WO2015003292A1 - Composite electrode material and process for preparing front electrode of photovoltaic cell - Google Patents

Composite electrode material and process for preparing front electrode of photovoltaic cell Download PDF

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Publication number
WO2015003292A1
WO2015003292A1 PCT/CN2013/001010 CN2013001010W WO2015003292A1 WO 2015003292 A1 WO2015003292 A1 WO 2015003292A1 CN 2013001010 W CN2013001010 W CN 2013001010W WO 2015003292 A1 WO2015003292 A1 WO 2015003292A1
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Prior art keywords
electrode material
composite electrode
conductive
metal
paste
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PCT/CN2013/001010
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French (fr)
Chinese (zh)
Inventor
余小翠
Original Assignee
Yu Xiaocui
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Publication date
Priority claimed from CN2013102835631A external-priority patent/CN103366854A/en
Priority claimed from CN2013102916982A external-priority patent/CN103367546A/en
Application filed by Yu Xiaocui filed Critical Yu Xiaocui
Publication of WO2015003292A1 publication Critical patent/WO2015003292A1/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
    • 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
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells

Definitions

  • the invention belongs to the technical field of photovoltaic cells, and in particular relates to a composite electrode material and a process for preparing a front electrode of a photovoltaic cell. Background technique
  • the front metallization of photovoltaic cells is mainly achieved by screen printing conductive paste.
  • the prepared electrode has a small aspect ratio, large electrode width, uneven width and severe edge collapse, and the electrode height is small and the height is not uniform.
  • large electrode width and severe collapse mean that the front side has a large light-shielding area, and the low electrode height and unevenness means that the electrode has poor conductivity and large internal resistance, which seriously affects and restricts the efficiency of the photovoltaic cell.
  • the front electrode of the photovoltaic cell mainly has two functions: On the one hand, the lower part of the electrode forms an alloy and ohmic contact with the front surface of the battery, and functions as an electrical connection; on the other hand, the electrode body conducts current and acts as a conductor.
  • the current silver paste can play a better effect, achieving a lower contact resistance, but for the role of the conductor, since the silver paste itself is composed of silver powder, the electrode prepared therefrom is a porous
  • the structure has much lower conductivity than the dense conductor of pure metal, which also limits the improvement of the conductivity of the electrode, thereby restricting the efficiency of the photovoltaic cell.
  • the conductive paste used for the front metallization of photovoltaic cells is mainly silver paste. Due to the requirement of conductivity, the content of silver in silver paste is very high, reaching about 90%, silver is a precious metal, and the current electrode materials for photovoltaic cells are also selected. It has seriously restricted the further decline in the manufacturing cost of photovoltaic cells.
  • the traditional process of realizing the metallization of the front side of the photovoltaic cell by screen printing and silver paste is to use the permeability of the mesh version to squeeze the high viscosity silver paste through the mesh under a certain pressure.
  • the front of the photovoltaic cell due to the high viscosity of the slurry and the small opening of the screen, it requires a lot of pressure to form the electrode pattern that meets the standard. Such a large pressure increases the fragmentation rate when printing the battery. Under the trend that the battery will become thinner and thinner, the traditional screen printing metallization scheme hinders the application of new technologies. Summary of the invention
  • the object of the present invention is to provide a composite electrode material and a process for preparing a front electrode of a photovoltaic cell with high cost and low efficiency of the photovoltaic cell, which has the advantages of low cost and high efficiency of the photovoltaic cell. , not only can improve the efficiency of cell conversion, but also reduce production costs.
  • the embodiment of the invention is realized by the composite electrode material for preparing the front electrode of the photovoltaic cell, and the composite electrode material for preparing the front electrode of the photovoltaic cell comprises:
  • the conductive core is selected from the group consisting of gold wire, silver wire, copper wire, aluminum wire, silicon aluminum wire, and conductive fiber of polymer fiber or carbon fiber, and the conductive core has a diameter of 5 ⁇ m to 50 ⁇ m.
  • the thickness of the connecting layer is 3 micrometers to 20 micrometers
  • the conductive paste is selected from the group consisting of silver paste, copper paste, nickel paste, a paste made of metal powder, and the curing temperature is 50 ° C - 200 ° C
  • conductive Pastes include metal powders, metal or non-metal oxides, organic solvents, organic binders, and additives.
  • composition and weight percentage of the conductive paste include: metal powder 70-90%; metal or non-metal oxide 1-10%; organic binder 1-10%; organic solvent 1-10%; additive 1 -5%.
  • the temperature reaches 100 ° C - 500 ° C
  • the connection layer after drying and curing has viscosity
  • the composite electrode material is used for preparing the front electrode of the photovoltaic cell.
  • the metal powder has a particle size of 0.1-2 ⁇ m, a spherical or quasi-spherical shape, and the metal or non-metal oxide is lead, bismuth, calcium, magnesium, zinc, platinum, rhodium, ruthenium, nickel, chromium, palladium, boron, One or a mixture of phosphorus oxides;
  • the organic binder is selected from the group consisting of ethyl cellulose, acrylic resin, nitrocellulose, phenol resin, and mixtures thereof;
  • the organic solvent is selected from the group consisting of terpineol, carbitol, diethylene glycol acetate, and mixtures thereof;
  • Additives include surfactants, thixotropic agents, defoamers, dispersants, sintering inhibitors, oxidation inhibitors Formulations and swelling inhibitors.
  • Another object of the present invention is to provide a process for preparing a front electrode of a photovoltaic cell using the above composite electrode material.
  • the process for preparing the front electrode of the photovoltaic cell comprises the following steps:
  • Step one preparing a conductive paste: mixing metal powder, metal or non-metal oxide, organic binder, organic solvent and additive to obtain a conductive paste; in the conductive paste, the mass percentage of the metal powder is 70-90%, the metal or non-metal oxide content is 1-10% by mass, the organic binder is 1-10% by mass, and the organic solvent is 1-10% by mass.
  • the mass percentage of the additive is 1-5%;
  • Step 2 preparing a composite electrode material: the conductive paste is uniformly coated on the surface of the conductive wire, and is cured by drying;
  • Step 3 heating the battery sheet or the composite electrode material to melt the organic binder in the composite electrode material partially or completely, restore the viscosity, and firmly bond the composite electrode material to the front surface of the battery sheet according to the design pattern. Bonding treatment;
  • Step 4 preparing a main grid line on the front side of the battery sheet: spraying the conductive paste body on the surface of the battery sheet to form a main grid line;
  • Step 5 The battery piece is placed in a reheating furnace and a sintering furnace, dried at 200 ° C - 500 ° C, and sintered at 500 ° C - 900 ° C to form a front electrode.
  • the two ends of the composite electrode material disposed on the front surface of the battery sheet are 0.5-1.5 mm apart from the front edge of the battery sheet, the ends of the main grid line are 0.5-1.5 mm from the edge of the battery sheet, and the number of main grid lines is 1-10. .
  • the metal powder has a particle size ranging from 0.1 to 2 ⁇ m, and the shape is spherical or quasi-spherical;
  • the heating of the composite electrode material or the cell sheet can be achieved by means of thermosonic, infrared or laser. It is preferably infrared heating, and the heating temperature is from 80 ° C to 500 ° C.
  • the diameter of the conductive wire is 5 micrometers to 50 micrometers
  • the thickness of the conductive paste after drying and curing is 3 micrometers to 20 micrometers
  • the drying and curing temperature of the conductive paste is 50 ° C - 200 ° C.
  • the conductive core of the electrode material is disposed as a wire or a conductive fiber, and the wire or the conductive fiber used serves to conduct a current, and the conductivity is greatly improved compared to the electrode prepared by the silver paste, thereby improving the conductive effect; the composite electrode of the present invention
  • the connecting layer of the material is uniformly coated on the surface of the conductive core by a conductive paste made of metal powder, and has a certain viscosity at a certain temperature, so that the electrode material itself can be firmly attached to the surface of the substrate, thereby avoiding the existence in the subsequent use.
  • the conductive paste of the present invention is uniformly coated on the surface of the conductive core and then dried and solidified.
  • the amount of silver can be greatly reduced, and the P strip has a low solar energy.
  • the electrode manufacturing cost of the battery sheet when the composite electrode material of the invention is used for preparing the front electrode of the solar cell sheet, the width of the fine grid line on the front side of the solar cell is reduced, and a fine grid line having a width of 20-50 micrometers is prepared, and the height can be Up to 15-40 microns, the electrode aspect ratio is large; the conductivity of the fine grid line can be increased by 20% compared to the conventional silver paste grid line.
  • the electrode resistance is small, the internal resistance of the battery is small, and the conversion efficiency of the photovoltaic cell is improved.
  • FIG. 1 is a schematic view showing a cross section of a composite electrode material according to an embodiment of the present invention
  • FIG. 2 is a schematic structural view of a composite electrode material according to an embodiment of the present invention.
  • FIG. 3 is a front structural view of a photovoltaic cell in which a main gate line is prepared according to an embodiment of the present invention
  • FIG. 4 is a front structural view of a photovoltaic cell according to an embodiment of the present invention
  • FIG. 6 is a schematic cross-sectional view of a junction between a battery chip and a composite electrode for completing the preparation of the front electrode according to an embodiment of the present invention
  • FIG. 7 is a flow chart showing a process of preparing a front electrode of a photovoltaic cell according to an embodiment of the present invention.
  • Figure 1 shows the composite electrode material structure for the preparation of front side electrodes of photovoltaic cells provided by the present invention. For the convenience of description, only the parts related to the present invention are shown.
  • the composite electrode material for preparing the front electrode of the photovoltaic cell comprises:
  • the conductive core is selected from the group consisting of gold wire, silver wire, copper wire, aluminum wire, silicon aluminum wire, and conductive fiber of polymer fiber or carbon fiber, and the diameter of the conductive core is 5 micrometers. 50 microns.
  • the thickness of the connecting layer is 3 micrometers to 20 micrometers
  • the conductive paste is selected from the group consisting of silver paste, copper paste, nickel paste, paste made of metal powder, and the curing temperature is 50. °C-200 ° C
  • conductive paste includes metal powder, metal or non-metal oxides, organic solvents, organic binders and additives.
  • the composition and the weight percentage content of the conductive paste include: metal powder 70-90%; metal or non-metal oxide 1-10%; organic binder 1-10%; organic Solvent 1-10%; Additive 1-5%.
  • the temperature reaches 100° C.-500° C.
  • the connection layer after drying and curing has viscosity
  • the composite electrode material is used for preparing the front surface of the photovoltaic cell. electrode.
  • the metal powder has a particle size of 0.1-2 ⁇ , the shape is spherical or quasi-spherical, and the metal or non-metal oxide is lead, antimony, calcium, magnesium, zinc, platinum, rhodium, ruthenium, a mixture of one or more of nickel, chromium, palladium, boron, and phosphorus oxide;
  • the organic binder is selected from the group consisting of ethyl cellulose, acrylic resin, nitrocellulose, phenolic resin and their mixture;
  • the organic solvent is selected from the group consisting of terpineol, carbitol, diethylene glycol acetate, and mixtures thereof;
  • Additives include surfactants, thixotropic agents, antifoaming agents, dispersing agents, sintering inhibitors, oxidation inhibitors, and swelling inhibitors.
