CN111564235A - Crystalline silicon solar cell, front main grid electrode silver paste and preparation method thereof - Google Patents

Crystalline silicon solar cell, front main grid electrode silver paste and preparation method thereof Download PDF

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CN111564235A
CN111564235A CN202010489936.0A CN202010489936A CN111564235A CN 111564235 A CN111564235 A CN 111564235A CN 202010489936 A CN202010489936 A CN 202010489936A CN 111564235 A CN111564235 A CN 111564235A
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powder
spherical silver
silver powder
silver paste
glass
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黄耀浩
贺克成
蔺旭利
杨至灏
黄良辉
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Foshan Ruina New Material Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The front main grid electrode silver paste comprises: spherical silver powder A, spherical silver powder B, glass powder, an auxiliary agent and an adhesive; the tap density of the spherical silver powder A is 4.5-7.5g/cm3(ii) a The tap density of the spherical silver powder B is 2.5-5.5g/cm3(ii) a The glass powder comprises: pb, Si, Ti, Bi, Cu, Mn, B, Mg, W, Ca, Zn, Li, Na, and K; the preparation method of the front main gate electrode silver paste is used for preparing the front main gate electrode silver paste; the front main grid electrode silver paste is printed on a silicon wafer as a main grid electrode by adopting screen printing. The invention relates to spherical silver powder A and spherical silver based on specific particle diameter and specific tap densityThe added glass powder can effectively solve the problem of black spots after the battery piece is sintered, and further control the black spot probability to be 0.08%.

Description

Crystalline silicon solar cell, front main grid electrode silver paste and preparation method thereof
Technical Field
The invention relates to the technical field of solar cells, in particular to a crystalline silicon solar cell, front main grid electrode silver paste and a preparation method thereof.
Background
In the prior art, the technology of the main grid silver paste has a space for improving, and particularly, the performances of the paste in the aspects of tension and resistance reduction need to be perfected; generally, when the tensile force and the electrical property of the main grid silver paste are improved, the silver content of the paste is increased, which is not beneficial to the manufacturing cost of enterprises; meanwhile, the existing main grid silver paste has the phenomena of darkening, blackening, black spots and the like after the battery piece is sintered.
Disclosure of Invention
The invention aims to provide front main gate electrode silver paste of a solar cell, which comprises the following components: spherical silver powder A, spherical silver powder B, glass powder, an auxiliary agent and an adhesive; the tap density of the spherical silver powder A is 4.5-7.5g/cm3(ii) a The tap density of the spherical silver powder B is 2.5-5.5g/cm3(ii) a The glass powder comprises the following simple substances and/or oxides: pb, Si, Ti, Bi, Cu, Mn, B, Mg, W, Ca, Zn, Li, Na, and K.
The invention also provides a preparation method of the front main grid electrode silver paste, which is characterized in that the front main grid electrode silver paste is prepared from the spherical silver powder A, the spherical silver powder B, the glass powder, the auxiliary agent and the adhesive.
The invention also provides a crystalline silicon solar cell, which adopts screen printing to print the front main grid electrode silver paste on a silicon wafer as a main grid electrode; the front main gate electrode silver paste is the front main gate electrode silver paste.
In order to achieve the purpose, the invention adopts the following technical scheme:
the front main grid electrode silver paste of the solar cell comprises: spherical silver powder A, spherical silver powder B, glass powder, an auxiliary agent and an adhesive;
of the spherical silver powder AThe particle size distribution is as follows: d10 is 0.5-1.5 μm, D50 is 1.0-2.5 μm, and D90 is 2.0-3.0 μm; the tap density of the spherical silver powder A is 4.5-7.5g/cm3；
The particle size distribution of the spherical silver powder B is as follows: d10 is 0.3-0.7 μm, D50 is 0.6-1.0 μm, and D90 is 1.0-1.5 μm; the tap density of the spherical silver powder B is 2.5-5.5g/cm3；
The glass powder comprises the following simple substances and/or oxides: pb, Si, Ti, Bi, Cu, Mn, B, Mg, W, Ca, Zn, Li, Na, and K.
Preferably, the composition comprises the following components in percentage by weight: 50-60% of spherical silver powder A, 20-30% of spherical silver powder B, 1.5-3% of glass powder, 0-2% of auxiliary agent and the balance of adhesive.
Preferably, the glass powder comprises the following elements and/or oxides in percentage by weight: 50-85% of Pb, 3-10% of Si, 3-10% of Ti, 0.1-10% of Bi, 0.1-10% of Cu, 0.1-10% of Mn, 3-5% of B, 0.1-5% of Mg, 0.1-5% of W, 0.1-5% of Ca, 0.1-3% of Zn, 0.1-3% of Li, 0.1-3% of Na and 0.1-3% of K.
