WO2020220393A1 - 一种玻璃粉及包括该玻璃粉的n型双面太阳能电池正面用银铝浆 - Google Patents

一种玻璃粉及包括该玻璃粉的n型双面太阳能电池正面用银铝浆 Download PDF

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WO2020220393A1
WO2020220393A1 PCT/CN2019/086561 CN2019086561W WO2020220393A1 WO 2020220393 A1 WO2020220393 A1 WO 2020220393A1 CN 2019086561 W CN2019086561 W CN 2019086561W WO 2020220393 A1 WO2020220393 A1 WO 2020220393A1
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powder
silver
aluminum
glass powder
glass
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PCT/CN2019/086561
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English (en)
French (fr)
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朱鹏
施赛杰
郑金华
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南通天盛新能源股份有限公司
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Priority to US17/439,818 priority Critical patent/US20220153627A1/en
Publication of WO2020220393A1 publication Critical patent/WO2020220393A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
    • C03C3/072—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0545—Dispersions or suspensions of nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/09—Mixtures of metallic powders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C12/00—Powdered glass; Bead compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
    • C03C3/072—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron
    • C03C3/074—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/10—Frit compositions, i.e. in a powdered or comminuted form containing lead
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0408—Light metal alloys
    • C22C1/0416—Aluminium-based alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0466—Alloys based on noble metals
    • 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
    • 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
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0488—Double glass encapsulation, e.g. photovoltaic cells arranged between front and rear glass sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
    • B22F2301/255—Silver or gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/45—Others, including non-metals
    • 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