  • the composite electrode material of the present invention is composed of a conductive core 7 at the core of the electrode material and a connecting layer 8 at the surface layer of the conductive core 7, and the connecting layer 8 is cured by drying of the conductive silver paste uniformly coated on the surface of the conductive core 7.
  • the drying curing temperature is 50°C-200°C
  • the conductive core 7 is 10-20 micron copper wire
  • the conductive silver paste is 5% by weight of the conductive silver paste, metal or non-metal oxide.
  • the organic binder accounts for 5%
  • the organic solvent accounts for 5%
  • the additive accounts for 1%
  • the rest is silver powder.
  • the silver powder has a particle size range of 0.1 -2 ⁇ ⁇ , the shape is spherical or quasi-spherical, and the thickness of the connecting layer 8 is 5-10 micron, metal or non-metal oxide is a mixture of one or more of lead, bismuth, calcium, magnesium, zinc, platinum, rhodium, ruthenium, nickel, chromium, palladium, boron, phosphorus, etc.
  • the organic binder is ethyl cellulose
  • the organic solvent is diethylene glycol diethyl ether
  • the additives include surfactants, thixotropic agents, antifoaming agents, dispersing agents, sintering inhibitors, oxidation inhibitors, swelling inhibitors, and composites.
  • Electrode material is used to make the front When the electrode temperature reaches 100 ° C -500 ° C, after drying the cured connecting layer 8 having a viscosity at this time;
  • the composite electrode material of the present invention is composed of a conductive core 7 at the core of the electrode material and a connecting layer 8 at the surface layer of the conductive core 7.
  • the connecting layer 8 is cured by a conductive silver paste uniformly coated on the surface of the conductive core.
  • the drying and curing temperature is 50°C-200°C
  • the conductive core 7 is 10-20 micrometers of silver wire
  • the conductive silver paste is 8% by weight of the conductive silver paste, metal or non-metal oxide.
  • the organic binder accounts for 5%
  • the organic solvent accounts for 5%
  • the additive accounts for 2%
  • the rest is silver powder.
  • the silver powder has a particle size ranging from 0.1 to 2 ⁇ m, the shape is spherical or quasi-spherical, and the thickness of the connecting layer 8 is 5-10 microns, metal or
  • the non-metal oxide is a mixture of one or more of lead, bismuth, calcium, magnesium, rhodium, platinum, rhodium, ruthenium, nickel, chromium, palladium, boron, phosphorus, etc., and the organic binder is B.
  • organic solvent is diethylene glycol ether
  • additives include surfactants, thixotropic agents, defoamers, dispersants, sintering inhibitors, oxidation inhibitors, expansion inhibitors, composite electrode materials used in the production of positive When the electrode is at a temperature of 100 ° C to 500 ° C, the connection layer 8 after drying and curing is sticky at this time;
  • the composite electrode material of the present invention is composed of a conductive core 7 at the core of the electrode material and a connecting layer 8 at the surface layer of the conductive core 7, and the connecting layer 8 is cured by drying of the conductive silver paste uniformly coated on the surface of the conductive core 7.
  • the drying curing temperature is 50°C-200°C
  • the conductive core 7 is 10-20 micrometer aluminum wire
  • the conductive silver paste is 10% by weight of the conductive silver paste, metal or non-metal oxide.
  • the organic binder accounts for 1%
  • the organic solvent accounts for 1%
  • the additive accounts for 1%
  • the rest is silver powder.
  • the silver powder has a particle size ranging from 0.1 to 2 ⁇ m, the shape is spherical or quasi-spherical, and the thickness of the connecting layer 8 is 5-10 micron, metal or non-metal oxide is a mixture of one or more of lead, bismuth, calcium, magnesium, rhodium, platinum, rhodium, ruthenium, nickel, chromium, palladium, boron, phosphorus, etc.
  • the organic binder is ethyl cellulose
  • the organic solvent is diethylene glycol diethyl ether
  • the additives include surfactants, thixotropic agents, antifoaming agents, dispersing agents, sintering inhibitors, oxidation inhibitors, swelling inhibitors, and composites.
  • Electrode material is used in the production At the front electrode, the temperature reaches 100. C-500 ° C, the connection layer after drying and curing 8 is sticky at this time;
  • the composite electrode material of the present invention is composed of a conductive core 7 at the core of the electrode material and a connecting layer 8 at the surface layer of the conductive core 7.
  • the connecting layer 8 is cured by a conductive paste uniformly coated on the surface of the conductive core 7.
  • the conductive paste is a conductive nickel-silver mixed paste, the drying and curing temperature is 50° C.-200° C., the conductive core 7 is a 10-20 micron copper wire, and the conductive silver paste is in the weight percentage of the conductive paste.
  • Metal or non-metal oxides accounted for 8%, organic binders accounted for 3%, organic solvents accounted for 3%, additives accounted for 3%, and the balance was a mixture of silver powder and nickel powder.
  • the weight ratio of silver powder to nickel powder was 7: 1, silver powder and nickel powder particle size range of 0.1-2 ⁇ ⁇ , the shape is spherical or quasi-spherical, the thickness of the connecting layer is 5-10 microns, metal or non-metal oxides are lead, antimony, calcium, magnesium, Zinc, platinum, rhodium, ruthenium, nickel, chromium, palladium, boron, One or more of phosphorus oxides, the organic binder is ethyl cellulose, the organic solvent is carbitol, and the additives include surfactants, thixotropic agents, defoamers, dispersants, and sintering. Inhibitor, oxidation inhibitor, expansion inhibitor, composite electrode material used in the preparation of the front electrode, the temperature reaches 100 ° C -500 ° C, the connection layer 8 after drying and curing is sticky at this time;
  • the paste of the invention has excellent coating effect and can be stably and evenly coated on the surface of the conductive core 7.
  • the different components in the conductive paste can promote the uniform and adjustable coating of the paste on the conductive core.
  • 7 surface layer on the other hand, can promote the bonding strength between the substrate and the conductive wire in the subsequent process, and optimize the electrical contact performance between the substrate and the substrate, and the connecting layer 8 is dried and solidified. , has a certain viscosity at a certain temperature, so that the electrode itself can be firmly attached to the surface of the device;
  • the composite electrode material of the invention has the appearance of a front electrode of the battery, which has better morphology and plasticity, less shading, and higher conductivity on the other hand.
  • the subdivision of the composite electrode material on its own function is more conducive to further improving and improving the performance from the two aspects of electrical conductivity and contact performance;
  • the composite electrode material of the invention is simple to use: it is laid at equal intervals according to the designed front electrode pattern and adhered to the front surface of the battery sheet, and then subjected to bonding treatment by infrared or ultrasonic method to make the composite electrode
  • the bonding layer of the material forms a strong alloy bond with the front surface of the battery sheet and excellent electrical connection, so that the front surface fine electrode can be fabricated, and when the film is adhered and adhered to the front surface of the battery sheet, the pressure applied by the screen printing can be avoided. , causing the problem of chip fragmentation;
  • the preparation process of the front electrode of the photovoltaic cell of the embodiment of the invention includes the following steps:
  • the conductive paste is uniformly coated on the surface of the conductive wire, and is cured by flooding to prepare a composite electrode material;
  • S703 heating the composite electrode material or the battery sheet to a certain temperature, so that the composite electrode material is firmly bonded to the front surface of the battery sheet according to the design pattern, and the bonding treatment is completed;
  • S704 spraying a conductive paste on the surface of the battery sheet to form a main grid line;
  • S705 The battery piece is placed in a drying furnace and a sintering furnace to be dried/sintered to form a front electrode; the specific steps of the preparation process of the front electrode of the photovoltaic cell of the present invention are:
  • Step one preparing a conductive paste: mixing and stirring metal powder, metal or non-metal oxide, organic binder, organic solvent and additive to obtain a conductive paste; in the conductive paste, the mass percentage of the metal powder is 70 -90%, the metal or non-metal oxide content is 1-10% by mass, the organic binder is 1-10% by mass, and the organic solvent is 1-10% by mass. The mass percentage is 1-5%;
  • Step 2 preparing a composite electrode material: the conductive paste is uniformly coated on the surface of the conductive wire 1 and dried and solidified.
  • the drying and curing temperature of the conductive paste is 50° C.-200° C., and the conductive paste is dried and cured.
  • the thickness of the conductive wire is 3 micrometers to 20 micrometers; the diameter of the conductive filaments is 5 micrometers to 50 micrometers, and the conductive filaments are selected from the group consisting of gold wires, silver wires, copper wires, aluminum wires, silicon aluminum wires, etc., and the conductive wires can also be used.
  • Conductive fibers such as polymer fibers or carbon fibers;
  • Step 3 heating the battery sheet 2 or the composite electrode material 4 at 100 ° C - 500 ° C, so that the composite electrode material 4 is firmly and firmly bonded to the front surface of the battery sheet 2, and is bonded to form a composite electrode material.
  • the bonded cell sheet 2 and the composite electrode material 4 are joined to form a bonding interface 5, and the two ends of the composite electrode material bonded to the front surface of the cell sheet and the two sides are 0.5-1.5 mm apart from the front edge of the cell sheet, and the composite electrode
  • the heating of the material 4 or the battery sheet 2 can be achieved by means of thermosonic, infrared or laser, preferably infrared heating;
  • Step 4 preparing a main gate line on the front side of the battery sheet: spraying the conductive paste on the surface of the battery sheet 2 to form a main gate line 3, the number of main gate lines is 1-10, and the ends of the main grid line are from the edge of the battery 0.5-1.5mm; medium, drying at 200 ° C - 500 ° C, sintering at 500 ° C - 900 ° C, forming a front electrode, forming a bonding interface between the bonded cell sheet and the composite electrode material joint 6;
  • the composite electrode material used in the invention has viscosity when the temperature reaches 100 ° C - 500 ° C;
  • conductive paste The body is selected from the group consisting of silver paste, copper paste, nickel paste and the like, and the metal powder in the conductive paste has a particle size ranging from 0.1 to 2 ⁇ m, and the shape is spherical or quasi-spherical; metal or non-metal oxide It is a mixture of one or more of lead, bismuth, calcium, magnesium, zinc, platinum, rhodium, ruthenium, nickel, chromium, palladium, boron, phosphorus, etc.; the organic binder is selected from ethyl cellulose , acrylic resin, nitrocellulose, phenolic resin and mixtures thereof; the organic solvent is selected from the group consisting of terpineol, carbitol, diethylene glycol ethyl ether and mixtures thereof; additives include surfactants, thixotropic agents, defoaming Agent,
  • preparing a conductive paste mixing metal powder, metal or non-metal oxide, organic binder, organic solvent and additive to obtain a conductive paste; in the conductive paste used, the metal powder is silver powder, conductive Silver paste is 5% by weight of conductive silver paste, 5% by metal or non-metal oxide, 5% by organic binder, 5% by organic solvent, 1% by additive, the rest is silver powder, and the particle size of silver powder. The range is 0.1-2 ⁇ ;
  • the conductive paste is uniformly coated on the surface of the copper wire with a diameter of 10-20 micrometers, and is dried and solidified.
