CN114334215A - Electrode slurry for ohmic contact of P-type emitter region of silicon solar cell - Google Patents
Electrode slurry for ohmic contact of P-type emitter region of silicon solar cell Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 42
- 239000010703 silicon Substances 0.000 title claims abstract description 42
- 239000011267 electrode slurry Substances 0.000 title description 18
- 239000000843 powder Substances 0.000 claims abstract description 79
- 239000011521 glass Substances 0.000 claims abstract description 41
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000654 additive Substances 0.000 claims abstract description 26
- 230000000996 additive effect Effects 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 229910052709 silver Inorganic materials 0.000 claims abstract description 19
- 239000004332 silver Substances 0.000 claims abstract description 19
- 239000010953 base metal Substances 0.000 claims abstract description 13
- 239000002003 electrode paste Substances 0.000 claims abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 6
- 239000001856 Ethyl cellulose Substances 0.000 claims description 5
- 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 5
- 229910006776 Si—Zn Inorganic materials 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 229920001249 ethyl cellulose Polymers 0.000 claims description 5
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 5
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 4
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 4
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 claims description 3
- 229940063655 aluminum stearate Drugs 0.000 claims description 3
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-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
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 3
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 238000000889 atomisation Methods 0.000 claims description 2
- FPHIOHCCQGUGKU-UHFFFAOYSA-L difluorolead Chemical compound F[Pb]F FPHIOHCCQGUGKU-UHFFFAOYSA-L 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 229920005749 polyurethane resin Polymers 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 239000002562 thickening agent Substances 0.000 claims description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 2
- 238000005245 sintering Methods 0.000 abstract description 27
- 238000000034 method Methods 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 229910017982 Ag—Si Inorganic materials 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000002002 slurry Substances 0.000 description 24
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 238000002161 passivation Methods 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910004205 SiNX Inorganic materials 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 235000013350 formula milk Nutrition 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical group CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 235000020610 powder formula Nutrition 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229940116411 terpineol Drugs 0.000 description 3
- 239000013008 thixotropic agent Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 1
- XNRNVYYTHRPBDD-UHFFFAOYSA-N [Si][Ag] Chemical compound [Si][Ag] XNRNVYYTHRPBDD-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
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- Photovoltaic Devices (AREA)
Abstract
The invention discloses an electrode paste for ohmic contact of a P-type emitter region of a silicon solar cell, which comprises the following components in percentage by weight: 78-89 parts of metal silver powder, 2-10 parts of base metal powder, 0.5-5 parts of glass powder, 0.5-3 parts of additive and 8-12 parts of organic carrier. The additive developed by the invention is effectively matched with base metal powder and glass powder, can obviously enhance the corrosion effect of glass in the sintering process, and solves the problem of Al2O3The film is difficult to corrode, so that the contact of silver and silicon is better, and the Ag-Si contact resistance of the P-type emitting region is effectively reduced. Meanwhile, base metal powder is used for replacing part of silver powder, so that the cost of the electrode paste is reduced.
Description
Technical Field
The invention relates to the technical field of silicon solar cells, in particular to electrode slurry for ohmic contact of a P-type emitter region of a silicon solar cell.