Preferably, the preparation method of the glass powder comprises the steps of mixing raw materials in proportion, stirring and mixing uniformly, smelting for 2 hours until molten glass is clear and transparent, taking out the molten glass and quenching to obtain smelted glass slag; and ball-milling and drying the glass slag to obtain the required glass powder.
Preferably, the auxiliary agent comprises one or more of the following simple substances and/or oxides: mg, Si, Sr, Ba, Ti, Zr, Cr, Mo, W, Mn, Ni, Cu, Zn, Al and C.
Preferably, the auxiliary agent comprises the following elements and/or oxides: mg, Si, Ti, Zr, W, Mn, Ni and Cu.
Preferably, the adhesive comprises: polymer resin, dispersant, thixotropic agent and solvent.
Preferably, the polymer resin includes: any one of acrylic resin, polyurethane resin, epoxy resin, ethyl cellulose resin, hydroxyethyl cellulose resin, hydroxypropyl cellulose resin, rosin resin, hydrogenated rosin tetrapentanol ester resin and polyamide resin and a combination of two or more of the same;
the dispersant comprises: an aliphatic amide dispersant;
the thixotropic agent comprises: at least one of hydrogenated castor oil and polyamide wax.
A preparation method of front main gate electrode silver paste comprises the following steps:
mixing the spherical silver powder A, the spherical silver powder B, the flake silver powder, the glass powder, the auxiliary agent and the adhesive in proportion, and stirring until the materials are uniform; wetting and grinding by a three-roller machine to obtain slurry with the fineness of not more than 7 mu m; and filtering the slurry by adopting filter cloth to obtain the front main grid electrode silver paste.
A crystalline silicon solar cell is characterized in that silver paste of a front main grid electrode is printed on a silicon wafer by adopting screen printing to serve as the main grid electrode;
the front main gate electrode silver paste is the front main gate electrode silver paste.
The invention has the beneficial effects that:
the front main grid electrode silver paste is used for a front main grid electrode of a crystalline silicon solar cell, and the conductivity and peel strength of the product can be improved by matching the spherical silver powder A and the spherical silver powder B with specific particle sizes and specific tap densities with the glass powder prepared from Pb, Si, Ti, Bi, Cu, Mn, B, Mg, W, Ca, Zn, Li, Na and K; meanwhile, based on the spherical silver powder A and the spherical silver powder B with specific particle sizes and specific tap densities, the added glass powder can effectively solve the problems of darkening, blackening and black spots in an EL test after the battery piece is sintered, and further control the black spot probability to be 0.08%.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
The front main grid electrode silver paste of the solar cell comprises: spherical silver powder A, spherical silver powder B, glass powder, an auxiliary agent and an adhesive;
the particle size distribution of the spherical silver powder A is as follows: d10 is 0.5-1.5 μm, D50 is 1.0-2.5 μm, D90 is 2.0-3.0 μm; the tap density of the spherical silver powder A is 4.5-7.5g/cm3；
The particle size distribution of the spherical silver powder B is as follows: d10 is 0.3-0.7 μm, D50 is 0.6-1.0 μm, and D90 is 1.0-1.5 μm; the tap density of the spherical silver powder B is 2.5-5.5g/cm3；
The glass powder comprises the following simple substances and/or oxides: pb, Si, Ti, Bi, Cu, Mn, B, Mg, W, Ca, Zn, Li, Na, and K.
The front main grid electrode silver paste is used for a front main grid electrode of a crystalline silicon solar cell, and the conductivity and peel strength of the product can be improved by matching the spherical silver powder A and the spherical silver powder B with specific particle sizes and specific tap densities with the glass powder prepared from Pb, Si, Ti, Bi, Cu, Mn, B, Mg, W, Ca, Zn, Li, Na and K; meanwhile, based on the spherical silver powder A and the spherical silver powder B with specific particle sizes and specific tap densities, the added glass powder can effectively solve the problems of darkening, blackening and black spots in an EL test after the battery piece is sintered, and further control the black spot probability to be 0.08%.
Preferably, the composition comprises the following components in percentage by weight: 50-60% of spherical silver powder A, 20-30% of spherical silver powder B, 1.5-3% of glass powder, 0-2% of auxiliary agent and the balance of adhesive.
The spherical silver powder content in the scheme is more than 78%, and the spherical silver powder can reduce the resistance of the sintered electrode by matching with the glass powder, improve the compactness of the electrode after the slurry is sintered at high temperature (740 + 800 ℃), lower the body resistance and the line resistance of the sintered main grid slurry, lower the lap resistance between the main grid electrode and the auxiliary grid electrode, improve the IV characteristic of the crystalline silicon solar cell and improve the adhesive force of the electrode.