  • the drying and curing temperature of the conductive paste is 50 ° C - 200 ° C, conductive
  • the paste is dried and cured to a thickness of 5 micrometers to 10 micrometers;
  • the cell or composite electrode material heating the cell or composite electrode material at 100 ° C - 500 ° C, so that the composite electrode material is evenly and firmly bonded to the front surface of the cell sheet, thereby completing the bonding process and bonding to the cell sheet.
  • the two ends of the composite electrode material on the front surface are 0.5-1.5 mm away from the front edge of the cell sheet, and the heating of the composite electrode material can be achieved by means of thermosonic, infrared or laser, preferably infrared heating;
  • Preparing a main grid line on the front side of the cell sheet spraying a conductive paste on the surface of the cell sheet to form a main gate line, the number of main gate lines is three, and the ends of the main grid line are 0.5-1.5 mm from the edge of the battery. ;
  • the composite electrode material used has a viscosity when the temperature reaches 100 ° C - 500 ° C, and the metal or non-metal oxide in the conductive paste is lead, antimony, calcium, magnesium, zinc, platinum, rhodium, iridium, nickel, chromium. And one or more of palladium, boron, phosphorus and the like;
  • the organic binder is selected from the group consisting of ethyl cellulose;
  • the organic solvent is selected from the group consisting of diethylene glycol ethyl ether;
  • the additive includes a surfactant, a thixotropic agent , defoamers, dispersants, sintering inhibitors, oxidation inhibitors and expansion inhibitors;
  • the front electrode of the photovoltaic cell according to the same procedure as in the first embodiment, except that the conductive silver paste in the second embodiment is in the weight percentage of the conductive silver paste, the metal or non-metal oxide accounts for 8%, and the organic binder accounts for 5%.
  • Organic solvent accounts for 5%, additive accounts for 2%, and the rest is silver powder; the number of main grid lines is 5;
  • the front electrode of the photovoltaic cell according to the same procedure as in the first embodiment, except that the conductive silver paste in the third embodiment is in the weight percentage of the conductive silver paste, the metal or non-metal oxide accounts for 10%, and the organic binder accounts for 1%.
  • Organic solvent accounts for 1%, additive accounts for 1%, and the rest is silver powder; the number of main grid lines is 7;
  • the front electrode of the photovoltaic cell according to the same procedure as in Example 3, except that the metal powder used in the conductive paste of Example 4 is a mixture of silver powder and nickel powder, and the weight percentage of the conductive paste in the conductive paste, metal or non- Metal oxides accounted for 8%, organic binders accounted for 3%, organic solvents accounted for 3%, additives accounted for 3%, and the balance was a mixture of silver powder and nickel powder.
  • the weight ratio of silver powder to nickel powder was 7:1, silver.
  • the powder and the nickel powder have a particle size ranging from 0.1 to 2 ⁇ m; and the conductive filament used is an aluminum wire; the organic solvent used in the conductive paste is carbitol;
  • the front electrode of the photovoltaic cell according to the same procedure as in the fourth embodiment, except that in the conductive paste used in the embodiment 5, the metal powder is copper powder, and the conductive copper paste is oxidized by metal or non-metal according to the weight percentage of the conductive copper paste.
  • the composite electrode material has two functions, namely, the function of conducting current and the bonding with the surface of the cell sheet during the process, and then forming a stable alloy bond and electrical combination; the two ends of the composite electrode are separated from the front side of the cell The edge is 0.5mm-1.5mm, avoiding the extension of the composite electrode to the edge etched area, causing leakage of the battery edge;
  • the invention greatly reduces the width of the fine grid line on the front side of the solar cell, and can prepare a fine grid line having a width of 20-50 micrometers, and the height can reach 15-40 micrometers, and the aspect ratio of the electrode is large; the conductivity of the fine grid line Compared with the conventional silver paste grid line, the electrode resistance can be increased by more than 20%, the electrode resistance is small, and the internal resistance of the battery is small, thereby improving the conversion efficiency of the photovoltaic cell; the invention can prepare a front electrode with small light-shielding area, higher conductivity and low cost. At the same time, the process greatly reduces the occurrence of fragmentation during the preparation process of the front electrode.

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Abstract

Provided are a composite electrode material (4) and process for preparing the front electrode of a photovoltaic cell. The composite material comprises a conductive core (7) disposed inside the composite electrode material, and a connecting layer (8) disposed on the surface of the conductive core. The preparation process comprises: preparing conductive paste; coating the surface of a conductive metal wire with the conductive paste, and drying and solidifying the conductive metal wire coated with the conductive paste to form the composite electrode material; heating a cell plate (2) or the composite electrode material to partially or completely melt the organic adhesive in the composite electrode material to restore viscidity of the composite electrode material, such that the composite electrode material is bonded to the front surface of the cell plate according to a designed pattern; employing spray coating to spray the conductive paste on the front of the cell plate to prepare a main gate line (3); putting the cell plate into a drying stove and a sintering furnace for drying at 200°C-500°C and sintering at 500°C-900°C respectively to form a front electrode. The contact function and conductive function of an electrode are separated to improve the conductivity of the electrode. The front electrode of a photovoltaic cell plate has less shielding and high conductivity.

Description

说 明 书 一种用于制备光伏电池正面电极的复合电极材料及工艺 技术领域  Composite electrode material and process for preparing front electrode of photovoltaic cell
本发明属于光伏电池技术领域， 尤其涉及一种用于制备光伏电池正面电极 的复合电极材料及工艺。 背景技术  The invention belongs to the technical field of photovoltaic cells, and in particular relates to a composite electrode material and a process for preparing a front electrode of a photovoltaic cell. Background technique
光伏电池正面金属化目前主要是通过丝网印刷导电浆料的方式来实现， 其 制备的电极高宽比小， 电极宽度大、 宽度不均匀且边缘塌陷严重， 电极高度小 且高度不均匀。 对于光伏电池来说， 电极宽度大和塌陷严重意味着正面遮光面 积大， 电极高度低且不均匀意味着电极导电性差、 电池内阻大， 这些都严重地 影响和制约了光伏电池效率的提升。  The front metallization of photovoltaic cells is mainly achieved by screen printing conductive paste. The prepared electrode has a small aspect ratio, large electrode width, uneven width and severe edge collapse, and the electrode height is small and the height is not uniform. For photovoltaic cells, large electrode width and severe collapse mean that the front side has a large light-shielding area, and the low electrode height and unevenness means that the electrode has poor conductivity and large internal resistance, which seriously affects and restricts the efficiency of the photovoltaic cell.
光伏电池正面电极主要有两方面的作用： 一方面是电极下部与电池正表面 形成合金和欧姆接触， 起电气连接的作用； 一方面是电极主体传导电流， 起到 导体的作用。 对于电气连接的作用， 目前的银浆可以起到比较好的效杲， 达到 比较低的接触电阻， 但是对于导体的作用， 由于银浆本身是由银粉构成， 由其 制备的电极是一种多孔的结构， 其导电性能比纯金属的致密导体要差很多， 这 些也限制了电极导电性能的提高， 从而制约了光伏电池效率的提高。 目前用于 光伏电池正面金属化的导电浆料主要是银浆， 由于导电性的要求， 银浆中银的 含量非常高， 达到 90%左右， 银是贵金属， 目前的光伏电池正面电极用料选择 也严重地制约了光伏电池制造成本的进一步下降。  The front electrode of the photovoltaic cell mainly has two functions: On the one hand, the lower part of the electrode forms an alloy and ohmic contact with the front surface of the battery, and functions as an electrical connection; on the other hand, the electrode body conducts current and acts as a conductor. For the role of electrical connection, the current silver paste can play a better effect, achieving a lower contact resistance, but for the role of the conductor, since the silver paste itself is composed of silver powder, the electrode prepared therefrom is a porous The structure has much lower conductivity than the dense conductor of pure metal, which also limits the improvement of the conductivity of the electrode, thereby restricting the efficiency of the photovoltaic cell. At present, the conductive paste used for the front metallization of photovoltaic cells is mainly silver paste. Due to the requirement of conductivity, the content of silver in silver paste is very high, reaching about 90%, silver is a precious metal, and the current electrode materials for photovoltaic cells are also selected. It has seriously restricted the further decline in the manufacturing cost of photovoltaic cells.
另外， 传统的用丝网印刷和银浆来实现光伏电池正面金属化的工艺， 是利 用网版本身的通透性， 在一定的压力下， 将黏度很高的银浆透过网孔挤压到光 伏电池正面， 由于浆料黏度很高， 且网版开口很小， 所以需要很大的压力才能 形成达标的电极图型， 如此大的压力增大了印刷电池时的破片率， 在未来光伏 电池片将越来越薄的趋势下，传统的丝网印刷金属化方案阻碍了新技术的应用。 发明内容 In addition, the traditional process of realizing the metallization of the front side of the photovoltaic cell by screen printing and silver paste is to use the permeability of the mesh version to squeeze the high viscosity silver paste through the mesh under a certain pressure. To the front of the photovoltaic cell, due to the high viscosity of the slurry and the small opening of the screen, it requires a lot of pressure to form the electrode pattern that meets the standard. Such a large pressure increases the fragmentation rate when printing the battery. Under the trend that the battery will become thinner and thinner, the traditional screen printing metallization scheme hinders the application of new technologies. Summary of the invention
本发明的目的是针对现有技术存在的成本高， 光伏电池效率低的问题， 提 供一种用于制备光伏电池正面电极的复合电极材料及工艺，该方法具有成本低， 光伏电池效率高的优点， 不仅能使电池片转换效率提高， 还能降低生产成本。  The object of the present invention is to provide a composite electrode material and a process for preparing a front electrode of a photovoltaic cell with high cost and low efficiency of the photovoltaic cell, which has the advantages of low cost and high efficiency of the photovoltaic cell. , not only can improve the efficiency of cell conversion, but also reduce production costs.
本发明实施例是这样实现的， 一种用于光伏电池正面电极制备的复合电极 材料， 该用于光伏电池正面电极制备的复合电极材料包括：  The embodiment of the invention is realized by the composite electrode material for preparing the front electrode of the photovoltaic cell, and the composite electrode material for preparing the front electrode of the photovoltaic cell comprises:
设置在复合电极材料内部的导电芯和设置在导电芯表面的连接层， 连接层 通过涂覆在导电芯表面的导电膏体经烘干固化而成。  A conductive core disposed inside the composite electrode material and a connection layer disposed on the surface of the conductive core, the connection layer being formed by drying and curing the conductive paste coated on the surface of the conductive core.
进一步， 导电芯选自金丝、 银丝、 铜丝、 铝丝、 硅铝丝， 也可以是聚合物 纤維或碳纤维的导电纤维， 导电芯的直径为 5微米到 50微米。  Further, the conductive core is selected from the group consisting of gold wire, silver wire, copper wire, aluminum wire, silicon aluminum wire, and conductive fiber of polymer fiber or carbon fiber, and the conductive core has a diameter of 5 μm to 50 μm.
