CN114334215B - 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 46
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 45
- 239000010703 silicon Substances 0.000 title claims abstract description 45
- 239000011267 electrode slurry Substances 0.000 title claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 73
- 239000011521 glass Substances 0.000 claims abstract description 42
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000654 additive Substances 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 230000000996 additive effect Effects 0.000 claims abstract description 22
- 239000010953 base metal Substances 0.000 claims abstract description 12
- 229910018072 Al 2 O 3 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
- 239000002003 electrode paste Substances 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 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
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910006776 Si—Zn 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
- 101710134784 Agnoprotein Proteins 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 4
- 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
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 229910016036 BaF 2 Inorganic materials 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
- 239000004014 plasticizer Substances 0.000 claims description 2
- 229920005749 polyurethane resin Polymers 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 2
- 229910052708 sodium 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 26
- 238000000034 method Methods 0.000 abstract description 14
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- XNRNVYYTHRPBDD-UHFFFAOYSA-N [Si][Ag] Chemical compound [Si][Ag] XNRNVYYTHRPBDD-UHFFFAOYSA-N 0.000 abstract description 4
- 229910017982 Ag—Si Inorganic materials 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 24
- 229910052709 silver Inorganic materials 0.000 description 14
- 239000004332 silver Substances 0.000 description 14
- 238000009472 formulation Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 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
- 238000011056 performance test Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 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
- 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
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229940116411 terpineol Drugs 0.000 description 3
- 239000013008 thixotropic agent Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- 229910004205 SiNX 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002156 mixing Methods 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
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Abstract
The invention discloses electrode slurry for ohmic contact of a P-type emission area 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 problems of Al 2 O 3 The problem of film corrosion resistance ensures better silver-silicon contact and effectively reduces the Ag-Si contact resistance of the P-type emission region. Meanwhile, the base metal powder is used for replacing part of silver powder, so that the cost of the electrode slurry 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 emission area 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 as the substrate is doped with boron, a boron-oxygen pair is formed and efficiency attenuation is caused, and the problem cannot occur in an N-type silicon battery. N-type silicon has longer minority carrier lifetime than P-type silicon, and the photoelectric conversion efficiency can exceed 24%, so that the N-type silicon is the development direction of future solar cells. Because the emitter region of the N-type battery is made of P-type silicon, if the paste is still used for contacting with the emitter region of the P-type silicon substrate battery, the contact resistance is very high, so that the series resistance of the battery is too high, the conversion efficiency is reduced, and therefore, one of the key materials of the N-type battery is to develop an anode paste which can form good ohmic contact with the P-type emitter region. The passivation layer of the N-type cell emission area is usually an inner layer of Al 2 O 3 Composite structure of film plus outer SiNx film due to Al 2 O 3 The physical and chemical properties are very stable, the composite film is more difficult to corrode compared with the SiNx film on the front surface of the 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 requires comprehensive consideration of Al 2 O 3 +SiN x The corrosiveness of the passivation layer has limited effect of forming good ohmic contact between silver and silicon only by glass due to factors such as the bonding strength of silver powder and silicon wafer. The patent cn20151017. X adds aluminum silicon alloy powder to the electrode paste to reduce contact resistance by alloying with P-type silicon. However, the additive contains only aluminum-silicon alloy powder, which is specific to Al 2 O 3 +SiN x The passivation layer has limited corrosion andsilicon contained in the alloy powder can inhibit mutual expansion of aluminum and silicon on the surface of the silicon wafer, so that formed silver-silicon contact points are fewer, and good ohmic contact is difficult to form. In addition, since the bulk resistance of silicon is large, its large introduction causes the series resistance to become further large. In order to solve the problems, the invention develops electrode slurry, and improves the conversion efficiency of the N-type silicon battery and reduces the material cost by using Pb-B-Si-Zn glass, base metal powder and additives.
Development of a glass frit and additive that can etch the passivation layer and form a good ohmic contact with P-type silicon is a problem to be solved in the art.
