WO2019183933A1 - Front-side conductive paste of crystalline silicon solar cell, preparation method thereof, and solar cell - Google Patents

Front-side conductive paste of crystalline silicon solar cell, preparation method thereof, and solar cell Download PDF

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Publication number
WO2019183933A1
WO2019183933A1 PCT/CN2018/081376 CN2018081376W WO2019183933A1 WO 2019183933 A1 WO2019183933 A1 WO 2019183933A1 CN 2018081376 W CN2018081376 W CN 2018081376W WO 2019183933 A1 WO2019183933 A1 WO 2019183933A1
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solar cell
crystalline silicon
silicon solar
oxide etchant
conductive paste
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PCT/CN2018/081376
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French (fr)
Chinese (zh)
Inventor
张�杰
刘小丽
孙丰振
李宇
黄玉平
李德林
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深圳市首骋新材料科技有限公司
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Priority to CN201880000363.1A priority Critical patent/CN110557965B/en
Priority to PCT/CN2018/081376 priority patent/WO2019183933A1/en
Publication of WO2019183933A1 publication Critical patent/WO2019183933A1/en

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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
    • H01B1/20—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

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  • the invention belongs to the technical field of solar cells, and particularly relates to a front side conductive paste of a crystalline silicon solar cell, a preparation method thereof and a solar cell.
  • Solar energy is an inexhaustible clean energy source. With the depletion of non-renewable energy sources such as coal and oil, the development and use of solar energy has become a hot spot. Solar cells developed based on this idea are an important means of utilizing solar energy. At present, the realization of industrialized crystalline silicon solar cells has become a model for solar cell applications.
  • a conductive paste is applied to the silicon wafer by screen printing, and a front electrode is formed on the front surface of the silicon wafer by sintering.
  • the front electrode of the sintered crystalline silicon solar cell needs to be firmly adhered on the silicon wafer, the gate line is narrow and high, the light shielding area is small, and the welding is easy, and the conductive paste for the front electrode of the silicon solar cell needs to have the silicon nitride penetrated during the sintering process.
  • a common conductive paste on the front side of a crystalline silicon solar cell contains silver powder, glass frit, and an organic carrier, and the conductive paste is sintered to form a front electrode.
  • the oxide etchant in the conductive paste etches and penetrates the anti-reflective insulating layer of the front side or the illuminated side of the crystalline silicon solar cell such as silicon nitride, titanium oxide, aluminum oxide, silicon oxide or silicon oxide/oxidation. Titanium causes the silver powder to contact the substrate of the crystalline silicon solar cell to form a front electrode.
  • the conventional front conductive paste and the used glass powder can not well etch the anti-reflection insulating layer on the surface of the cell, and the surface electrode formed by the front electrode and the surface of the silicon wafer has high contact resistance, thereby affecting The photoelectric conversion efficiency of the battery sheet.
  • the technical problem to be solved by the present invention is to provide a front side conductive paste of a crystalline silicon solar cell and a preparation method thereof, so as to solve the problem that the existing front conductive paste cannot effectively etch the anti-reflective insulating layer on the surface of the cell sheet. Therefore, the resistance value of the front electrode contacting the surface of the silicon wafer is increased, and finally the photoelectric conversion efficiency of the battery sheet is lowered.
  • the present invention also provides a method for fabricating a front electrode of a crystalline silicon solar cell and a solar cell.
  • a front side conductive paste of a crystalline silicon solar cell in terms of 100 parts by weight, comprising the following raw material components:
  • the oxide etchant contains at least Pb 3 O 4 , CuO, P 2 O 5 and Li 2 O, and the weight ratio of the CuO to Pb 3 O 4 is from 0.1:24 to 10:6.
  • the weight ratio of CuO to P 2 O 5 is from 0.1:10 to 10:0.1, and the weight ratio of CuO to Li 2 O is from 0.1:20 to 10:5.
  • a method for preparing a conductive paste on a front side of a crystalline silicon solar cell comprises at least the following steps:
  • Step S01 Melt the oxide etchant raw material component to obtain an oxide etchant melt, and quench the molten liquid to obtain oxide etchant particles, and obtain a particle size of 0.1 to 5.0 after crushing. Mm of an oxide etchant powder;
  • Step S02. The organic carrier raw material is placed in an environment of 40 to 100 ° C for mixing treatment to obtain an organic vehicle;
  • Step S03. The metal powder is mixed with the oxide etchant powder obtained in the step S01 and the organic vehicle obtained in the step S02 to obtain a front side conductive paste of the crystalline silicon solar cell.
  • a method for fabricating a front electrode of a crystalline silicon solar cell includes at least the following steps:
  • the front side conductive paste of the crystalline silicon solar cell as described above is printed on the surface of the insulating film by printing, and then sequentially dried, sintered, and cooled to obtain a front surface electrode of the crystalline silicon solar cell.
  • the front surface conductive paste of the crystalline silicon solar cell provided by the present invention contains Pb 3 O 4 , CuO, P 2 O 5 and Li 2 O components in the oxide etchant, and these The components are present in a specific weight ratio, and the components of these specific weight ratios can exhibit excellent etching performance and adhesion, so that the oxide etchant can dissolve enough silver from the silver powder during the sintering process to dissolve the silver.
  • One part of the oxide etchant liquid is used to wet the metal powder and promote sintering thereof, and the other part flows to the surface of the solar cell to react with the anti-reflection layer, which can effectively etch the anti-reflection layer and dissolve in the cooling process.
  • the silver in the oxide etchant liquid precipitates to form tiny nano silver particles, which makes the metal powder form good ohmic contact with silicon, greatly reduces the resistance of the front electrode, and finally obtains low contact resistance, good electrical conductivity, and adhesion. Strong frontal electrode.
  • the preparation method of the front side conductive paste of the crystalline silicon solar cell provided by the invention has simple process conditions, and the obtained front conductive paste component has uniform composition and good performance, and is suitable for industrial mass production.
  • the method for fabricating the front electrode of the crystalline silicon solar cell provided by the invention adopts the conductive paste on the front side of the crystalline silicon solar cell provided above, and the oxide etchant can dissolve enough silver from the silver powder during the sintering process to dissolve the silver.
  • One part of the oxide etchant liquid is used to wet the metal powder and promote sintering thereof, and the other part flows to the surface of the solar cell to react with the anti-reflection layer, which can effectively etch the anti-reflection layer and dissolve in the cooling process.
  • the silver in the oxide etchant liquid precipitates to form tiny nano silver particles, which makes the metal powder form good ohmic contact with silicon, greatly reduces the resistance of the front electrode, and finally obtains low contact resistance, good electrical conductivity, and adhesion. Strong frontal electrode.
  • the crystalline silicon solar cell provided by the invention adopts the above-mentioned front electrode structure of the crystalline silicon solar cell, and the solar cell structure exhibits good adhesion, and the silver electrode and the silicon wafer have good ohmic contact, small electrical resistance and good electrical conductivity. The conversion efficiency of the solar cell is improved.
  • FIG. 1 is a schematic view showing a process flow of a method for preparing a conductive paste on a front side of a crystalline silicon solar cell according to the present invention
  • FIG. 2 is a schematic view showing a process flow of a method for fabricating a front electrode of a crystalline silicon solar cell according to the present invention
  • FIG. 3 is a schematic view showing the front conductive paste of the present invention printed on a crystalline silicon semiconductor device having an insulating film on its surface according to the present invention
  • Figure 4 is a schematic view showing the sintered crystalline silicon semiconductor device with the front and back pastes printed in Figure 3 of the present invention
  • Figure 5 is a schematic diagram of a 180 degree tensile test.
  • the invention provides a front side conductive paste of a crystalline silicon solar cell, which comprises the following raw material components in terms of 100 parts by weight:
  • the oxide etchant contains at least Pb 3 O 4 , CuO, P 2 O 5 and Li 2 O, and the weight ratio of the CuO to Pb 3 O 4 is from 0.1:24 to 10:6.
  • the weight ratio of CuO to P 2 O 5 is from 0.1:10 to 10:0; and the weight ratio of CuO to Li 2 O is from 0.1:20 to 10:5.
  • the oxide etchant comprises the following components in an amount of 100% by weight of the total oxide etchant:
  • the oxide of the added element is 0 to 5.0%.
  • the oxide etchant contains components such as Pb 3 O 4 , CuO, P 2 O 5 and Li 2 O, and these components are present in a specific weight ratio, these The composition of a specific weight ratio can exhibit excellent etching performance and adhesion.
  • the oxide etchant is melted into a liquid during the sintering process, sufficient silver can be dissolved from the silver powder, and the oxide etching of the dissolved silver is performed.
  • Part of the liquid is used to wet the metal powder and promote the sintering of the metal powder; another part of the silver oxide etchant liquid flows to the surface of the solar cell to react with the anti-reflection layer, which can effectively etch the anti-reflection layer.
  • the silver dissolved in the oxide etchant liquid precipitates to form tiny nano-silver particles, which makes the metal powder form good ohmic contact with silicon, reduces the resistance, forms low contact resistance, and has good electrical conductivity.
  • a strong front electrode After sintering, during the cooling process, the silver dissolved in the oxide etchant liquid precipitates to form tiny nano-silver particles, which makes the metal powder form good ohmic contact with silicon, reduces the resistance, forms low contact resistance, and has good electrical conductivity.
  • a strong front electrode is used to form tiny nano-silver particles, which makes the metal powder form good ohmic contact with silicon, reduces the resistance, forms low contact resistance, and has good electrical conductivity.
  • the added elements in the oxide of the added element are titanium, aluminum, silver, chromium, lanthanum, copper, cerium, vanadium, sodium, lanthanum, cerium, bromine, cobalt, lanthanum, cerium, lanthanum, cerium, iron, lanthanum, One or two or more of manganese, magnesium, nickel, calcium, tin, arsenic, zirconium, potassium, phosphorus, indium, gallium, antimony, and the like.
  • the oxide etchant includes not only oxides obtained by chemical methods and oxides obtained after high-temperature treatment, but also carbonates, phosphates, fluorides thereof and the like containing cations, for example,
  • the lithium oxide Li 2 O can be substituted with Li 2 CO 3 .
  • the oxide of copper includes CuO and Cu 2 (OH) 2 CO 3 CuO
  • the oxide of zinc includes ZnO and Zn 3 (PO 4 ) 2
  • the oxide of calcium includes CaO and CaCO 3 . .
  • the oxide etchant may be crystalline or amorphous or a mixture of amorphous and crystalline.
  • the metal powder is at least one of silver, gold, platinum, copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminum, manganese, palladium, and rhodium.
  • the metal powder is at least one of silver-coated copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminum, and manganese, wherein the silver coating layer has a thickness of 10 to 50 nm.
  • the metal powder is a mixture of a non-silver-coated metal powder and a silver-coated metal powder, wherein a weight ratio of the non-silver-coated metal powder to the silver-coated metal powder is 5/ 95 ⁇ 95/5, the non-silver coated metal powder is at least one of silver, gold, platinum, copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminum, manganese, palladium, iridium; The metal powder is at least one of copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminum, and manganese, and the silver coating layer has a thickness of 10 to 50 nm.
  • the organic vehicle in the present invention includes an organic solvent, a polymer, a wetting and dispersing agent, a thixotropic agent, and other functional additives.
  • the weight of the organic vehicle is 100 parts by weight, including the following components: 50 to 95 parts of an organic solvent; 1 to 40 parts of a polymer; 0.1 to 10 parts of a wetting and dispersing agent; and 1 to 20 parts of a thixotropic agent.
  • the organic solvent is selected from the group consisting of terpineol, ethylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate, dodecyl alcohol ester, diethylene glycol butyl ether, triethylene glycol butyl ether, and tripropylene glycol methyl ether.
  • terpineol ethylene glycol butyl ether acetate
  • ethylene glycol ethyl ether acetate ethylene glycol ethyl ether acetate
  • dodecyl alcohol ester diethylene glycol butyl ether
  • triethylene glycol butyl ether triethylene glycol butyl ether
  • tripropylene glycol methyl ether At least one of high boiling solvents such as terpenes.
  • the polymer is selected from at least one of ethyl cellulose, methyl cellulose, cellulose and derivatives thereof, acrylic resin, alkyd resin, and polyester resin.
  • the wetting and dispersing agent is selected from the group consisting of fatty acids (oleic acid, stearic acid, etc.), amide derivatives of fatty acids (oleic acid amide, stearic acid amide, etc.), ester derivatives of fatty acids, polyethylene wax, polyethylene glycol. One or more of them are mainly used to help disperse inorganic powders in an organic vehicle.
  • the thixotropic agent is selected from one or more of hydrogenated castor oil derivatives, polyamide waxes, polyureas, fumed silicas, and is mainly used to increase the thixotropy of the slurry during printing, so that the silver paste When sheared during printing, the consistency becomes small, and it is easy to screen-print. When the shearing is stopped, the consistency is increased to ensure that the electrode has an excellent aspect ratio.
  • the organic vehicle may further include other functional assistants in an amount of 0.1-20 parts by weight, selected from the group consisting of polymethylphenylsiloxane, polyphenylsiloxane, and phthalic acid.
  • Ester such as diethyl phthalate, dibutyl phthalate, etc.
  • microcrystalline wax such as diethyl phthalate, dibutyl phthalate, etc.
  • PVB polyvinyl butyral
  • polyether polyester modification One or more of an organosiloxane and an alkyl-modified organosiloxane.
  • the other functional assistants may be optionally added according to requirements, such as adding microcrystalline wax to reduce surface tension, adding dibutyl phthalate (DBP), etc. to improve the flexibility of the slurry, and adding polyvinyl butyral. (PVB) and the like improve adhesion.
  • the method for preparing a front side conductive paste of a crystalline silicon solar cell comprises the following steps:
  • the step of preparing the oxide etchant is as follows: the oxide etchant raw material is weighed according to the raw material ratio as described above and uniformly mixed; and the uniformly mixed oxide etchant raw material is placed in a heating furnace for heating Up to 900-1100 ° C, and maintaining at 900-1100 ° C for 60-180 min, to obtain a molten liquid oxide etchant; quenching the molten liquid oxide etchant to obtain oxide etchant particles
  • the oxide etchant particles are dried at a temperature of 60 to 80 ° C; the dried oxide etchant particles are subjected to crushing treatment to obtain an oxide etchant powder having a particle size of 0.5 to 5.0 ⁇ m. Then, it is dried in a drying oven at 80 to 100 ° C to obtain a dried oxide etchant powder.
  • the quenching method is to pour the molten liquid oxide etchant into water at 5-25 ° C or to cool in flowing room temperature air at a temperature of 25 ° C or below.
  • the above-mentioned crushing of the oxide etched particles may be performed by a ball mill for ball milling, or other methods may be used to make the particle size of the oxide etchant smaller.
  • the organic carrier is prepared as follows: the raw materials of the organic carrier are sequentially weighed according to the weight ratio of the organic carrier raw materials mentioned above, and the weighed organic carrier raw materials are placed in a container, and stirred and mixed at a temperature of 40 to 100 ° C for 100 to 160 minutes. An organic vehicle is obtained.
  • the method for fabricating the front side conductive paste of the crystalline silicon solar cell of the present invention further has the following alternative method:
  • the oxide etchant and the metal powder are first mixed to obtain a first mixture, and the first mixture is mixed with an organic vehicle, and then subjected to a grinding treatment to obtain a front electrode conductive paste of the crystalline silicon solar cell. material.
  • the above oxide etchant and the organic carrier are first mixed to obtain a first mixture, and then the metal powder is added to the first mixture, and then ground to obtain a front electrode of the crystalline silicon solar cell. Slurry.
  • the metal powder and the organic carrier are first mixed to obtain a first mixture, and then an oxide etchant is added to the first mixture, followed by grinding treatment to obtain a front electrode conductive paste of the crystalline silicon solar cell. material.
  • 20 to 60 parts by weight of the metal powder and 20 to 60 parts by weight of the organic vehicle are first mixed with 100 parts by weight of the metal powder, the organic vehicle, and the oxide etchant, respectively. a first mixture; further mixing 40 to 80 parts by weight of the oxide etchant and a portion of the organic vehicle to obtain a second mixture, and then mixing the first mixture and the second mixture, and grinding to obtain a crystalline silicon solar cell
  • the front electrode is conductive paste.
  • the present invention also provides a method for fabricating a front electrode of a crystalline silicon solar cell.
  • the manufacturing method relates to a crystalline silicon semiconductor device having an insulating film laminated on its surface, the crystalline silicon semiconductor device having a structure as shown in FIG. 3, 100 being a crystalline silicon cell having a first surface and a second surface, in the first A P/N junction 200 and an insulating film 300 are sequentially stacked on a surface, and a back surface silver paste 500 and a back aluminum paste 600 are printed on the first surface.