Preferably, the glass powder comprises the following elements and/or oxides in percentage by weight: 50-85% of Pb, 3-10% of Si, 3-10% of Ti, 0.1-10% of Bi, 0.1-10% of Cu, 0.1-10% of Mn, 3-5% of B, 0.1-5% of Mg, 0.1-5% of W, 0.1-5% of Ca, 0.1-3% of Zn, 0.1-3% of Li, 0.1-3% of Na and 0.1-3% of K.
The glass powder has a wide sintering window, and when Pb, Si, Ti, Bi, Cu, Mn, B, Mg, W, Ca, Zn, Li, Na and K are used in a matching way, the glass powder can be suitable for sintering a battery piece at the temperature of 740 plus materials of 800 ℃, the sintered electrode has good tension, and the spherical silver powder A and the spherical silver powder B are matched, so that the open-circuit voltage and the stripping strength of the battery piece can be effectively improved, and the blackening of the battery piece can be reduced.
Preferably, the preparation method of the glass powder comprises the steps of mixing raw materials in proportion, stirring and mixing uniformly, smelting in a muffle furnace at 800-1000 ℃ for 2 hours until glass liquid is clear and transparent, taking out the glass liquid and quenching to obtain smelted glass slag; and ball-milling and drying the glass slag to obtain the required glass powder.
Preferably, the auxiliary agent comprises one or more of the following simple substances and/or oxides: mg, Si, Sr, Ba, Ti, Zr, Cr, Mo, W, Mn, Ni, Cu, Zn, Al and C.
Preferably, the auxiliary agent comprises the following elements and/or oxides: mg, Si, Ti, Zr, W, Mn, Ni and Cu.
Preferably, the adhesive comprises: polymer resin, dispersant, thixotropic agent and solvent.
Preferably, the polymer resin includes: any one of acrylic resin, polyurethane resin, epoxy resin, ethyl cellulose resin, hydroxyethyl cellulose resin, hydroxypropyl cellulose resin, rosin resin, hydrogenated rosin tetrapentanol ester resin and polyamide resin and a combination of two or more of the same;
the dispersant comprises: an aliphatic amide dispersant;
the thixotropic agent comprises: at least one of hydrogenated castor oil and polyamide wax.
The adhesive comprises the following components in percentage by weight: 5-20% of high molecular resin, 1-8% of dispersant, 1-8% of thixotropic agent and the balance of solvent.
A preparation method of front main gate electrode silver paste comprises the following steps:
mixing the spherical silver powder A, the spherical silver powder B, the flake silver powder, the glass powder, the auxiliary agent and the adhesive in proportion, and stirring until the materials are uniform; wetting and grinding by a three-roller machine to obtain slurry with the fineness of not more than 7 mu m; and filtering the slurry by adopting filter cloth to obtain the front main grid electrode silver paste.
A crystalline silicon solar cell is characterized in that silver paste of a front main grid electrode is printed on a silicon wafer by adopting screen printing to serve as the main grid electrode;
the front main gate electrode silver paste is the front main gate electrode silver paste.
And (3) performance testing:
1. IV electrical property test:
and (4) carrying out IV electrical property test on the monocrystalline silicon wafer printed with the main grid slurry and the fine grid silver paste by adopting an IV tester, and testing the open-circuit voltage of the monocrystalline silicon wafer. And (4) adopting a HALM tester for testing the electrical property of the battery piece IV.
2. Peel strength:
and (3) adopting a KJ1065D-B peel strength testing machine to carry out tension test on the monocrystalline silicon wafer, clamping the silicon wafer by using a clamp, and testing the peel strength of the silicon wafer.
Example A:
weighing the following components in percentage by weight: stirring 55% of spherical silver powder A, 25% of spherical silver powder B, 2% of glass powder, 2% of auxiliary agent and the balance of adhesive until the materials are uniform; wetting and grinding by a three-roller machine to obtain slurry with the fineness of not more than 7 mu m; and filtering the slurry by adopting filter cloth to obtain the front main grid electrode silver paste.
Wherein:
the particle size distribution of the spherical silver powder A is as follows: d10 is 0.5-1.5 μm, D50 is 1.0-2.5 μm, and D90 is 2.0-3.0 μm; the tap density of the spherical silver powder A is shown in Table 1;
the particle size distribution of the spherical silver powder B is as follows: d10 is 0.3-0.7 μm, D50 is 0.6-1.0 μm, and D90 is 1.0-1.5 μm; the tap density of the spherical silver powder B is shown in Table 1;
the glass powder comprises the following oxides in percentage by weight: 50% Pb, 5% Si, 5% Ti, 10% Bi, 10% Cu, 5% Mn, 3% B, 2% Mg, 5% W, 1% Ca, 1% Zn, 1% Li, 1% Na, and 1% K. Mixing the raw materials of the glass powder according to a proportion, stirring and mixing uniformly, smelting for 2 hours in a muffle furnace at 1000 ℃ until glass liquid is clear and transparent, taking out the glass liquid and quenching to obtain smelted glass slag; and ball-milling and drying the glass slag to obtain the required glass powder.