Background
The solar cell can convert light energy into electric energy, is a novel environment-friendly renewable energy source, and has wide application prospect. Currently, the main stream of the crystalline silicon battery is a P-type battery, but because the matrix of the crystalline silicon battery is doped with boron, a boron-oxygen pair can be formed and efficiency attenuation is caused, but the problem can not occur in an N-type silicon battery. Compared with P-type silicon, N-type silicon has a longer minority carrier lifetime and a photoelectric conversion efficiency of over 24%, and is the development direction of future solar cells. Since the emitter region of the N-type cell is P-type silicon, if the emitter region of the P-type silicon-based cell is still in contact with the slurry, the contact resistance is very high, which causes the series resistance of the cell to be too high and the conversion efficiency to be reduced, so that the key material of the N-type cellOne of them is to develop a positive electrode paste capable of forming a good ohmic contact with the P-type emitter region. The passivation layer of the N-type cell emitting region is usually inner Al2O3Composite structure of film plus outer SiNx film due to Al2O3The physical and chemical properties are stable, the composite film is more difficult to corrode compared with a positive SiNx film of a P-type battery, and the conventional positive silver paste is difficult to burn through the composite film and form ohmic contact with silicon. The selection of the glass material needs to be comprehensively considered for Al2O3+SiNxThe corrosion of the passivation layer, the bonding strength of silver powder and silicon wafers and other factors only depend on glass to limit the good ohmic contact effect formed by silver and silicon. Patent cn201510207.x adds aluminum-silicon alloy powder to the electrode slurry to reduce contact resistance by alloying with P-type silicon. However, the additives of this patent contain only aluminum-silicon alloy powder, which is specific to Al2O3+SiNxThe corrosion of the passivation layer is limited, and the silicon contained in the alloy powder can inhibit the mutual expansion of aluminum and silicon on the surface of the silicon chip, so that the formed silver-silicon contact points are less, and good ohmic contact is difficult to form. In addition, since the bulk resistance of silicon is large, its introduction in a large amount causes the series resistance to become further large. Aiming at the problems, the invention develops the electrode slurry, and utilizes Pb-B-Si-Zn glass, base metal powder and an additive to improve the conversion efficiency of the N-type silicon battery and reduce the material cost.
The development of a glass frit and an additive which can etch the passivation layer and can form good ohmic contact with P-type silicon is a problem to be solved in the field.
Disclosure of Invention
In view of the above, the present invention develops an electrode paste for ohmic contact of P-type emitter region of silicon solar cell, which comprises the following components: silver metal powder, base metal powder, glass powder, an additive and an organic carrier. The invention designs the glass powder of the Pb-B-Si-Zn series material, which is used together with base metal powder and an additive, thereby realizing the improvement of the conversion efficiency of the N-type silicon battery and the reduction of the material cost. Wherein the additives comprise: metal organic compounds (e.g., stearates) which reduce glass melting, metal fluorides and boron powdersThe point is used for enhancing the corrosion of the point to the passivation layer; the metal fluoride can be mixed with Al which is not easy to corrode2O3Layer reaction to promote the silver and silicon to be in direct contact; and the base metal powder can form an alloy with silicon, so that the Ag-Si contact resistance is further reduced. The electrode slurry developed by the invention is screen-printed on the surface of a P-type emitting region of an N-type silicon cell and sintered, the electrode has good ohmic contact with silicon, the series resistance (Rs) of the cell (156 cell) is less than or equal to 1.5m omega, and the conversion efficiency of the cell is more than or equal to 23.8 percent.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an electrode paste for ohmic contact of a P-type emitter region of a silicon solar cell, the electrode paste comprising the following components (wt%): 78-89 parts of metal silver powder, 2-10 parts of base metal powder, 0.5-5 parts of glass powder, 0.5-3 parts of additive and 8-12 parts of organic carrier;
wherein the base metal powder comprises N2The aluminum powder prepared by the protective atomization method also comprises one or more of Ni powder, Cu powder, Sn powder and Sb powder;
the glass powder is Pb-B-Si-Zn glass, and the glass comprises the following components in percentage by weight: PbO 10-50, B2O310-30、SiO22-20、ZnO 5-30；
The glass powder also contains alkali metal oxide Li2O and Na2One or two of O, the addition amount is 1-5 wt%;
the glass powder also contains one or more of alkaline earth metals BaO, SrO and MgO, and the addition amount is 0.5-3 wt%;
the glass powder also contains transition metal oxides NiO and MnO2、TiO2、Cr2O3And Al2O3One or more of them, the addition amount is 0.5-3 wt%;
the glass powder also contains rare earth metal oxide Yb2O3、Sm2O3And Gd2O3One or more of them, the addition amount is 0.5-3 wt%;
the glass powder also contains AgO or AgNO3One or two of the components are added in an amount of 0.5 to 3 weight percent; the glass powder comprises the following components(wt％)：
The additive is prepared by mixing metal organic salt, metal fluoride and boron powder, wherein the metal organic salt is stearate comprising one or more of lithium stearate, zinc stearate and aluminum stearate, and the addition amount is 20-50 wt%; the metal fluoride comprises LiF, PbF2、BaF2One or more of them, the addition amount is 10-30 wt%; the boron powder is amorphous B powder or crystalline B powder with a particle size D500.5-2.0 μm, and 10-50 wt% of additive;
the additive comprises the following components in percentage by weight:
the organic carrier is composed of resin, solvent, thickener, plasticizer and surfactant, wherein the resin is one or more of ethyl cellulose, acrylic resin, organic silicon resin and polyurethane resin.