进一步， 连接层的厚度为 3微米到 20微米， 导电膏体选自银膏、 铜膏、镍 膏， 采用金属粉制成的膏体， 烘干固化温度为 50°C-200°C , 导电膏体包括金属 粉末、 金属或非金属氧化物、 有机溶剂、 有机粘合剂及添加剂。  Further, the thickness of the connecting layer is 3 micrometers to 20 micrometers, and the conductive paste is selected from the group consisting of silver paste, copper paste, nickel paste, a paste made of metal powder, and the curing temperature is 50 ° C - 200 ° C, conductive Pastes include metal powders, metal or non-metal oxides, organic solvents, organic binders, and additives.
进一步， 导电膏体的组分和重量百分比含量包括： 金属粉末 70-90%; 金属 或非金属氧化物 1-10%; 有机粘合剂 1-10%; 有机溶剂 1-10%; 添加剂 1-5%。  Further, the composition and weight percentage of the conductive paste include: metal powder 70-90%; metal or non-metal oxide 1-10%; organic binder 1-10%; organic solvent 1-10%; additive 1 -5%.
进一步， 复合电极材料在用于制作正面电极时， 温度达到 100°C-500°C , 烘干固化后的连接层具有粘性， 复合电极材料用于制备光伏电池正面电极。  Further, when the composite electrode material is used for the front electrode, the temperature reaches 100 ° C - 500 ° C, the connection layer after drying and curing has viscosity, and the composite electrode material is used for preparing the front electrode of the photovoltaic cell.
进一步， 金属粉末的颗粒大小为 0.1-2μπι, 形态为球形或准球形， 金属或 非金属氧化物为铅、 铋、 钙、 镁、 锌、 铂、 钽、 铑、 镍、 铬、 钯、 硼、 磷氧化 物中的一种或几种混合而成；  Further, the metal powder has a particle size of 0.1-2 μm, a spherical or quasi-spherical shape, and the metal or non-metal oxide is lead, bismuth, calcium, magnesium, zinc, platinum, rhodium, ruthenium, nickel, chromium, palladium, boron, One or a mixture of phosphorus oxides;
有机粘合剂选自乙基纤维素、 丙烯酸树脂、 硝基纤维素、 酚 树脂及它们 的混合物；  The organic binder is selected from the group consisting of ethyl cellulose, acrylic resin, nitrocellulose, phenol resin, and mixtures thereof;
有机溶剂选自松油醇、 卡必醇、 二乙二醇乙酸及它们的混合物；  The organic solvent is selected from the group consisting of terpineol, carbitol, diethylene glycol acetate, and mixtures thereof;
添加剂包括表面活性剂、 触变剂、 消泡剂、 分散剂、 烧结抑制剂、 氧化抑 制剂和膨胀抑制剂。 Additives include surfactants, thixotropic agents, defoamers, dispersants, sintering inhibitors, oxidation inhibitors Formulations and swelling inhibitors.
本发明的另一目的在于提供一种用上述复合电极材料制备光伏电池正面电 极的工艺， 该光伏电池正面电极的制备工艺包括以下步骤：  Another object of the present invention is to provide a process for preparing a front electrode of a photovoltaic cell using the above composite electrode material. The process for preparing the front electrode of the photovoltaic cell comprises the following steps:
步骤一， 制备导电膏体： 将金属粉末， 金属或非金属氧化物， 有机粘合剂， 有机溶剂和添加剂混合搅拌均勾得到导电膏体； 导电膏体中， 金属粉末的 质量百分含量为 70-90%， 金属或非金属氧化物的质量百分含量为 1-10%， 有机 粘合剂的质量百分含量为 1-10%， 有机溶剂的质量百分含量为 1-10%, 添加剂的质量百分含量为 1-5%;  Step one, preparing a conductive paste: mixing metal powder, metal or non-metal oxide, organic binder, organic solvent and additive to obtain a conductive paste; in the conductive paste, the mass percentage of the metal powder is 70-90%, the metal or non-metal oxide content is 1-10% by mass, the organic binder is 1-10% by mass, and the organic solvent is 1-10% by mass. The mass percentage of the additive is 1-5%;
步骤二， 制备复合电极材料： 导电膏体均匀涂覆在导电金属丝表面， 经烘 干固化而成；  Step 2, preparing a composite electrode material: the conductive paste is uniformly coated on the surface of the conductive wire, and is cured by drying;
步骤三， 对电池片或复合电极材料进行加热， 使复合电极材料中的有机粘 合剂能够部分或全部融化， 恢复粘性， 使复合电极材料按设计图案牢固地粘结 于电池片正表面， 完成粘结处理；  Step 3: heating the battery sheet or the composite electrode material to melt the organic binder in the composite electrode material partially or completely, restore the viscosity, and firmly bond the composite electrode material to the front surface of the battery sheet according to the design pattern. Bonding treatment;
步骤四， 在电池片的正面制备主栅线： 电池片表面上用喷涂的方式喷涂导 电膏体制作主栅线；  Step 4, preparing a main grid line on the front side of the battery sheet: spraying the conductive paste body on the surface of the battery sheet to form a main grid line;
步骤五， 将电池片放入到煥干炉和烧结炉中， 在 200°C-500°C烘干， 在 500°C-900°C进行烧结， 形成正面电极。  Step 5: The battery piece is placed in a reheating furnace and a sintering furnace, dried at 200 ° C - 500 ° C, and sintered at 500 ° C - 900 ° C to form a front electrode.
进一步， 铺设置在电池片正表面的复合电极材料两端和两边相距电池片正 面边缘 0.5-1.5mm， 主栅线两端距电池片边缘 0.5-1.5mm， 主栅线数量为 1-10 根。  Further, the two ends of the composite electrode material disposed on the front surface of the battery sheet are 0.5-1.5 mm apart from the front edge of the battery sheet, the ends of the main grid line are 0.5-1.5 mm from the edge of the battery sheet, and the number of main grid lines is 1-10. .
进一步， 在步骤一中， 金属粉末的颗粒大小范围为 0.1-2μηι, 形态为球形 或准球形； 在步骤三中复合电极材料或电池片的加热可以通过热超声、 红外或 激光的方式来实现， 优选为红外加热， 加热温度为 80°C-500°C。 进一步， 在步骤二中， 导电丝的直径为 5微米到 50微米， 导电膏体烘干固 化后的的厚度为 3微米到 20微米， 导电膏体的烘干固化温度为 50°C-200°C。  Further, in the first step, the metal powder has a particle size ranging from 0.1 to 2 μm, and the shape is spherical or quasi-spherical; in the third step, the heating of the composite electrode material or the cell sheet can be achieved by means of thermosonic, infrared or laser. It is preferably infrared heating, and the heating temperature is from 80 ° C to 500 ° C. Further, in the second step, the diameter of the conductive wire is 5 micrometers to 50 micrometers, the thickness of the conductive paste after drying and curing is 3 micrometers to 20 micrometers, and the drying and curing temperature of the conductive paste is 50 ° C - 200 ° C.
本发明提供的用于制备光伏电池正面电极的复合电极材料及工艺， 通过复 合电极材料的导电芯设置为金属丝或导电纤维， 使用的金属丝或导电纤维起到 传导电流的作用， 导电性能相比银浆制备的电极大大提高， 提高了导电效果； 本发明的复合电极材料的连接层采用金属粉制成的导电膏体经均匀涂覆在导电 芯表面， 在一定温度具有一定粘性， 以使电极材料本身能够牢固地附着在基体 表面， 避免了在后续使用过程中存在的翘线问题， 提高了粘结附着性； 本发明 的导电膏体均匀涂覆在导电芯表面再烘干固化而成， 在制作电极时， 可大量降 低银的使用量， P条低了太阳能电池片的电极制作成本； 本发明的复合电极材料 用于制备太阳能电池片正面电极时， 降低了太阳能电池正面细栅线的宽度， 制 备出宽度达到 20-50微米的精细栅线， 同时高度可以达到 15- 40微米， 电极高 宽比大； 细栅线的导电率比传统银浆栅线可以提高 20%以上， 使电极电阻小、 电池内阻小， 提升了光伏电池的转换效率。 附图说明 Composite electrode material and process for preparing front electrode of photovoltaic cell provided by the invention The conductive core of the electrode material is disposed as a wire or a conductive fiber, and the wire or the conductive fiber used serves to conduct a current, and the conductivity is greatly improved compared to the electrode prepared by the silver paste, thereby improving the conductive effect; the composite electrode of the present invention The connecting layer of the material is uniformly coated on the surface of the conductive core by a conductive paste made of metal powder, and has a certain viscosity at a certain temperature, so that the electrode material itself can be firmly attached to the surface of the substrate, thereby avoiding the existence in the subsequent use. The problem of the warpage improves the adhesion and adhesion; the conductive paste of the present invention is uniformly coated on the surface of the conductive core and then dried and solidified. When the electrode is fabricated, the amount of silver can be greatly reduced, and the P strip has a low solar energy. The electrode manufacturing cost of the battery sheet; when the composite electrode material of the invention is used for preparing the front electrode of the solar cell sheet, the width of the fine grid line on the front side of the solar cell is reduced, and a fine grid line having a width of 20-50 micrometers is prepared, and the height can be Up to 15-40 microns, the electrode aspect ratio is large; the conductivity of the fine grid line can be increased by 20% compared to the conventional silver paste grid line The above, the electrode resistance is small, the internal resistance of the battery is small, and the conversion efficiency of the photovoltaic cell is improved. DRAWINGS
图 1是本发明实施例提供的复合电极材料截面的示意图；  1 is a schematic view showing a cross section of a composite electrode material according to an embodiment of the present invention;
图 2是本发明实施例提供的复合电极材料的结构示意图；  2 is a schematic structural view of a composite electrode material according to an embodiment of the present invention;
图 3是本发明实施例提供的制备了主栅线的光伏电池正面结构图； 图 4是本发明实施例提供的完成正面电极制备的光伏电池正面结构图； 图 5是本发明实施例提供的完成了粘接处理的电池片和复合电极结合处横 截面示意图；  3 is a front structural view of a photovoltaic cell in which a main gate line is prepared according to an embodiment of the present invention; FIG. 4 is a front structural view of a photovoltaic cell according to an embodiment of the present invention; A cross-sectional view of the junction of the cell sheet and the composite electrode in which the bonding treatment is completed;
图 6是本发明实施例提供的完成正面电极制备的电池片和复合电极结合处 横堆面示意图；  6 is a schematic cross-sectional view of a junction between a battery chip and a composite electrode for completing the preparation of the front electrode according to an embodiment of the present invention;
图 7是本发明实施例的光伏电池正面电极的制备工艺的流程图。  7 is a flow chart showing a process of preparing a front electrode of a photovoltaic cell according to an embodiment of the present invention.
图中： 1、 导电丝； 2、 电池片； 3、 主栅线； 4、 复合电极材料； 5、 粘结界 面； 6、 键合界面； 7、 导电芯； 8、 连接层。 具体实施方式 为了使本发明的目的、 技术方案及优点更加清楚明白， 以下结合实施例， 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 the figure: 1, conductive wire; 2, battery; 3, main grid line; 4, composite electrode material; 5, bonding interface; 6, bonding interface; 7, conductive core; 8, connecting layer. detailed description In order to make the objects, technical solutions and advantages of the present invention more comprehensible, the present invention will be further described in detail below with reference to the embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
图 1示出了本发明提供的用于光伏电池正面电极制备的复合电极材料结 构。 为了便于说明， 仅仅示出了与本发明相关的部分。  BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows the composite electrode material structure for the preparation of front side electrodes of photovoltaic cells provided by the present invention. For the convenience of description, only the parts related to the present invention are shown.
