CN111415766B - Conductive paste for front electrode of solar cell, preparation method and application - Google Patents
Conductive paste for front electrode of solar cell, preparation method and application Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000011521 glass Substances 0.000 claims abstract description 109
- 239000000843 powder Substances 0.000 claims abstract description 107
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 23
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000009477 glass transition Effects 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 229910052681 coesite Inorganic materials 0.000 claims description 17
- 229910052906 cristobalite Inorganic materials 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 229910052682 stishovite Inorganic materials 0.000 claims description 17
- 229910052905 tridymite Inorganic materials 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052593 corundum Inorganic materials 0.000 claims description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- 239000003085 diluting agent Substances 0.000 claims description 11
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 229910017970 MgO-SiO2 Inorganic materials 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 6
- 229910003069 TeO2 Inorganic materials 0.000 claims description 6
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 239000013618 particulate matter Substances 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- 229910003460 diamond Inorganic materials 0.000 abstract description 16
- 239000010432 diamond Substances 0.000 abstract description 16
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 5
- 238000005530 etching Methods 0.000 abstract description 3
- 239000006060 molten glass Substances 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 238000005520 cutting process Methods 0.000 description 15
- 235000012431 wafers Nutrition 0.000 description 13
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 11
- 238000007639 printing Methods 0.000 description 8
- 238000005245 sintering Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920002545 silicone oil Polymers 0.000 description 6
- 239000001856 Ethyl cellulose Substances 0.000 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 description 5
- 229920001249 ethyl cellulose Polymers 0.000 description 5
- 235000019325 ethyl cellulose Nutrition 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- IFPMZBBHBZQTOV-UHFFFAOYSA-N 1,3,5-trinitro-2-(2,4,6-trinitrophenyl)-4-[2,4,6-trinitro-3-(2,4,6-trinitrophenyl)phenyl]benzene Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C(C=2C(=C(C=3C(=CC(=CC=3[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)C(=CC=2[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)=C1[N+]([O-])=O IFPMZBBHBZQTOV-UHFFFAOYSA-N 0.000 description 4
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 4
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000013008 thixotropic agent Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- FSCIDASGDAWVED-UHFFFAOYSA-N dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC FSCIDASGDAWVED-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
Classifications
-
- H01L31/022425—
-
- 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Photovoltaic Devices (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses conductive paste for a solar cell front electrode, which is added with 1.7-4% by mass of glass powder A and 0.1-1% by mass of glass powder B; the glass transition temperature of the glass powder A is 250-350 ℃; the glass transition temperature of the glass powder B is 350-450 ℃. The invention also discloses a preparation method of the conductive silver paste and a solar cell front electrode prepared by applying the conductive silver paste to a silicon wafer cut by a diamond wire. The conductive paste for the front electrode of the solar cell disclosed by the invention adopts the glass powder A and the glass powder B with different glass state softening temperatures as inorganic adhesives of the conductive paste, so that the adhesive property of the conductive paste on the surface of a silicon wafer is improved, the degree of etching the surface of the silicon wafer by molten glass powder in the conductive paste is improved, the doping is improved, the smaller the ohmic contact of a metal-semiconductor contact layer on the surface of the silicon wafer is, and the unit consumption ratio of the front electrode of the solar cell is reduced by 5-10%.
Description
Technical Field
The invention relates to the technical field of conductive silver paste, in particular to conductive paste for a front electrode of a solar cell, a preparation method and application.
Background
Since 2015, the cost of single crystal is rapidly reduced due to the introduction of diamond wire slices at the ends of silicon wafers, so that the market permeability is continuously increased, and the pressure is applied to the majority of industrial enterprises mainly including polycrystals. Compared with diamond wire cutting, the diamond wire cutting has been applied to the production of monocrystalline silicon wafers on a large scale, and polycrystalline slicing is still mainly performed by mortar cutting at present. The use of diamond wire cutting in the field of polycrystallization has been widely discussed in the industry. At present, the main obstacle of using diamond wire slices for cutting polycrystalline silicon slices is that the reflectivity of the polycrystalline silicon slices cut by using the diamond wires is higher, and the conventional polycrystalline texturing process cannot achieve good effect.