Preferably, the aluminum powder is spherical aluminum powder, and the particle diameter D of the aluminum powder50Is 1-6 μm.
Preferably, the Ni powder, the Cu powder, the Sn powder and the Sb powder are spherical powder, and the particle diameter D of the spherical powder50Is 0.3-2.0 μm.
Preferably, the silver powder is one of spherical or spheroidal powder, and the particle diameter D of the silver powder501.2-1.8 μm, tap density > 5.0g/cm3。
The invention has the following beneficial effects:
the Pb-B-Si-Zn glass designed by the invention has lower melting point (350-2O3+SiNxThe passivation film makes the silver in the slurry directly contact with the silicon, and meanwhile, the glass has good sintering aiding effect, is beneficial to forming a compact silver conductive film and has good electrode adhesion.
The aluminum powder and other base metal powder are added in the slurry formula, so that the conversion efficiency of the battery is improved and the cost of the slurry is reduced. The silver is used as a noble metal, the cost of the silver paste is higher, and the added aluminum powder and other metal powder (copper powder, nickel powder and the like) can obviously reduce the cost of the electrode paste. Meanwhile, the added aluminum powder and base metal powder have lower melting points and are easy to form alloy with silicon, thereby being beneficial to reducing the ohmic contact resistance of the electrode.
The additive can obviously enhance the corrosion effect of glass in the sintering process and solve the problem of Al2O3The film is difficult to corrode, so that the contact between silver and silicon is better, and the contact resistance is effectively reduced. After the electrode slurry is printed on the surface of a P-type emitting region of an N-type silicon crystal solar cell and sintered, the conversion efficiency of the cell is more than or equal to 23.8 percent, and the cost is lower.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment 1 of the invention discloses electrode slurry for ohmic contact of a P-type emitter region of a silicon solar cell (100 g is prepared), and the production process comprises the following steps:
(1) glass powder formula (100 g prepared): PbO 45g, B2O317g，SiO27g，ZnO 15g，Li2O 4g，BaO 3g，Al2O33g，Yb2O33g，Ag2O 3g；
(2) The glass melting and ball milling process comprises the following steps: quenching and ball-milling to less than 2um at 1000 ℃ for 30 min;
(3) the metal silver powder is spherical silver powder prepared by silver nitrate wet chemical reduction method, and the particle diameter of the silver powder is D501.5 μm;
(4) the metal aluminum powder is spherical aluminum powder prepared by adopting a nitrogen protection melting spraying method, and the aluminumParticle diameter D of the powder50Is 6 μm;
(5) other alkali metal powders are Ni powders having a particle diameter D50Is 1 μm;
(6) additive formula (10 g prepared): 5g of lithium stearate, 3g of LiF and 2g of B powder;
(7) the organic carrier consists of an organic solvent, resin, a thixotropic agent, a diluent and the like, wherein the organic solvent is diethylene glycol butyl ether acetate and terpineol, and the organic resin is ethyl cellulose and acrylic acid;
(8) preparing slurry: weighing 76.5g of metal silver powder, 2.5g of metal aluminum powder, 5g of metal nickel powder, 4g of glass powder, 1g of additive and 11g of organic carrier, stirring and mixing uniformly by using a double-planet stirrer, and then rolling for 3-6 times by using a three-roll grinder to obtain the electrode slurry.
