be seen from the table, in the examples 1 to 3, compared with the comparative examples 7 and 8, the contact resistivity is gradually reduced along with the increase of the smelting furnace temperature, and the metal composition is firstly reduced and then increased; when the smelting time is 850 ℃, the glass powder cannot obtain enough energy because the smelting temperature is too low, so that the glass powder cannot be completely fused together to form a complete glass system, and when the glass powder is applied to TOPCon back silver paste, the glass powder cannot form good contact with the back surface of a silicon wafer, so that the performance is poor. Namely, when the temperature of the smelting furnace is 900-1100 ℃, the obtained glass powder can balance the contact resistivity and the metal compounding.
Compared with comparative examples 9 and 10, in examples 1 to 3, the contact resistivity is gradually reduced with the increase of the smelting time, and the metal recombination is firstly reduced and then increased; when the smelting time is 30min, the glass powder is not fused together for enough time, so that the glass system is incomplete, the performance of the formed finished glass powder is poor, the contact resistance is high when the glass powder is applied to TOPCon back silver paste, and meanwhile, the metal recombination is obviously increased, so that the comprehensive performance is poor. Namely, when the smelting time is 60-120min, a better smelting effect can be obtained, and if the smelting time is continuously increased, although the contact resistivity tends to be reduced to a small extent, the metal recombination increase extent is obvious, and obviously is not suitable.
Compared with the comparative examples 11 and 12, the examples 1 to 3 have the advantages that the contact resistivity is gradually reduced and the metal recombination is gradually increased along with the increase of the ball milling time, and the metal recombination change is obvious when the ball milling time is increased to 20 hours from 15 hours, because the particle diameter of the glass powder is too small due to too long ball milling time, the corrosivity of the glass powder to the silicon wafer is too large, and the contact is not obviously improved; when the ball milling time is 4 hours, large-particle glass powder in the formed finished glass powder is more, so that when the glass powder is applied to TOPCon back silver paste, the glass powder is difficult to form good contact with the back surface of a silicon wafer, the contact resistivity is higher, the metal compounding is not reduced, and the final performance is poor. Therefore, the ball milling time is preferably 6 to 18 hours.
Experimental example 3 client test results
The glass frit prepared in example 2 was applied to TOPCon battery silver paste as examples 4-6, where the silver paste formulations are shown in table 6:
table 6 selection of parts by weight of components in TOPCon battery silver pastes of examples 4-6
The client test results are shown in table 7:
TABLE 7 client test results
Of all electrical performance parameters, only voltage and current are measured values, and the others are calculated values. The short-circuit current means that when the positive electrode and the negative electrode of the solar cell are short-circuited and U =0 is obtained, the current at the moment is the short-circuit current of the cell, and the short-circuit current changes along with the change of the light intensity; the open-circuit voltage refers to that when the positive electrode and the negative electrode of the solar cell are not connected with a load and I =0, the voltage between the positive electrode and the negative electrode of the solar cell is the open-circuit voltage; the cell conversion efficiency is the most important parameter of the crystalline silicon solar cell, and refers to the ratio of the maximum output power of the solar cell when the solar cell is illuminated to the solar energy power irradiated on the cell; the fill factor is an important parameter for evaluating the output characteristics of the solar cell, and the higher the fill factor value is, the more the output characteristics of the solar cell tend to be rectangular, and the higher the photoelectric conversion efficiency of the cell is.