Because the gap loss of the diamond wire cutting is obviously reduced compared with that of a mortar cutting knife, the requirement for polycrystalline silicon under the same production capacity is greatly reduced. If the qualified number of silicon slices per kg of silicon rod is increased from 48 to 62 current silicon slices by cutting with diamond wires, the corresponding demand for polycrystalline silicon is reduced by 23%. If 70% of the polycrystalline silicon wafers in China can be completely cut by diamond wires at present, the requirement of polycrystalline silicon of more than 3 ten thousand tons per year is reduced, and the requirement of polycrystalline silicon is influenced by more than 10%. Without a large amount of additional capacity being added downstream (actually, the downstream has been seriously excessive in capacity), the reduction of the demand for polycrystalline silicon shifts the demand curve to the left, thereby further lowering the price of polycrystalline silicon.
Previously, the logic of single crystal during the process of leading in diamond wire slicing is realized, but the pressing effect required by polycrystalline silicon material is difficult to show due to the small amount of single crystal. In the process of the gradual popularization of polycrystalline silicon wafer diamond wire cutting, the indirect cost reduction path has acceleration effect, so that the reduction of silicon cost is further promoted.
After the diamond wire is used for cutting, the surface of the battery piece is smoother, the surface of the cut silicon wafer has obvious cutting lines, and the traditional slurry is used, so that the tensile force cannot meet the requirement, and the printing requirement cannot meet the requirement of a novel silicon wafer cutting process.
Disclosure of Invention
Aiming at the prior art, the invention provides the conductive paste for the front electrode of the solar cell, which adopts glass powder with different glass transition temperatures as an inorganic adhesive of the conductive paste, and improves the conversion efficiency and the tensile force of the solar cell.
The invention also provides a preparation method of the conductive paste for the front electrode of the solar cell aiming at the prior art.
The invention also provides a front electrode of the solar cell, which applies the conductive slurry adopting the glass powder with different glass transition temperatures as the inorganic adhesive on the silicon chip, improves the printing performance of the front electrode of the solar cell and reduces the unit consumption.
The invention is realized by the following technical scheme: the conductive paste for the solar cell front electrode is added with 1.7-4% by mass of glass powder A and 0.1-1% by mass of glass powder B; the glass transition temperature of the glass powder A is 250-350 ℃, and preferably 260-300 ℃; the glass transition temperature of the glass powder B is 350-450 ℃, and preferably 370-420 ℃.
In the technical scheme, the glass transition temperatures of the glass powder A and the glass powder B have a temperature difference, preferably, the temperature difference is preferably 70-150 ℃.
In the technical scheme, because the glass transition temperature between the glass powder A and the glass powder B has temperature difference, in the sintering process of sintering the conductive silver paste, the glass powder A with lower glass transition temperature is firstly softened and melted, the fluidity is enhanced, the silver powder in the conductive paste is carried to the surface of the silicon wafer, and the surface of the silicon wafer is etched; along with the continuous rise of the sintering temperature, the glass powder B with higher glass transition temperature is softened and melted, the surface of the silicon chip is further etched, the etching degree of the surface of the silicon chip is higher,
further, the glass powder A is TeO2-PbO-Bi2O3-SiO2A glass powder system; the glass powder B is TeO2-Bi2O3-WO3-MgO-SiO2The system is glass powder.
Further, the TeO2-PbO-Bi2O3-SiO2The system glass powder comprises the following components in parts by mass: 25-45 parts of TeO215-30 parts of PbO and 17-32 parts of Bi2O31 to 10 parts of SiO2。
Further, the TeO2-PbO-Bi2O3-SiO2Trace additives are also added into the system glass powder; the mass portion of the trace additive is 0.1-15.
Further, the micro additive is WO3、ZnO、Al2O3、B2O3、CaO、Na2O, MgO, respectively. Preferably, the micro additive comprises WO3、ZnO、Al2O3、B2O3、CaO、Na2O、MgO。
Further, the TeO2-Bi2O3-WO3-MgO-SiO2The system glass powder comprises the following components in parts by mass: 8-15 parts of TeO250 to 70 parts of Bi2O310 to 20 portions of WO35 to 10 parts of MgO, 1 to 3 parts of SiO2。
Further, the TeO2-Bi2O3-WO3-MgO-SiO2A trace amount of inorganic oxide is also added into the system glass powder; the mass portion of the trace inorganic oxide is 0.1-15.
Further, the trace inorganic oxide is Al2O3、Li2O、Na2One or more of O. Preferably, the trace inorganic oxide comprises Al2O3、Li2O、Na2O。
Further, the conductive paste also comprises the following components in percentage by mass: 85-92% of spherical silver powder, 1.5-6% of organic carrier, 2-5% of diluent and 1.0-2.0% of auxiliary agent.