The electrode slurry prepared above was subjected to the following performance tests:
1. the technical indexes of the slurry are as follows:
viscosity: 160-270 Pa.s (24-26 ℃, 20 rpm);
fineness of the slurry: less than or equal to 10 mu m;
2. performance of the battery after sintering:
the prepared slurry is screen-printed on the surface of a P-type emitting area of an N-type cell (the side length of a cell piece is 156mm), an infrared tunnel sintering furnace is used for sintering, the sintering peak temperature is 760 ℃, a silver electrode is formed on the surface of the P-type emitting area after sintering, and the cell is subjected to electrical performance test (the same slurry is printed on 5 sample silicon chips, and the series resistance and the conversion efficiency of 5 samples are respectively tested), and the results are shown in the following table 1:
TABLE 1
| Electrical property parameter | Series resistance Rs (m omega) | Conversion efficiency Eff (%) |
| Sample 1 | 1.29 | 23.82 |
| Sample 2 | 1.30 | 23.76 |
| Sample 3 | 1.27 | 23.81 |
| Sample No. 4 | 1.25 | 23.83 |
| Sample No. 5 | 1.26 | 23.87 |
| Mean value of | 1.274 | 23.818 |
The test result shows that the average value of the series resistance of the battery is 1.274m omega, and the average value of the conversion efficiency is 23.818%. The additive well corrodes the passivation layer of the N-type cell, the slurry does not burn through a PN junction during sintering, the silver electrode and silicon form good ohmic contact, and the prepared N-type solar cell is high in conversion efficiency.
Example 2
The embodiment 2 of the invention discloses electrode slurry for ohmic contact of a P-type emitter region of a silicon solar cell (100 g is prepared), and the production process comprises the following steps:
(1) glass powder formula (preparation 100g)：PbO 22g，B2O330g，SiO220g,ZnO 12g，Na2O 4g，SrO 3g，TiO23g,Gd2O33g,AgNO33g；
(2) The glass melting and ball milling process comprises the steps of quenching and ball milling to less than 2um at the temperature of 1000 ℃ for 30 min;
(3) the metal silver powder is spherical silver powder prepared by silver nitrate wet chemical reduction method, and the particle diameter of the silver powder is D501.8 μm;
(4) the metal aluminum powder is spherical aluminum powder prepared by adopting a nitrogen protection melting spraying method, and the particle diameter of the aluminum powder is D50Is 2 μm;
(5) other alkali metal powders are Cu powders having a particle diameter D50Is 1 μm;
(6) additive formula (10 g prepared): zinc stearate 2g, PbF23g, 5g of B powder;
(7) the organic carrier consists of an organic solvent, resin, a thixotropic agent, a diluent and the like, wherein the organic solvent is diethylene glycol butyl ether acetate and terpineol, and the organic resin is ethyl cellulose and acrylic acid;
(8) preparing slurry: weighing 78g of metal silver powder, 5.0g of metal aluminum powder, 5g of metal copper powder, 1g of glass powder, 3g of additive and 8g of organic carrier, stirring and mixing uniformly by using a double-planet stirrer, and then rolling for 3-6 times by using a three-roll grinder to obtain the electrode slurry.
The electrode slurry prepared above was subjected to the following performance tests
1. The technical indexes of the slurry are as follows:
viscosity: 160-260 Pa.s (24-26 ℃, 20 rpm);
fineness of the slurry: less than or equal to 10 mu m;
2. performance of the battery after sintering:
the prepared slurry is screen-printed on the surface of a P-type emitting area of an N-type cell (the side length of a cell piece is 156mm), an infrared tunnel sintering furnace is used for sintering, the sintering peak temperature is 760 ℃, a silver electrode is formed on the surface of the P-type emitting area after sintering, and the cell is subjected to electrical performance test (the same slurry is printed on 5 sample silicon chips, and the series resistance and the conversion efficiency of 5 samples are respectively tested), and the results are shown in the following table 2:
TABLE 2
| Electrical property parameter | Series resistance Rs (m omega) | Conversion efficiency Eff (%) |
| Sample 1 | 1.35 | 23.77 |
| Sample 2 | 1.32 | 23.79 |
| Sample 3 | 1.30 | 23.82 |
| Sample No. 4 | 1.29 | 23.83 |
| Sample No. 5 | 1.37 | 23.68 |
| Mean value of | 1.326 | 23.778 |
The test result shows that the average value of the series resistance of the battery is 1.326m omega, and the average value of the conversion efficiency is 23.778%. The additive well corrodes the passivation layer of the N-type cell, the slurry does not burn through a PN junction during sintering, the silver electrode and silicon form good ohmic contact, and the prepared N-type cell is high in conversion efficiency.