  • the insulating film 300 may be a silicon nitride film or a titanium oxide film. At least one of an aluminum oxide film and a silicon oxide film.
  • the method for fabricating the front electrode of the crystalline silicon solar cell includes at least the following steps:
  • Step S04. Providing a crystalline silicon semiconductor component having an insulating film 300 on its surface;
  • Step S05 Printing the crystalline silicon solar cell front conductive paste 400 (where 401 is metal powder, 402 is an organic carrier, and 403 is an oxide etchant) on the insulating film by printing. 300 surface;
  • Step S06 The crystalline silicon semiconductor device processed in the step S05 is sequentially dried, sintered, and cooled to obtain a crystalline silicon solar cell front electrode 700.
  • the drying temperature is 80 to 400 ° C
  • the sintering temperature is 700 to 820 ° C
  • the cooling condition is natural cooling.
  • the present invention still further provides a crystalline silicon solar cell using the front surface electrode of a crystalline silicon solar cell as described above.
  • a front side conductive paste of a crystalline silicon solar cell calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
  • the oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 ⁇ m. The powder was then dried in a dry box at 100 ° C to obtain a dry oxide etchant powder.
  • the organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% Polyamide wax 5%.
  • the preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
  • a method for manufacturing a front electrode of a crystalline silicon solar cell comprising the following steps:
  • the front surface conductive paste of the crystalline silicon solar cell of Embodiment 1 is printed on the front surface of the crystalline silicon solar cell with the insulating film by screen printing, and the back surface of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 770 ° C to obtain the front electrode of the crystalline silicon solar cell.
  • a front side conductive paste of a crystalline silicon solar cell calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
  • the oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 ⁇ m. The powder was then dried in a dry box at 100 ° C to obtain a dry oxide etchant powder.
  • the organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% Polyamide wax 5%.
  • the preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
  • a method for manufacturing a front electrode of a crystalline silicon solar cell comprising the following steps:
  • the front side conductive paste of the crystalline silicon solar cell of Embodiment 2 is printed on the front side of the crystalline silicon solar cell with the insulating film by screen printing, and the back side of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 800 ° C to obtain the front electrode of the crystalline silicon solar cell.
  • a front side conductive paste of a crystalline silicon solar cell calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
  • the oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1 000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles
  • the oxide etchant particles are placed in a dry box and dried at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide oxide having a particle size of 0.5 to 7.0 ⁇ m.
  • the etchant powder was then dried in a dry box at 100 ° C to obtain a dried oxide etchant powder.
  • the organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% Polyamide wax 5%.
  • the preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
  • a method for manufacturing a front electrode of a crystalline silicon solar cell comprising the following steps:
  • the front side conductive paste of the crystalline silicon solar cell of Embodiment 3 is printed on the front surface of the crystalline silicon solar cell having the insulating film by screen printing, and the back surface of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 780 ° C to obtain the front electrode of the crystalline silicon solar cell.
  • a front side conductive paste of a crystalline silicon solar cell calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
  • the oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 ⁇ m. The powder was then dried in a dry box at 100 ° C to obtain a dry oxide etchant powder.
  • the organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% Polyamide wax 5%.
  • the preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
  • a method for manufacturing a front electrode of a crystalline silicon solar cell comprising the following steps:
  • the front side conductive paste of the crystalline silicon solar cell of Example 4 was printed on the front side of the crystalline silicon solar cell with an insulating film by screen printing, and the back side of the solar cell was screen printed with back silver and back aluminum, and then Sintering was carried out at 780 ° C to obtain the front electrode of the crystalline silicon solar cell.
  • a front side conductive paste of a crystalline silicon solar cell calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
  • the oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 ⁇ m. The powder was then dried in a dry box at 100 ° C to obtain a dry oxide etchant powder.
  • the organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% Polyamide wax 5%.
  • the preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
  • a method for manufacturing a front electrode of a crystalline silicon solar cell comprising the following steps:
  • the front side conductive paste of the crystalline silicon solar cell in Embodiment 5 is printed on the front surface of the crystalline silicon solar cell having the insulating film by screen printing, and the back surface of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 790 ° C to obtain the front electrode of the crystalline silicon solar cell.
  • a front side conductive paste of a crystalline silicon solar cell calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
  • the oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 ⁇ m. The powder was then dried in a dry box at 100 ° C to obtain a dry oxide etchant powder.
  • the organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% Polyamide wax 5%.
  • the preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
  • a method for manufacturing a front electrode of a crystalline silicon solar cell comprising the following steps:
  • the front side conductive paste of the crystalline silicon solar cell of Example 6 is printed on the front side of the crystalline silicon solar cell having the insulating film by screen printing, and the back side of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 800 ° C to obtain the front electrode of the crystalline silicon solar cell.
  • a front side conductive paste of a crystalline silicon solar cell calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
  • Pb 3 O 4 13%, TeO 2 30%, Li 2 O 16%, SiO 2 12%, B 2 O 3 0.3%, Bi 2 O 3 5%, ZnO 15%, WO 3 5%, CuO 3.4%.
  • the oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 ⁇ m. The powder was then dried in a dry box at 100 ° C to obtain a dry oxide etchant powder.
  • the organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% Polyamide wax 5%.
  • the preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
  • a method for manufacturing a front electrode of a crystalline silicon solar cell comprising the following steps:
  • the front side conductive paste of the crystalline silicon solar cell in Embodiment 7 is printed on the front surface of the crystalline silicon solar cell having the insulating film by screen printing, and the back surface of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 800 ° C to obtain the front electrode of the crystalline silicon solar cell.
  • a front side conductive paste of a crystalline silicon solar cell calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
  • the oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 ⁇ m. The powder was then dried in a dry box at 100 ° C to obtain a dried oxide etchant powder.
  • the organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% Polyamide wax 5%.
  • the preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
  • a method for manufacturing a front electrode of a crystalline silicon solar cell comprising the following steps:
  • the front side conductive paste of the crystalline silicon solar cell of Example 8 is printed on the front side of the crystalline silicon solar cell with an insulating film by screen printing, and the back side of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 800 ° C to obtain the front electrode of the crystalline silicon solar cell.
  • a front side conductive paste of a crystalline silicon solar cell calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
  • the oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 ⁇ m. The powder was then dried in a dry box at 100 ° C to obtain a dry oxide etchant powder.
  • the organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% Polyamide wax 5%.
  • the preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
  • a method for manufacturing a front electrode of a crystalline silicon solar cell comprising the following steps:
  • the front side conductive paste of the crystalline silicon solar cell of Example 9 is printed on the front side of the crystalline silicon solar cell having the insulating film by screen printing, and the back side of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 800 ° C to obtain the front electrode of the crystalline silicon solar cell.
  • a front side conductive paste of a crystalline silicon solar cell calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
  • the oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1 000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles
  • the oxide etchant particles are placed in a dry box and dried at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide oxide having a particle size of 0.5 to 7.0 ⁇ m.
  • the etchant powder was then dried in a dry box at 100 ° C to obtain a dried oxide etchant powder.
  • the organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% Polyamide wax 5%.
  • the preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
  • a method for manufacturing a front electrode of a crystalline silicon solar cell comprising the following steps:
  • the front side conductive paste of the crystalline silicon solar cell in Embodiment 10 is printed on the front surface of the crystalline silicon solar cell having the insulating film by screen printing, and the back surface of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 800 ° C to obtain the front electrode of the crystalline silicon solar cell.
  • a front side conductive paste of a crystalline silicon solar cell calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
  • the oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 ⁇ m. The powder was then dried in a dry box at 100 ° C to obtain a dry oxide etchant powder.
  • the organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% Polyamide wax 5%.
  • the preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
  • a method for manufacturing a front electrode of a crystalline silicon solar cell comprising the following steps:
  • the front side conductive paste of the crystalline silicon solar cell in Example 11 was printed on the front side of the crystalline silicon solar cell having the insulating film by screen printing, and the back side of the solar cell was screen printed with back silver and back aluminum, and then Sintering was carried out at 800 ° C to obtain the front electrode of the crystalline silicon solar cell.
  • a front side conductive paste of a crystalline silicon solar cell calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
  • the oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 ⁇ m. The powder was then dried in a dry box at 100 ° C to obtain a dry oxide etchant powder.
  • the organic vehicle contains the following components in an amount of 100% by weight of the organic vehicle: 70% of a mixture of terpineol, dodecyl alcohol and decene; 10% of ethyl cellulose, 15% of rosin resin, and polyamide wax 5 %.
  • the preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
  • a method for manufacturing a front electrode of a crystalline silicon solar cell comprising the following steps:
  • the front side conductive paste of the crystalline silicon solar cell of Example 12 is printed on the front side of the crystalline silicon solar cell having the insulating film by screen printing, and the back side of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 770 ° C to obtain the front electrode of the crystalline silicon solar cell.
  • a front side conductive paste of a crystalline silicon solar cell calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
  • the oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 ⁇ m. The powder was then dried in a dry box at 100 ° C to obtain a dry oxide etchant powder.
  • the organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% Polyamide wax 5%.
  • the preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
  • a method for manufacturing a front electrode of a crystalline silicon solar cell comprising the following steps:
  • the front side conductive paste of the crystalline silicon solar cell of Embodiment 13 is printed on the front surface of the crystalline silicon solar cell having the insulating film by screen printing, and the back surface of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 800 ° C to obtain the front electrode of the crystalline silicon solar cell.
  • a front side conductive paste of a crystalline silicon solar cell calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
  • the oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 ⁇ m. The powder was then dried in a dry box at 100 ° C to obtain a dry oxide etchant powder.
  • the organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle.
  • Polyamide wax 5% Polyamide wax 5%.
  • the preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
  • a method for manufacturing a front electrode of a crystalline silicon solar cell comprising the following steps:
  • the front side conductive paste of the crystalline silicon solar cell of Example 14 is printed on the front side of the crystalline silicon solar cell having the insulating film by screen printing, and the back side of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 800 ° C to obtain the front electrode of the crystalline silicon solar cell.
  • the efficiency of the obtained cell sheets was tested, and the I-V test results are summarized in Table 1.
  • a crystalline silicon solar cell front conductive paste PV1B screen widely used in the market is screen printed on the front surface of a crystalline silicon solar cell having the same insulating film as the embodiment, and the back surface of the solar cell is screen printed with back silver and The aluminum was backed and then sintered to 800 ° C for sintering to obtain the front electrode of the crystalline silicon solar cell, and then the efficiency of the cell was tested.
  • the IV test results are summarized in Table 1.
  • solder the strip to the main grid for 180 degree tensile test tensile force the main grid width is 0.7mm, and the 0.9mm wide strip is soldered to the main grid.
  • the strip width is 0.9mm and the thickness is 0.23mm. It is 96.5% Sn3.5% Ag.
  • 5 is a schematic diagram of a 180 degree tensile test, specifically, the solder ribbon 800 is first soldered to the surface of the main grid, and then the crystalline silicon cell sheet 100 is fixed to the stretching machine 900 by the first fixing bolt 901 and the second fixing bolt 902.
  • the tensile test is performed in the direction of the pulling force F.
  • the tensile test results are shown in Table 1.
  • the solar cell sheets of Examples 1-8 have the advantages of high conversion rate, low R s , and high tensile force as compared with the comparative examples, indicating that the oxide etchant used in Examples 1-8 is superior.
  • the etching performance not only effectively wets and sinters the silver powder, but also effectively etches away the insulating film on the surface of the solar cell sheet, so that the silver electrode and the surface of the solar cell sheet form a good ohmic contact, thereby converting the solar cell sheet.
  • High efficiency, low contact resistance R s and high tensile force are examples of the solar cell sheets of Examples 1-8 have the advantages of high conversion rate, low R s , and high tensile force as compared with the comparative examples, indicating that the oxide etchant used in Examples 1-8 is superior.
  • the etching performance not only effectively wets and sinters the silver powder, but also effectively etches away the insulating film on the surface of the solar cell sheet, so that the silver electrode
  • the weight ratio of CuO to Pb 3 O 4 in the oxide etching etchant used in Examples 1-8 is in the range of 0.1:24 to 10:6, and the weight ratio of CuO to Li 2 O is from 0.1:20 to 10:5.
  • the weight ratio of CuO to P 2 O 5 in the oxide etching etchant used in Example 1-2 is in the range of 0.1:10 to 10:0.1, and its unique oxide component ratio makes the oxide thereof
  • the etchant can dissolve enough silver during the sintering process, and can completely etch the insulating layer on the surface of the battery sheet without excessively etching the silicon cell sheet, so that the silver electrode and the silicon wafer not only form a good ohmic contact, but also have a very good Good adhesion.
  • the solar cell conversion rates of Examples 9-14 were lower than those of the comparative examples, and also lower than the cell sheet conversion rates of Examples 1-8, and the series resistance (R s ) was significantly higher than that of Examples 1-8. It is caused by the difference in the proportion of the oxide etchant used.
  • the low conversion rate of the cell sheets of Examples 9-10 is due to the low content of Pb 3 O 4 in the oxide etchant used and the high CuO content, indicating that CuO/Pb 3 O 4 is etched for the oxide of the present invention.
  • the performance of the agent has a great influence and the proper CuO/Pb 3 O 4 ratio must be maintained.
  • the efficiency of the cell sheets of Examples 11-12 was lower than that of the comparative cell, and also lower than the cell efficiency of Examples 1-8, due to the high content of Pb 3 O 4 in the oxide etchant used therein.
  • the weight content of Pb 3 O 4 in the oxide etchant of the invention is 6-24%, and if the weight content of Pb 3 O 4 is less than 6% or higher than 24%, the surface of the cell sheet during the sintering process may be insulated. The layer cannot be completely corroded or excessively corroded, so that the silver electrode does not form a good ohmic contact with the silicon wafer.
  • the efficiency of the cell sheets of Examples 13-14 was lower than that of the comparative cell, and also lower than the cell efficiency of Examples 1-8, which was caused by the high content of P 2 O 5 in the oxide etchant used.
  • the weight content of P 2 O 5 in the oxide etchant of the invention is from 0.1 to 10%.

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Abstract

A front-side conductive paste of a crystalline silicon solar cell. The front side conductive paste of a crystalline silicon solar cell comprises the following components in parts by weight: 80.0 to 93.0 parts of metal powder; 6.0 to 15.0 parts of an organic vehicle; and 1.0 to 5.0 parts of an oxide etchant; wherein the oxide etchant at least comprises Pb3O4, CuO and Li2O, the weight ratio of CuO to Pb3O4 is 0.02 to 2.5, and the weight ratio of CuO to Li2O is 0.025 to 3. The front-side conductive paste enables good ohmic contact formed between metal powder and silicon in the process of sintering, greatly reducing the resistance to obtain a final front-side electrode having a low contact resistance, good conductivity and strong adhesion.

Description

晶硅太阳能电池正面导电浆料及其制备方法和太阳能电池Crystalline solar cell front conductive paste, preparation method thereof and solar cell 技术领域Technical field
本发明属于太阳能电池技术领域，特别涉及一种晶硅太阳能电池正面导电浆料及其制备方法和太阳能电池。The invention belongs to the technical field of solar cells, and particularly relates to a front side conductive paste of a crystalline silicon solar cell, a preparation method thereof and a solar cell.
背景技术Background technique
太阳能是一种取之不尽、用之不竭的清洁型能源。随着煤炭、石油等不可再生能源的日益枯竭，开发并利用太阳能成为大热点。基于这种思路开发的太阳能电池就是利用太阳能的一种重要手段。目前，实现产业化的晶硅太阳能电池已经成为太阳能电池应用的典范。Solar energy is an inexhaustible clean energy source. With the depletion of non-renewable energy sources such as coal and oil, the development and use of solar energy has become a hot spot. Solar cells developed based on this idea are an important means of utilizing solar energy. At present, the realization of industrialized crystalline silicon solar cells has become a model for solar cell applications.
电池片作为晶硅太阳能电池的核心的组成部分，为了将光照下产生的电流收集并导出，需要在电池片的正面及背面上分别制作一个电极。制造电极的方法多种多样，其中丝网印刷及共烧是目前最为普遍的一种生产工艺。如正面电极的制造中，采用丝网印刷的方式将导电浆料涂覆于硅片上，并通过烧结在硅片正面上形成正面电极。烧结后的晶硅太阳能电池正面电极需要在硅片上附着牢固，栅线窄而高，遮光面积小，易于焊接，硅太阳能电池正面电极用导电浆料要具备在烧结过程中穿透氮化硅减反射膜的能力，与硅电池片形成良好的欧姆接触。As a component of the core of a crystalline silicon solar cell, in order to collect and derive the current generated by illumination, it is necessary to fabricate an electrode on the front and back sides of the cell. There are various methods for manufacturing electrodes, and screen printing and co-firing are currently the most common production processes. In the manufacture of the front electrode, a conductive paste is applied to the silicon wafer by screen printing, and a front electrode is formed on the front surface of the silicon wafer by sintering. The front electrode of the sintered crystalline silicon solar cell needs to be firmly adhered on the silicon wafer, the gate line is narrow and high, the light shielding area is small, and the welding is easy, and the conductive paste for the front electrode of the silicon solar cell needs to have the silicon nitride penetrated during the sintering process. The ability of the anti-reflective film to form a good ohmic contact with the silicon cell.