Disclosure of Invention
In view of this, the present invention has developed an electrode paste for ohmic contact of P-type emitter region of silicon solar cell, comprising the following components: silver powder, base metal powder, glass powder, additives and organic carriers. The invention designs the glass powder of Pb-B-Si-Zn series material, which is matched with base metal powder and additive for use, thereby improving the conversion efficiency of the N-type silicon battery and reducing the material cost. Wherein the additive comprises: the metal organic compound (such as stearate) can lower the melting point of the glass and strengthen the corrosion of the glass to the passivation layer; the metal fluoride can be combined with Al which is not easy to corrode 2 O 3 Layer reaction, promoting silver silicon to generate direct contact; and the base metal powder can form an alloy with silicon, so that the Ag-Si contact resistance is further reduced. After the electrode paste developed by the invention is screen printed on the surface of a P-type emission area of an N-type silicon battery and sintered, the electrode is in good ohmic contact with silicon, and the battery serial resistance (Rs) (156 battery pieces) is less than or equal to 1.5mΩ and the conversion efficiency of the battery pieces is more than or equal to 23.8 percent.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
an electrode paste for ohmic contact of a P-type emission region of a silicon solar cell, wherein the electrode paste 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;
wherein the base metalThe powder comprises N 2 Protecting aluminum powder prepared by an atomization method, and further comprising 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, B 2 O 3 10-30、SiO 2 2-20、ZnO 5-30；
The glass frit also contains alkali metal oxide Li 2 O and Na 2 One or two of O with the addition amount of 1-5wt%;
the glass powder also contains one or more of alkaline earth metals BaO, srO and MgO, and the addition amount is 0.5-3wt%;
the glass powder also contains transition metal oxide NiO, mnO 2 、TiO 2 、Cr 2 O 3 And Al 2 O 3 One or more of the components is/are added in an amount of 0.5-3wt%;
the glass powder also contains rare earth metal oxide Yb 2 O 3 、Sm 2 O 3 And Gd 2 O 3 One or more of the components is/are added in an amount of 0.5-3wt%;
the glass powder also contains AgO or AgNO 3 One or two of the components are added in an amount of 0.5-3wt%; the glass powder comprises the following components in percentage by weight:
the additive is prepared by mixing metal organic salt, metal fluoride and boron powder, wherein the metal organic salt is stearate, and comprises one or more of lithium stearate, zinc stearate and aluminum stearate, and the addition amount is 20-50wt%; the metal fluoride comprises LiF and PbF 2 、BaF 2 One or more of the components is/are added in an amount of 10-30wt%; the boron powder is amorphous B powder or crystalline B powder, and has a particle diameter D 50 0.5-2.0 μm, and the addition amount is 10-50wt%;
the additive comprises the following components in percentage by weight:
the organic carrier consists of resin, solvent, thickener, plasticizer and surfactant, wherein the resin is one or more of ethylcellulose, acrylic resin, organic silicon resin and polyurethane resin.
Preferably, the aluminum powder is spherical aluminum powder, and the particle diameter D of the aluminum powder 50 1-6 μm.
Preferably, the Ni powder, cu powder, sn powder and Sb powder are spherical powder with the particle diameter D 50 0.3-2.0 μm.
Preferably, the metal silver powder is one of spherical or spheroidal powder, and the particle diameter D of the silver powder 50 Is 1.2-1.8 mu m, and the tap density is more than 5.0g/cm 3 。
The beneficial effects of the invention are as follows:
the Pb-B-Si-Zn glass designed by the invention has low melting point (350-500 ℃) and can better corrode the Al of the P-type surface of the battery 2 O 3 +SiN x The passivation film enables silver in the slurry to be in direct contact with silicon, and meanwhile, the glass has good sintering assisting effect, is favorable for 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 battery conversion efficiency is improved, and the slurry cost is reduced. The silver is used as a noble metal, the cost of the silver paste is high, 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, are easy to form alloy with silicon, and are beneficial to reducing the ohmic contact resistance of the electrode.