As can be seen from table 7, the optimized glass powder and silver paste have an average effect improvement of 0.1% in the client test result; the contact resistivity and the metal composite performance are superior to those of a comparison sample, and the comparison sample refers to TOPCon back silver paste applied to a production line. The composition and the manufacturing process of the glass powder are optimized, the balance of contact resistivity and metal composition can be well considered when the glass powder is applied to TOPCon, the powder falling phenomenon is avoided after drying, and the performance stability of the battery piece is improved.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (6)
1. The glass powder is characterized by comprising the following components in parts by weight: 38 parts of lead oxide, 30 parts of tellurium oxide, 17 parts of bismuth oxide, 4 parts of molybdenum oxide, 4 parts of silicon dioxide, 3.5 parts of boron oxide, 2 parts of alkaline earth metal oxide, 3.5 parts of alkali metal oxide and 1.5 parts of rare earth metal oxide;
the alkali metal oxide is at least one of lithium oxide, potassium oxide and sodium oxide; the alkaline earth metal oxide is at least one of magnesium oxide, calcium oxide and barium oxide;
the preparation method of the glass powder comprises the following steps:
(1) Weighing lead oxide, tellurium oxide, bismuth oxide, molybdenum oxide, silicon dioxide, boron oxide, alkaline earth metal oxide, alkali metal oxide and rare earth metal oxide, uniformly dispersing, smelting in a high-temperature furnace, taking out purified water, quenching and cooling to obtain light yellow fragments A;
(2) Performing ball milling treatment on the light yellow fragment A obtained in the step (1), sieving, standing, removing supernatant, drying and crushing to obtain the glass powder;
in the step (1), the smelting temperature is 900-1100 ℃, and the smelting time is 60-120min; in the step (2), the ball milling time is 6-18h, the sieve after ball milling treatment is a 300-mesh sieve, and the particle size D50 of the glass powder is 0.8-1.0 μm.
2. Use of the glass frit of claim 1 in TOPCon battery silver paste.
3. A TOPCon battery silver paste comprising the glass frit of claim 1.
4. The TOPCon battery silver paste of claim 3, comprising the following components in parts by weight: 81-91 parts of spheroidal silver powder, 0.3-1.5 parts of metal oxide, 0.7-2.5 parts of nano silver powder, 1-4 parts of glass powder and 7-11 parts of organic adhesive;
the average grain diameter of the sphere-like silver powder is 0.8-2.8 μm.
5. The TOPCon battery silver paste of claim 4, wherein the metal oxide is at least one of bismuth oxide, lead oxide, antimony oxide, molybdenum oxide, the particle size D50 of the metal oxide is 0.6-1.0 μm; the average grain diameter of the nano silver powder is 300-700nm; the organic binder includes a solvent, a thickener, a plasticizer, and a thixotropic agent.
6. The preparation method of TOPCon battery silver paste as claimed in claim 4 or 5, characterized by comprising the following steps: and weighing the sphere-like silver powder, the metal oxide, the nano silver powder, the glass powder and the organic adhesive, and grinding to obtain the TOPCon battery silver paste.
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| CN113979641B (en) * | 2021-10-15 | 2022-10-04 | 广州市儒兴科技股份有限公司 | Glass powder, preparation method thereof and battery silver paste with wide application window |
| CN114409262B (en) * | 2022-02-09 | 2023-05-16 | 广州市儒兴科技股份有限公司 | Conductive glass powder and preparation method thereof, conductive slurry and preparation method and application thereof |
| CN115073011B (en) * | 2022-04-27 | 2023-07-07 | 中南大学 | Low-lead glass powder, preparation method and application thereof, back silver paste and application thereof |
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| JPH01138150A (en) * | 1987-11-25 | 1989-05-31 | Ohara Inc | Low-melting glass |
| JPH11106236A (en) * | 1997-10-02 | 1999-04-20 | Nippon Electric Glass Co Ltd | Low melting point glass for magnetic head |
| KR100772501B1 (en) * | 2005-06-30 | 2007-11-01 | 한국전자통신연구원 | Tellurite glass composite, optical waveguide and optical amplifier using the same |
| KR101518500B1 (en) * | 2012-12-21 | 2015-05-11 | 제일모직주식회사 | Glass frit, electrode paste composition comprising the same, and electrode prepared using the same |
| KR101608123B1 (en) * | 2013-09-13 | 2016-03-31 | 제일모직주식회사 | Composition for forming solar cell electrode and electrode prepared using the same |
| CN105097071B (en) * | 2015-07-22 | 2017-01-25 | 深圳市春仰科技有限公司 | Positive conductive silver paste of silicon solar cell and preparation method of positive conductive silver paste |
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| CN107673623B (en) * | 2017-08-28 | 2020-09-15 | 广州市儒兴科技开发有限公司 | Glass powder for double-sided PERC aluminum paste and preparation method thereof |
| CN109659064B (en) * | 2018-12-07 | 2020-06-12 | 浙江中希电子科技有限公司 | Front silver paste with high tensile force for crystalline silicon Perc battery and preparation process thereof |
| CN111599509B (en) * | 2019-02-21 | 2022-04-26 | 大州电子材料 | Paste composition for solar cell front electrode and preparation method thereof |
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