常见的晶硅太阳能电池正面导电浆料含有银粉、玻璃粉、有机载体，导电浆料经过烧结形成正面电极。在烧结过程中，导电浆料中的氧化物刻蚀剂蚀刻并穿透晶硅太阳能电池正面或光照面的减反射绝缘层如氮化硅、氧化钛、氧化铝、氧化硅或氧化硅/氧化钛，使银粉与晶硅太阳能电池基体接触，形成正面电极。随着太阳能电池方阻的提升，传统的正面导电浆料以及使用的玻璃粉不能很好的刻蚀电池片表面的减反射绝缘层，其形成的正面电极与硅片表面接触电阻高，从而影响了电池片的光电转化效率。A common conductive paste on the front side of a crystalline silicon solar cell contains silver powder, glass frit, and an organic carrier, and the conductive paste is sintered to form a front electrode. During the sintering process, the oxide etchant in the conductive paste etches and penetrates the anti-reflective insulating layer of the front side or the illuminated side of the crystalline silicon solar cell such as silicon nitride, titanium oxide, aluminum oxide, silicon oxide or silicon oxide/oxidation. Titanium causes the silver powder to contact the substrate of the crystalline silicon solar cell to form a front electrode. With the increase of the square resistance of the solar cell, the conventional front conductive paste and the used glass powder can not well etch the anti-reflection insulating layer on the surface of the cell, and the surface electrode formed by the front electrode and the surface of the silicon wafer has high contact resistance, thereby affecting The photoelectric conversion efficiency of the battery sheet.
发明概述Summary of invention
技术问题technical problem
本发明所要解决的技术问题是：提供一种晶硅太阳能电池正面导电浆料及其制备方法，以解决现有正面导电浆料存在的不能有效的对电池片表面的减反射绝缘层进行刻蚀，从而导致正面电极与硅片表面接触的电阻值升高，最终使得电池片光电转化效率降低等问题。The technical problem to be solved by the present invention is to provide a front side conductive paste of a crystalline silicon solar cell and a preparation method thereof, so as to solve the problem that the existing front conductive paste cannot effectively etch the anti-reflective insulating layer on the surface of the cell sheet. Therefore, the resistance value of the front electrode contacting the surface of the silicon wafer is increased, and finally the photoelectric conversion efficiency of the battery sheet is lowered.
进一步地，本发明还提供一种晶硅太阳能电池正面电极的制作方法及太阳能电池。Further, the present invention also provides a method for fabricating a front electrode of a crystalline silicon solar cell and a solar cell.
问题的解决方案Problem solution
技术解决方案Technical solution
为了实现上述发明目的，本发明采用的技术方案如下：In order to achieve the above object, the technical solution adopted by the present invention is as follows:
一种晶硅太阳能电池正面导电浆料，按照重量份为100计，包括以下原料组分：A front side conductive paste of a crystalline silicon solar cell, in terms of 100 parts by weight, comprising the following raw material components:
金属粉 80.0～93.0份；Metal powder 80.0-93.0 parts;
有机载体 6.0～15.0份；Organic carrier 6.0 to 15.0 parts;
氧化物刻蚀剂 1.0～5.0份；Oxide etchant 1.0 to 5.0 parts;
其中，所述氧化物刻蚀剂至少含有Pb 3O 4、CuO、P 2O 5及Li 2O，且所述CuO和Pb 3O 4的重量比为0.1∶24～10∶6，所述CuO和P 2O 5的重量比为0.1∶10～10∶0.1，所述CuO和Li 2O的重量比为0.1∶20～10∶5。 Wherein the oxide etchant contains at least Pb 3 O 4 , CuO, P 2 O 5 and Li 2 O, and the weight ratio of the CuO to Pb 3 O 4 is from 0.1:24 to 10:6. The weight ratio of CuO to P 2 O 5 is from 0.1:10 to 10:0.1, and the weight ratio of CuO to Li 2 O is from 0.1:20 to 10:5.
相应地，一种晶硅太阳能电池正面导电浆料的制备方法，至少包括以下步骤：Correspondingly, a method for preparing a conductive paste on a front side of a crystalline silicon solar cell comprises at least the following steps:
步骤S01.将氧化物刻蚀剂原料组分进行熔融得到氧化物刻蚀剂熔液，对所述熔液进行骤冷处理，得到氧化物刻蚀剂颗粒，并经过破碎获得粒径在0.1～5.0μm的氧化物刻蚀剂粉末；Step S01. Melt the oxide etchant raw material component to obtain an oxide etchant melt, and quench the molten liquid to obtain oxide etchant particles, and obtain a particle size of 0.1 to 5.0 after crushing. Mm of an oxide etchant powder;
步骤S02.将有机载体原料置于40～100℃环境中进行混合处理，得到有机载体；Step S02. The organic carrier raw material is placed in an environment of 40 to 100 ° C for mixing treatment to obtain an organic vehicle;
步骤S03.将金属粉与步骤S01得到的氧化物刻蚀剂粉末、步骤S02得到的有机载体三者进行混料处理，获得晶硅太阳能电池正面导电浆料。Step S03. The metal powder is mixed with the oxide etchant powder obtained in the step S01 and the organic vehicle obtained in the step S02 to obtain a front side conductive paste of the crystalline silicon solar cell.
相应地，一种晶硅太阳能电池正面电极的制作方法，至少包括以下步骤：Correspondingly, a method for fabricating a front electrode of a crystalline silicon solar cell includes at least the following steps:
提供表面叠设有绝缘膜的晶体硅半导体元件；Providing a crystalline silicon semiconductor component having an insulating film on its surface;
通过印制的方式将如上所述的晶硅太阳能电池正面导电浆料印制于所述绝缘膜 表面，随后依次进行干燥、烧结、冷却处理，得到晶硅太阳能电池正面电极。The front side conductive paste of the crystalline silicon solar cell as described above is printed on the surface of the insulating film by printing, and then sequentially dried, sintered, and cooled to obtain a front surface electrode of the crystalline silicon solar cell.
以及，一种晶硅太阳能电池，所述晶硅太阳能电池采用如上所述的晶硅太阳能电池正面电极。And, a crystalline silicon solar cell using the front surface electrode of the crystalline silicon solar cell as described above.
发明的有益效果Advantageous effects of the invention
有益效果Beneficial effect
相对于现有技术，本发明提供的晶硅太阳能电池正面导电浆料由于氧化物刻蚀剂中含有Pb 3O 4、CuO、P 2O 5及Li 2O这几种组分，且这几种组分以特定重量比例存在，这些特定重量比例的组分能表现出优异的刻蚀性能和附着力，使得氧化物刻蚀剂在烧结过程中能够从银粉中溶解足够的银，溶解了银的所述氧化物刻蚀剂液体一部分用于润湿金属粉并促使其烧结，另一部分则流动至太阳能电池表面与减反射层反应，能够有效的刻蚀减反射层，在冷却过程中，溶解在氧化物刻蚀剂液体中的银析出形成微小的纳米银颗粒，使金属粉与硅形成良好的欧姆接触，极大的降低正面电极的电阻，最终获得接触电阻低、导电性能好、附着力强的正面电极。 Compared with the prior art, the front surface conductive paste of the crystalline silicon solar cell provided by the present invention contains Pb 3 O 4 , CuO, P 2 O 5 and Li 2 O components in the oxide etchant, and these The components are present in a specific weight ratio, and the components of these specific weight ratios can exhibit excellent etching performance and adhesion, so that the oxide etchant can dissolve enough silver from the silver powder during the sintering process to dissolve the silver. One part of the oxide etchant liquid is used to wet the metal powder and promote sintering thereof, and the other part flows to the surface of the solar cell to react with the anti-reflection layer, which can effectively etch the anti-reflection layer and dissolve in the cooling process. The silver in the oxide etchant liquid precipitates to form tiny nano silver particles, which makes the metal powder form good ohmic contact with silicon, greatly reduces the resistance of the front electrode, and finally obtains low contact resistance, good electrical conductivity, and adhesion. Strong frontal electrode.
本发明提供的晶硅太阳能电池正面导电浆料的制备方法，工艺条件简单，获得的正面导电浆料组分均匀且性能良好，适于工业大规模生产。The preparation method of the front side conductive paste of the crystalline silicon solar cell provided by the invention has simple process conditions, and the obtained front conductive paste component has uniform composition and good performance, and is suitable for industrial mass production.
本发明提供的晶硅太阳能电池正面电极的制作方法，由于采用了上述提供的晶硅太阳能电池正面导电浆料，氧化物刻蚀剂在烧结过程中能够从银粉中溶解足够的银，溶解了银的所述氧化物刻蚀剂液体一部分用于润湿金属粉并促使其烧结，另一部分则流动至太阳能电池表面与减反射层反应，能够有效的刻蚀减反射层，在冷却过程中，溶解在氧化物刻蚀剂液体中的银析出形成微小的纳米银颗粒，使金属粉与硅形成良好的欧姆接触，极大的降低正面电极的电阻，最终获得接触电阻低、导电性能好、附着力强的正面电极。The method for fabricating the front electrode of the crystalline silicon solar cell provided by the invention adopts the conductive paste on the front side of the crystalline silicon solar cell provided above, and the oxide etchant can dissolve enough silver from the silver powder during the sintering process to dissolve the silver. One part of the oxide etchant liquid is used to wet the metal powder and promote sintering thereof, and the other part flows to the surface of the solar cell to react with the anti-reflection layer, which can effectively etch the anti-reflection layer and dissolve in the cooling process. The silver in the oxide etchant liquid precipitates to form tiny nano silver particles, which makes the metal powder form good ohmic contact with silicon, greatly reduces the resistance of the front electrode, and finally obtains low contact resistance, good electrical conductivity, and adhesion. Strong frontal electrode.
本发明提供的晶硅太阳能电池，由于采用了上述的晶硅太阳能电池正面电极结构，太阳能电池结构表现出良好的附着力，同时银电极和硅片具有良好的欧姆接触，电阻小，导电性能好，使得太阳能电池的转换效率得到提高。The crystalline silicon solar cell provided by the invention adopts the above-mentioned front electrode structure of the crystalline silicon solar cell, and the solar cell structure exhibits good adhesion, and the silver electrode and the silicon wafer have good ohmic contact, small electrical resistance and good electrical conductivity. The conversion efficiency of the solar cell is improved.
对附图的简要说明Brief description of the drawing
附图说明DRAWINGS
图1为本发明提供的晶硅太阳能电池正面导电浆料的制备方法工艺流程示意图；1 is a schematic view showing a process flow of a method for preparing a conductive paste on a front side of a crystalline silicon solar cell according to the present invention;
图2为本发明提供的晶硅太阳能电池正面电极的制作方法工艺流程示意图；2 is a schematic view showing a process flow of a method for fabricating a front electrode of a crystalline silicon solar cell according to the present invention;
图3为本发明提供的在表面具有绝缘膜的晶体硅半导体元件上印刷了本发明所述的正面导电浆料的示意图；3 is a schematic view showing the front conductive paste of the present invention printed on a crystalline silicon semiconductor device having an insulating film on its surface according to the present invention;
图4为本发明图3中印刷了正面和背面浆料的晶体硅半导体元件烧结后的示意图；Figure 4 is a schematic view showing the sintered crystalline silicon semiconductor device with the front and back pastes printed in Figure 3 of the present invention;
图5为180度拉伸测试示意图。Figure 5 is a schematic diagram of a 180 degree tensile test.
其中，100-晶体硅电池片；200-P/N结；300-绝缘膜；400-印刷的正面导电浆料，401-金属粉，402-有机载体，403-氧化物刻蚀剂；500-印刷的背面银浆；600-印刷的背面铝浆；700-正面电极；800-焊带；900-拉伸机；901-拉伸机样品第一固定螺栓；902-拉伸机样品第二固定螺栓；F-拉力方向。Among them, 100-crystalline silicon cell sheet; 200-P/N junction; 300-insulating film; 400-printed front conductive paste, 401-metal powder, 402-organic carrier, 403-oxide etchant; Printed back silver paste; 600-printed back aluminum paste; 700-front electrode; 800-weld strip; 900-stretcher; 901-stretcher sample first fixing bolt; 902-stretcher sample second fixed Bolt; F-pull direction.
发明实施例Invention embodiment
本发明的实施方式Embodiments of the invention
为了使本发明要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例和附图，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly, the present invention will be further described in detail below with reference to the embodiments and the accompanying drawings. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
本发明提供一种晶硅太阳能电池正面导电浆料，按照重量份为100计，包括以下原料组分：The invention provides a front side conductive paste of a crystalline silicon solar cell, which comprises the following raw material components in terms of 100 parts by weight:
金属粉 80.0～93.0份；Metal powder 80.0-93.0 parts;
有机载体 6.0～15.0份；Organic carrier 6.0 to 15.0 parts;
氧化物刻蚀剂 1.0～5.0份；Oxide etchant 1.0 to 5.0 parts;
其中，所述氧化物刻蚀剂至少含有Pb 3O 4、CuO、P 2O 5及Li 2O，且所述CuO和Pb 3O 4的重量比为0.1∶24～10∶6，所述CuO和P 2O 5的重量比为0.1∶10～10∶0；所述CuO和Li 2O的重量比为0.1∶20～10∶5。 Wherein the oxide etchant contains at least Pb 3 O 4 , CuO, P 2 O 5 and Li 2 O, and the weight ratio of the CuO to Pb 3 O 4 is from 0.1:24 to 10:6. The weight ratio of CuO to P 2 O 5 is from 0.1:10 to 10:0; and the weight ratio of CuO to Li 2 O is from 0.1:20 to 10:5.
更为具体地，以所述氧化物刻蚀剂总重量100％计，所述氧化物刻蚀剂包括以下组分：More specifically, the oxide etchant comprises the following components in an amount of 100% by weight of the total oxide etchant:
Figure PCTCN2018081376-appb-000001
Figure PCTCN2018081376-appb-000001
Figure PCTCN2018081376-appb-000002
Figure PCTCN2018081376-appb-000002
添加元素的氧化物0～5.0％。The oxide of the added element is 0 to 5.0%.
本发明的配方组分中，由于氧化物刻蚀剂中含有Pb 3O 4、CuO、P 2O 5及Li 2O这几种组分，并且这几种组分以特定重量比例存在，这些特定重量比例的组分能表现出优异的刻蚀性能和附着力，当氧化物刻蚀剂在烧结过程中熔融为液体能够从银粉中溶解足够的银，溶解了银的所述氧化物刻蚀剂液体的一部分用于对金属粉进行润湿并促使金属粉烧结；另一部分溶解了银的氧化物刻蚀剂液体流动至太阳能电池表面与减反射层反应，能够有效的刻蚀减反射层，烧结后在冷却过程中，溶解在氧化物刻蚀剂液体中的银析出形成微小的纳米银颗粒，使金属粉与硅形成良好的欧姆接触，降低了电阻，形成接触电阻低、导电性能好、附着力强的正面电极。 In the formulation component of the present invention, since the oxide etchant contains components such as Pb 3 O 4 , CuO, P 2 O 5 and Li 2 O, and these components are present in a specific weight ratio, these The composition of a specific weight ratio can exhibit excellent etching performance and adhesion. When the oxide etchant is melted into a liquid during the sintering process, sufficient silver can be dissolved from the silver powder, and the oxide etching of the dissolved silver is performed. Part of the liquid is used to wet the metal powder and promote the sintering of the metal powder; another part of the silver oxide etchant liquid flows to the surface of the solar cell to react with the anti-reflection layer, which can effectively etch the anti-reflection layer. After sintering, during the cooling process, the silver dissolved in the oxide etchant liquid precipitates to form tiny nano-silver particles, which makes the metal powder form good ohmic contact with silicon, reduces the resistance, forms low contact resistance, and has good electrical conductivity. A strong front electrode.
优选地，添加元素的氧化物中添加元素为钛、铝、银、铬、钪、铜、铌、钒、钠、钽、锶、溴、钴、铪、镧、钇、镱、铁、钡、锰、镁、镍、钙、锡、砷、锆、钾、磷、铟、镓、锗等中的一种或者两种及以上。Preferably, the added elements in the oxide of the added element are titanium, aluminum, silver, chromium, lanthanum, copper, cerium, vanadium, sodium, lanthanum, cerium, bromine, cobalt, lanthanum, cerium, lanthanum, cerium, iron, lanthanum, One or two or more of manganese, magnesium, nickel, calcium, tin, arsenic, zirconium, potassium, phosphorus, indium, gallium, antimony, and the like.