Furthermore, D50 of the glass powder A and the glass powder B is 0.5-2.2 μm, preferably 0.8-2.0 μm, more preferably 1.4-1.8 μm, and D100 is not more than 6.0 μm.
Further, the organic carrier comprises the following components in parts by weight: 6-10 parts of ethyl cellulose resin, 2-5 parts of acrylic resin, 1-4 parts of PVB resin and 86-90 parts of solvent. Wherein the solvent is one or more of butyl carbitol acetate, butyl carbitol and alcohol ester dodeca, and the function of the solvent is to adjust the viscosity and the solubility of the organic carrier.
Further, the diluent is one or more of butyl carbitol acetate, butyl carbitol, alcohol ester dodeca and DBE-3.
Further, the auxiliary agent is preferably silicone oil, a thixotropic agent and a dispersing agent. Wherein the silicone oil can be selected from silicone oil with the viscosity of 1000-5000 cst; the thixotropic agent is preferably Thixatrol ST and MT, either alone or in admixture; the non-dispersant is preferably one or more of OP-83RAT, 1561 and ED-350.
The invention also discloses a preparation method of the conductive paste for the front electrode of the solar cell, which comprises the following steps:
preparing glass powder A and glass powder B: mixing the components of the glass powder A according to a formula, and then carrying out hot melting, cooling, ball milling and sieving to obtain the glass powder A; mixing the components for forming the glass powder B according to a formula, and then carrying out hot melting, cooling, ball milling and sieving to obtain glass powder B;
preparing an organic carrier: adding the resin into a solvent, preserving the heat for 1-3 hours at the temperature of 70-90 ℃, and filtering to obtain an organic carrier;
preparing conductive slurry: adding the glass powder A and the glass powder B into the organic carrier, adding other components of the conductive paste, mixing and dispersing until the particle size of the particulate matter is not more than 7 mu m, and filtering to obtain the conductive paste.
The invention also discloses application of the conductive paste to a front electrode of a solar cell, and particularly discloses a front electrode which is formed by printing conductive silver paste on a silicon chip of the solar cell in a silk screen manner by a silk screen printing technology and sintering the conductive silver paste at the temperature of 500-900 ℃.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the conductive paste for the front electrode of the solar cell, provided by the invention, the glass powder A and the glass powder B with different glass state softening temperatures are used as inorganic adhesives of the conductive paste, so that the adhesive property of the conductive paste on the surface of a silicon wafer is improved, the degree of etching the surface of the silicon wafer by molten glass powder in the conductive paste is improved, the doping is improved, the smaller the ohmic contact of a metal-semiconductor contact layer on the surface of the silicon wafer is, and the unit consumption ratio of the front electrode of the solar cell is reduced by 5-10%.
(2) According to the conductive paste for the front electrode of the solar cell, provided by the invention, the ethyl cellulose carrier is added to improve the printability and sintering temperature of the conductive silver paste, so that the grid line printed by the conductive silver paste is not easy to have the problems of grid breakage, virtual printing and the like; the viscosity of the conductive paste is adjusted by adjusting the proportion of the components in the organic carrier, so that the conductive paste has good printing lines, and the phenomenon of poor printing in the printing process is avoided; and the weight ratio relationship between the glass powder system and the spherical silver powder is adjusted, so that the requirement of the current diamond wire cutting battery piece is met.
(3) According to the preparation method of the conductive paste for the front electrode of the solar cell, disclosed by the invention, the glass powder A and the glass powder B with different glass state softening temperatures are added into the conductive paste, so that the conductive paste with low contact resistance, higher cell conversion rate and good printing performance is obtained.
(4) According to the solar cell front electrode disclosed by the invention, the silver conductive grid line is printed by adopting the conductive slurry added with the glass powder A and the glass powder B with different glass transition temperatures as inorganic adhesives and is sintered into the solar cell front electrode, the conversion rate of the front electrode is higher, the contact resistance is low, and the single consumption is reduced by 5-10% compared with that of the conventional solar cell.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
In the prior art, after the diamond wire is used for cutting, the surface of a battery piece is smoother, the surface of a cut silicon wafer has obvious cutting lines, and the traditional slurry is used, so that the requirements on tension and printability cannot be met.
Based on the problems, the application discloses conductive paste for a front electrode of a solar cell, which comprises 85-92% of spherical silver powder, 1.5-6% of organic carrier, 2-5% of diluent, 1.0-2.0% of auxiliary agent, 1.7-4% of glass powder A and 0.1-1% of glass powder B by mass; the glass transition temperature of the glass powder A is 250-350 ℃, and preferably 260-300 ℃; the glass transition temperature of the glass powder B is 350-450 ℃, and preferably 370-420 ℃.