The research and development of the additive can obviously enhance the corrosion effect of glass in the sintering process, and solve the problems of Al 2 O 3 The problem of film corrosion resistance makes silver-silicon contact better, effectively reducing contact resistance. After the electrode slurry is printed on the surface of the P-type emission area of the N-type silicon solar cell and sintered, the conversion efficiency of the cell is more than or equal to 23.8%, and the cost is lower.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment 1 of the invention discloses an electrode slurry (100 g) for ohmic contact of a P-type emitter region of a silicon solar cell, which comprises the following production processes:
(1) Glass powder formulation (formulation 100 g): pbO 45g, B 2 O 3 17g，SiO 2 7g，ZnO 15g，Li 2 O 4g，BaO 3g，Al 2 O 3 3g，Yb 2 O 3 3g，Ag 2 O 3g；
(2) Glass melting and ball milling processes: quenching and ball milling to less than 2um at 1000 ℃ for 30 min;
(3) Spherical silver powder prepared by adopting wet chemical reduction method of silver nitrate and having particle diameter D 50 1.5 μm;
(4) Spherical aluminum powder prepared by adopting nitrogen protection melting spray method for metal aluminum powder, and aluminum powder particle size D 50 Is 6 mu m;
(5) Other alkali metal powder adopts Ni powder with particle diameter D 50 1 μm;
(6) Additive formulation (formulation 10 g): 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: 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 are weighed, stirred and mixed uniformly by a double-planetary stirrer, and then the electrode slurry is obtained by rolling slurry for 3-6 times by a three-roller grinder.
The electrode slurry prepared above was subjected to the following performance test:
1. the technical index of the slurry is as follows:
viscosity: 160-270 Pa.s (24-26 ℃,20 rpm);
fineness of the slurry: less than or equal to 10 mu m;
2. cell performance after sintering:
the prepared slurry was screen-printed on the surface of a P-type emitter region of an N-type battery (the side length of a battery piece is 156 mm), and sintered in an infrared tunnel sintering furnace, wherein the peak temperature of sintering is 760 ℃, silver electrodes are formed on the surface of the P-type emitter region after sintering, and the battery was subjected to electrical performance test (the same slurry was printed on 5 sample silicon wafers, and series resistance and conversion efficiency of 5 samples were respectively tested), and the results are shown in the following table 1:
TABLE 1
| Electrical performance parameters | Series resistance Rs (mΩ) | Conversion efficiency Eff (%) |
| Sample 1 | 1.29 | 23.82 |
| Sample 2 | 1.30 | 23.76 |
| Sample 3 | 1.27 | 23.81 |
| Sample 4 | 1.25 | 23.83 |
| Sample 5 | 1.26 | 23.87 |
| Average value of | 1.274 | 23.818 |
The test result shows that the average value of the series resistance of the battery is 1.274mΩ, and the average value of the conversion efficiency is 23.818%. The additive well corrodes the passivation layer of the N-type solar cell, the PN junction is not burnt through by the slurry during sintering, good ohmic contact is formed between the silver electrode and silicon, and the prepared N-type solar cell has high conversion efficiency.
Example 2
The embodiment 2 of the invention discloses an electrode paste (100 g) for ohmic contact of a P-type emitter region of a silicon solar cell, which comprises the following production processes:
(1) Glass powder formulation (formulation 100 g): pbO 22g, B 2 O 3 30g，SiO 2 20g,ZnO 12g，Na 2 O 4g，SrO 3g，TiO 2 3g,Gd 2 O 3 3g,AgNO 3 3g；
(2) Glass melting and ball milling process, 1000 ℃,30min, quenching and ball milling to less than 2um;
(3) Spherical silver powder prepared by adopting wet chemical reduction method of silver nitrate and having particle diameter D 50 1.8 μm;
(4) Spherical aluminum powder prepared by adopting nitrogen protection melting spray method for metal aluminum powder, and aluminum powder particle size D 50 Is 2 mu m;
(5) Other alkali metal powder adopts Cu powder with particle diameter D 50 1 μm;
(6) Additive formulation (formulation 10 g): zinc stearate 2g, pbF 2 3g, 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: 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 are weighed, stirred and mixed uniformly by a double-planetary stirrer, and then the electrode slurry is obtained by rolling slurry for 3-6 times by a three-roller grinder.