本发明中，氧化物刻蚀剂不仅包括使用化学方法制成的氧化物和经过高温处理后得到的氧化物，还包括其含有阳离子的碳酸盐、磷酸盐、氟化物等，例如所述的锂的氧化物Li 2O可以使用Li 2CO 3取代。所述的铜的氧化物包括CuO和Cu 2(OH) 2CO 3CuO，所述的锌的氧化物包括ZnO和Zn 3(PO 4) 2，所述的钙的氧化物包括CaO和CaCO 3。 In the present invention, the oxide etchant includes not only oxides obtained by chemical methods and oxides obtained after high-temperature treatment, but also carbonates, phosphates, fluorides thereof and the like containing cations, for example, The lithium oxide Li 2 O can be substituted with Li 2 CO 3 . The oxide of copper includes CuO and Cu 2 (OH) 2 CO 3 CuO, the oxide of zinc includes ZnO and Zn 3 (PO 4 ) 2 , and the oxide of calcium includes CaO and CaCO 3 . .
优选地，氧化物刻蚀剂可以为晶体或者非晶体或者非晶体与晶体的混合物。Preferably, the oxide etchant may be crystalline or amorphous or a mixture of amorphous and crystalline.
优选地，所述金属粉为银、金、铂、铜、铁、镍、锌、钛、钴、铬、铝、锰、钯、铑中的至少一种。Preferably, the metal powder is at least one of silver, gold, platinum, copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminum, manganese, palladium, and rhodium.
进一步优选地，所述金属粉为银包覆的铜、铁、镍、锌、钛、钴、铬、铝、锰中的至少一种，其中，银包覆层的厚度为10～50nm。Further preferably, the metal powder is at least one of silver-coated copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminum, and manganese, wherein the silver coating layer has a thickness of 10 to 50 nm.
优选地，所述金属粉为非银包覆的金属粉和银包覆的金属粉的混合体，其中，所述非银包覆的金属粉与银包覆的金属粉的重量比为5/95～95/5，非银包覆的金属粉为银、金、铂、铜、铁、镍、锌、钛、钴、铬、铝、锰、钯、铑中的至少一种；银包覆的金属粉为铜、铁、镍、锌、钛、钴、铬、铝、锰中的至少一种，所述银包覆层的厚度为10～50nm。Preferably, the metal powder is a mixture of a non-silver-coated metal powder and a silver-coated metal powder, wherein a weight ratio of the non-silver-coated metal powder to the silver-coated metal powder is 5/ 95~95/5, the non-silver coated metal powder is at least one of silver, gold, platinum, copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminum, manganese, palladium, iridium; The metal powder is at least one of copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminum, and manganese, and the silver coating layer has a thickness of 10 to 50 nm.
本发明中所述有机载体包括有机溶剂、聚合物、润湿分散剂、触变剂及其他功能助剂等。The organic vehicle in the present invention includes an organic solvent, a polymer, a wetting and dispersing agent, a thixotropic agent, and other functional additives.
以所述有机载体重量为100份计，包括以下组分：有机溶剂50～95份；聚合物1～40份；润湿分散剂0.1～10份；触变剂1～20份。The weight of the organic vehicle is 100 parts by weight, including the following components: 50 to 95 parts of an organic solvent; 1 to 40 parts of a polymer; 0.1 to 10 parts of a wetting and dispersing agent; and 1 to 20 parts of a thixotropic agent.
其中，所述有机溶剂选自松油醇、乙二醇丁醚醋酸酯、乙二醇***醋酸酯、十二醇酯、二乙二醇丁醚、三乙二醇丁醚、三丙二醇甲醚、萜烯类等高沸点的溶剂中的至少一种。Wherein, the organic solvent is selected from the group consisting of terpineol, ethylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate, dodecyl alcohol ester, diethylene glycol butyl ether, triethylene glycol butyl ether, and tripropylene glycol methyl ether. At least one of high boiling solvents such as terpenes.
所述聚合物选自乙基纤维素、甲基纤维素、纤维素及其衍生物、丙烯酸树脂、醇酸树脂、聚酯树脂中的至少一种。The polymer is selected from at least one of ethyl cellulose, methyl cellulose, cellulose and derivatives thereof, acrylic resin, alkyd resin, and polyester resin.
所述润湿分散剂选自脂肪酸(油酸、硬酯酸等)、脂肪酸的酰胺衍生物(油酸酰胺、硬脂酰胺等)、脂肪酸的酯类衍生物、聚乙烯蜡、聚乙二醇中的一种或者两种以上，主要用于帮助无机粉体在有机载体中的分散。The wetting and dispersing agent is selected from the group consisting of fatty acids (oleic acid, stearic acid, etc.), amide derivatives of fatty acids (oleic acid amide, stearic acid amide, etc.), ester derivatives of fatty acids, polyethylene wax, polyethylene glycol. One or more of them are mainly used to help disperse inorganic powders in an organic vehicle.
所述触变剂选自氢化蓖麻油衍生物、聚酰胺蜡、聚脲、气相二氧化硅中的一种或者两种以上，主要用于增加浆料在印刷过程中的触变性，使银浆在印刷过程中受到剪切时，稠度变小，容易丝网印刷，停止剪切时，稠度又增加，以保证电极有优异的高宽比。The thixotropic agent is selected from one or more of hydrogenated castor oil derivatives, polyamide waxes, polyureas, fumed silicas, and is mainly used to increase the thixotropy of the slurry during printing, so that the silver paste When sheared during printing, the consistency becomes small, and it is easy to screen-print. When the shearing is stopped, the consistency is increased to ensure that the electrode has an excellent aspect ratio.
进一步地，有机载体还可以包括其他功能助剂，所述其他功能助剂的重量份为0.1-20份，选自聚甲基苯基硅氧烷、聚苯基硅氧烷、邻苯二甲酸酯类(如邻苯二甲酸二乙酯、邻苯二甲酸二丁酯等)、微晶蜡、聚二甲基硅氧烷、聚乙烯醇缩丁醛( PVB)、聚醚聚酯改性有机硅氧烷、烷基改性有机硅氧烷中的一种或者两种以上。所述其他功能助剂可根据需要选择添加，如加入微晶蜡等以降低表面张力，加入邻苯二甲酸二丁酯(DBP)等以改善浆料的柔韧性，加入聚乙烯醇缩丁醛(PVB)等改善黏附力。Further, the organic vehicle may further include other functional assistants in an amount of 0.1-20 parts by weight, selected from the group consisting of polymethylphenylsiloxane, polyphenylsiloxane, and phthalic acid. Ester (such as diethyl phthalate, dibutyl phthalate, etc.), microcrystalline wax, polydimethylsiloxane, polyvinyl butyral (PVB), polyether polyester modification One or more of an organosiloxane and an alkyl-modified organosiloxane. The other functional assistants may be optionally added according to requirements, such as adding microcrystalline wax to reduce surface tension, adding dibutyl phthalate (DBP), etc. to improve the flexibility of the slurry, and adding polyvinyl butyral. (PVB) and the like improve adhesion.
如图1所示，本发明所述的晶硅太阳能电池正面导电浆料的制备方法包括以下步骤：As shown in FIG. 1, the method for preparing a front side conductive paste of a crystalline silicon solar cell according to the present invention comprises the following steps:
S01.氧化物刻蚀剂的制备步骤如下：按照如上所述的原料比例称取氧化物刻蚀剂原料并且进行均匀混合；将所述的均匀混合的氧化物刻蚀剂原料放入加热炉加热至900～1100℃，并在900-1100℃下保温60-180min，得到熔融的液态氧化物刻蚀剂；将所述熔融的液态氧化物刻蚀剂进行骤冷处理，得到氧化物刻蚀剂颗粒；将所述氧化物刻蚀剂颗粒置于60～80℃温度中烘干；将所述的干燥的氧化物刻蚀剂颗粒进行破碎处理得到粒度0.5-5.0μm的氧化物刻蚀剂粉，然后置于干燥箱中在80～100℃烘干得到干燥的氧化物刻蚀剂粉。S01. The step of preparing the oxide etchant is as follows: the oxide etchant raw material is weighed according to the raw material ratio as described above and uniformly mixed; and the uniformly mixed oxide etchant raw material is placed in a heating furnace for heating Up to 900-1100 ° C, and maintaining at 900-1100 ° C for 60-180 min, to obtain a molten liquid oxide etchant; quenching the molten liquid oxide etchant to obtain oxide etchant particles The oxide etchant particles are dried at a temperature of 60 to 80 ° C; the dried oxide etchant particles are subjected to crushing treatment to obtain an oxide etchant powder having a particle size of 0.5 to 5.0 μm. Then, it is dried in a drying oven at 80 to 100 ° C to obtain a dried oxide etchant powder.
优选地，所述骤冷方式为将熔融的液态氧化物刻蚀剂倒入5-25℃水中冷却或者在流动的室温空气中冷却，流动的冷空气温度在25℃及以下。Preferably, the quenching method is to pour the molten liquid oxide etchant into water at 5-25 ° C or to cool in flowing room temperature air at a temperature of 25 ° C or below.
上述对氧化物刻蚀颗粒的破碎，可以采用球磨机进行球磨处理，也可以使用其他方式使得氧化物刻蚀剂颗粒粒径变小。The above-mentioned crushing of the oxide etched particles may be performed by a ball mill for ball milling, or other methods may be used to make the particle size of the oxide etchant smaller.
S02.有机载体的制备如下：按上所述有机载体原料重量比例依次称取有机载体的原料，将称取的有机载体原料放入容器，在40～100℃的温度下搅拌混合100～160min，得到有机载体。S02. The organic carrier is prepared as follows: the raw materials of the organic carrier are sequentially weighed according to the weight ratio of the organic carrier raw materials mentioned above, and the weighed organic carrier raw materials are placed in a container, and stirred and mixed at a temperature of 40 to 100 ° C for 100 to 160 minutes. An organic vehicle is obtained.
S03.正面电极导电浆料的制备，将金属粉与上述制备的氧化物刻蚀剂、有机载体进行混合、破碎得到所述正面电极导电浆料。S03. Preparation of a front electrode conductive paste, mixing the metal powder with the above-prepared oxide etchant and organic carrier, and crushing to obtain the front electrode conductive paste.
本发明所述晶硅太阳能电池正面导电浆料的制作方法还有如下替换方法：The method for fabricating the front side conductive paste of the crystalline silicon solar cell of the present invention further has the following alternative method:
在一个实施方案中，先将氧化物刻蚀剂和金属粉进行混合，得到第一混合物，再将该第一混合物与有机载体进行混合，然后进行研磨处理，得到晶硅太阳能电池正面电极导电浆料。In one embodiment, the oxide etchant and the metal powder are first mixed to obtain a first mixture, and the first mixture is mixed with an organic vehicle, and then subjected to a grinding treatment to obtain a front electrode conductive paste of the crystalline silicon solar cell. material.
在另一个实施方案中，先将上述氧化物刻蚀剂和有机载体进行混合，得到第一混合物，再往该第一混合物中加入金属粉，然后进行研磨处理，得到晶硅太阳 能电池正面电极导电浆料。In another embodiment, the above oxide etchant and the organic carrier are first mixed to obtain a first mixture, and then the metal powder is added to the first mixture, and then ground to obtain a front electrode of the crystalline silicon solar cell. Slurry.
在又一个实施方案中，先将金属粉和有机载体进行混合，得到第一混合物，再向该第一混合物中加入氧化物刻蚀剂，然后进行研磨处理，得到晶硅太阳能电池正面电极导电浆料。In still another embodiment, the metal powder and the organic carrier are first mixed to obtain a first mixture, and then an oxide etchant is added to the first mixture, followed by grinding treatment to obtain a front electrode conductive paste of the crystalline silicon solar cell. material.
在再一个实施方案中，分别以金属粉、有机载体、氧化物刻蚀剂各自重量份为100计，先将20～60重量份的金属粉和20～60重量份的有机载体进行混合，得到第一混合物；再将40～80重量份氧化物刻蚀剂和部分有机载体进行混合，得到第二混合物，然后再将该第一混合物和第二混合物进行混合，研磨处理，得到晶硅太阳能电池正面电极导电浆料。In still another embodiment, 20 to 60 parts by weight of the metal powder and 20 to 60 parts by weight of the organic vehicle are first mixed with 100 parts by weight of the metal powder, the organic vehicle, and the oxide etchant, respectively. a first mixture; further mixing 40 to 80 parts by weight of the oxide etchant and a portion of the organic vehicle to obtain a second mixture, and then mixing the first mixture and the second mixture, and grinding to obtain a crystalline silicon solar cell The front electrode is conductive paste.
请参考图2、图3及图4，本发明还提供一种晶硅太阳能电池正面电极的制作方法。Referring to FIG. 2, FIG. 3 and FIG. 4, the present invention also provides a method for fabricating a front electrode of a crystalline silicon solar cell.
所述制作方法涉及表面叠设有绝缘膜的晶体硅半导体元件，所述晶体硅半导体元件的结构如图3所示，100为具有相对第一表面和第二表面的晶体硅电池片，在第一表面向外依次叠设有P/N结200、绝缘膜300，在第一表面上印刷有背面银浆500、背面铝浆600，其中，绝缘膜300可以是氮化硅膜、氧化钛膜、氧化铝膜、氧化硅膜中的至少一种。The manufacturing method relates to a crystalline silicon semiconductor device having an insulating film laminated on its surface, the crystalline silicon semiconductor device having a structure as shown in FIG. 3, 100 being a crystalline silicon cell having a first surface and a second surface, in the first A P/N junction 200 and an insulating film 300 are sequentially stacked on a surface, and a back surface silver paste 500 and a back aluminum paste 600 are printed on the first surface. The insulating film 300 may be a silicon nitride film or a titanium oxide film. At least one of an aluminum oxide film and a silicon oxide film.
具体地，所述晶硅太阳能电池正面电极的制作方法，至少包括以下步骤：Specifically, the method for fabricating the front electrode of the crystalline silicon solar cell includes at least the following steps:
步骤S04.提供表面叠设有绝缘膜300的晶体硅半导体元件；Step S04. Providing a crystalline silicon semiconductor component having an insulating film 300 on its surface;
步骤S05.通过印制的方式将如上所述的晶硅太阳能电池正面导电浆料400(其中，401为金属粉、402为有机载体、403为氧化物刻蚀剂)印制于所述绝缘膜300表面；Step S05. Printing the crystalline silicon solar cell front conductive paste 400 (where 401 is metal powder, 402 is an organic carrier, and 403 is an oxide etchant) on the insulating film by printing. 300 surface;
步骤S06.对步骤S05处理后的晶体硅半导体元件依次进行干燥、烧结、冷却处理，得到晶硅太阳能电池正面电极700。Step S06. The crystalline silicon semiconductor device processed in the step S05 is sequentially dried, sintered, and cooled to obtain a crystalline silicon solar cell front electrode 700.
具体地，干燥温度为80～400℃，烧结温度为700～820℃，冷却条件为自然冷却。Specifically, the drying temperature is 80 to 400 ° C, the sintering temperature is 700 to 820 ° C, and the cooling condition is natural cooling.
本发明还进一步地提供一种晶硅太阳能电池，所述晶硅太阳能电池采用如上所述的晶硅太阳能电池正面电极。The present invention still further provides a crystalline silicon solar cell using the front surface electrode of a crystalline silicon solar cell as described above.
为了更好的说明本发明实施例提供的晶硅太阳能电池正面导电浆料及其制备方 法，下面通过多个实施例进一步解释说明。In order to better illustrate the front side conductive paste of the crystalline silicon solar cell provided by the embodiment of the present invention and a method for preparing the same, the following further explains by way of various embodiments.
实施例1Example 1
一种晶硅太阳能电池正面导电浆料，按总重量为100份计算，包括如下配方比例的组分：银粉88.5份；有机载体9.0份；氧化物刻蚀剂2.5份。A front side conductive paste of a crystalline silicon solar cell, calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
其中，以所述氧化物刻蚀剂重量为100％计，包括以下组分：Wherein, based on 100% by weight of the oxide etchant, the following components are included:
Pb 3O 46％、TeO 255％、Li 2O 5％、SiO 220％、B 2O 32.9％、Bi 2O 32％、ZnO 3％、WO 31％、CuO 0.1％、P 2O 55％。 Pb 3 O 4 6%, TeO 2 55%, Li 2 O 5%, SiO 2 20%, B 2 O 3 2.9%, Bi 2 O 3 2%, ZnO 3%, WO 3 1%, CuO 0.1%, P 2 O 5 5%.