本发明实施例的用于光伏电池正面电极制备的复合电极材料， 该用于光伏 电池正面电极制备的复合电极材料包括：  The composite electrode material for preparing the front electrode of the photovoltaic cell according to the embodiment of the invention, the composite electrode material for preparing the front electrode of the photovoltaic cell comprises:
设置在复合电极材料内部的导电芯和设置在导电芯表面的连接层， 连接层 通过涂覆在导电芯表面的导电膏体经烘干固化而成。  A conductive core disposed inside the composite electrode material and a connection layer disposed on the surface of the conductive core, the connection layer being formed by drying and curing the conductive paste coated on the surface of the conductive core.
作为本发明实施例的一优化方案， 导电芯选自金丝、 银丝、 铜丝、 铝丝、 硅铝丝， 也可以是聚合物纤维或碳纤维的导电纤维， 导电芯的直径为 5微米到 50微米。  As an optimization scheme of the embodiment of the present invention, the conductive core is selected from the group consisting of gold wire, silver wire, copper wire, aluminum wire, silicon aluminum wire, and conductive fiber of polymer fiber or carbon fiber, and the diameter of the conductive core is 5 micrometers. 50 microns.
作为本发明实施例的一优化方案，连接层的厚度为 3微米到 20微米，导电 膏体选自银膏、 铜膏、 镍膏， 采用金属粉制成的膏体， 烘干固化温度为 50°C-200°C , 导电膏体包括金属粉末、 金属或非金属氧化物、 有机溶剂、 有机 粘合剂及添加剂。  As an optimization scheme of the embodiment of the present invention, the thickness of the connecting layer is 3 micrometers to 20 micrometers, and the conductive paste is selected from the group consisting of silver paste, copper paste, nickel paste, paste made of metal powder, and the curing temperature is 50. °C-200 ° C, conductive paste includes metal powder, metal or non-metal oxides, organic solvents, organic binders and additives.
作为本发明实施例的一优化方案，导电膏体的组分和重量百分比含量包括： 金属粉末 70-90%; 金属或非金属氧化物 1-10%; 有机粘合剂 1-10%; 有机溶剂 1-10%; 添加剂 1-5%。  As an optimization scheme of the embodiment of the present invention, the composition and the weight percentage content of the conductive paste include: metal powder 70-90%; metal or non-metal oxide 1-10%; organic binder 1-10%; organic Solvent 1-10%; Additive 1-5%.
作为本发明实施例的一优化方案， 复合电极材料在用于制作正面电极时， 温度达到 100°C-500°C , 烘干固化后的连接层具有粘性， 复合电极材料用于制 备光伏电池正面电极。  As an optimization scheme of the embodiment of the present invention, when the composite electrode material is used for the front electrode, the temperature reaches 100° C.-500° C., the connection layer after drying and curing has viscosity, and the composite electrode material is used for preparing the front surface of the photovoltaic cell. electrode.
作为本发明实施例的一优化方案， 金属粉末的颗粒大小为 0.1-2μη, 形态 为球形或准球形， 金属或非金属氧化物为铅、 铋、 钙、 镁、 锌、 铂、 钽、 铑、 镍、 铬、 钯、 硼、 磷氧化物中的一种或几种混合而成；  As an optimization scheme of the embodiment of the present invention, the metal powder has a particle size of 0.1-2 μη, the shape is spherical or quasi-spherical, and the metal or non-metal oxide is lead, antimony, calcium, magnesium, zinc, platinum, rhodium, ruthenium, a mixture of one or more of nickel, chromium, palladium, boron, and phosphorus oxide;
有机粘合剂选自乙基纤维素、 丙烯酸树脂、 硝基纤维素、 酚酸树脂及它们 的混合物； The organic binder is selected from the group consisting of ethyl cellulose, acrylic resin, nitrocellulose, phenolic resin and their mixture;
有机溶剂选自松油醇、 卡必醇、 二乙二醇乙酸及它们的混合物；  The organic solvent is selected from the group consisting of terpineol, carbitol, diethylene glycol acetate, and mixtures thereof;
添加剂包括表面活性剂、 触变剂、 消泡剂、 分散剂、 烧结抑制剂、 氧化抑 制剂和膨胀抑制剂。  Additives include surfactants, thixotropic agents, antifoaming agents, dispersing agents, sintering inhibitors, oxidation inhibitors, and swelling inhibitors.
下面结合附图及具体实施例对本发明的应用原理作进一步描述。  The application principle of the present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.
结合附图 1及光伏电池正面电极的复合电极材料的具体实施方案做进一步 的说明：  The specific implementation of the composite electrode material of the front electrode of the photovoltaic cell is further described in conjunction with FIG. 1 :
实施例 1 :  Example 1
本发明的复合电极材料， 由处于电极材料芯部的导电芯 7和处于导电芯 7 表层的连接层 8组成， 连接层 8是由均匀涂覆在导电芯 7表面的导电银膏经烘 干固化而成， 烘干固化温度为 50°C-200°C , 导电芯 7为 10-20微米的铜丝， 导 电银膏中按导电银膏的重量百分比， 金属或非金属氧化物占 5%, 有机粘合剂 占 5% , 有机溶剂占 5%， 添加剂占 1%, 其余为银粉末， 银粉末的颗粒大小范 围为 0.1 -2 μ πι, 形态为球形或准球形， 连接层 8的厚度为 5-10微米， 金属或 非金属氧化物为铅、 铋、 钙、 镁、 锌、 铂、 钽、 铑、 镍、 铬、 钯、 硼、 磷等氧 化物中的一种或几种混合而成， 有机粘合剂为乙基纤维素， 有机溶剂为二乙二 醇乙醚， 添加剂包括表面活性剂、 触变剂、 消泡剂、 分散剂、 烧结抑制剂、 氧 化抑制剂、 膨胀抑制剂， 复合电极材料在用于制作正面电极时， 温度达到 100 °C -500°C , 烘干固化后的连接层 8此时具有粘性；  The composite electrode material of the present invention is composed of a conductive core 7 at the core of the electrode material and a connecting layer 8 at the surface layer of the conductive core 7, and the connecting layer 8 is cured by drying of the conductive silver paste uniformly coated on the surface of the conductive core 7. The drying curing temperature is 50°C-200°C, the conductive core 7 is 10-20 micron copper wire, and the conductive silver paste is 5% by weight of the conductive silver paste, metal or non-metal oxide. The organic binder accounts for 5%, the organic solvent accounts for 5%, the additive accounts for 1%, and the rest is silver powder. The silver powder has a particle size range of 0.1 -2 μ πι, the shape is spherical or quasi-spherical, and the thickness of the connecting layer 8 is 5-10 micron, metal or non-metal oxide is a mixture of one or more of lead, bismuth, calcium, magnesium, zinc, platinum, rhodium, ruthenium, nickel, chromium, palladium, boron, phosphorus, etc. The organic binder is ethyl cellulose, the organic solvent is diethylene glycol diethyl ether, and the additives include surfactants, thixotropic agents, antifoaming agents, dispersing agents, sintering inhibitors, oxidation inhibitors, swelling inhibitors, and composites. Electrode material is used to make the front When the electrode temperature reaches 100 ° C -500 ° C, after drying the cured connecting layer 8 having a viscosity at this time;
实施例 2:  Example 2:
本发明的复合电极材料， 由处于电极材料芯部的导电芯 7和处于导电芯 7 表层的连接层 8组成， 连接层 8是由均匀涂覆在导电芯 Ί表面的导电银膏经烘 干固化而成， 烘干固化温度为 50°C-200°C， 导电芯 7为 10-20微米的银丝， 导 电银膏中按导电银膏的重量百分比， 金属或非金属氧化物占 8% , 有机粘合剂 占 5% , 有机溶剂占 5%, 添加剂占 2%, 其余为银粉末， 银粉末的颗粒大小范 围为 0.1-2 μ ιη, 形态为球形或准球形， 连接层 8的厚度为 5-10微米， 金属或 非金属氧化物为铅、 铋、 钙、 镁、 辞、 铂、 钽、 铑、 镍、 铬、 钯、 硼、 磷等氧 化物中的一种或几种混合而成， 有机粘合剂为乙基纤维素， 有机溶剂为二乙二 醇乙醚， 添加剂包括表面活性剂、 触变剂、 消泡剂、 分散剂、 烧结抑制剂、 氧 化抑制剂、 膨胀抑制剂， 复合电极材料在用于制作正面电极时， 温度达到 100 °C-500°C， 烘干固化后的连接层 8此时具有粘性； The composite electrode material of the present invention is composed of a conductive core 7 at the core of the electrode material and a connecting layer 8 at the surface layer of the conductive core 7. The connecting layer 8 is cured by a conductive silver paste uniformly coated on the surface of the conductive core. The drying and curing temperature is 50°C-200°C, the conductive core 7 is 10-20 micrometers of silver wire, and the conductive silver paste is 8% by weight of the conductive silver paste, metal or non-metal oxide. The organic binder accounts for 5%, the organic solvent accounts for 5%, the additive accounts for 2%, and the rest is silver powder. The silver powder has a particle size ranging from 0.1 to 2 μm, the shape is spherical or quasi-spherical, and the thickness of the connecting layer 8 is 5-10 microns, metal or The non-metal oxide is a mixture of one or more of lead, bismuth, calcium, magnesium, rhodium, platinum, rhodium, ruthenium, nickel, chromium, palladium, boron, phosphorus, etc., and the organic binder is B. Cellulose, organic solvent is diethylene glycol ether, additives include surfactants, thixotropic agents, defoamers, dispersants, sintering inhibitors, oxidation inhibitors, expansion inhibitors, composite electrode materials used in the production of positive When the electrode is at a temperature of 100 ° C to 500 ° C, the connection layer 8 after drying and curing is sticky at this time;
实施例 3:  Example 3:
本发明的复合电极材料， 由处于电极材料芯部的导电芯 7和处于导电芯 7 表层的连接层 8组成， 连接层 8是由均匀涂覆在导电芯 7表面的导电银膏经烘 干固化而成， 烘干固化温度为 50°C- 200°C， 导电芯 7为 10-20微米的铝丝， 导 电银膏中按导电银膏的重量百分比， 金属或非金属氧化物占 10%， 有机粘合剂 占 1%， 有机溶剂占 1%， 添加剂占 1%， 其余为银粉末， 银粉末的颗粒大小范 围为 0.1-2 μ πι, 形态为球形或准球形， 连接层 8的厚度为 5-10微米， 金属或 非金属氧化物为铅、 铋、 钙、 镁、 辞、 铂、 钽、 铑、 镍、 铬、 钯、 硼、 磷等氧 化物中的一种或几种混合而成， 有机粘合剂为乙基纤维素， 有机溶剂为二乙二 醇乙醚， 添加剂包括表面活性剂、 触变剂、 消泡剂、 分散剂、 烧结抑制剂、 氧 化抑制剂、 膨胀抑制剂， 复合电极材料在用于制作正面电极时， 温度达到 100 。C- 500°C , 烘干固化后的连接层 8此时具有粘性；  The composite electrode material of the present invention is composed of a conductive core 7 at the core of the electrode material and a connecting layer 8 at the surface layer of the conductive core 7, and the connecting layer 8 is cured by drying of the conductive silver paste uniformly coated on the surface of the conductive core 7. The drying curing temperature is 50°C-200°C, the conductive core 7 is 10-20 micrometer aluminum wire, and the conductive silver paste is 10% by weight of the conductive silver paste, metal or non-metal oxide. The organic binder accounts for 1%, the organic solvent accounts for 1%, the additive accounts for 1%, and the rest is silver powder. The silver powder has a particle size ranging from 0.1 to 2 μm, the shape is spherical or quasi-spherical, and the thickness of the connecting layer 8 is 5-10 micron, metal or non-metal oxide is a mixture of one or more of lead, bismuth, calcium, magnesium, rhodium, platinum, rhodium, ruthenium, nickel, chromium, palladium, boron, phosphorus, etc. The organic binder is ethyl cellulose, the organic solvent is diethylene glycol diethyl ether, and the additives include surfactants, thixotropic agents, antifoaming agents, dispersing agents, sintering inhibitors, oxidation inhibitors, swelling inhibitors, and composites. Electrode material is used in the production At the front electrode, the temperature reaches 100. C-500 ° C, the connection layer after drying and curing 8 is sticky at this time;
实施例 4:  Example 4:
本发明的复合电极材料， 由处于电极材料芯部的导电芯 7和处于导电芯 7 表层的连接层 8组成， 连接层 8是由均匀涂覆在导电芯 7表面的导电膏体经烘 干固化而成， 导电膏体为导电镍银混合膏， 烘干固化温度为 50°C-200°C， 导电 芯 7为 10-20微米的铜丝， 导电银膏中按导电膏体的重量百分比， 金属或非金 属氧化物占 8%, 有机粘合剂占 3%， 有机溶剂占 3%， 添加剂占 3%, 其余为银 粉末和镍粉末的混合物，银粉末和镍粉末的重量比为 7:1，银粉末和镍粉末的颗 粒大小范围为 0.1-2 μ ηι, 形态为球形或准球形， 连接层的厚度为 5-10微米， 金属或非金属氧化物为铅、 铋、 钙、 镁、 锌、 铂、 钽、 铑、 镍、 铬、 钯、 硼、 磷等氧化物中的一种或几种混合而成， 有机粘合剂为乙基纤维素， 有机溶剂为 卡必醇， 添加剂包括表面活性剂、 触变剂、 消泡剂、 分散剂、 烧结抑制剂、 氧 化抑制剂、 膨胀抑制剂， 复合电极材料在用于制作正面电极时， 温度达到 100 °C-500°C , 烘干固化后的连接层 8此时具有粘性； The composite electrode material of the present invention is composed of a conductive core 7 at the core of the electrode material and a connecting layer 8 at the surface layer of the conductive core 7. The connecting layer 8 is cured by a conductive paste uniformly coated on the surface of the conductive core 7. The conductive paste is a conductive nickel-silver mixed paste, the drying and curing temperature is 50° C.-200° C., the conductive core 7 is a 10-20 micron copper wire, and the conductive silver paste is in the weight percentage of the conductive paste. Metal or non-metal oxides accounted for 8%, organic binders accounted for 3%, organic solvents accounted for 3%, additives accounted for 3%, and the balance was a mixture of silver powder and nickel powder. The weight ratio of silver powder to nickel powder was 7: 1, silver powder and nickel powder particle size range of 0.1-2 μ ηι, the shape is spherical or quasi-spherical, the thickness of the connecting layer is 5-10 microns, metal or non-metal oxides are lead, antimony, calcium, magnesium, Zinc, platinum, rhodium, ruthenium, nickel, chromium, palladium, boron, One or more of phosphorus oxides, the organic binder is ethyl cellulose, the organic solvent is carbitol, and the additives include surfactants, thixotropic agents, defoamers, dispersants, and sintering. Inhibitor, oxidation inhibitor, expansion inhibitor, composite electrode material used in the preparation of the front electrode, the temperature reaches 100 ° C -500 ° C, the connection layer 8 after drying and curing is sticky at this time;
本发明的膏体具有优良的涂覆效果， 能稳定、均匀地包覆在导电芯 7表面， 导电膏体中不同的成份一方面能促使此膏体能方便地均匀可调地涂覆在导电芯 7表层， 另一方面在后续的工艺使用过程中既能促进其对基片和导电丝的粘结 强度， 也能优化其与基片间的电学接触性能， 并且连接层 8在烘干固化后， 在 一定温度下又具有一定粘性， 以使电极本身能够牢固地附着在器件表面；  The paste of the invention has excellent coating effect and can be stably and evenly coated on the surface of the conductive core 7. The different components in the conductive paste can promote the uniform and adjustable coating of the paste on the conductive core. 7 surface layer, on the other hand, can promote the bonding strength between the substrate and the conductive wire in the subsequent process, and optimize the electrical contact performance between the substrate and the substrate, and the connecting layer 8 is dried and solidified. , has a certain viscosity at a certain temperature, so that the electrode itself can be firmly attached to the surface of the device;
本发明的复合电极材料相比于丝网印刷的银浆料，制作出的电池正面电极， 一方面形貌、 塑性更好， 遮光更少， 另一方面导电率也更高， 另外， 由于本复 合电极材料对其本身功能的细分， 更利于进一步分别从导电性能和接触性能两 方面进行性能改进和提升；  Compared with the silver paste of screen printing, the composite electrode material of the invention has the appearance of a front electrode of the battery, which has better morphology and plasticity, less shading, and higher conductivity on the other hand. The subdivision of the composite electrode material on its own function is more conducive to further improving and improving the performance from the two aspects of electrical conductivity and contact performance;
本发明的复合电极材料使用简便： 将其按照设计的正面电极图型等间距地 铺设并粘结附着在电池片正面上， 再通过红外或超声的方式对其进进行键合处 理， 使复合电极材料的粘接层与电池片正面形成牢固的合金结合和优良的电学 连通， 即可完成正面细电极的制作， 铺设并粘结附着在电池片正面时， 还能避 免丝网印刷存在的施加压力， 导致硅片碎裂的问题；  The composite electrode material of the invention is simple to use: it is laid at equal intervals according to the designed front electrode pattern and adhered to the front surface of the battery sheet, and then subjected to bonding treatment by infrared or ultrasonic method to make the composite electrode The bonding layer of the material forms a strong alloy bond with the front surface of the battery sheet and excellent electrical connection, so that the front surface fine electrode can be fabricated, and when the film is adhered and adhered to the front surface of the battery sheet, the pressure applied by the screen printing can be avoided. , causing the problem of chip fragmentation;
如图 7所示， 本发明实施例的光伏电池正面电极的制备工艺， 包括以下步 骤：  As shown in FIG. 7, the preparation process of the front electrode of the photovoltaic cell of the embodiment of the invention includes the following steps:
S701 : 金属粉末， 金属或非金属氧化物， 有机粘合剂， 有机溶剂和添加剂 混合搅拌均匀得到导电膏体；  S701 : metal powder, metal or non-metal oxide, organic binder, organic solvent and additive, uniformly mixed to obtain a conductive paste;
S702: 导电膏体均匀涂覆在导电金属丝表面， 经洪干固化制备复合电极材 料；  S702: the conductive paste is uniformly coated on the surface of the conductive wire, and is cured by flooding to prepare a composite electrode material;
S703: 将复合电极材料或电池片加热至一定温度， 使复合电极材料按设计 图案牢固地粘结于电池片正表面， 完成粘结处理； S704: 电池片表面上用喷涂的方式喷涂导电膏体制作主栅线；S703: heating the composite electrode material or the battery sheet to a certain temperature, so that the composite electrode material is firmly bonded to the front surface of the battery sheet according to the design pattern, and the bonding treatment is completed; S704: spraying a conductive paste on the surface of the battery sheet to form a main grid line;
S705: 将电池片放入到烘干炉和烧结炉中烘干 /烧结， 形成正面电极； 本发明的光伏电池正面电极的制备工艺具体步骤为： S705: The battery piece is placed in a drying furnace and a sintering furnace to be dried/sintered to form a front electrode; the specific steps of the preparation process of the front electrode of the photovoltaic cell of the present invention are:
步骤一， 制备导电膏体： 将金属粉末， 金属或非金属氧化物， 有机粘合剂， 有机溶剂和添加剂混合搅拌均匀得到导电膏体； 导电膏体中， 金属粉末的质量 百分含量为 70-90%, 金属或非金属氧化物的质量百分含量为 1-10%, 有机粘合 剂的质量百分含量为 1-10%, 有机溶剂的质量百分含量为 1-10%， 添加剂的质 量百分含量为 1-5%;  Step one, preparing a conductive paste: mixing and stirring metal powder, metal or non-metal oxide, organic binder, organic solvent and additive to obtain a conductive paste; in the conductive paste, the mass percentage of the metal powder is 70 -90%, the metal or non-metal oxide content is 1-10% by mass, the organic binder is 1-10% by mass, and the organic solvent is 1-10% by mass. The mass percentage is 1-5%;
步骤二， 制备复合电极材料： 导电膏体均匀涂覆在导电丝 1表面， 经烘干 固化而成， 导电膏体的烘干固化温度为 50°C-200°C， 导电膏体烘干固化后的的 厚度为 3微米到 20微米； 导电丝的直径为 5微米到 50微米，导电丝选自金丝、 银丝、 铜丝、 铝丝、 硅铝丝等金属丝， 导电丝也可以用聚合物纤维或碳纤维等 导电纤维；  Step 2: preparing a composite electrode material: the conductive paste is uniformly coated on the surface of the conductive wire 1 and dried and solidified. The drying and curing temperature of the conductive paste is 50° C.-200° C., and the conductive paste is dried and cured. The thickness of the conductive wire is 3 micrometers to 20 micrometers; the diameter of the conductive filaments is 5 micrometers to 50 micrometers, and the conductive filaments are selected from the group consisting of gold wires, silver wires, copper wires, aluminum wires, silicon aluminum wires, etc., and the conductive wires can also be used. Conductive fibers such as polymer fibers or carbon fibers;
步骤三， 在 100°C-500°C对电池片 2或复合电极材料 4进行加热， 使复合 电极材料 4平直牢固地粘结于电池片 2正表面， 进行粘结处理， 形成复合电极 材料行列， 经过粘接处理的电池片 2和复合电极材料 4结合处形成粘结界面 5 , 粘结于电池片正表面的复合电极材料两端和两边相距电池片正面边缘 0.5-1.5mm, 复合电极材料 4或电池片 2的加热可以通过热超声、 红外或激光的 方式来实现， 优选为红外加热；  Step 3, heating the battery sheet 2 or the composite electrode material 4 at 100 ° C - 500 ° C, so that the composite electrode material 4 is firmly and firmly bonded to the front surface of the battery sheet 2, and is bonded to form a composite electrode material. In the row, the bonded cell sheet 2 and the composite electrode material 4 are joined to form a bonding interface 5, and the two ends of the composite electrode material bonded to the front surface of the cell sheet and the two sides are 0.5-1.5 mm apart from the front edge of the cell sheet, and the composite electrode The heating of the material 4 or the battery sheet 2 can be achieved by means of thermosonic, infrared or laser, preferably infrared heating;
步骤四， 在电池片的正面制备主栅线： 电池片 2表面上用喷涂的方式喷涂 导电膏体制作主栅线 3 , 主栅线数量为 1-10根， 主栅线两端距电池边缘 0.5-1.5mm; 中， 在 200°C- 500°C烘干， 在 500°C-900°C进行烧结， 形成正面电极， 经键合处 理的电池片和复合电极材料结合处形成键合界面 6;  Step 4, preparing a main gate line on the front side of the battery sheet: spraying the conductive paste on the surface of the battery sheet 2 to form a main gate line 3, the number of main gate lines is 1-10, and the ends of the main grid line are from the edge of the battery 0.5-1.5mm; medium, drying at 200 ° C - 500 ° C, sintering at 500 ° C - 900 ° C, forming a front electrode, forming a bonding interface between the bonded cell sheet and the composite electrode material joint 6;
本发明使用的复合电极材料当温度达到 100°C-500°C , 具有粘性； 导电膏 体选自银膏、 铜膏、 镍膏等由金属粉制成的膏体， 导电膏体中的金属粉末的颗 粒大小范围为 0.1-2μηι， 形态为球形或准球形； 金属或非金属氧化物为铅、 铋、 钙、 镁、 锌、 铂、 钽、 铑、 镍、 铬、 钯、 硼、 磷等氧化物中的一种或几种混合 而成； 有机粘合剂选自乙基纤维素、 丙烯酸树脂、 硝基纤维素、 酚醛树脂及它 们的混合物； 有机溶剂选自松油醇、 卡必醇、 二乙二醇乙醚及它们的混合物； 添加剂包括表面活性剂、 触变剂、 消泡剂、 分散剂、 烧结抑制剂、 氧化抑制剂 和膨胀抑制剂； The composite electrode material used in the invention has viscosity when the temperature reaches 100 ° C - 500 ° C; conductive paste The body is selected from the group consisting of silver paste, copper paste, nickel paste and the like, and the metal powder in the conductive paste has a particle size ranging from 0.1 to 2 μm, and the shape is spherical or quasi-spherical; metal or non-metal oxide It is a mixture of one or more of lead, bismuth, calcium, magnesium, zinc, platinum, rhodium, ruthenium, nickel, chromium, palladium, boron, phosphorus, etc.; the organic binder is selected from ethyl cellulose , acrylic resin, nitrocellulose, phenolic resin and mixtures thereof; the organic solvent is selected from the group consisting of terpineol, carbitol, diethylene glycol ethyl ether and mixtures thereof; additives include surfactants, thixotropic agents, defoaming Agent, dispersant, sintering inhibitor, oxidation inhibitor and expansion inhibitor;
结合图 2-图 7和本发明的光伏电池正面电极的制备工艺的具体实施例进一 步说明：  A specific embodiment of the preparation process of the front electrode of the photovoltaic cell of the present invention will be further described with reference to Figs. 2-7.