The auxiliary agent comprises the following oxides and simple substances: mg, Si, Ti, Zr, W, Mn, Ni and Cu;
the adhesive is commercially available.
Printing front main grid electrode silver paste and fine grid electrode silver paste on the crystalline silicon solar cell piece by adopting screen printing; the fine grid adopts commercially available fine grid silver paste.
Selecting a 90-square resistance single crystal 156.75-sized silicon wafer as the crystalline silicon solar cell; the printing machine is a BACCINI solar cell printing system; the sintering adopts a CT sintering furnace, and the peak temperature is 760-780 ℃.
TABLE 1 tap Density distribution for example A
Figure BDA0002520679230000071
TABLE 2 Performance testing of example A
Figure BDA0002520679230000072
Description of the drawings:
1. as is clear from comparison of comparative examples A1-A2 and example A1, the tap density of spherical silver powder A in comparative example A1 is 3.5g/cm3Comparative example A2 in which the tap density of spherical silver powder A was 8.5g/cm3The tap density of the spherical silver powder A in the two pairs of proportions is not between 4.5 and 7.5g/cm3In the range although the tap density of the spherical silver powder B is in the range of 2.5 to 5.5g/cm3Within the range, comparative example a1 had an open circuit voltage of only 0.6433V and a peel strength of 3.00N; comparative example a2 has an open circuit voltage of only 0.6426V and a peel strength of 2.88N; similarly, as can be seen from comparison of comparative examples A3-A4 and example A1, in comparative example A3, the tap density of spherical silver powder B is 1.5g/cm3，(ii) a Comparative example A4, the tap density of spherical silver powder B is 6.5g/cm3，The tap density of the spherical silver powder A is maintained at 4.5-7.5g/cm3Within this range, comparative example a3 has an open circuit voltage of only 0.6402V and a peel strength of 2.90N; comparative example a4 has an open circuit voltage of only 0.6412V and a peel strength of 2.98N; comparative examples A1-A4 fail to satisfy the tap density of spherical silver powder A at 4.5-7.5g/cm3In the range of 2.5 to 5.5g/cm and the tap density of the spherical silver powder B3The conditions within the range, and hence the properties, were all significantly different from those of example A1.
2. In this example A1, the tap density of spherical silver powder A was 4.5 to 7.5g/cm3In the range of 2.5 to 5.5g/cm and the tap density of the spherical silver powder B3In the range, the particle size distribution of the spherical silver powder A in the product is as follows: d10 is 0.5-1.5 μm, D50 is 1.0-2.5 μm, and D90 is 2.0-3.0 μm; the particle size distribution of the spherical silver powder B is as follows: d10 is 0.3-0.7 μm, D50 is 0.6-1.0 μm, and D90 is 1.0-1.5 μm; the spherical silver powder A and the spherical silver powder B have the best physical mixing state, the mixing state among the particles is good, and the compactness of the electrode after the slurry is sintered at high temperature can be improved by matching the glass powder mixed by oxides of Pb, Si, Ti, Bi, Cu, Mn, B, Mg, W, Ca, Zn, Li, Na and K, so that the volume resistance and the line resistance of the front main grid electrode sintered silver paste are lower, the lap resistance between the main grid electrode and the auxiliary grid electrode is lower, the stripping force is higher, the open-circuit voltage of the embodiment A1 is 0.6472V, and the stripping strength is 3.69N.
Example B:
based on the weight percentage, weighing according to the following table 3: stirring the spherical silver powder A, the spherical silver powder B, the glass powder, the auxiliary agent and the adhesive until the materials are uniform; wetting and grinding by a three-roller machine to obtain slurry with the fineness of not more than 7 mu m; and filtering the slurry by adopting filter cloth to obtain the front main grid electrode silver paste.
Wherein:
the particle size distribution of the spherical silver powder A is as follows: d10 is 0.5-1.5 μm, D50 is 1.0-2.5 μm, and D90 is 2.0-3.0 μm; the tap density of the spherical silver powder A was 6.0g/cm3；
The particle size distribution of the spherical silver powder B is as follows: d10 is 0.3-0.7 μm, D50 is 0.6-1.0 μm, and D90 is 1.0-1.5 μm; the tap density of the spherical silver powder B was 4.0g/cm3；
The glass powder comprises the following oxides in percentage by weight: 50% Pb, 5% Si, 5% Ti, 10% Bi, 10% Cu, 5% Mn, 3% B, 2% Mg, 5% W, 1% Ca, 1% Zn, 1% Li, 1% Na, and 1% K. Mixing the raw materials of the glass powder according to a proportion, stirring and mixing uniformly, smelting for 2 hours in a muffle furnace at 1000 ℃ until glass liquid is clear and transparent, taking out the glass liquid and quenching to obtain smelted glass slag; and ball-milling and drying the glass slag to obtain the required glass powder.