所述氧化物刻蚀剂的制备方法为：按照以上所述的比例称取氧化物刻蚀剂原料并且进行均匀混合；将所述的均匀混合的氧化物刻蚀剂原料放入加热炉加热至1000℃，并在1000℃下保温120min，得到熔融的液态氧化物刻蚀剂；将所述的熔融的液态氧化物刻蚀剂倒入常温(25℃)水中冷却得到氧化物刻蚀剂颗粒；将所述的氧化物刻蚀剂颗粒置于干燥箱中在80℃烘干；将所述的干燥的氧化物刻蚀剂颗粒置于球磨机中进行研磨得到粒度0.5～7.0μm的氧化物刻蚀剂粉，然后置于干燥箱中在100℃烘干得到干燥的氧化物刻蚀剂粉。The oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 μm. The powder was then dried in a dry box at 100 ° C to obtain a dry oxide etchant powder.
以所述有机载体重量为100％计，所述有机载体含有以下组分：松油醇、十二醇酯、萜烯三者的混合物70％；乙基纤维素10％、松香树脂15％、聚酰胺蜡5％。The organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle. Polyamide wax 5%.
所述晶硅太阳能电池正面导电浆料的制备方法包括以下步骤：The preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
按照以上所述配方重量比例称取银粉88.5份，有机载体9.0份和所述氧化物刻蚀剂粉2.5份，均匀混合和研磨处理，得到所述晶硅太阳能电池正面导电浆料。88.5 parts of silver powder, 9.0 parts of organic carrier and 2.5 parts of the oxide etchant powder were weighed according to the above formula weight ratio, uniformly mixed and ground to obtain a front conductive paste of the crystalline silicon solar cell.
一种晶硅太阳能电池正面电极的制作方法，包括以下步骤：A method for manufacturing a front electrode of a crystalline silicon solar cell, comprising the following steps:
通过丝网印制的方式，将实施例1中晶硅太阳能电池正面导电浆料印制在具有绝缘膜的晶硅太阳能电池正面，其太阳能电池背面丝网印制了背银和背铝，然后于770℃进行烧结，得到所述的晶硅太阳能电池正面电极。The front surface conductive paste of the crystalline silicon solar cell of Embodiment 1 is printed on the front surface of the crystalline silicon solar cell with the insulating film by screen printing, and the back surface of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 770 ° C to obtain the front electrode of the crystalline silicon solar cell.
测试获得的所述电池片的效率，I-V测试结果汇总在表1中。The efficiency of the obtained cell sheets was tested, and the I-V test results are summarized in Table 1.
实施例2Example 2
一种晶硅太阳能电池正面导电浆料，按总重量为100份计算，包括如下配方比例的组分：银粉88.5份；有机载体9.0份；氧化物刻蚀剂2.5份。A front side conductive paste of a crystalline silicon solar cell, calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
其中，以所述氧化物刻蚀剂重量为100％计，包括以下组分：Wherein, based on 100% by weight of the oxide etchant, the following components are included:
Pb 3O 424％、TeO 220％、Li 2O 11％、SiO 22％、B 2O 39.9％、Bi 2O 35％、ZnO 13％、WO 35％、CuO 10％、P 2O 50.1％。 Pb 3 O 4 24%, TeO 2 20%, Li 2 O 11%, SiO 2 2%, B 2 O 3 9.9%, Bi 2 O 3 5%, ZnO 13%, WO 3 5%, CuO 10%, P 2 O 5 0.1%.
所述氧化物刻蚀剂的制备方法为：按照以上所述的比例称取氧化物刻蚀剂原料并且进行均匀混合；将所述的均匀混合的氧化物刻蚀剂原料放入加热炉加热至1000℃，并在1000℃下保温120min，得到熔融的液态氧化物刻蚀剂；将所述的熔融的液态氧化物刻蚀剂倒入常温(25℃)水中冷却得到氧化物刻蚀剂颗粒；将所述的氧化物刻蚀剂颗粒置于干燥箱中在80℃烘干；将所述的干燥的氧化物刻蚀剂颗粒置于球磨机中进行研磨得到粒度0.5～7.0μm的氧化物刻蚀剂粉，然后置于干燥箱中在100℃烘干得到干燥的氧化物刻蚀剂粉。The oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 μm. The powder was then dried in a dry box at 100 ° C to obtain a dry oxide etchant powder.
以所述有机载体重量为100％计，所述有机载体含有以下组分：松油醇、十二醇酯、萜烯三者的混合物70％；乙基纤维素10％、松香树脂15％、聚酰胺蜡5％。The organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle. Polyamide wax 5%.
所述晶硅太阳能电池正面导电浆料的制备方法包括以下步骤：The preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
按照以上所述配方重量比例称取银粉88.5份，有机载体9.0份，和所述氧化物刻蚀剂粉2.5份，进行均匀混合和研磨处理，得到所述晶硅太阳能电池正面导电浆料。88.5 parts of silver powder, 9.0 parts of organic carrier, and 2.5 parts of the oxide etchant powder were weighed according to the above formula weight ratio, and uniformly mixed and polished to obtain a front conductive paste of the crystalline silicon solar cell.
一种晶硅太阳能电池正面电极的制作方法，包括以下步骤：A method for manufacturing a front electrode of a crystalline silicon solar cell, comprising the following steps:
通过丝网印制的方式，将实施例2中晶硅太阳能电池正面导电浆料印制在具有绝缘膜的晶硅太阳能电池正面，其太阳能电池背面丝网印制了背银和背铝，然后于800℃进行烧结，得到所述的晶硅太阳能电池正面电极。The front side conductive paste of the crystalline silicon solar cell of Embodiment 2 is printed on the front side of the crystalline silicon solar cell with the insulating film by screen printing, and the back side of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 800 ° C to obtain the front electrode of the crystalline silicon solar cell.
测试获得的所述电池片的效率，I-V测试结果汇总在表1中。The efficiency of the obtained cell sheets was tested, and the I-V test results are summarized in Table 1.
实施例3Example 3
一种晶硅太阳能电池正面导电浆料，按总重量为100份计算，包括如下配方比例的组分：银粉88.5份；有机载体9.0份；氧化物刻蚀剂2.5份。A front side conductive paste of a crystalline silicon solar cell, calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
其中，以所述氧化物刻蚀剂重量为100％计，包括以下组分：Wherein, based on 100% by weight of the oxide etchant, the following components are included:
Pb 3O 412％、TeO 250％、Li 2O 20％、SiO 212％、B 2O 30.1％、Bi 2O 31％、ZnO 1％、WO 33.4％、CuO 0.5％。 Pb 3 O 4 12%, TeO 2 50%, Li 2 O 20%, SiO 2 12%, B 2 O 3 0.1%, Bi 2 O 3 1%, ZnO 1%, WO 3 3.4%, CuO 0.5%.
所述氧化物刻蚀剂的制备方法为：按照以上所述的比例称取氧化物刻蚀剂原料并且进行均匀混合；将所述的均匀混合的氧化物刻蚀剂原料放入加热炉加热至1 000℃，并在1000℃下保温120min，得到熔融的液态氧化物刻蚀剂；将所述的熔融的液态氧化物刻蚀剂倒入常温(25℃)水中冷却得到氧化物刻蚀剂颗粒；将所述的氧化物刻蚀剂颗粒置于干燥箱中在80℃烘干；将所述的干燥的氧化物刻蚀剂颗粒置于球磨机中进行研磨得到粒度0.5～7.0μm的氧化物刻蚀剂粉，然后置于干燥箱中在100℃烘干得到干燥的氧化物刻蚀剂粉。The oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1 000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles The oxide etchant particles are placed in a dry box and dried at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide oxide having a particle size of 0.5 to 7.0 μm. The etchant powder was then dried in a dry box at 100 ° C to obtain a dried oxide etchant powder.
以所述有机载体重量为100％计，所述有机载体含有以下组分：松油醇、十二醇酯、萜烯三者的混合物70％；乙基纤维素10％、松香树脂15％、聚酰胺蜡5％。The organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle. Polyamide wax 5%.
所述晶硅太阳能电池正面导电浆料的制备方法包括以下步骤：The preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
按照以上所述配方重量比例称取银粉88.5份，有机载体9.0份，和所述氧化物刻蚀剂粉2.5份，进行均匀混合和研磨处理，得到所述晶硅太阳能电池正面导电浆料。88.5 parts of silver powder, 9.0 parts of organic carrier, and 2.5 parts of the oxide etchant powder were weighed according to the above formula weight ratio, and uniformly mixed and polished to obtain a front conductive paste of the crystalline silicon solar cell.
一种晶硅太阳能电池正面电极的制作方法，包括以下步骤：A method for manufacturing a front electrode of a crystalline silicon solar cell, comprising the following steps:
通过丝网印制的方式，将实施例3中晶硅太阳能电池正面导电浆料印制在具有绝缘膜的晶硅太阳能电池正面，其太阳能电池背面丝网印制了背银和背铝，然后于780℃进行烧结，得到所述的晶硅太阳能电池正面电极。The front side conductive paste of the crystalline silicon solar cell of Embodiment 3 is printed on the front surface of the crystalline silicon solar cell having the insulating film by screen printing, and the back surface of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 780 ° C to obtain the front electrode of the crystalline silicon solar cell.
测试获得的所述电池片的效率，I-V测试结果汇总在表1中。The efficiency of the obtained cell sheets was tested, and the I-V test results are summarized in Table 1.
实施例4Example 4
一种晶硅太阳能电池正面导电浆料，按总重量为100份计算，包括如下配方比例的组分：银粉88.5份；有机载体9.0份；氧化物刻蚀剂2.5份。A front side conductive paste of a crystalline silicon solar cell, calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
其中，以所述氧化物刻蚀剂重量为100％计，包括以下组分：Wherein, based on 100% by weight of the oxide etchant, the following components are included:
Pb 3O 415％、TeO 221％、Li 2O 15％、SiO 211％、B 2O 32％、Bi 2O 32％、ZnO 11％、WO 315％、CuO 8％。 Pb 3 O 4 15%, TeO 2 21%, Li 2 O 15%, SiO 2 11%, B 2 O 3 2%, Bi 2 O 3 2%, ZnO 11%, WO 3 15%, CuO 8%.
所述氧化物刻蚀剂的制备方法为：按照以上所述的比例称取氧化物刻蚀剂原料并且进行均匀混合；将所述的均匀混合的氧化物刻蚀剂原料放入加热炉加热至1000℃，并在1000℃下保温120min，得到熔融的液态氧化物刻蚀剂；将所述的熔融的液态氧化物刻蚀剂倒入常温(25℃)水中冷却得到氧化物刻蚀剂颗粒；将所述的氧化物刻蚀剂颗粒置于干燥箱中在80℃烘干；将所述的干燥的氧化物刻蚀剂颗粒置于球磨机中进行研磨得到粒度0.5～7.0μm的氧化物刻蚀剂粉，然后置于干燥 箱中在100℃烘干得到干燥的氧化物刻蚀剂粉。The oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 μm. The powder was then dried in a dry box at 100 ° C to obtain a dry oxide etchant powder.
以所述有机载体重量为100％计，所述有机载体含有以下组分：松油醇、十二醇酯、萜烯三者的混合物70％；乙基纤维素10％、松香树脂15％、聚酰胺蜡5％。The organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle. Polyamide wax 5%.
所述晶硅太阳能电池正面导电浆料的制备方法包括以下步骤：The preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
按照以上所述配方重量比例称取银粉88.5份，有机载体9.0份，和所述氧化物刻蚀剂粉2.5份，进行均匀混合和研磨处理，得到所述晶硅太阳能电池正面导电浆料。88.5 parts of silver powder, 9.0 parts of organic carrier, and 2.5 parts of the oxide etchant powder were weighed according to the above formula weight ratio, and uniformly mixed and polished to obtain a front conductive paste of the crystalline silicon solar cell.
一种晶硅太阳能电池正面电极的制作方法，包括以下步骤：A method for manufacturing a front electrode of a crystalline silicon solar cell, comprising the following steps:
通过丝网印制的方式，将实施例4中晶硅太阳能电池正面导电浆料印制在具有绝缘膜的晶硅太阳能电池正面，其太阳能电池背面丝网印制了背银和背铝，然后于780℃进行烧结，得到所述的晶硅太阳能电池正面电极。The front side conductive paste of the crystalline silicon solar cell of Example 4 was printed on the front side of the crystalline silicon solar cell with an insulating film by screen printing, and the back side of the solar cell was screen printed with back silver and back aluminum, and then Sintering was carried out at 780 ° C to obtain the front electrode of the crystalline silicon solar cell.
测试获得的所述电池片的效率，I-V测试结果汇总在表1中。The efficiency of the obtained cell sheets was tested, and the I-V test results are summarized in Table 1.
实施例5Example 5
一种晶硅太阳能电池正面导电浆料，按总重量为100份计算，包括如下配方比例的组分：银粉88.5份；有机载体9.0份；氧化物刻蚀剂2.5份。A front side conductive paste of a crystalline silicon solar cell, calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
其中，以所述氧化物刻蚀剂重量为100％计，包括以下组分：Wherein, based on 100% by weight of the oxide etchant, the following components are included:
Pb 3O 48％、TeO 231％、Li 2O 15％、SiO 25％、B 2O 35％、Bi 2O 320％、ZnO 10％、WO 34％、CuO 2％。 Pb 3 O 4 8%, TeO 2 31%, Li 2 O 15%, SiO 2 5%, B 2 O 3 5%, Bi 2 O 3 20%, ZnO 10%, WO 3 4%, CuO 2%.
所述氧化物刻蚀剂的制备方法为：按照以上所述的比例称取氧化物刻蚀剂原料并且进行均匀混合；将所述的均匀混合的氧化物刻蚀剂原料放入加热炉加热至1000℃，并在1000℃下保温120min，得到熔融的液态氧化物刻蚀剂；将所述的熔融的液态氧化物刻蚀剂倒入常温(25℃)水中冷却得到氧化物刻蚀剂颗粒；将所述的氧化物刻蚀剂颗粒置于干燥箱中在80℃烘干；将所述的干燥的氧化物刻蚀剂颗粒置于球磨机中进行研磨得到粒度0.5～7.0μm的氧化物刻蚀剂粉，然后置于干燥箱中在100℃烘干得到干燥的氧化物刻蚀剂粉。The oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 μm. The powder was then dried in a dry box at 100 ° C to obtain a dry oxide etchant powder.
以所述有机载体重量为100％计，所述有机载体含有以下组分：松油醇、十二醇酯、萜烯三者的混合物70％；乙基纤维素10％、松香树脂15％、聚酰胺蜡5％。The organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle. Polyamide wax 5%.
所述晶硅太阳能电池正面导电浆料的制备方法包括以下步骤：The preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
按照以上所述配方重量比例称取银粉88.5份，有机载体9.0份，和所述氧化物刻蚀剂粉2.5份，进行均匀混合和研磨处理，得到所述晶硅太阳能电池正面导电浆料。88.5 parts of silver powder, 9.0 parts of organic carrier, and 2.5 parts of the oxide etchant powder were weighed according to the above formula weight ratio, and uniformly mixed and polished to obtain a front conductive paste of the crystalline silicon solar cell.
一种晶硅太阳能电池正面电极的制作方法，包括以下步骤：A method for manufacturing a front electrode of a crystalline silicon solar cell, comprising the following steps:
通过丝网印制的方式，将实施例5中晶硅太阳能电池正面导电浆料印制在具有绝缘膜的晶硅太阳能电池正面，其太阳能电池背面丝网印制了背银和背铝，然后于790℃进行烧结，得到所述的晶硅太阳能电池正面电极。The front side conductive paste of the crystalline silicon solar cell in Embodiment 5 is printed on the front surface of the crystalline silicon solar cell having the insulating film by screen printing, and the back surface of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 790 ° C to obtain the front electrode of the crystalline silicon solar cell.
测试获得的所述电池片的效率，I-V测试结果汇总在表1中。The efficiency of the obtained cell sheets was tested, and the I-V test results are summarized in Table 1.
实施例6Example 6
一种晶硅太阳能电池正面导电浆料，按总重量为100份计算，包括如下配方比例的组分：银粉88.5份；有机载体9.0份；氧化物刻蚀剂2.5份。A front side conductive paste of a crystalline silicon solar cell, calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
其中，以所述氧化物刻蚀剂重量为100％计，包括以下组分：Wherein, based on 100% by weight of the oxide etchant, the following components are included:
Pb 3O 410％、TeO 232％、Li 2O 20％、SiO 211.5％、B 2O 38％、Bi 2O 33％、ZnO 9％、WO 31％、CuO 5％。 Pb 3 O 4 10%, TeO 2 32%, Li 2 O 20%, SiO 2 11.5%, B 2 O 3 8%, Bi 2 O 3 3%, ZnO 9%, WO 3 1%, CuO 5%.