Example 3
The embodiment 3 of the invention discloses electrode slurry for ohmic contact of a P-type emitter region of a silicon solar cell (100 g is prepared), and the production process comprises the following steps:
(1) glass powder formula (100 g prepared): PbO 30g, B2O320g，SiO212g，ZnO 13g，Li2O 2g，Na2O 1g，MgO 1g，SrO 2g，Cr2O31g，TiO22g，Sm2O32g，Gd2O31g，Ag2O 2g，AgNO31g；
(2) The glass melting and ball milling process comprises the following steps: quenching and ball-milling to less than 2um at 1000 ℃ for 30 min;
(3) the metal silver powder is spherical silver powder prepared by a silver nitrate wet chemical reduction method, and the particle size D50 of the silver powder is 1.6 mu m;
(4) the metal aluminum powder is spherical aluminum powder prepared by a nitrogen protection melting spraying method, and the particle size D50 of the aluminum powder is 4 mu m;
(5) the other alkali metal powder adopts tin powder and nickel powder, and the particle size D50 is 1 mu m;
(6) additive formula (10 g prepared): 2g of aluminum stearate, 2g of zinc stearate and BaF21g，PbF 21g, 4g of B powder;
(7) the organic carrier consists of an organic solvent, resin, a thixotropic agent, a diluent and the like, wherein the organic solvent is diethylene glycol butyl ether acetate and terpineol, and the organic resin is ethyl cellulose and acrylic acid;
(8) preparing slurry: weighing 76g of metal silver powder, 4.0g of metal aluminum powder, 2g of metal nickel powder, 3g of metal tin powder, 3g of glass powder, 2g of additive and 10g of organic carrier, stirring and mixing uniformly by using a double-planet stirrer, and then rolling for 3-6 times by using a three-roll grinder to obtain the electrode slurry.
The electrode slurry prepared above was subjected to the following performance tests
1. The technical indexes of the slurry are as follows:
viscosity: 160-260 Pa.s (24-26 ℃, 20 rpm);
fineness of the slurry: less than or equal to 10 mu m;
2. performance of the battery after sintering:
the prepared slurry is screen-printed on the surface of a P-type emitting area of an N-type cell (the side length of a cell piece is 156mm), an infrared tunnel sintering furnace is used for sintering, the sintering peak temperature is 760 ℃, a silver electrode is formed on the surface of the P-type emitting area after sintering, and the cell is subjected to electrical performance test (the same slurry is printed on 5 sample silicon chips, and the series resistance and the conversion efficiency of 5 samples are respectively tested), and the results are shown in the following table 3:
TABLE 3
| Electrical property parameter | Series resistance Rs (m omega) | Conversion efficiency Eff (%) |
| Sample 1 | 1.25 | 23.82 |
| Sample 2 | 1.28 | 23.80 |
| Sample 3 | 1.22 | 23.92 |
| Sample No. 4 | 1.27 | 23.81 |
| Sample No. 5 | 1.26 | 23.84 |
| Mean value of | 1.256 | 23.838 |
The test result shows that the average value of the series resistance of the battery is 1.256m omega, and the average value of the conversion efficiency is 23.838%. The additive well corrodes the passivation layer of the N-type cell, the slurry does not burn through a PN junction during sintering, the silver electrode and silicon form good ohmic contact, and the prepared N-type solar cell is high in conversion efficiency.