The auxiliary agent comprises the following oxides and simple substances: mg, Si, Ti, Zr, W, Mn, Ni and Cu;
the adhesive is commercially available.
Printing front main grid electrode silver paste and fine grid electrode silver paste on the crystalline silicon solar cell piece by adopting screen printing; the fine grid adopts commercially available fine grid silver paste.
Selecting a 90-square resistance single crystal 156.75-sized silicon wafer as the crystalline silicon solar cell; the printing machine is a BACCINI solar cell printing system; the sintering adopts a CT sintering furnace, and the peak temperature is 760-780 ℃.
TABLE 3 proportioning of front main gate electrode silver paste in example B
Figure BDA0002520679230000091
The solar cell sheet from example B was subjected to IV electrical property testing and peel strength testing as in table 4.
TABLE 4 Properties of example B
Figure BDA0002520679230000092
Description of the drawings:
example B1-example B5, example B1 had a spherical silver powder A content of 45%, corresponding to an open circuit voltage of 0.6423V and a peel strength of 2.80N; when the content of the spherical silver powder A in the example B1 is increased to 50% of that in the example B2, the open-circuit voltage of the example B2 is increased to 0.6468V, the open-circuit voltage is increased by 0.0045V, the peel strength is increased to 3.66N, and the peel strength is increased by 0.86N; with the increase of the content of the spherical silver powder A, the open-circuit voltage of the embodiment B2-the embodiment B4 is kept about 0.6470V and the peel strength can reach more than 3.60N when the spherical silver powder A is in the range of 50-60%; when the content of the spherical silver powder A is increased to 65%, the open-circuit voltage of the example B5 is reduced instead, from 0.6472V of the example B4 to 0.6450V; the peel strength was reduced from 3.69N of example B4 to 3.42N; in the scheme, based on the selection of glass powder formed by combining Pb, Si, Ti, Bi, Cu, Mn, B, Mg, W, Ca, Zn, Li, Na and K, the optimal total surface area of the silver powder is obtained by adjusting the proportion of the two silver powders, so that the tensile force between the main gate electrode and the solar cell silicon wafer after sintering is optimal, and the spherical silver powder A cannot be added too little or too much; in order to not affect the open-circuit voltage of the battery plate and maintain the optimal tensile force of the product, the content of the spherical silver powder A is controlled within the range of 50-60%.
Example C:
based on the weight percentage, weighing according to the following table 5: stirring the spherical silver powder A, the spherical silver powder B, the glass powder, the auxiliary agent and the adhesive until the materials are uniform; wetting and grinding by a three-roller machine to obtain slurry with the fineness of not more than 7 mu m; and filtering the slurry by adopting filter cloth to obtain the front main grid electrode silver paste.
Wherein:
the particle size distribution of the spherical silver powder A is as follows: d10 is 0.5-1.5 μm, D50 is 1.0-2.5 μm, and D90 is 2.0-3.0 μm; the tap density of the spherical silver powder A was 6.0g/cm3；
The particle size distribution of the spherical silver powder B is as follows: d10 is 0.3-0.7 μm, D50 is 0.6-1.0 μm, and D90 is 1.0-1.5 μm; the tap density of the spherical silver powder B was 4.0g/cm3；
The glass powder comprises the following oxides in percentage by weight: 50% Pb, 5% Si, 5% Ti, 10% Bi, 10% Cu, 5% Mn, 3% B, 2% Mg, 5% W, 1% Ca, 1% Zn, 1% Li, 1% Na, and 1% K. Mixing the raw materials of the glass powder according to a proportion, stirring and mixing uniformly, smelting for 2 hours in a muffle furnace at 1000 ℃ until glass liquid is clear and transparent, taking out the glass liquid and quenching to obtain smelted glass slag; and ball-milling and drying the glass slag to obtain the required glass powder.
The auxiliary agent comprises the following oxides and simple substances: mg, Si, Ti, Zr, W, Mn, Ni and Cu;
the adhesive is commercially available.
The front main grid electrode silver paste and the fine grid electrode silver paste are printed on a silicon wafer by adopting screen printing; the fine grid adopts commercially available fine grid silver paste.
Selecting a 90-square resistance single crystal 156.75-sized silicon wafer as the crystalline silicon solar cell; the printing machine is a BACCINI solar cell printing system; the sintering adopts a CT sintering furnace, and the peak temperature is 760-780 ℃.
TABLE 5 proportioning of front main gate electrode silver paste in example C
Figure BDA0002520679230000111
The solar cell sheet from example C was subjected to IV electrical property testing and peel strength testing as in table 6.