所述氧化物刻蚀剂的制备方法为：按照以上所述的比例称取氧化物刻蚀剂原料并且进行均匀混合；将所述的均匀混合的氧化物刻蚀剂原料放入加热炉加热至1000℃，并在1000℃下保温120min，得到熔融的液态氧化物刻蚀剂；将所述的熔融的液态氧化物刻蚀剂倒入常温(25℃)水中冷却得到氧化物刻蚀剂颗粒；将所述的氧化物刻蚀剂颗粒置于干燥箱中在80℃烘干；将所述的干燥的氧化物刻蚀剂颗粒置于球磨机中进行研磨得到粒度0.5～7.0μm的氧化物刻蚀剂粉，然后置于干燥箱中在100℃烘干得到干燥的氧化物刻蚀剂粉。The oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 μm. The powder was then dried in a dry box at 100 ° C to obtain a dry oxide etchant powder.
以所述有机载体重量为100％计，所述有机载体含有以下组分：松油醇、十二醇酯、萜烯三者的混合物70％；乙基纤维素10％、松香树脂15％、聚酰胺蜡5％。The organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle. Polyamide wax 5%.
所述晶硅太阳能电池正面导电浆料的制备方法包括以下步骤：The preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
按照以上所述配方重量比例称取银粉88.5份，有机载体9.0份，和所述氧化物刻蚀剂粉2.5份，进行均匀混合和研磨处理，得到所述晶硅太阳能电池正面导电浆料。88.5 parts of silver powder, 9.0 parts of organic carrier, and 2.5 parts of the oxide etchant powder were weighed according to the above formula weight ratio, and uniformly mixed and polished to obtain a front conductive paste of the crystalline silicon solar cell.
一种晶硅太阳能电池正面电极的制作方法，包括以下步骤：A method for manufacturing a front electrode of a crystalline silicon solar cell, comprising the following steps:
通过丝网印制的方式，将实施例6中晶硅太阳能电池正面导电浆料印制在具有绝缘膜的晶硅太阳能电池正面，其太阳能电池背面丝网印制了背银和背铝，然后于800℃进行烧结，得到所述的晶硅太阳能电池正面电极。The front side conductive paste of the crystalline silicon solar cell of Example 6 is printed on the front side of the crystalline silicon solar cell having the insulating film by screen printing, and the back side of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 800 ° C to obtain the front electrode of the crystalline silicon solar cell.
测试获得的所述电池片的效率，I-V测试结果汇总在表1中。The efficiency of the obtained cell sheets was tested, and the I-V test results are summarized in Table 1.
实施例7Example 7
一种晶硅太阳能电池正面导电浆料，按总重量为100份计算，包括如下配方比例的组分：银粉88.5份；有机载体9.0份；氧化物刻蚀剂2.5份。A front side conductive paste of a crystalline silicon solar cell, calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
其中，以所述氧化物刻蚀剂重量为100％计，包括以下组分：Wherein, based on 100% by weight of the oxide etchant, the following components are included:
Pb 3O 413％、TeO 230％、Li 2O 16％、SiO 212％、B 2O 30.3％、Bi 2O 35％、ZnO 15％、WO 35％、CuO 3.4％。 Pb 3 O 4 13%, TeO 2 30%, Li 2 O 16%, SiO 2 12%, B 2 O 3 0.3%, Bi 2 O 3 5%, ZnO 15%, WO 3 5%, CuO 3.4%.
所述氧化物刻蚀剂的制备方法为：按照以上所述的比例称取氧化物刻蚀剂原料并且进行均匀混合；将所述的均匀混合的氧化物刻蚀剂原料放入加热炉加热至1000℃，并在1000℃下保温120min，得到熔融的液态氧化物刻蚀剂；将所述的熔融的液态氧化物刻蚀剂倒入常温(25℃)水中冷却得到氧化物刻蚀剂颗粒；将所述的氧化物刻蚀剂颗粒置于干燥箱中在80℃烘干；将所述的干燥的氧化物刻蚀剂颗粒置于球磨机中进行研磨得到粒度0.5～7.0μm的氧化物刻蚀剂粉，然后置于干燥箱中在100℃烘干得到干燥的氧化物刻蚀剂粉。The oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 μm. The powder was then dried in a dry box at 100 ° C to obtain a dry oxide etchant powder.
以所述有机载体重量为100％计，所述有机载体含有以下组分：松油醇、十二醇酯、萜烯三者的混合物70％；乙基纤维素10％、松香树脂15％、聚酰胺蜡5％。The organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle. Polyamide wax 5%.
所述晶硅太阳能电池正面导电浆料的制备方法包括以下步骤：The preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
按照以上所述配方重量比例称取银粉88.5份，有机载体9.0份，和所述氧化物刻蚀剂粉2.5份，进行均匀混合和研磨处理，得到所述晶硅太阳能电池正面导电浆料。88.5 parts of silver powder, 9.0 parts of organic carrier, and 2.5 parts of the oxide etchant powder were weighed according to the above formula weight ratio, and uniformly mixed and polished to obtain a front conductive paste of the crystalline silicon solar cell.
一种晶硅太阳能电池正面电极的制作方法，包括以下步骤：A method for manufacturing a front electrode of a crystalline silicon solar cell, comprising the following steps:
通过丝网印制的方式，将实施例7中晶硅太阳能电池正面导电浆料印制在具有绝缘膜的晶硅太阳能电池正面，其太阳能电池背面丝网印制了背银和背铝，然后于800℃进行烧结，得到所述的晶硅太阳能电池正面电极。The front side conductive paste of the crystalline silicon solar cell in Embodiment 7 is printed on the front surface of the crystalline silicon solar cell having the insulating film by screen printing, and the back surface of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 800 ° C to obtain the front electrode of the crystalline silicon solar cell.
测试获得的所述电池片的效率，I-V测试结果汇总在表1中。The efficiency of the obtained cell sheets was tested, and the I-V test results are summarized in Table 1.
实施例8Example 8
一种晶硅太阳能电池正面导电浆料，按总重量为100份计算，包括如下配方比例的组分：银粉88.5份；有机载体9.0份；氧化物刻蚀剂2.5份。A front side conductive paste of a crystalline silicon solar cell, calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
其中，以所述氧化物刻蚀剂重量为100％计，包括以下组分：Wherein, based on 100% by weight of the oxide etchant, the following components are included:
Pb 3O 411％、TeO 234.8％、Li 2O 15％、SiO 21％、B 2O 33％、Bi 2O 31％、ZnO 10％、WO 314％、CuO 10％。 Pb 3 O 4 11%, TeO 2 34.8%, Li 2 O 15%, SiO 2 1%, B 2 O 3 3%, Bi 2 O 3 1%, ZnO 10%, WO 3 14%, CuO 10%.
所述氧化物刻蚀剂的制备方法为：按照以上所述的比例称取氧化物刻蚀剂原料并且进行均匀混合；将所述的均匀混合的氧化物刻蚀剂原料放入加热炉加热至1000℃，并在1000℃下保温120min，得到熔融的液态氧化物刻蚀剂；将所述的熔融的液态氧化物刻蚀剂倒入常温(25℃)水中冷却得到氧化物刻蚀剂颗粒；将所述的氧化物刻蚀剂颗粒置于干燥箱中在80℃烘干；将所述的干燥的氧化物刻蚀剂颗粒置于球磨机中进行研磨得到粒度0.5～7.0μm的氧化物刻蚀剂粉，然后置于干燥箱中在100℃下进行烘干，得到干燥的氧化物刻蚀剂粉。The oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 μm. The powder was then dried in a dry box at 100 ° C to obtain a dried oxide etchant powder.
以所述有机载体重量为100％计，所述有机载体含有以下组分：松油醇、十二醇酯、萜烯三者的混合物70％；乙基纤维素10％、松香树脂15％、聚酰胺蜡5％。The organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle. Polyamide wax 5%.
所述晶硅太阳能电池正面导电浆料的制备方法包括以下步骤：The preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
按照以上所述配方重量比例称取银粉88.5份，有机载体9.0份，和所述氧化物刻蚀剂粉2.5份，进行均匀混合和研磨处理，得到所述晶硅太阳能电池正面导电浆料。88.5 parts of silver powder, 9.0 parts of organic carrier, and 2.5 parts of the oxide etchant powder were weighed according to the above formula weight ratio, and uniformly mixed and polished to obtain a front conductive paste of the crystalline silicon solar cell.
一种晶硅太阳能电池正面电极的制作方法，包括以下步骤：A method for manufacturing a front electrode of a crystalline silicon solar cell, comprising the following steps:
通过丝网印制的方式，将实施例8中晶硅太阳能电池正面导电浆料印制在具有绝缘膜的晶硅太阳能电池正面，其太阳能电池背面丝网印制了背银和背铝，然后于800℃进行烧结，得到所述的晶硅太阳能电池正面电极。The front side conductive paste of the crystalline silicon solar cell of Example 8 is printed on the front side of the crystalline silicon solar cell with an insulating film by screen printing, and the back side of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 800 ° C to obtain the front electrode of the crystalline silicon solar cell.
测试获得的所述电池片的效率，I-V测试结果汇总在表1中。The efficiency of the obtained cell sheets was tested, and the I-V test results are summarized in Table 1.
实施例9Example 9
一种晶硅太阳能电池正面导电浆料，按总重量为100份计算，包括如下配方比例的组分：银粉88.5份；有机载体9.0份；氧化物刻蚀剂2.5份。A front side conductive paste of a crystalline silicon solar cell, calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
其中，以所述氧化物刻蚀剂重量为100％计，包括以下组分：Wherein, based on 100% by weight of the oxide etchant, the following components are included:
Pb 3O 45％、TeO 232％、Li 2O 15％、SiO 215％、B 2O 33％、Bi 2O 34％、ZnO 9％、WO 31％、CuO 16％。 Pb 3 O 4 5%, TeO 2 32%, Li 2 O 15%, SiO 2 15%, B 2 O 3 3%, Bi 2 O 3 4%, ZnO 9%, WO 3 1%, CuO 16%.
所述氧化物刻蚀剂的制备方法为：按照以上所述的比例称取氧化物刻蚀剂原料并且进行均匀混合；将所述的均匀混合的氧化物刻蚀剂原料放入加热炉加热至1000℃，并在1000℃下保温120min，得到熔融的液态氧化物刻蚀剂；将所述的熔融的液态氧化物刻蚀剂倒入常温(25℃)水中冷却得到氧化物刻蚀剂颗粒；将所述的氧化物刻蚀剂颗粒置于干燥箱中在80℃烘干；将所述的干燥的氧化物刻蚀剂颗粒置于球磨机中进行研磨得到粒度0.5～7.0μm的氧化物刻蚀剂粉，然后置于干燥箱中在100℃烘干得到干燥的氧化物刻蚀剂粉。The oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 μm. The powder was then dried in a dry box at 100 ° C to obtain a dry oxide etchant powder.
以所述有机载体重量为100％计，所述有机载体含有以下组分：松油醇、十二醇酯、萜烯三者的混合物70％；乙基纤维素10％、松香树脂15％、聚酰胺蜡5％。The organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle. Polyamide wax 5%.
所述晶硅太阳能电池正面导电浆料的制备方法包括以下步骤：The preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
按照以上所述配方重量比例称取银粉88.5份，有机载体9.0份，和所述氧化物刻蚀剂粉2.5份，进行均匀混合和研磨处理，得到所述晶硅太阳能电池正面导电浆料。88.5 parts of silver powder, 9.0 parts of organic carrier, and 2.5 parts of the oxide etchant powder were weighed according to the above formula weight ratio, and uniformly mixed and polished to obtain a front conductive paste of the crystalline silicon solar cell.
一种晶硅太阳能电池正面电极的制作方法，包括以下步骤：A method for manufacturing a front electrode of a crystalline silicon solar cell, comprising the following steps:
通过丝网印制的方式，将实施例9中晶硅太阳能电池正面导电浆料印制在具有绝缘膜的晶硅太阳能电池正面，其太阳能电池背面丝网印制了背银和背铝，然后于800℃进行烧结，得到所述的晶硅太阳能电池正面电极。The front side conductive paste of the crystalline silicon solar cell of Example 9 is printed on the front side of the crystalline silicon solar cell having the insulating film by screen printing, and the back side of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 800 ° C to obtain the front electrode of the crystalline silicon solar cell.
测试获得的所述电池片的效率，I-V测试结果汇总在表1中。The efficiency of the obtained cell sheets was tested, and the I-V test results are summarized in Table 1.
实施例10Example 10
一种晶硅太阳能电池正面导电浆料，按总重量为100份计算，包括如下配方比例的组分：银粉88.5份；有机载体9.0份；氧化物刻蚀剂2.5份。A front side conductive paste of a crystalline silicon solar cell, calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
其中，以所述氧化物刻蚀剂重量为100％计，包括以下组分：Wherein, based on 100% by weight of the oxide etchant, the following components are included:
Pb 3O 43％、TeO 230％、Li 2O 18％、SiO 215％、B 2O 31％、Bi 2O 31％、ZnO 9％、WO 33％、CuO 20％。 Pb 3 O 4 3%, TeO 2 30%, Li 2 O 18%, SiO 2 15%, B 2 O 3 1%, Bi 2 O 3 1%, ZnO 9%, WO 3 3%, CuO 20%.
所述氧化物刻蚀剂的制备方法为：按照以上所述的比例称取氧化物刻蚀剂原料并且进行均匀混合；将所述的均匀混合的氧化物刻蚀剂原料放入加热炉加热至1 000℃，并在1000℃下保温120min，得到熔融的液态氧化物刻蚀剂；将所述的熔融的液态氧化物刻蚀剂倒入常温(25℃)水中冷却得到氧化物刻蚀剂颗粒；将所述的氧化物刻蚀剂颗粒置于干燥箱中在80℃烘干；将所述的干燥的氧化物刻蚀剂颗粒置于球磨机中进行研磨得到粒度0.5～7.0μm的氧化物刻蚀剂粉，然后置于干燥箱中在100℃烘干得到干燥的氧化物刻蚀剂粉。The oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1 000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles The oxide etchant particles are placed in a dry box and dried at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide oxide having a particle size of 0.5 to 7.0 μm. The etchant powder was then dried in a dry box at 100 ° C to obtain a dried oxide etchant powder.
以所述有机载体重量为100％计，所述有机载体含有以下组分：松油醇、十二醇酯、萜烯三者的混合物70％；乙基纤维素10％、松香树脂15％、聚酰胺蜡5％。The organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle. Polyamide wax 5%.
所述晶硅太阳能电池正面导电浆料的制备方法包括以下步骤：The preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
按照以上所述配方重量比例称取银粉88.5份，有机载体9.0份，和所述氧化物刻蚀剂粉2.5份，进行均匀混合和研磨处理，得到所述晶硅太阳能电池正面导电浆料。88.5 parts of silver powder, 9.0 parts of organic carrier, and 2.5 parts of the oxide etchant powder were weighed according to the above formula weight ratio, and uniformly mixed and polished to obtain a front conductive paste of the crystalline silicon solar cell.
一种晶硅太阳能电池正面电极的制作方法，包括以下步骤：A method for manufacturing a front electrode of a crystalline silicon solar cell, comprising the following steps:
通过丝网印制的方式，将实施例10中晶硅太阳能电池正面导电浆料印制在具有绝缘膜的晶硅太阳能电池正面，其太阳能电池背面丝网印制了背银和背铝，然后于800℃进行烧结，得到所述的晶硅太阳能电池正面电极。The front side conductive paste of the crystalline silicon solar cell in Embodiment 10 is printed on the front surface of the crystalline silicon solar cell having the insulating film by screen printing, and the back surface of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 800 ° C to obtain the front electrode of the crystalline silicon solar cell.
测试获得的所述电池片的效率，I-V测试结果汇总在表1中。The efficiency of the obtained cell sheets was tested, and the I-V test results are summarized in Table 1.
实施例11Example 11
一种晶硅太阳能电池正面导电浆料，按总重量为100份计算，包括如下配方比例的组分：银粉88.5份；有机载体9.0份；氧化物刻蚀剂2.5份。A front side conductive paste of a crystalline silicon solar cell, calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
其中，以所述氧化物刻蚀剂重量为100％计，包括以下组分：Wherein, based on 100% by weight of the oxide etchant, the following components are included:
Pb 3O 425％、TeO 225％、Li 2O 15％、SiO 210％、B 2O 31％、Bi 2O 31％、ZnO 9％、WO 32％、CuO 12％。 Pb 3 O 4 25%, TeO 2 25%, Li 2 O 15%, SiO 2 10%, B 2 O 3 1%, Bi 2 O 3 1%, ZnO 9%, WO 3 2%, CuO 12%.