In some embodiments, the glass frit A is TeO2-PbO-Bi2O3-SiO2A glass powder system; the glass powder B is TeO2-Bi2O3-WO3-MgO-SiO2The system is glass powder.
In some embodiments, the TeO2-PbO-Bi2O3-SiO2The system glass powder comprises the following components in parts by mass: 25-45 parts of TeO215-30 parts of PbO and 17-32 parts of Bi2O31 to 10 parts of SiO2。
In some embodiments, the TeO2-PbO-Bi2O3-SiO2Trace additives are also added into the system glass powder; the mass portion of the trace additive is 0.1-15.
In some embodiments, the micro-additive is WO3、ZnO、Al2O3、B2O3、CaO、Na2O, MgO, respectively. Preferably, the micro additive comprises WO3、ZnO、Al2O3、B2O3、CaO、Na2O、MgO。
In some embodiments, the TeO2-Bi2O3-WO3-MgO-SiO2The system glass powder comprises the following components in parts by mass: 8-15 parts of TeO250 to 70 parts of Bi2O310 to 20 portions of WO35 to 10 parts of MgO, 1 to 3 parts of SiO2。
In some embodiments, the TeO2-Bi2O3-WO3-MgO-SiO2A trace amount of inorganic oxide is also added into the system glass powder; the mass portion of the trace inorganic oxide is 0.1-15.
In some embodiments, the trace inorganic oxide is Al2O3、Li2O、Na2One or more of O. Preferably, the trace inorganic oxide comprises Al2O3、Li2O、Na2O。
In some embodiments, D50 of the glass powder A and the glass powder B is 0.5-2.2 μm, preferably 0.8-2.0 μm, more preferably 1.4-1.8 μm, and D100 is not more than 6.0 μm.
In some embodiments, the organic vehicle comprises the following ingredients, listed in parts by weight: 6-10 parts of ethyl cellulose resin, 2-5 parts of acrylic resin, 1-4 parts of PVB resin and 86-90 parts of solvent. Wherein the solvent is one or more of butyl carbitol acetate, butyl carbitol and alcohol ester dodeca, and the function of the solvent is to adjust the viscosity and the solubility of the organic carrier.
In some embodiments, the diluent is one or more of butyl carbitol acetate, butyl carbitol, alcohol ester dodeca, DBE-3.
In some embodiments, the adjuvant is preferably a silicone oil, a thixotropic agent, and a dispersing agent. Wherein the silicone oil can be selected from silicone oil with the viscosity of 1000-5000 cst; the thixotropic agent is preferably Thixatrol ST and MT, either alone or in admixture; the non-dispersant is preferably one or more of OP-83RAT, 1561 and ED-350.
The conductive paste for the front electrode of the solar cell disclosed in the present document can be prepared by the following method:
A1) preparing glass powder A and glass powder B: mixing the components of the glass powder A according to a formula, and then carrying out hot melting, cooling, ball milling and sieving to obtain the glass powder A; mixing the components for forming the glass powder B according to a formula, and then carrying out hot melting, cooling, ball milling and sieving to obtain glass powder B;
A2) preparing an organic carrier: adding the resin into a solvent, preserving the heat for 1-3 hours at the temperature of 70-90 ℃, and filtering to obtain an organic carrier;
A3) preparing conductive slurry: adding the glass powder A and the glass powder B into the organic carrier, adding other components of the conductive paste, mixing and dispersing until the particle size of the particulate matter is not more than 7 mu m, and filtering to obtain the conductive paste.
The conductive paste for the front electrode of the solar cell disclosed in the present application can be applied to the solar cell in the following manner
The invention is further illustrated by the following specific application examples:
example 1
The conductive paste used in this example was formulated as follows: 1.7 percent of glass powder A, 1 percent of glass powder B, 90 percent of spherical silver powder, 2.2 percent of organic carrier, 3.65 percent of diluent and 1.45 percent of auxiliary agent, and the specific formula components are shown in Table 1.
The preparation method specifically comprises the following steps:
A1) preparing glass powder A and glass powder B:
A11) according to the raw materials and the proportion shown in Table 1, TeO is added2、PbO、Bi2O3、SiO2、WO3、ZnO、Al2O3、B2O3、CaO、Na2And mixing O and MgO uniformly, heating, then carrying out hot melting, cooling, ball milling and sieving to obtain glass powder A, wherein D50 of the glass powder is preferably 1.8 mu m.