TABLE 6 Properties of example C
Performance of Example C1 Example C2 Example C3 Example C4 Example C5
Open circuit voltage (V) 0.6432 0.6468 0.6471 0.6467 0.6438
Peel strength (N) 2.78 3.66 3.70 3.68 3.45
Description of the drawings:
the content of spherical silver powder B in example C1 was 15%, the open-circuit voltage was 0.6432V, and the peel strength was 2.78N; when the content of the spherical silver powder B was increased to 20% of that of example C2, the open circuit voltage of example C2 was increased from 0.6432V to 0.6468V of example C1, and the peel strength was increased from 2.78N to 3.66N. In examples C2-C3, as the content of the spherical silver powder B increased, the open circuit voltage and peel strength of the product increased in order, and the best effect was obtained in example C3, which was 0.6471V for example C3 and 3.70N for peel strength. While after example C3, increasing the content of the spherical silver powder B to example C4, the open circuit voltage and peel strength of example C4 were slightly decreased, but the open circuit voltage was maintained at 0.6467V, and the peel strength was maintained at 3.68N. And when the content of the spherical silver powder B was increased to 35% of example C5, with the addition of 5% of the spherical silver powder B, the open circuit voltage of example C5 decreased from 0.6467V to 0.6438V, but the open circuit voltage decreased by 0.0029V, the peel strength decreased from 3.68N to 3.45N, and the peel strength decreased by 0.23N.
In the scheme, based on the selection of glass powder formed by combining Pb, Si, Ti, Bi, Cu, Mn, B, Mg, W, Ca, Zn, Li, Na and K, the optimal total surface area of the silver powder is obtained by adjusting the proportion of the two silver powders, so that the tensile force between the main gate electrode and the solar cell silicon wafer after sintering is optimal, and the spherical silver powder B cannot be added too little or too much; in order to not affect the open-circuit voltage of the battery plate and maintain the optimal tensile force of the product, the content of the spherical silver powder B is controlled to be in the range of 20-30%. In order to ensure the best performance of the battery piece, the content of the spherical silver powder A is controlled within the range of 50-60%, and the content of the spherical silver powder B is controlled within the range of 20-30%.
Comparative example D:
comparative example D no glass frit was added and based on weight percent, the following were weighed: stirring 55% of spherical silver powder A, 25% of spherical silver powder B, 2% of auxiliary agent and 18% of adhesive until the materials are uniform; wetting and grinding by a three-roller machine to obtain slurry with the fineness of not more than 7 mu m; and filtering the slurry by adopting filter cloth to obtain the front main grid electrode silver paste.
Wherein:
the particle size distribution of the spherical silver powder A is as follows: d10 is 0.5-1.5 μm, D50 is 1.0-2.5 μm, and D90 is 2.0-3.0 μm; the tap density of the spherical silver powder A was 6.0g/cm3；
The particle size distribution of the spherical silver powder B is as follows: d10 is 0.3-0.7 μm, D50 is 0.6-1.0 μm, and D90 is 1.0-1.5 μm; the tap density of the spherical silver powder B was 4.0g/cm3；
The auxiliary agent comprises the following oxides and simple substances: mg, Si, Sr, Ti, Zr, W, Mn, Ni and Cu;
the adhesive is commercially available.
Printing front main grid electrode silver paste and fine grid electrode silver paste on the crystalline silicon solar cell piece by adopting screen printing; the fine grid adopts commercially available fine grid silver paste.
Selecting a 90-square resistance single crystal 156.75-sized silicon wafer as the crystalline silicon solar cell; the printing machine is a BACCINI solar cell printing system; the sintering adopts a CT sintering furnace, and the peak temperature is 760-780 ℃.
The products of example A1 and comparative example D were subjected to surface inspection using an EL tester to check the blackening of the cell sheets and to compare the black spot probabilities of example A1 and comparative example D. And comparative example D was compared to example a1 for performance as in table 7.
TABLE 7 comparison of the Performance of comparative example D with example A1
Performance of Comparative example D Example A1
Open circuit voltage (V) 0.6459 0.6472
Peel strength (N) 2.88 3.69
Black spot probability (%) 0.3 0.08
Description of the drawings:
comparative example D, in which no glass frit was added, had lower open circuit voltage and peel strength than example a1 because no glass frit was effectively matched with the spherical silver powder a and the spherical silver powder B having the specific particle diameter and the specific tap density; the glass powder can improve the open-circuit voltage in the scheme, so that the open-circuit voltage of the comparative example D is reduced from 0.6472V to 0.6459V, and is reduced by 0.0013V; meanwhile, the softening point of the glass powder used in the scheme is 400-plus-500 ℃, the sintering window is wide, the glass powder can be suitable for sintering the battery piece at the temperature of 740-plus-800 ℃, and the electrode tension is improved after sintering; thus, the peel strength of comparative example D, without the glass frit added, decreased from 3.69N to 2.88N, by 0.81N. Furthermore, because the sintering window of the glass powder is wide, the probability of black spots of the battery piece can be reduced, the quality of the product is improved, and the black spot probability of the embodiment A1 added with the glass powder is only 0.08 percent and is far lower than 0.3 percent of that of the comparative example D.