所述氧化物刻蚀剂的制备方法为：按照以上所述的比例称取氧化物刻蚀剂原料并且进行均匀混合；将所述的均匀混合的氧化物刻蚀剂原料放入加热炉加热至1000℃，并在1000℃下保温120min，得到熔融的液态氧化物刻蚀剂；将所述的熔融的液态氧化物刻蚀剂倒入常温(25℃)水中冷却得到氧化物刻蚀剂颗粒；将所述的氧化物刻蚀剂颗粒置于干燥箱中在80℃烘干；将所述的干燥的氧化物刻蚀剂颗粒置于球磨机中进行研磨得到粒度0.5～7.0μm的氧化物刻蚀剂粉，然后置于干燥 箱中在100℃烘干得到干燥的氧化物刻蚀剂粉。The oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 μm. The powder was then dried in a dry box at 100 ° C to obtain a dry oxide etchant powder.
以所述有机载体重量为100％计，所述有机载体含有以下组分：松油醇、十二醇酯、萜烯三者的混合物70％；乙基纤维素10％、松香树脂15％、聚酰胺蜡5％。The organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle. Polyamide wax 5%.
所述晶硅太阳能电池正面导电浆料的制备方法包括以下步骤：The preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
按照以上所述配方重量比例称取银粉88.5份，有机载体9.0份，和所述氧化物刻蚀剂粉2.5份，进行均匀混合和研磨处理，得到所述晶硅太阳能电池正面导电浆料。88.5 parts of silver powder, 9.0 parts of organic carrier, and 2.5 parts of the oxide etchant powder were weighed according to the above formula weight ratio, and uniformly mixed and polished to obtain a front conductive paste of the crystalline silicon solar cell.
一种晶硅太阳能电池正面电极的制作方法，包括以下步骤：A method for manufacturing a front electrode of a crystalline silicon solar cell, comprising the following steps:
通过丝网印制的方式，将实施例11中晶硅太阳能电池正面导电浆料印制在具有绝缘膜的晶硅太阳能电池正面，其太阳能电池背面丝网印制了背银和背铝，然后于800℃进行烧结，得到所述的晶硅太阳能电池正面电极。The front side conductive paste of the crystalline silicon solar cell in Example 11 was printed on the front side of the crystalline silicon solar cell having the insulating film by screen printing, and the back side of the solar cell was screen printed with back silver and back aluminum, and then Sintering was carried out at 800 ° C to obtain the front electrode of the crystalline silicon solar cell.
测试获得的所述电池片的效率，I-V测试结果汇总在表1中。The efficiency of the obtained cell sheets was tested, and the I-V test results are summarized in Table 1.
实施例12Example 12
一种晶硅太阳能电池正面导电浆料，按总重量为100份计算，包括如下配方比例的组分：银粉88.5份；有机载体9.0份；氧化物刻蚀剂2.5份。A front side conductive paste of a crystalline silicon solar cell, calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
其中，以所述氧化物刻蚀剂重量份为100％计，包括以下组分：Wherein, based on 100% by weight of the oxide etchant, the following components are included:
Pb 3O 430％、TeO 214％、Li 2O 15％、SiO 210％、B 2O 31％、Bi 2O 31％、ZnO 8％、WO 33％、CuO 18％。 Pb 3 O 4 30%, TeO 2 14%, Li 2 O 15%, SiO 2 10%, B 2 O 3 1%, Bi 2 O 3 1%, ZnO 8%, WO 3 3%, CuO 18%.
所述氧化物刻蚀剂的制备方法为：按照以上所述的比例称取氧化物刻蚀剂原料并且进行均匀混合；将所述的均匀混合的氧化物刻蚀剂原料放入加热炉加热至1000℃，并在1000℃下保温120min，得到熔融的液态氧化物刻蚀剂；将所述的熔融的液态氧化物刻蚀剂倒入常温(25℃)水中冷却得到氧化物刻蚀剂颗粒；将所述的氧化物刻蚀剂颗粒置于干燥箱中在80℃烘干；将所述的干燥的氧化物刻蚀剂颗粒置于球磨机中进行研磨得到粒度0.5～7.0μm的氧化物刻蚀剂粉，然后置于干燥箱中在100℃烘干得到干燥的氧化物刻蚀剂粉。The oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 μm. The powder was then dried in a dry box at 100 ° C to obtain a dry oxide etchant powder.
以有机载体重量为100％计，有机载体含有以下组分：松油醇、十二醇酯、萜烯三者的混合物70％；乙基纤维素10％、松香树脂15％、聚酰胺蜡5％。The organic vehicle contains the following components in an amount of 100% by weight of the organic vehicle: 70% of a mixture of terpineol, dodecyl alcohol and decene; 10% of ethyl cellulose, 15% of rosin resin, and polyamide wax 5 %.
所述晶硅太阳能电池正面导电浆料的制备方法包括以下步骤：The preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
按照以上所述配方重量比例称取银粉88.5份，有机载体9.0份，和所述氧化物刻蚀剂粉2.5份，进行均匀混合和研磨处理，得到所述晶硅太阳能电池正面导电浆料。88.5 parts of silver powder, 9.0 parts of organic carrier, and 2.5 parts of the oxide etchant powder were weighed according to the above formula weight ratio, and uniformly mixed and polished to obtain a front conductive paste of the crystalline silicon solar cell.
一种晶硅太阳能电池正面电极的制作方法，包括以下步骤：A method for manufacturing a front electrode of a crystalline silicon solar cell, comprising the following steps:
通过丝网印制的方式，将实施例12中晶硅太阳能电池正面导电浆料印制在具有绝缘膜的晶硅太阳能电池正面，其太阳能电池背面丝网印制了背银和背铝，然后于770℃进行烧结，得到所述的晶硅太阳能电池正面电极。The front side conductive paste of the crystalline silicon solar cell of Example 12 is printed on the front side of the crystalline silicon solar cell having the insulating film by screen printing, and the back side of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 770 ° C to obtain the front electrode of the crystalline silicon solar cell.
测试获得的所述电池片的效率，I-V测试结果汇总在表1中。The efficiency of the obtained cell sheets was tested, and the I-V test results are summarized in Table 1.
实施例13Example 13
一种晶硅太阳能电池正面导电浆料，按总重量为100份计算，包括如下配方比例的组分：银粉88.5份；有机载体9.0份；氧化物刻蚀剂2.5份。A front side conductive paste of a crystalline silicon solar cell, calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
其中，以所述氧化物刻蚀剂重量为100％计，包括以下组分：Wherein, based on 100% by weight of the oxide etchant, the following components are included:
Pb 3O 46％、TeO 248％、Li 2O 5％、SiO 220％、B 2O 32.9％、Bi 2O 32％、ZnO 3％、WO 31％、CuO 0.1％、P 2O 512％。 Pb 3 O 4 6%, TeO 2 48%, Li 2 O 5%, SiO 2 20%, B 2 O 3 2.9%, Bi 2 O 3 2%, ZnO 3%, WO 3 1%, CuO 0.1%, P 2 O 5 12%.
所述氧化物刻蚀剂的制备方法为：按照以上所述的比例称取氧化物刻蚀剂原料并且进行均匀混合；将所述的均匀混合的氧化物刻蚀剂原料放入加热炉加热至1000℃，并在1000℃下保温120min，得到熔融的液态氧化物刻蚀剂；将所述的熔融的液态氧化物刻蚀剂倒入常温(25℃)水中冷却得到氧化物刻蚀剂颗粒；将所述的氧化物刻蚀剂颗粒置于干燥箱中在80℃烘干；将所述的干燥的氧化物刻蚀剂颗粒置于球磨机中进行研磨得到粒度0.5～7.0μm的氧化物刻蚀剂粉，然后置于干燥箱中在100℃烘干得到干燥的氧化物刻蚀剂粉。The oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 μm. The powder was then dried in a dry box at 100 ° C to obtain a dry oxide etchant powder.
以所述有机载体重量为100％计，所述有机载体含有以下组分：松油醇、十二醇酯、萜烯三者的混合物70％；乙基纤维素10％、松香树脂15％、聚酰胺蜡5％。The organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle. Polyamide wax 5%.
所述晶硅太阳能电池正面导电浆料的制备方法包括以下步骤：The preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
按照以上所述配方重量比例称取银粉88.5份，有机载体9.0份，和所述氧化物刻蚀剂粉2.5份，进行均匀混合和研磨处理，得到所述晶硅太阳能电池正面导电浆料。88.5 parts of silver powder, 9.0 parts of organic carrier, and 2.5 parts of the oxide etchant powder were weighed according to the above formula weight ratio, and uniformly mixed and polished to obtain a front conductive paste of the crystalline silicon solar cell.
一种晶硅太阳能电池正面电极的制作方法，包括以下步骤：A method for manufacturing a front electrode of a crystalline silicon solar cell, comprising the following steps:
通过丝网印制的方式，将实施例13中晶硅太阳能电池正面导电浆料印制在具有绝缘膜的晶硅太阳能电池正面，其太阳能电池背面丝网印制了背银和背铝，然后于800℃进行烧结，得到所述的晶硅太阳能电池正面电极。The front side conductive paste of the crystalline silicon solar cell of Embodiment 13 is printed on the front surface of the crystalline silicon solar cell having the insulating film by screen printing, and the back surface of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 800 ° C to obtain the front electrode of the crystalline silicon solar cell.
测试获得的所述电池片的效率，I-V测试结果汇总在表1中。The efficiency of the obtained cell sheets was tested, and the I-V test results are summarized in Table 1.
实施例14Example 14
一种晶硅太阳能电池正面导电浆料，按总重量为100份计算，包括如下配方比例的组分：银粉88.5份；有机载体9.0份；氧化物刻蚀剂2.5份。A front side conductive paste of a crystalline silicon solar cell, calculated based on a total weight of 100 parts, comprising components of the following formulation ratio: 88.5 parts of silver powder; 9.0 parts of organic vehicle; and 2.5 parts of an oxide etchant.
其中，以所述氧化物刻蚀剂重量为100％计，包括以下组分：Wherein, based on 100% by weight of the oxide etchant, the following components are included:
Pb 3O 427％、TeO 220％、Li 2O 11％、SiO 22％、B 2O 37％、Bi 2O 35％、ZnO 13％、WO 35％、CuO 10％。 Pb 3 O 4 27%, TeO 2 20%, Li 2 O 11%, SiO 2 2%, B 2 O 3 7%, Bi 2 O 3 5%, ZnO 13%, WO 3 5%, CuO 10%.
所述氧化物刻蚀剂的制备方法为：按照以上所述的比例称取氧化物刻蚀剂原料并且进行均匀混合；将所述的均匀混合的氧化物刻蚀剂原料放入加热炉加热至1000℃，并在1000℃下保温120min，得到熔融的液态氧化物刻蚀剂；将所述的熔融的液态氧化物刻蚀剂倒入常温(25℃)水中冷却得到氧化物刻蚀剂颗粒；将所述的氧化物刻蚀剂颗粒置于干燥箱中在80℃烘干；将所述的干燥的氧化物刻蚀剂颗粒置于球磨机中进行研磨得到粒度0.5～7.0μm的氧化物刻蚀剂粉，然后置于干燥箱中在100℃烘干得到干燥的氧化物刻蚀剂粉。The oxide etchant is prepared by weighing the oxide etchant raw material according to the ratio described above and performing uniform mixing; and heating the uniformly mixed oxide etchant raw material into a heating furnace to 1000 ° C, and maintained at 1000 ° C for 120 min, to obtain a molten liquid oxide etchant; the molten liquid oxide etchant is poured into water at room temperature (25 ° C) to obtain oxide etchant particles; The oxide etchant particles are dried in a drying oven at 80 ° C; the dried oxide etchant particles are placed in a ball mill for grinding to obtain an oxide etching having a particle size of 0.5 to 7.0 μm. The powder was then dried in a dry box at 100 ° C to obtain a dry oxide etchant powder.
以所述有机载体重量为100％计，所述有机载体含有以下组分：松油醇、十二醇酯、萜烯三者的混合物70％；乙基纤维素10％、松香树脂15％、聚酰胺蜡5％。The organic vehicle contains 70% of a mixture of terpineol, dodecyl alcohol, and decene; ethyl cellulose 10%, rosin resin 15%, based on 100% by weight of the organic vehicle. Polyamide wax 5%.
所述晶硅太阳能电池正面导电浆料的制备方法包括以下步骤：The preparation method of the front side conductive paste of the crystalline silicon solar cell comprises the following steps:
按照以上所述配方重量比例称取银粉88.5份，有机载体9.0份，和所述氧化物刻蚀剂粉2.5份，进行均匀混合和研磨处理，得到所述晶硅太阳能电池正面导电浆料。88.5 parts of silver powder, 9.0 parts of organic carrier, and 2.5 parts of the oxide etchant powder were weighed according to the above formula weight ratio, and uniformly mixed and polished to obtain a front conductive paste of the crystalline silicon solar cell.
一种晶硅太阳能电池正面电极的制作方法，包括以下步骤：A method for manufacturing a front electrode of a crystalline silicon solar cell, comprising the following steps:
通过丝网印制的方式，将实施例14中晶硅太阳能电池正面导电浆料印制在具有绝缘膜的晶硅太阳能电池正面，其太阳能电池背面丝网印制了背银和背铝，然后于800℃进行烧结，得到所述的晶硅太阳能电池正面电极。测试获得的所述电池片的效率，I-V测试结果汇总在表1中。The front side conductive paste of the crystalline silicon solar cell of Example 14 is printed on the front side of the crystalline silicon solar cell having the insulating film by screen printing, and the back side of the solar cell is screen printed with back silver and back aluminum, and then Sintering was carried out at 800 ° C to obtain the front electrode of the crystalline silicon solar cell. The efficiency of the obtained cell sheets was tested, and the I-V test results are summarized in Table 1.
对比例Comparative example
将市场上广泛使用的一种晶硅太阳能电池正面导电浆料PV1B丝网印制在和实施例具有完全相同的绝缘膜的晶硅太阳能电池正面，其太阳能电池背面丝网印制了背银和背铝，然后加热到800℃进行烧结，得到所述的晶硅太阳能电池正面电极，然后测试所述电池片的效率，I-V测试结果汇总在表1中。A crystalline silicon solar cell front conductive paste PV1B screen widely used in the market is screen printed on the front surface of a crystalline silicon solar cell having the same insulating film as the embodiment, and the back surface of the solar cell is screen printed with back silver and The aluminum was backed and then sintered to 800 ° C for sintering to obtain the front electrode of the crystalline silicon solar cell, and then the efficiency of the cell was tested. The IV test results are summarized in Table 1.
性能测试：Performance Testing:
(1)I-V测试(1) I-V test
将实施例1～15的电池片和对比例的电池片在HALM IV测试仪上进行了I-V测试，结果如表1所示。The cell sheets of Examples 1 to 15 and the cell sheets of Comparative Examples were subjected to I-V test on a HALM IV tester, and the results are shown in Table 1.
(2)拉力测试(2) Tensile test
将焊带焊接到主栅上180度拉伸测试拉力，主栅宽度是0.7mm，将0.9mm宽的焊带焊接到主栅上，焊带宽度为0.9mm，厚度为0.23mm，焊带材料是96.5％Sn3.5％Ag。图5是180度拉伸测试示意图，具体是先将焊带800焊接于主栅表面，然后通过第一固定螺栓901和第二固定螺栓902将晶体硅电池片100固定于拉伸机900上，按照拉力F的方向进行拉力测试。拉力测试结果如表1所示。Solder the strip to the main grid for 180 degree tensile test tensile force, the main grid width is 0.7mm, and the 0.9mm wide strip is soldered to the main grid. The strip width is 0.9mm and the thickness is 0.23mm. It is 96.5% Sn3.5% Ag. 5 is a schematic diagram of a 180 degree tensile test, specifically, the solder ribbon 800 is first soldered to the surface of the main grid, and then the crystalline silicon cell sheet 100 is fixed to the stretching machine 900 by the first fixing bolt 901 and the second fixing bolt 902. The tensile test is performed in the direction of the pulling force F. The tensile test results are shown in Table 1.