实施例 5  Example 5
光伏电池正面电极， 按照以下步骤进行：  Photovoltaic cell front electrode, follow these steps:
( 1 )制备导电膏体： 将金属粉末， 金属或非金属氧化物， 有机粘合剂，有 机溶剂和添加剂混合搅拌均匀得到导电膏体； 使用的导电膏体中， 金属粉末为 银粉末， 导电银膏中按导电银膏的重量百分比， 金属或非金属氧化物占 5%, 有机粘合剂占 5%, 有机溶剂占 5%, 添加剂占 1%, 其余为银粉末， 银粉末的 颗粒大小范围为 0.1-2 μητ;  (1) preparing a conductive paste: mixing metal powder, metal or non-metal oxide, organic binder, organic solvent and additive to obtain a conductive paste; in the conductive paste used, the metal powder is silver powder, conductive Silver paste is 5% by weight of conductive silver paste, 5% by metal or non-metal oxide, 5% by organic binder, 5% by organic solvent, 1% by additive, the rest is silver powder, and the particle size of silver powder. The range is 0.1-2 μητ;
( 2 )制备复合电极材料：导电膏体均匀涂覆在直径 10-20微米的铜丝表面， 经烘干固化而成， 导电膏体的烘干固化温度为 50°C-200°C , 导电膏体烘干固化 后的厚度为 5微米到 10微米；  (2) Preparation of composite electrode material: the conductive paste is uniformly coated on the surface of the copper wire with a diameter of 10-20 micrometers, and is dried and solidified. The drying and curing temperature of the conductive paste is 50 ° C - 200 ° C, conductive The paste is dried and cured to a thickness of 5 micrometers to 10 micrometers;
( 3 )在 100°C-500°C对电池片或复合电极材料进行加热， 使复合电极材料 等间距平直牢固地粘结于电池片正表面， 从而完成粘结处理， 粘结于电池片正 表面的复合电极材料两端和两边相距电池片正面边缘 0.5-1.5mm, 复合电极材 料的加热可以通过热超声、 红外或激光的方式来实现， 优选为红外加热；  (3) heating the cell or composite electrode material at 100 ° C - 500 ° C, so that the composite electrode material is evenly and firmly bonded to the front surface of the cell sheet, thereby completing the bonding process and bonding to the cell sheet. The two ends of the composite electrode material on the front surface are 0.5-1.5 mm away from the front edge of the cell sheet, and the heating of the composite electrode material can be achieved by means of thermosonic, infrared or laser, preferably infrared heating;
( 4 )在电池片的正面制备主栅线： 电池片表面上用喷涂的方式喷涂导电膏 体制作主栅线， 主栅线数量为 3根， 主栅线两端距电池边缘 0.5-1.5mm;  (4) Preparing a main grid line on the front side of the cell sheet: spraying a conductive paste on the surface of the cell sheet to form a main gate line, the number of main gate lines is three, and the ends of the main grid line are 0.5-1.5 mm from the edge of the battery. ;
( 5 )将经过粘接处理的电池片放入到烘干炉和烧结炉中， 在 200-500°C烘 干， 在 500°C-90(TC进行烧结， 形成正面电极； (5) Put the bonded cell sheet into a drying oven and a sintering furnace, and bake at 200-500 ° C Dry, sintered at 500 ° C - 90 (TC, forming a front electrode;
使用的复合电极材料当温度达到 100°C-500°C , 具有粘性， 导电膏体中的 金属或非金属氧化物为铅、 铋、 钙、 镁、 锌、 铂、 钽、 铑、 镍、 铬、 钯、 硼、 磷等氧化物中的一种或几种混合而成； 有机粘合剂选自乙基纤维素； 有机溶剂 选自二乙二醇乙醚； 添加剂包括表面活性剂、 触变剂、 消泡剂、 分散剂、 烧结 抑制剂、 氧化抑制剂和膨胀抑制剂；  The composite electrode material used has a viscosity when the temperature reaches 100 ° C - 500 ° C, and the metal or non-metal oxide in the conductive paste is lead, antimony, calcium, magnesium, zinc, platinum, rhodium, iridium, nickel, chromium. And one or more of palladium, boron, phosphorus and the like; the organic binder is selected from the group consisting of ethyl cellulose; the organic solvent is selected from the group consisting of diethylene glycol ethyl ether; the additive includes a surfactant, a thixotropic agent , defoamers, dispersants, sintering inhibitors, oxidation inhibitors and expansion inhibitors;
实施例 6  Example 6
光伏电池正面电极， 按照的步骤同实施例 1， 不同的是实施例 2中导电银 膏中按导电银膏的重量百分比，金属或非金属氧化物占 8%,有机粘合剂占 5%, 有机溶剂占 5%， 添加剂占 2%， 其余为银粉末； 主栅线数量为 5根；  The front electrode of the photovoltaic cell, according to the same procedure as in the first embodiment, except that the conductive silver paste in the second embodiment is in the weight percentage of the conductive silver paste, the metal or non-metal oxide accounts for 8%, and the organic binder accounts for 5%. Organic solvent accounts for 5%, additive accounts for 2%, and the rest is silver powder; the number of main grid lines is 5;
实施例 7  Example 7
光伏电池正面电极， 按照的步骤同实施例 1， 不同的是实施例 3中导电银 膏中按导电银膏的重量百分比，金属或非金属氧化物占 10%,有机粘合剂占 1%, 有机溶剂占 1%, 添加剂占 1%, 其余为银粉末； 主栅线数量为 7根；  The front electrode of the photovoltaic cell, according to the same procedure as in the first embodiment, except that the conductive silver paste in the third embodiment is in the weight percentage of the conductive silver paste, the metal or non-metal oxide accounts for 10%, and the organic binder accounts for 1%. Organic solvent accounts for 1%, additive accounts for 1%, and the rest is silver powder; the number of main grid lines is 7;
实施例 8  Example 8
光伏电池正面电极， 按照的步骤同实施例 3 , 不同的是实施例 4导电膏体 使用的金属粉末为银粉末和镍粉末的混合物， 导电膏体中按导电膏体的重量百 分比， 金属或非金属氧化物占 8%, 有机粘合剂占 3%, 有机溶剂占 3%， 添加 剂占 3%, 其余为银粉末和镍粉末的混合物， 银粉末和镍粉末的重量比为 7: 1 , 银粉末和镍粉末的颗粒大小范围为 0.1-2 μιη; 并且使用的导电丝为铝丝； 导电 膏体中使用的有机溶剂为卡必醇；  The front electrode of the photovoltaic cell, according to the same procedure as in Example 3, except that the metal powder used in the conductive paste of Example 4 is a mixture of silver powder and nickel powder, and the weight percentage of the conductive paste in the conductive paste, metal or non- Metal oxides accounted for 8%, organic binders accounted for 3%, organic solvents accounted for 3%, additives accounted for 3%, and the balance was a mixture of silver powder and nickel powder. The weight ratio of silver powder to nickel powder was 7:1, silver. The powder and the nickel powder have a particle size ranging from 0.1 to 2 μm; and the conductive filament used is an aluminum wire; the organic solvent used in the conductive paste is carbitol;
实施例 9  Example 9
光伏电池正面电极， 按照的步骤同实施例 4， 不同的是实施例 5中使用的 导电膏体中， 金属粉末为铜粉末， 导电铜膏中按导电铜膏的重量百分比， 金属 或非金属氧化物占 8%, 有机粘合剂占 5%, 有机溶剂占 5%, 添加剂占 2%,其 余为铜粉末； 复合电极材料有两种作用， 分别为起传导电流的作用和在工艺过程中能与 电池片表面牢固粘接并且之后再形成稳固的合金结合和电学结合； 复合电极两 端和两边相距电池片正面边缘 0.5mm- 1.5mm, 避免复合电极延伸到边缘刻蚀区 域， 造成电池边缘漏电的情况发生； The front electrode of the photovoltaic cell, according to the same procedure as in the fourth embodiment, except that in the conductive paste used in the embodiment 5, the metal powder is copper powder, and the conductive copper paste is oxidized by metal or non-metal according to the weight percentage of the conductive copper paste. 8%, organic binders accounted for 5%, organic solvents accounted for 5%, additives accounted for 2%, and the rest were copper powder; The composite electrode material has two functions, namely, the function of conducting current and the bonding with the surface of the cell sheet during the process, and then forming a stable alloy bond and electrical combination; the two ends of the composite electrode are separated from the front side of the cell The edge is 0.5mm-1.5mm, avoiding the extension of the composite electrode to the edge etched area, causing leakage of the battery edge;
本发明较大地降低了太阳能电池正面细栅线的宽度， 可以制备出宽度达到 20-50微米的精细栅线， 同时高度可以达到 15-40微米， 电极高宽比大； 细栅线 的导电率比传统银浆栅线可以提高 20%以上， 使电极电阻小、 电池内阻小， 从 而提升了光伏电池的转换效率； 本发明能够制备遮光面积小、 导电性更高、 成 本低的正面电极， 同时该工艺过程大大降低了在正面电极制备工序时的破片现 象发生。  The invention greatly reduces the width of the fine grid line on the front side of the solar cell, and can prepare a fine grid line having a width of 20-50 micrometers, and the height can reach 15-40 micrometers, and the aspect ratio of the electrode is large; the conductivity of the fine grid line Compared with the conventional silver paste grid line, the electrode resistance can be increased by more than 20%, the electrode resistance is small, and the internal resistance of the battery is small, thereby improving the conversion efficiency of the photovoltaic cell; the invention can prepare a front electrode with small light-shielding area, higher conductivity and low cost. At the same time, the process greatly reduces the occurrence of fragmentation during the preparation process of the front electrode.