Example E:
weighing the following components in percentage by weight: stirring 60% of spherical silver powder A, 25% of spherical silver powder B, 1.5% of glass powder, 1.5% of auxiliary agent and the balance of adhesive until the materials are uniform; wetting and grinding by a three-roller machine to obtain slurry with the fineness of not more than 7 mu m; and filtering the slurry by adopting filter cloth to obtain the front main grid electrode silver paste.
Wherein:
the particle size distribution of the spherical silver powder A is as follows: d10 is 0.5-1.5 μm, D50 is 1.0-2.5 μm, and D90 is 2.0-3.0 μm; the tap density of the spherical silver powder A was 6.0g/cm3；
The particle size distribution of the spherical silver powder B is as follows: d10 is 0.3-0.7 μm, D50 is 0.6-1.0 μm, and D90 is 1.0-1.5 μm; the tap density of the spherical silver powder B was 4.0g/cm3；
The glass powder comprises the following oxides in percentage by weight: 85% of Pb, 3% of Si, 3% of Ti, 1% of Bi, 1% of Cu, 0.5% of Mn, 3% of B, 0.5% of Mg, 0.5% of W, 0.5% of Ca, 0.5% of Zn, 0.5% of Li, 0.5% of Na and 0.5% of K. Mixing the raw materials of the glass powder according to a proportion, stirring and mixing uniformly, smelting for 2 hours in a muffle furnace at 1000 ℃ until glass liquid is clear and transparent, taking out the glass liquid and quenching to obtain smelted glass slag; and ball-milling and drying the glass slag to obtain the required glass powder.
The auxiliary agent comprises the following oxides: mg, Si, Ti, Zr, W, Mn, Ni, Cu, Cr and Al;
the adhesive comprises the following components in percentage by weight: 10% of high molecular resin, 8% of dispersant, 2% of thixotropic agent and the balance of solvent. The high polymer resin is the combination of acrylic resin and polyurethane resin; the dispersant is aliphatic amide dispersant; the thixotropic agent is hydrogenated castor oil.
Example F:
weighing the following components in percentage by weight: stirring 60% of spherical silver powder A, 25% of spherical silver powder B, 1.5% of glass powder, 1.5% of auxiliary agent and the balance of adhesive until the materials are uniform; wetting and grinding by a three-roller machine to obtain slurry with the fineness of not more than 7 mu m; and filtering the slurry by adopting filter cloth to obtain the front main grid electrode silver paste.
Wherein:
the particle size distribution of the spherical silver powder A is as follows: d10 is 0.5-1.5 μm, D50 is 1.0-2.5 μm, and D90 is 2.0-3.0 μm; the tap density of the spherical silver powder A was 6.0g/cm3；
The particle size distribution of the spherical silver powder B is as follows: d10 is 0.3-0.7 μm, D50 is 0.6-1.0 μm, and D90 is 1.0-1.5 μm; the tap density of the spherical silver powder B was 4.0g/cm3；
The glass powder comprises the following oxides in percentage by weight: 50% Pb, 5% Si, 5% Ti, 10% Bi, 10% Cu, 5% Mn, 3% B, 2% Mg, 5% W, 1% Ca, 1% Zn, 1% Li, 1% Na, and 1% K. Mixing the raw materials of the glass powder according to a proportion, stirring and mixing uniformly, smelting for 2 hours in a muffle furnace at 1000 ℃ until glass liquid is clear and transparent, taking out the glass liquid and quenching to obtain smelted glass slag; and ball-milling and drying the glass slag to obtain the required glass powder.
The auxiliary agent comprises the following oxides: mg, Si, Ti, Zr, W, Mn, Ni, Cu, Cr and Al;
the adhesive comprises the following components in percentage by weight: 10% of high molecular resin, 8% of dispersant, 2% of thixotropic agent and the balance of solvent. The high polymer resin is the combination of acrylic resin and polyurethane resin; the dispersant is aliphatic amide dispersant; the thixotropic agent is hydrogenated castor oil.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.

Claims (10)

1. The utility model provides a positive main grid electrode silver thick liquid of solar wafer which characterized in that includes: spherical silver powder A, spherical silver powder B, glass powder, an auxiliary agent and an adhesive;
the particle size distribution of the spherical silver powder A is as follows: d10 is 0.5-1.5 μm, D50 is 1.0-2.5 μm, and D90 is 2.0-3.0 μm; the tap density of the spherical silver powder A is 4.5-7.5g/cm3；
The particle size distribution of the spherical silver powder B is as follows: d10 is 0.3-0.7 μm, D50 is 0.6-1.0 μm, and D90 is 1.0-1.5 μm; the tap density of the spherical silver powder B is 2.5-5.5g/cm3；
The glass powder comprises the following simple substances and/or oxides: pb, Si, Ti, Bi, Cu, Mn, B, Mg, W, Ca, Zn, Li, Na, and K.