A12) According to the raw materials and the proportion shown in Table 1, TeO is added2、Bi2O3、WO3、MgO、SiO2、Al2O3、Li2O、Na2And O is uniformly mixed, heated, melted, cooled, ball-milled and sieved to obtain the glass powder B, wherein D50 of the glass powder is preferably 1.6 mu m.
A2) Preparing an organic carrier:
adding ethyl cellulose resin, acrylic resin and PVB resin into a solvent according to the raw materials and the proportion shown in the table 1, completely dissolving the ethyl cellulose resin, the acrylic resin and the PVB resin at the constant temperature of 80 ℃, preserving the temperature for 2 hours, and filtering the mixture by using a 250-mesh standard sieve to obtain the organic carrier.
A3) Preparing conductive slurry:
uniformly mixing the glass powder prepared in the step A1), the organic carrier prepared in the step A2), the spherical silver powder, the diluent and the auxiliary agent according to the raw materials and the proportion shown in the table 1, dispersing the mixture on a three-roll machine to be less than 7 microns, adjusting the mixture to be proper in viscosity, and filtering the mixture to obtain the conductive paste for the front electrode of the solar cell.
Example 2
The conductive paste used in this example was formulated as follows: the glass powder comprises 2% of glass powder A, 0.2% of glass powder B, 92% of spherical silver powder, 1.5% of organic carrier, 3% of diluent and 1.3% of auxiliary agent, and the specific formula components are shown in Table 1. The preparation method is basically the same as that of example 1, and therefore, detailed description is omitted.
Example 3
The conductive paste used in this example was formulated as follows: 2.1 percent of glass powder A, 0.5 percent of glass powder B, 85 percent of spherical silver powder, 6 percent of organic carrier, 4.85 percent of diluent and 1.55 percent of auxiliary agent, and the specific formula components are shown in Table 1. The preparation method is basically the same as that of example 1, and therefore, detailed description is omitted.
Example 4
The conductive paste used in this example was formulated as follows: the glass powder comprises 1.8% of glass powder A, 0.4% of glass powder B, 87% of spherical silver powder, 4.6% of organic carrier, 4.55% of diluent and 1.65% of auxiliary agent, and the specific formula components are shown in Table 1. The preparation method is basically the same as that of example 1, and therefore, detailed description is omitted.
Example 5
The conductive paste used in this example was formulated as follows: 2.5 percent of glass powder A, 0.45 percent of glass powder B, 88 percent of spherical silver powder, 3.5 percent of organic carrier, 3.85 percent of diluent and 1.7 percent of auxiliary agent, and the specific formula components are shown in Table 1. The preparation method is basically the same as that of example 1, and therefore, detailed description is omitted.
TABLE 1
Printing the conductive paste prepared in the above embodiments 1 to 5 on the front electrode of the solar cell of the diamond wire-cut silicon wafer by using a non-mesh screen with a fine grid line width of 24 μm, and sintering at a sintering temperature of: room temperature → 300 ℃ → 360 ℃ → 520 ℃ → 540 ℃ → 640 ℃ → 820 ℃ → room temperature.
Tensile force, unit consumption and photoelectric conversion efficiency performance detection are carried out on the sintered solar cell front electrode, and the detection results are shown in table 2:
| example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Aspect ratio | 0.4632 | 0.4452 | 0.4562 | 0.4485 | 0.4535 |
| Pulling force (N) | 2.7 | 3.5 | 2.6 | 2.8 | 3.0 |
| Unit consumption (g) | 0.0785 | 0.0772 | 0.0788 | 0.0754 | 0.0763 |
| Photoelectric conversion efficiency Eff (%) | 18.94 | 18.97 | 19.12 | 19.21 | 19.02 |
TABLE 2
As shown in table 2, when the conductive paste disclosed in this document is applied to the front electrode of the solar cell, the photoelectric conversion rate is high, the unit consumption is low, and the adhesion performance is good.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiments according to the technical spirit of the present invention are included in the scope of the present invention.