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

权 利 要 求 书 claims
1、一种用于光伏电池正面电极制备的复合电极材料， 其特征在于， 该用于 光伏电池正面电极制备的复合电极材料包括： 1. A composite electrode material used for the preparation of front electrodes of photovoltaic cells, characterized in that the composite electrode material used for the preparation of front electrodes of photovoltaic cells includes:
设置在复合电极材料内部的导电芯和设置在导电芯表面的连接层， 连接层 通过涂覆在导电芯表面的导电膏体经烘干固化而成。 A conductive core is provided inside the composite electrode material and a connection layer is provided on the surface of the conductive core. The connection layer is formed by drying and solidifying the conductive paste coated on the surface of the conductive core.
2、 根据权利要求 1所述的用于光伏电池正面电极制备的复合电极材料，其 特征在于， 导电芯选自金丝、 银丝、 铜丝、 铝丝、 硅铝丝， 也可以是聚合物纤 维或碳纤维的导电纤维， 导电芯的直径为 5微米到 50微米。 2. The composite electrode material for preparing the front electrode of photovoltaic cells according to claim 1, characterized in that the conductive core is selected from the group consisting of gold wire, silver wire, copper wire, aluminum wire, silicon-aluminum wire, and can also be a polymer Conductive fibers of fiber or carbon fiber with a conductive core diameter of 5 microns to 50 microns.
3、 根据权利要求 1所述的用于光伏电池正面电极制备的复合电极材料，其 特征在于，连接层的厚度为 3微米到 20微米，导电膏体选自银膏、铜膏、镍膏， 采用金属粉制成的膏体，烘干固化温度为 50°C-200°C，导电膏体包括金属粉末、 金属或非金属氧化物、 有机溶剂、 有机粘合剂及添加剂。 3. The composite electrode material for preparing the front electrode of photovoltaic cells according to claim 1, characterized in that the thickness of the connection layer is 3 microns to 20 microns, and the conductive paste is selected from silver paste, copper paste, and nickel paste. The paste is made of metal powder, and the drying and curing temperature is 50°C-200°C. The conductive paste includes metal powder, metal or non-metal oxides, organic solvents, organic binders and additives.
4、 根据权利要求 1所述的用于光伏电池正面电极制备的复合电极材料，其 特征在于， 导电膏体的组分和重量百分比含量包括： 4. The composite electrode material used for the preparation of front electrodes of photovoltaic cells according to claim 1, characterized in that the components and weight percentage content of the conductive paste include:
金属粉末 70-90%； 金属或非金属氧化物 1-10%； 有机粘合剂 1-10%; 有机溶剂 1-10%; 添加剂 1-5%。 Metal powder 70-90%; Metal or non-metal oxide 1-10%; Organic binder 1-10%; Organic solvent 1-10%; Additive 1-5%.
5、 根据权利要求 1所述的用于光伏电池正面电极制备的复合电极材料，其 特征在于， 复合电极材料在用于制作正面电极时， 温度达到 100°C-500°C , 烘 干固化后的连接层具有粘性， 复合电极材料用于制备光伏电池正面电极。 5. The composite electrode material for preparing the front electrode of photovoltaic cells according to claim 1, characterized in that when the composite electrode material is used to prepare the front electrode, the temperature reaches 100°C-500°C, and after drying and solidification The connecting layer is sticky, and the composite electrode material is used to prepare the front electrode of photovoltaic cells.
6、根据权利要求 3或 4所述的用于光伏电池正面电极制备的复合电极材料， 其特征在于， 金属粉末的颗粒大小为 0.1-2μιη, 形态为球形或准球形， 金属或 非金属氧化物为铅、 铋、 钙、 镁、 锌、 铂、 钽、 铑、 镍、 铬、 钯、 硼、 磷氧化 物中的一种或几种混合而成； 6. The composite electrode material for photovoltaic cell front electrode preparation according to claim 3 or 4, characterized in that the particle size of the metal powder is 0.1-2 μm, the shape is spherical or quasi-spherical, and the metal or non-metal oxide It is one or a mixture of several of lead, bismuth, calcium, magnesium, zinc, platinum, tantalum, rhodium, nickel, chromium, palladium, boron and phosphorus oxide;
有机粘合剂选自乙基纤维素、 丙烯酸树脂、 硝基纤维素、 酚醛树脂及它们 的混合物； The organic binder is selected from ethyl cellulose, acrylic resin, nitrocellulose, phenolic resin and their mixtures;
有机溶剂选自松油醇、 卡必醇、 二乙二醇乙酸及它们的混合物； 添加剂包括表面活性剂、 触变剂、 消泡剂、 分散剂、 烧结抑制剂、 氧化抑 制剂和膨胀抑制剂。 The organic solvent is selected from terpineol, carbitol, diethylene glycol acetic acid and their mixtures; Additives include surfactants, thixotropic agents, defoamers, dispersants, sintering inhibitors, oxidation inhibitors and swelling inhibitors.
7、一种利用权利要求 1-6任意一项所述的复合电极材料制备光伏电池正面 电极的工艺， 其特征在于， 该光伏电池正面电极的制备工艺包括以下步骤： 步骤一， 制备导电膏体： 将金属粉末， 金属或非金属氧化物， 有机粘合剂， 有机溶剂和添加剂混合搅拌均勾得到导电膏体； 导电膏体中， 金属粉末的 质量百分含量为 70-90%, 金属或非金属氧化物的盾量百分含量为 1-10%, 有机 粘合剂的质量百分含量为 1-10% , 有机溶剂的质量百分含量为 1 -10%, 添加剂的质量百分含量为 1-5%; 7. A process for preparing the front electrode of a photovoltaic cell using the composite electrode material according to any one of claims 1 to 6, characterized in that the preparation process of the front electrode of the photovoltaic cell includes the following steps: Step 1: Preparing a conductive paste : Mix and stir metal powder, metal or non-metal oxide, organic binder, organic solvent and additives to obtain a conductive paste; in the conductive paste, the mass percentage of metal powder is 70-90%, and the metal or The mass percentage of non-metallic oxides is 1-10%, the mass percentage of organic binders is 1-10%, the mass percentage of organic solvents is 1-10%, and the mass percentage of additives is 1-5%;
步骤二， 制备复合电极材料： 导电膏体均匀涂覆在导电金属丝表面， 经烘 干固化而成； Step 2: Prepare the composite electrode material: the conductive paste is evenly coated on the surface of the conductive metal wire, and is dried and solidified;
步骤三， 对电池片或复合电极材料进行加热， 使复合电极材料中的有机粘 合剂能够部分或全部融化， 恢复粘性， 使复合电极材料按设计图案牢固地粘结 于电池片正表面， 完成粘结处理； Step 3: Heat the battery sheet or composite electrode material so that the organic binder in the composite electrode material can partially or completely melt and restore its viscosity, so that the composite electrode material can be firmly bonded to the front surface of the battery sheet according to the designed pattern. Completed bonding treatment;
步骤四， 在电池片的正面制备主栅线： 电池片表面上用喷涂的方式喷涂导 电膏体制作主栅线； Step 4: Prepare main grid lines on the front side of the battery sheet: Spray conductive paste on the surface of the battery sheet to make main grid lines;
步骤五， 将电池片放入到烘干炉和烧结炉中， 在 200°C-500°C烘干， 在 500°C-900°C进行烧结， 形成正面电极。 Step 5: Put the battery pieces into a drying furnace and a sintering furnace, dry them at 200°C-500°C, and sinter them at 500°C-900°C to form a front electrode.
8、 根据权利要求 Ί所述的制备光伏电池正面电极的工艺， 其特征在于，铺 设置在电池片正表面的复合电极材料两端和两边相距电池片正面边缘 0.5- 1.5mm , 主栅线两端距电池片边缘 0.5-1.5mm, 主栅线数量为 1-10根。 8. The process for preparing the front electrode of a photovoltaic cell according to claim Ί, characterized in that the two ends and sides of the composite electrode material laid on the front surface of the cell are 0.5-1.5mm away from the front edge of the cell, and the two main grid lines are The terminal distance is 0.5-1.5mm from the edge of the cell, and the number of main grid lines is 1-10.
9、 根据权利要求 7所述的制备光伏电池正面电极的工艺， 其特征在于，在 步骤一中， 金属粉末的颗粒大小范围为 0.1-2μιη , 形态为球形或准球形； 在步 骤三中复合电极材料或电池片的加热可以通过热超声、 红外或激光的方式来实 现， 优选为红外加热， 加热温度为 80°C-500°C。 9. The process for preparing the front electrode of a photovoltaic cell according to claim 7, characterized in that, in step one, the particle size range of the metal powder is 0.1-2 μm, and the shape is spherical or quasi-spherical; in step three, the composite electrode Heating of materials or cells can be achieved by thermo-ultrasound, infrared or laser. Infrared heating is preferred, and the heating temperature is 80°C-500°C.
10、 根据权利要求 7所述的制备光伏电池正面电极的工艺， 其特征在于， 在步骤二中，导电丝的直径为 5微米到 50微米，导电膏体烘干固化后的的厚度 为 3微米到 20微米， 导电膏体的烘干固化温度为 50°C-200°C。 10. The process for preparing the front electrode of a photovoltaic cell according to claim 7, characterized in that, In step two, the diameter of the conductive wire is 5 microns to 50 microns, the thickness of the conductive paste after drying and curing is 3 microns to 20 microns, and the drying and curing temperature of the conductive paste is 50°C-200°C.
PCT/CN2013/001010 2013-07-08 2013-08-26 Composite electrode material and process for preparing front electrode of photovoltaic cell WO2015003292A1 (en)

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