The electrode slurry prepared above was subjected to the following performance test
1. The technical index of the slurry is as follows:
viscosity: 160-260 Pa.s (24-26 ℃,20 rpm);
fineness of the slurry: less than or equal to 10 mu m;
2. cell performance after sintering:
the prepared slurry was screen-printed on the surface of a P-type emitter region of an N-type battery (the side length of a battery piece is 156 mm), and sintered in an infrared tunnel sintering furnace, wherein the peak temperature of sintering is 760 ℃, a silver electrode is formed on the surface of the P-type emitter region after sintering, and the battery was subjected to an electrical performance test (the same slurry was printed on 5 sample silicon wafers, and series resistance and conversion efficiency of 5 samples were respectively tested), and the results are shown in the following table 2:
TABLE 2
| Electrical performance parameters | Series resistance Rs (mΩ) | Conversion efficiency Eff (%) |
| Sample 1 | 1.35 | 23.77 |
| Sample 2 | 1.32 | 23.79 |
| Sample 3 | 1.30 | 23.82 |
| Sample 4 | 1.29 | 23.83 |
| Sample 5 | 1.37 | 23.68 |
| Average value of | 1.326 | 23.778 |
The test result shows that the average value of the series resistance of the battery is 1.326mΩ, and the average value of the conversion efficiency is 23.778%. The additive well corrodes the passivation layer of the N-type solar cell, the PN junction is not burnt through by the slurry during sintering, good ohmic contact is formed between the silver electrode and silicon, and the prepared N-type solar cell has high conversion efficiency.
Example 3
The embodiment 3 of the invention discloses an electrode slurry (100 g) for ohmic contact of a P-type emitter region of a silicon solar cell, which comprises the following production processes:
(1) Glass powder formulation (formulation 100 g): pbO 30g, B 2 O 3 20g，SiO 2 12g，ZnO 13g，Li 2 O 2g，Na 2 O 1g，MgO 1g，SrO 2g，Cr 2 O 3 1g，TiO 2 2g，Sm 2 O 3 2g，Gd 2 O 3 1g，Ag 2 O 2g，AgNO 3 1g；
(2) Glass melting and ball milling processes: quenching and ball milling to less than 2um at 1000 ℃ for 30 min;
(3) The spherical silver powder prepared by adopting the wet chemical reduction method of silver nitrate is adopted as the metal silver powder, and the particle diameter D50 of the silver powder is 1.6 mu m;
(4) Spherical aluminum powder prepared by adopting nitrogen protection melting spray method is adopted for the metal aluminum powder, and the grain diameter D50 of the aluminum powder is 4 mu m;
(5) The other alkali metal powder adopts tin powder and nickel powder, and the particle diameter D50 of the powder is 1 mu m;
(6) Additive formulation (formulation 10 g): aluminum stearate 2g, zinc stearate 2g, baF 2 1g，PbF 2 1g of B powder 4g;
(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: 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 are weighed, stirred and mixed uniformly by a double-planetary stirrer, and then rolled into slurry by a three-roller grinder for 3-6 times to obtain electrode slurry.
The electrode slurry prepared above was subjected to the following performance test
1. The technical index of the slurry is as follows:
viscosity: 160-260 Pa.s (24-26 ℃,20 rpm);
fineness of the slurry: less than or equal to 10 mu m;
2. cell performance after sintering:
the prepared slurry was screen-printed on the surface of a P-type emitter region of an N-type battery (the side length of a battery piece is 156 mm), and sintered in an infrared tunnel sintering furnace, wherein the peak temperature of sintering is 760 ℃, a silver electrode is formed on the surface of the P-type emitter region after sintering, and the battery was subjected to an electrical performance test (the same slurry was printed on 5 sample silicon wafers, and series resistance and conversion efficiency of 5 samples were respectively tested), and the results are shown in the following table 3:
TABLE 3 Table 3
| Electrical performance parameters | Series resistance Rs (mΩ) | Conversion efficiency Eff (%) |
| Sample 1 | 1.25 | 23.82 |
| Sample 2 | 1.28 | 23.80 |
| Sample 3 | 1.22 | 23.92 |
| Sample 4 | 1.27 | 23.81 |
| Sample 5 | 1.26 | 23.84 |
| Average value of | 1.256 | 23.838 |
The test result shows that the average value of the series resistance of the battery is 1.256mΩ, and the average value of the conversion efficiency is 23.838%. The additive well corrodes the passivation layer of the N-type solar cell, the PN junction is not burnt through by the slurry during sintering, and the silver electrode and the silicon form good ohmic contact, so that the prepared N-type solar cell has high conversion efficiency.