Claims (7)
1. The conductive paste for the front electrode of the solar cell is characterized in that: the conductive paste is added with 1.7-4% of glass powder A and 0.4-1% of glass powder B by mass; the glass transition temperature of the glass powder A is 260-300 ℃; the glass transition temperature of the glass powder B is 370-420 ℃; the glass powder A is TeO2-PbO- Bi2O3- SiO2A glass powder system; the glass powder B is TeO2-Bi2O3-WO3-MgO-SiO2A glass powder system;
the TeO2-PbO- Bi2O3- SiO2The system glass powder comprises the following components in parts by mass: 25-45 parts of TeO215-30 parts of PbO and 17-32 parts of Bi2O31 to 10 parts of SiO2(ii) a The TeO2-Bi2O3-WO3-MgO-SiO2The system glass powder comprises the following components in parts by mass: 8-15 parts of TeO250 to 70 parts of Bi2O310 to 20 portions of WO35 to 10 parts of MgO, 1 to 3 parts of SiO2。
2. The electroconductive paste for a front electrode of a solar cell according to claim 1, wherein: the TeO2-PbO-Bi2O3-SiO2Trace additives are also added into the system glass powder; the mass part of the trace additive is 0.1-15 parts; the micro additive is WO3、ZnO、Al2O3、B2O3、CaO、Na2O, MgO, respectively.
3. The electroconductive paste for a front electrode of a solar cell according to claim 1, wherein: the TeO2-Bi2O3- WO3-MgO-SiO2A trace amount of inorganic oxide is also added into the system glass powder; the mass part of the trace inorganic oxide is 0.1-15 parts; the trace inorganic oxide is Al2O3、Li2O、Na2One or more of O.
4. The electroconductive paste for a front electrode of a solar cell according to any one of claims 1 to 3, wherein: the conductive paste also comprises the following components in percentage by mass: 85-92% of spherical silver powder, 1.5-6% of organic carrier, 2-5% of diluent and 1.0-2.0% of auxiliary agent.
5. The electroconductive paste for a front electrode of a solar cell according to claim 4, wherein: the particle sizes D50 of the glass powder A and the glass powder B are both 0.5-2.2 mu m, and D100 is not more than 6.0 mu m; the particle size of the spherical silver powder is D50 and is 0.5-3 mu m, and D100 is not more than 6.0 mu m.
6. The method for preparing the conductive paste according to any one of claims 1 to 5, comprising the steps of:
preparing glass powder A and glass powder B: mixing the components of the glass powder A according to a formula, and then carrying out hot melting, cooling, ball milling and sieving to obtain the glass powder A; mixing the components for forming the glass powder B according to a formula, and then carrying out hot melting, cooling, ball milling and sieving to obtain glass powder B;
preparing an organic carrier: adding the resin into a solvent, preserving the heat for 1-3 hours at the temperature of 70-90 ℃, and filtering to obtain an organic carrier;
preparing conductive slurry: adding the glass powder A and the glass powder B into the organic carrier, adding other components of the conductive paste, mixing and dispersing until the particle size of the particulate matter is not more than 7 mu m, and filtering to obtain the conductive paste.
7. The front electrode of the solar cell is characterized in that the conductive silver paste of any one of claims 1 to 6 is screen-printed on a silicon wafer of the solar cell by a screen printing technology and is sintered at a temperature of 500 to 900 ℃.
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| CN103545017A (en) * | 2013-10-25 | 2014-01-29 | 江苏惠星新能源科技有限公司 | Conductor paste for positive electrode of solar cell and preparation method of conductor paste |
| CN103915129A (en) * | 2012-12-29 | 2014-07-09 | 第一毛织株式会社 | Composition for solar cell electrodes and electrode fabricated using the same |
| CN107293349A (en) * | 2016-04-13 | 2017-10-24 | E.I.内穆尔杜邦公司 | Conducting paste composition and the semiconductor device being made of it |
| US10014418B2 (en) * | 2012-04-17 | 2018-07-03 | Heraeus Precious Metals North America Conshohocken Llc | Conductive thick film paste for solar cell contacts |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10014418B2 (en) * | 2012-04-17 | 2018-07-03 | Heraeus Precious Metals North America Conshohocken Llc | Conductive thick film paste for solar cell contacts |
| CN103915129A (en) * | 2012-12-29 | 2014-07-09 | 第一毛织株式会社 | Composition for solar cell electrodes and electrode fabricated using the same |
| CN103545017A (en) * | 2013-10-25 | 2014-01-29 | 江苏惠星新能源科技有限公司 | Conductor paste for positive electrode of solar cell and preparation method of conductor paste |
| CN107293349A (en) * | 2016-04-13 | 2017-10-24 | E.I.内穆尔杜邦公司 | Conducting paste composition and the semiconductor device being made of it |
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