2. The front-side main gate electrode silver paste of claim 1, comprising, by weight: 50-60% of spherical silver powder A, 20-30% of spherical silver powder B, 1.5-3% of glass powder, 0-2% of auxiliary agent and the balance of adhesive.
3. The front-side main gate electrode silver paste according to claim 1 or 2, wherein the glass frit comprises the following elements and/or oxides in percentage by weight: 50-85% of Pb, 3-10% of Si, 3-10% of Ti, 0.1-10% of Bi, 0.1-10% of Cu, 0.1-10% of Mn, 3-5% of B, 0.1-5% of Mg, 0.1-5% of W, 0.1-5% of Ca, 0.1-3% of Zn, 0.1-3% of Li, 0.1-3% of Na and 0.1-3% of K.
4. The front-side main grid electrode silver paste according to claim 3, wherein the glass powder is prepared by mixing raw materials in proportion, uniformly stirring and mixing, smelting for 2 hours until molten glass is clear and transparent, taking out the molten glass and quenching to obtain molten glass slag; and ball-milling and drying the glass slag to obtain the required glass powder.
5. The front-side main gate electrode silver paste according to claim 4, wherein the auxiliary agent comprises one or more of the following elements and/or oxides: mg, Si, Sr, Ba, Ti, Zr, Cr, Mo, W, Mn, Ni, Cu, Zn, Al and C.
6. The front-side main gate electrode silver paste according to claim 5, wherein the auxiliary agent comprises the following elements and/or oxides: mg, Si, Ti, Zr, W, Mn, Ni and Cu.
7. The front side main gate electrode silver paste of claim 4, wherein the binder comprises: polymer resin, dispersant, thixotropic agent and solvent.
8. The front side main gate electrode silver paste of claim 7, wherein the polymer resin comprises: any one of acrylic resin, polyurethane resin, epoxy resin, ethyl cellulose resin, hydroxyethyl cellulose resin, hydroxypropyl cellulose resin, rosin resin, hydrogenated rosin tetrapentanol ester resin and polyamide resin and a combination of two or more of the same;
the dispersant comprises: an aliphatic amide dispersant;
the thixotropic agent comprises: at least one of hydrogenated castor oil and polyamide wax.
9. The method for preparing the front main gate electrode silver paste according to any one of claims 1 to 8, comprising the following steps:
mixing the spherical silver powder A, the spherical silver powder B, the flake silver powder, the glass powder, the auxiliary agent and the adhesive in proportion, and stirring until the materials are uniform; wetting and grinding by a three-roller machine to obtain slurry with the fineness of not more than 7 mu m; and filtering the slurry by adopting filter cloth to obtain the front main grid electrode silver paste.
10. A crystalline silicon solar cell is characterized in that front main grid electrode silver paste is printed on a silicon wafer by adopting screen printing to be used as a main grid electrode;
the front surface main gate electrode silver paste of any one of claims 1 to 8.
CN202010489936.0A 2020-06-02 2020-06-02 Crystalline silicon solar cell, front main grid electrode silver paste and preparation method thereof Pending CN111564235A (en)

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CN112037959A (en) * 2020-09-01 2020-12-04 深圳纳弘熠岦光学科技有限公司 Silver paste, silver paste preparation method and solar cell grid line
CN112867239A (en) * 2021-01-12 2021-05-28 深圳市鑫诺诚科技有限公司 Ultra-thick and low-resistance copper foil material
WO2022041538A1 (en) * 2020-08-26 2022-03-03 南通天盛新能源股份有限公司 Main gate high-tension silver paste for n-type solar cell and manufacturing method therefor
CN114315159A (en) * 2021-12-16 2022-04-12 浙江光达电子科技有限公司 Glass powder for TOPCon battery main gate electrode silver paste and preparation method and application thereof
CN114360768A (en) * 2021-12-31 2022-04-15 广东南海启明光大科技有限公司 Crystalline silicon solar TOPCON cell front electrode main grid silver paste and preparation method thereof
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CN112867239A (en) * 2021-01-12 2021-05-28 深圳市鑫诺诚科技有限公司 Ultra-thick and low-resistance copper foil material
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CN114360768B (en) * 2021-12-31 2024-01-05 广东南海启明光大科技有限公司 Main grid silver paste for front electrode of crystalline silicon solar TOPCO battery piece and preparation method thereof
CN115064300A (en) * 2022-08-18 2022-09-16 西安拓库米电子科技有限公司 Silver conductor paste for nickel-plating-free chip resistor

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Application publication date: 20200821