Comparative example:
the electrode paste of the P-type emitter region which is common in the market at present is screen printed on the surface of the P-type emitter region of an N-type battery (the side length of a battery piece is 156 mm), the electrode paste is sintered by an infrared tunnel sintering furnace, the sintering peak temperature is 760 ℃, a silver electrode is formed on the surface of the P-type emitter region after sintering, and the battery is subjected to electrical performance test (the same paste is printed on 5 sample silicon wafers, and the series resistance and the conversion efficiency of 5 samples are respectively tested), so that the results are shown in the following table 4:
TABLE 4 Table 4
The test results showed that the series resistance of the cells was 1.356mΩ on average and 23.542% on average, and the cells were significantly larger than those of examples 1-3 described above, with significantly lower conversion efficiency.
The invention develops an electrode paste, which is specific to Al 2 O 3 +SiN x The passivation layer has good corrosion effect, the PN junction is not damaged during sintering, and the electrode silver and silicon can form good ohmic contact. The additive has a low melting point (350-500 ℃), can be matched with the sintering process of the slurry, has a wide slurry sintering temperature zone, and meets the sintering process requirements of the battery. The sizing agent is printed on the surface of the P-type emission area of the N-type battery through a screen printing process, and after sintering, the sizing agent and the P-type emission area of the battery can form good ohmic contact, so that the contact resistance is low, and the conversion efficiency is high. The test result shows that the efficiency of the battery manufactured by the slurry developed by the invention is better than the conversion efficiency of the conventional P-type emitter contact electrode slurry in 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 slurry for ohmic contact of a P-type emission area of a silicon solar cell, which is characterized by comprising 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;
wherein the base metal powder comprises N 2 Protecting aluminum powder prepared by an atomization method, and further comprising 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, B 2 O 3 10-30、SiO 2 2-20、ZnO 5-30；
The glass frit also contains alkali metal oxide Li 2 O and Na 2 One or two of O with the addition amount of 1-5wt%;
the glass powder also contains one or more of alkaline earth metals BaO, srO and MgO, and the addition amount is 0.5-3wt%;
the glass powder also contains transition metal oxide NiO, mnO 2 、TiO 2 、Cr 2 O 3 And Al 2 O 3 One or more of the components is/are added in an amount of 0.5-3wt%;
the glass powder also contains rare earth metal oxide Yb 2 O 3 、Sm 2 O 3 And Gd 2 O 3 One or more of the components is/are added in an amount of 0.5-3wt%;
the glass powder also contains AgO or AgNO 3 One or two of the components are added in an amount of 0.5-3wt%;
the additive componentThe metal organic salt is stearate, and comprises one or more of lithium stearate, zinc stearate and aluminum stearate, and the addition amount is 20-50wt%; the metal fluoride comprises LiF and PbF 2 、BaF 2 One or more of the components is/are added in an amount of 10-30wt%; the boron powder is amorphous B powder or crystalline B powder, and has a particle diameter D 50 0.5-2.0 μm, and the addition amount is 10-50wt%;
the organic carrier consists of resin, solvent, thickener, plasticizer and surfactant, wherein the resin is one or more of ethylcellulose, 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 with particle diameter D 50 1-6 μm.
3. The electrode paste for ohmic contact of P-type emitter region of silicon solar cell according to claim 1, wherein the Ni powder, cu powder, sn powder and Sb powder are spherical powder with particle diameter D 50 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 the metal silver powder is one of spherical or spheroidal powder, and the particle diameter D of the silver powder 50 Is 1.2-1.8 mu m, and the tap density is more than 5.0g/cm 3 。
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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 |
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