表1实施例1～15及对比例获得的晶硅太阳能电池性能测试数据统计Table 1 Performance statistics of crystalline silicon solar cells obtained in Examples 1 to 15 and Comparative Examples
[Table 1][Table 1]
Figure PCTCN2018081376-appb-000003
Figure PCTCN2018081376-appb-000003
Figure PCTCN2018081376-appb-000004
Figure PCTCN2018081376-appb-000004
从表1可知，与对比例相比较，实施例1-8的太阳能电池片具有转化率高，R s低，拉力高的优点，说明实施例1-8使用的氧化物刻蚀剂具有优越的刻蚀性能，它不但有效的润湿烧结了银粉，而且有效的刻蚀掉了太阳能电池片表面的绝缘膜，使银电极和太阳能电池片表面形成良好的欧姆接触，从而使太阳能电池片具有转换效率高，接触电阻R s低，拉力高的特点。实施例1-8使用的氧化物刻蚀刻剂中的CuO和Pb 3O 4的重量比在0.1∶24～10∶6范围内、CuO和Li 2O的重量比在0.1∶20～10∶5范围内、且实施例1-2使用的氧化物刻蚀刻剂中的CuO和P 2O 5的重量比在0.1∶10～10∶0.1范围内，其独特的氧化物组分比例使得其氧化物刻蚀剂在烧结过程中能够溶解足够的银，能够充分刻蚀透电池片表面的绝缘层但是又不过分腐蚀硅电池片，使得银电极和硅片不但形成很好的欧姆接触，同时具有很好的附着力。实施例9-14的太阳能电池片转换率低于对比例的转换率，也低于实施例1-8的电池片转换率，其串联电阻(R s)明显高于实施例1-8，这是因为其使用的氧化物刻蚀剂成分比例不同导致的。实施例9-10电池片转换率低是由于其使用的氧化物刻蚀剂中Pb 3O 4的含量低，CuO含量高，显示CuO/Pb 3O 4对于本发明所述的氧化物刻蚀剂性能影响很大，必须保持合适的CuO/Pb 3O 4比例。实施例11-12电池片效率低于对比例电池片效率，也低于实施例1-8电池片效率，这是由于其使用的氧化物刻蚀剂中Pb 3O 4含量高导致的，本发明所述的氧化物刻蚀剂中Pb 3O 4的重量含量在6～24％，如果Pb 3O 4的重量含量低于6％或者高于24％会导致烧结过程中电池片表面的绝缘层不能被完全腐蚀或者过量腐蚀，使银电极不能和硅片形成良好的欧姆接触。实施例13-14电池片效率低于对比例电池片 效率，也低于实施例1-8电池片效率，这是由于其使用的氧化物刻蚀剂中P 2O 5含量高导致的，本发明所述的氧化物刻蚀剂中P 2O 5的重量含量在0.1～10％。 As can be seen from Table 1, the solar cell sheets of Examples 1-8 have the advantages of high conversion rate, low R s , and high tensile force as compared with the comparative examples, indicating that the oxide etchant used in Examples 1-8 is superior. The etching performance not only effectively wets and sinters the silver powder, but also effectively etches away the insulating film on the surface of the solar cell sheet, so that the silver electrode and the surface of the solar cell sheet form a good ohmic contact, thereby converting the solar cell sheet. High efficiency, low contact resistance R s and high tensile force. The weight ratio of CuO to Pb 3 O 4 in the oxide etching etchant used in Examples 1-8 is in the range of 0.1:24 to 10:6, and the weight ratio of CuO to Li 2 O is from 0.1:20 to 10:5. In the range, and the weight ratio of CuO to P 2 O 5 in the oxide etching etchant used in Example 1-2 is in the range of 0.1:10 to 10:0.1, and its unique oxide component ratio makes the oxide thereof The etchant can dissolve enough silver during the sintering process, and can completely etch the insulating layer on the surface of the battery sheet without excessively etching the silicon cell sheet, so that the silver electrode and the silicon wafer not only form a good ohmic contact, but also have a very good Good adhesion. The solar cell conversion rates of Examples 9-14 were lower than those of the comparative examples, and also lower than the cell sheet conversion rates of Examples 1-8, and the series resistance (R s ) was significantly higher than that of Examples 1-8. It is caused by the difference in the proportion of the oxide etchant used. The low conversion rate of the cell sheets of Examples 9-10 is due to the low content of Pb 3 O 4 in the oxide etchant used and the high CuO content, indicating that CuO/Pb 3 O 4 is etched for the oxide of the present invention. The performance of the agent has a great influence and the proper CuO/Pb 3 O 4 ratio must be maintained. The efficiency of the cell sheets of Examples 11-12 was lower than that of the comparative cell, and also lower than the cell efficiency of Examples 1-8, due to the high content of Pb 3 O 4 in the oxide etchant used therein. The weight content of Pb 3 O 4 in the oxide etchant of the invention is 6-24%, and if the weight content of Pb 3 O 4 is less than 6% or higher than 24%, the surface of the cell sheet during the sintering process may be insulated. The layer cannot be completely corroded or excessively corroded, so that the silver electrode does not form a good ohmic contact with the silicon wafer. The efficiency of the cell sheets of Examples 13-14 was lower than that of the comparative cell, and also lower than the cell efficiency of Examples 1-8, which was caused by the high content of P 2 O 5 in the oxide etchant used. The weight content of P 2 O 5 in the oxide etchant of the invention is from 0.1 to 10%.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。The above is only the preferred embodiment of the present invention, and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. Within the scope.

Claims (17)

  1. 一种晶硅太阳能电池正面导电浆料，其特征在于，按照重量份为100计，所述晶硅太阳能电池正面导电浆料包括以下原料组分：A front side conductive paste of a crystalline silicon solar cell, characterized in that the front side conductive paste of the crystalline silicon solar cell comprises the following raw material components in terms of 100 parts by weight:
    金属粉       80.0～93.0份；Metal powder 80.0-93.0 parts;
    有机载体     6.0～15.0份；Organic carrier 6.0 to 15.0 parts;
    氧化物刻蚀剂 1.0～5.0份；Oxide etchant 1.0 to 5.0 parts;
    其中，其中，所述氧化物刻蚀剂至少含有Pb 3O 4、CuO及Li 2O，且所述CuO和Pb 3O 4的重量比为0.1∶24～10∶6，所述CuO和Li 2O的重量比为0.1∶20～10∶5。 Wherein the oxide etchant contains at least Pb 3 O 4 , CuO and Li 2 O, and the weight ratio of the CuO to Pb 3 O 4 is from 0.1:24 to 10:6, the CuO and Li The weight ratio of 2 O is from 0.1:20 to 10:5.
  2. 如权利要求1所述的晶硅太阳能电池正面导电浆料，其特征在于，以所述氧化物刻蚀剂总重量100％计，所述氧化物刻蚀剂包括以下组分：The front side conductive paste of a crystalline silicon solar cell according to claim 1, wherein the oxide etchant comprises the following components in an amount of 100% by weight based on the total weight of the oxide etchant:
    Figure PCTCN2018081376-appb-100001
    Figure PCTCN2018081376-appb-100001
  3. 如权利要求1所述的晶硅太阳能电池正面导电浆料，其特征在于，所述氧化物刻蚀剂中还含有P 2O 5，其重量份为0.1～10.0。 The front side conductive paste of a crystalline silicon solar cell according to claim 1, wherein the oxide etchant further contains P 2 O 5 in an amount of 0.1 to 10.0 by weight.
  4. 如权利要求1所述的晶硅太阳能电池正面导电浆料，其特征在于，所述氧化物刻蚀剂中P 2O 5和CuO的重量比为0.1∶10～10∶0.1。 The front side conductive paste of a crystalline silicon solar cell according to claim 1, wherein a weight ratio of P 2 O 5 to CuO in the oxide etchant is from 0.1:10 to 10:0.1.
  5. 如权利要求1-4任一项所述的晶硅太阳能电池正面导电浆料，其特 征在于，所述添加元素的氧化物中添加元素为钛、铝、银、铬、钪、铜、铌、钒、钠、钽、锶、溴、钴、铪、镧、钇、镱、铁、钡、锰、镁、镍、钙、锡、砷、锆、钾、磷、铟、镓、锗等中的一种或者两种及以上。The front side conductive paste of a crystalline silicon solar cell according to any one of claims 1 to 4, wherein the additive element in the oxide of the additive element is titanium, aluminum, silver, chromium, bismuth, copper, bismuth, Vanadium, sodium, antimony, bismuth, bromine, cobalt, antimony, bismuth, antimony, bismuth, iron, antimony, manganese, magnesium, nickel, calcium, tin, arsenic, zirconium, potassium, phosphorus, indium, gallium, antimony, etc. One or two or more.
  6. 如权利要求1或2所述的晶硅太阳能电池正面导电浆料，其特征在于，所述氧化物刻蚀剂为晶体、非晶体中的至少一种。The front side conductive paste of a crystalline silicon solar cell according to claim 1 or 2, wherein the oxide etchant is at least one of a crystal and an amorphous.
  7. 如权利要求1所述的晶硅太阳能电池正面导电浆料，其特征在于，所述金属粉为银、金、铂、铜、铁、镍、锌、钛、钴、铬、铝、锰、钯、铑中的至少一种。The front side conductive paste of a crystalline silicon solar cell according to claim 1, wherein the metal powder is silver, gold, platinum, copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminum, manganese, palladium. At least one of them.
  8. 如权利要求1所述的晶硅太阳能电池正面导电浆料，其特征在于，所述金属粉为银包覆的铜、铁、镍、锌、钛、钴、铬、铝、锰中的至少一种，其中，银包覆层的厚度为10～50nm。The front side conductive paste of a crystalline silicon solar cell according to claim 1, wherein the metal powder is at least one of silver-coated copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminum, and manganese. The silver coating layer has a thickness of 10 to 50 nm.
  9. 如权利要求1所述的晶硅太阳能电池正面导电浆料，其特征在于，所述金属粉为非银包覆的金属粉和银包覆的金属粉的混合体，其中，所述非银包覆的金属粉与银包覆的金属粉的重量比为5/95～95/5，所述非银包覆的金属粉为银、金、铂、铜、铁、镍、锌、钛、钴、铬、铝、锰、钯、铑中的至少一种；所述银包覆的金属粉为铜、铁、镍、锌、钛、钴、铬、铝、锰中的至少一种，所述银包覆层的厚度为10～50nm。The front side conductive paste of a crystalline silicon solar cell according to claim 1, wherein the metal powder is a mixture of a non-silver coated metal powder and a silver coated metal powder, wherein the non-silver package The weight ratio of the coated metal powder to the silver-coated metal powder is 5/95 to 95/5, and the non-silver coated metal powder is silver, gold, platinum, copper, iron, nickel, zinc, titanium, cobalt. At least one of chromium, aluminum, manganese, palladium, and rhodium; the silver-coated metal powder is at least one of copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminum, and manganese. The thickness of the silver coating layer is 10 to 50 nm.
  10. 如权利要求1所述的晶硅太阳能电池正面导电浆料，其特征在于，所述有机载体包括有机溶剂、聚合物、润湿分散剂、触变剂、其他功能助剂；The front side conductive paste of a crystalline silicon solar cell according to claim 1 , wherein the organic carrier comprises an organic solvent, a polymer, a wetting and dispersing agent, a thixotropic agent, and other functional additives;
    以所述有机载体重量为100份计，有机溶剂50～95份；聚合物1～40份；润湿分散剂0.1～10份；触变剂1～20份；其他功能助剂0.1-20份。The organic solvent has a weight of 100 parts by weight, 50 to 95 parts by weight; 1 to 40 parts of the polymer; 0.1 to 10 parts of the wetting and dispersing agent; 1 to 20 parts of the thixotropic agent; 0.1 to 20 parts of other functional additives. .
  11. 如权利要求10所述的晶硅太阳能电池正面导电浆料，其特征在于，所述有机溶剂为松油醇、乙二醇丁醚醋酸酯、乙二醇***醋酸酯、十二醇酯、二乙二醇丁醚、三乙二醇丁醚、三丙二醇甲醚、 萜烯类中的至少一种；The front side conductive paste of a crystalline silicon solar cell according to claim 10, wherein the organic solvent is terpineol, ethylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate, dodecyl alcohol ester, and At least one of ethylene glycol butyl ether, triethylene glycol butyl ether, tripropylene glycol methyl ether, and terpenes;
    所述聚合物选自乙基纤维素、甲基纤维素、纤维素及其衍生物、丙烯酸树脂、醇酸树脂、聚酯树脂中的至少一种；The polymer is selected from at least one of ethyl cellulose, methyl cellulose, cellulose and derivatives thereof, acrylic resin, alkyd resin, and polyester resin;
    所述润湿分散剂选自脂肪酸、脂肪酸的酰胺衍生物、脂肪酸的酯类衍生物、聚乙烯蜡、聚乙二醇中的一种或者两种以上混合物；The wetting and dispersing agent is selected from the group consisting of a fatty acid, an amide derivative of a fatty acid, an ester derivative of a fatty acid, a polyethylene wax, a polyethylene glycol, or a mixture of two or more;
    所述触变剂选自氢化蓖麻油衍生物、聚酰胺蜡、聚脲、气相二氧化硅中的至少一种；The thixotropic agent is selected from at least one of a hydrogenated castor oil derivative, a polyamide wax, a polyurea, and a fumed silica;
    所述功能助剂选自聚甲基苯基硅氧烷、聚苯基硅氧烷、邻苯二甲酸酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯、微晶蜡、聚二甲基硅氧烷、聚乙烯醇缩丁醛、聚醚聚酯改性有机硅氧烷、烷基改性有机硅氧烷中的至少一种。The functional auxiliary is selected from the group consisting of polymethylphenylsiloxane, polyphenylsiloxane, phthalate, diethyl phthalate, dibutyl phthalate, microcrystalline wax, At least one of polydimethylsiloxane, polyvinyl butyral, polyether polyester-modified organosiloxane, and alkyl-modified organosiloxane.
  12. 如权利要求1～11任一项所述的晶硅太阳能电池正面导电浆料的制备方法，其特征在于，至少包括以下步骤：The method for preparing a front side conductive paste of a crystalline silicon solar cell according to any one of claims 1 to 11, characterized in that it comprises at least the following steps:
    步骤S01.将氧化物刻蚀剂原料组分进行熔融得到氧化物刻蚀剂熔液，对所述熔液进行骤冷处理，得到氧化物刻蚀剂颗粒，并经过破碎处理获得粒径在0.1～5.0μm的氧化物刻蚀剂粉末；Step S01. Melt the oxide etchant raw material component to obtain an oxide etchant melt, and quench the molten liquid to obtain an oxide etchant particle, and obtain a particle size of 0.1 to 0.1 by crushing treatment. 5.0 μm oxide etchant powder;
    步骤S02.将有机载体原料置于40～100℃环境中进行混合处理，得到有机载体；Step S02. The organic carrier raw material is placed in an environment of 40 to 100 ° C for mixing treatment to obtain an organic vehicle;
    步骤S03.将金属粉与步骤S01得到的氧化物刻蚀剂粉末、步骤S02得到的有机载体三者进行混料处理，获得晶硅太阳能电池正面导电浆料。Step S03. The metal powder is mixed with the oxide etchant powder obtained in the step S01 and the organic vehicle obtained in the step S02 to obtain a front side conductive paste of the crystalline silicon solar cell.
  13. 如权利要求12所述的晶硅太阳能电池正面导电浆料的制备方法，其特征在于，所述骤冷处理为水冷处理或者冷空气处理。The method according to claim 12, wherein the quenching treatment is water cooling treatment or cold air treatment.
  14. 一种晶硅太阳能电池正面电极的制作方法，其特征在于，至少包括以下步骤：A method for fabricating a front electrode of a crystalline silicon solar cell, characterized in that it comprises at least the following steps:
    提供表面叠设有绝缘膜的晶体硅半导体元件；Providing a crystalline silicon semiconductor component having an insulating film on its surface;
    通过印制的方式将如权利要求1～11任一项所述的晶硅太阳能电池正面导电浆料印制于所述绝缘膜表面，依次进行干燥、烧结、冷 却处理，得到晶硅太阳能电池正面电极。The surface conductive paste of the crystalline silicon solar cell according to any one of claims 1 to 11 is printed on the surface of the insulating film by printing, and sequentially dried, sintered, and cooled to obtain a front surface of the crystalline silicon solar cell. electrode.
  15. 如权利要求14所述的晶硅太阳能电池正面电极的制作方法，其特征在于，所述烧结温度为700～820℃；和/或所述干燥温度为80～400℃。The method of fabricating a front surface electrode of a crystalline silicon solar cell according to claim 14, wherein the sintering temperature is 700 to 820 ° C; and/or the drying temperature is 80 to 400 ° C.
  16. 如权利要求14所述的晶硅太阳能电池正面电极的制作方法，其特征在于，所述绝缘膜为氮化硅膜、氧化钛膜、氧化铝膜、氧化硅膜中的至少一种。The method of fabricating a front surface electrode of a crystalline silicon solar cell according to claim 14, wherein the insulating film is at least one of a silicon nitride film, a titanium oxide film, an aluminum oxide film, and a silicon oxide film.
  17. 一种晶硅太阳能电池，其特征在于，所述晶硅太阳能电池采用如权利要求14～16任一项所述的晶硅太阳能电池正面电极的制作方法制作的晶硅太阳能电池正面电极。A crystalline silicon solar cell characterized by using the crystalline silicon solar cell front electrode produced by the method for producing a front surface electrode of a crystalline silicon solar cell according to any one of claims 14 to 16.
PCT/CN2018/081376 2018-03-30 2018-03-30 Front-side conductive paste of crystalline silicon solar cell, preparation method thereof, and solar cell WO2019183933A1 (en)

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