Comparative example:
the method comprises the steps of screen printing a common P-type emitting region electrode slurry on the market at present on the surface of a P-type emitting region of an N-type battery (the side length of a battery piece is 156mm), sintering the P-type emitting region by using an infrared tunnel sintering furnace, wherein the sintering peak temperature is 760 ℃, forming a silver electrode on the surface of the P-type emitting region after sintering, and testing the electrical properties of the battery (the same slurry is printed on 5 sample silicon chips, and the series resistance and the conversion efficiency of 5 samples are respectively tested), wherein the results are shown in the following table 4:
TABLE 4
The test results showed that the average value of the series resistance of the cell was 1.356m Ω, the average value of the conversion efficiency was 23.542%, the cell was significantly larger than the series resistance of the above examples 1-3, and the conversion efficiency was significantly lower.
The invention develops an electrode paste for Al2O3+SiNxThe passivation layer has good corrosion effect, PN junctions cannot be damaged during sintering, and the electrode silver and the silicon can form good ohmic contact. The additive has a low melting point (350-. The paste is printed on the surface of the P-type emitting region of the N-type cell through a screen printing process, and after sintering, the paste and the P-type emitting region of the cell can form good ohmic contact, and the paste has low contact resistance and high conversion efficiency. Test results show that the efficiency of the battery manufactured by the slurry researched and developed by the invention is superior to the conversion efficiency of the common P-type emitter contact electrode slurry on the market at present, and the cost is lower.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (4)
1. An electrode paste for ohmic contact of a P-type emitter region of a silicon solar cell, the electrode paste comprising the following components (wt%): 78-89 parts of metal silver powder, 2-10 parts of base metal powder, 0.5-5 parts of glass powder, 0.5-3 parts of additive and 8-12 parts of organic carrier;
wherein the base metal powder comprises N2The aluminum powder prepared by the protective atomization method also comprises one or more of Ni powder, Cu powder, Sn powder and Sb powder;
the glass powder is Pb-B-Si-Zn glass, and the glass comprises the following components in percentage by weight: PbO 10-50, B2O3 10-30、SiO22-20、ZnO 5-30；
The glass powder also containsWith alkali metal oxides Li2O and Na2One or two of O, the addition amount is 1-5 wt%;
the glass powder also contains one or more of alkaline earth metals BaO, SrO and MgO, and the addition amount is 0.5-3 wt%;
the glass powder also contains transition metal oxides NiO and MnO2、TiO2、Cr2O3And Al2O3One or more of them, the addition amount is 0.5-3 wt%;
the glass powder also contains rare earth metal oxide Yb2O3、Sm2O3And Gd2O3One or more of them, the addition amount is 0.5-3 wt%;
the glass powder also contains AgO or AgNO3One or two of the components are added in an amount of 0.5 to 3 weight percent;
the additive is prepared by mixing metal organic salt, metal fluoride and boron powder, wherein the metal organic salt is stearate comprising one or more of lithium stearate, zinc stearate and aluminum stearate, and the addition amount is 20-50 wt%; the metal fluoride comprises LiF, PbF2、BaF2One or more of them, the addition amount is 10-30 wt%; the boron powder is amorphous B powder or crystalline B powder with a particle size D500.5-2.0 μm, and 10-50 wt% of additive;
the organic carrier is composed of resin, solvent, thickener, plasticizer and surfactant, wherein the resin is one or more of ethyl cellulose, acrylic resin, organic silicon resin and polyurethane resin.
2. The electrode paste for ohmic contact of P-type emitter region of silicon solar cell according to claim 1, wherein the aluminum powder is spherical aluminum powder, and the particle diameter D of the aluminum powder50Is 1-6 μm.
3. The electrode paste for ohmic contact of P-type emitter region of silicon solar cell as claimed in claim 1, wherein the Ni powder, Cu powder, Sn powder, Sb powder are spherical powders with a particle size D50Is 0.3-2.0 μm.
4. The electrode paste for ohmic contact of P-type emitter region of silicon solar cell according to claim 1, wherein said silver metal powder is one of spherical or spheroidal powder, and the particle diameter D of silver powder501.2-1.8 μm, tap density > 5.0g/cm3。
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Denomination of invention: An electrode paste for Ohmic contact in P-type emission region of silicon solar cells Granted publication date: 20231017 Pledgee: Wenzhou Bank Co.,Ltd. High tech Branch Pledgor: Zhejiang Youying Photoelectric Technology Co.,Ltd. Registration number: Y2024330000164 |