Definitions

  • the invention belongs to the field of solar cells, and in particular relates to a glass powder and a silver-aluminum paste for the front side of an N-type double-sided solar cell including the glass powder.
  • N-type monocrystalline silicon has a higher minority carrier life and a long lifetime. It has the advantages of small attenuation and more room for efficiency improvement.
  • the N-type single crystal module has the advantages of good weak light response and low temperature coefficient. Therefore, the N-type single crystal system has the dual advantages of high power generation and high reliability.
  • N-type single crystal high-efficiency batteries mainly include: PERT batteries, HIT batteries, and IBC batteries.
  • PERT has high compatibility with existing production lines, which has attracted close attention from many first-class manufacturers and markets.
  • PERT is a typical double-sided battery.
  • a double-sided solar battery refers to a solar battery that can receive light on both the front and back of the silicon wafer and can generate photovoltaic voltage and current.
  • the silver powder of the Chinese patent CN201610264780.X contains silver powder
  • the use of aluminum powder as the basis results in a metal component, in which aluminum and silver are used together as conductive metal powders. As aluminum powder replaces part of the silver powder, the cost of conductive paste is reduced.
  • the present invention adds graphene to increase the conductivity of the silver-aluminum paste after sintering.
  • the line resistance of the prepared silver-aluminum paste will be higher during printing, thereby increasing the series resistance.
  • the fine-grid printed wire frame is less than 30 ⁇ m, the amount of conductive aluminum in the silver-aluminum paste has a greater influence on the wire resistance.
  • the paste of Chinese patent CN201010294275.2 uses environmentally friendly glass powder without harmful substances as a binder, which is environmentally friendly Type organic reagents are used as solvents and diluents, and the prepared silver-aluminum paste does not contain six substances (Pb, Cd, Hg, Cr(VI), polybrominated biphenyls PBB, polybrominated diphenyl ethers PBDE) prohibited by the EU RoHS Directive, which achieves a true meaning It is environmentally friendly, but the slurry is not suitable for the use of low-temperature sintering slurry, and the glass powder that does not contain Pb is not suitable for the sintering of the passivation layer SiN x , and cannot meet the low-temperature sintering requirements.
  • the slurry is not suitable for the use of low-temperature sintering slurry
  • the glass powder that does not contain Pb is not suitable for the sintering of the passivation layer SiN x , and cannot meet the
  • the present invention provides a glass powder and a silver-aluminum paste for the front side of an N-type double-sided solar cell including the glass powder.
  • the first innovation of the present invention is to provide a glass powder, the weight content of the glass powder including the following components: 0-50% PbO, 0-50% BiO, 5-15 % B 2 O 3 , 8-9% SiO 2 , 2-3% Al 2 O 3 and 5-15% ZnO, wherein the mass ratio of silicon and aluminum in the glass powder is 4-5: 1.
  • the glass powder also includes 5-15% of the oxides of main group I elements and 5-15% of the oxides of main group II elements.
  • the oxide of the element of main group I is one of LiO, K 2 O, Na 2 O, Cs 2 O, Li 2 CO 3 , K 2 CO 3 , NaCl, and KCl, or Several compounds of main group I elements are prepared.
  • the oxide of the II main group element is prepared by one of MgO, CaO, BaO, SrO, CaCO 3 , MgCO 3 and BaCO 3 or a compound of several main group II elements of.
  • the softening temperature of the glass powder is 300 to 400° C.
  • the average particle size D50 of the glass powder is 0.5 to 5 ⁇ m.
  • the second innovation of the present invention is that it also provides a silver-aluminum paste for the front side of an N-type double-sided solar cell containing the glass powder, which includes conductive silver powder, silicon-aluminum alloy powder, glass powder and an organic carrier, It is characterized in that the content of the conductive silver powder is 80-90wt%, the conductive silver powder includes nano silver powder with an average particle size of 50-100 nm and silver alloy powder with an average particle size of 1-10 ⁇ m, the nano silver powder and silver The mass ratio of the alloy powder is 1:18-90, and the content of the glass powder is 5-10% by weight.
  • the content of the nano silver powder is greater than 99.9%, the bulk density of the nano silver powder is 1.4 to 1.90 g/cm 3 , and the tap density of the nano silver powder is 2.6 to 4.1 g/cm 3 , The square resistance of the nano silver powder is 0 ⁇ 0.002 ⁇ /sq.
  • the content of the aluminum silicon alloy powder is 1-10 wt%
  • the average particle size of the silicon aluminum alloy powder is 0.5-5 ⁇ m
  • the melting point of the aluminum silicon alloy powder is 450-650°C
  • the mass fraction of Si in the aluminum-silicon alloy powder is 12-25%.
  • the melting point of the aluminum-silicon alloy powder is 500-600°C
  • the silicon-aluminum alloy powder includes aluminum-silicon alloy powder with a mass fraction of Si of 12% and an aluminum-silicon alloy powder with a mass fraction of Si of 20%.
  • the mass fraction of powder and Si is at least one of 25% aluminum-silicon alloy powder.
  • the content of the organic vehicle is 5-10% by weight
  • the organic vehicle includes an organic binder, a surface dispersant and a thixotropic agent
  • the organic binder includes 1 to 3 parts by mass of organic Resin and 7-9 parts by mass of organic solvent.
  • the organic resin is selected from one or more of ethyl cellulose and butyl cellulose acetate
  • the organic solvent is selected from terpineol, alcohol ester twelve, and butyl carbitol.
  • One or more of alcohol, butyl carbitol acetate, and glycerin, the surface dispersant is selected from one or more of stearic acid, stearic acid derivatives and unsaturated fatty acids.
  • the thixotropic agent is selected from one or more of modified hydrogenated castor oil and polyamide wax.
  • the sintering temperature of the silver-aluminum paste is 700-750°C.
  • the glass powder provided by the present invention has a low softening temperature and a high degree of vitrification, and has good wettability to the passivation layer and silver powder in a high-temperature molten state, and can penetrate the anti-reflection film layer to form a good ohmic contact.
  • the glass powder of the present invention introduces the oxides of the elements of main group I and main group II, which not only increases the corrosion of the glass powder to the passivation layer, but also does not cause serious metal recombination; the glass powder of the present invention is introduced into the third group.
  • the main group elements increase doping; the glass powder of the present invention adjusts the ratio of silicon to aluminum during the production process to be appropriate, so the viscosity of the glass powder can be improved, thereby improving the size of silver particles, and reducing recombination and contact resistance.
  • the silver-aluminum paste of the present invention contains the glass powder.
  • the silver-aluminum paste of the present invention is a conductive metal compounded with nano-silver powder and ordinary silver powder.
  • the added nano-silver powder reduces the contact resistance; the invention also adds silicon-aluminum
  • the alloy reduces the precipitation of boron, ensures ohmic contact, and improves the opening pressure.
  • the content of glass powder in the silver-aluminum paste of the present invention is 5-10wt%, and the content of glass powder in the silver-aluminum paste of the present invention is high, which not only does little damage to SiNx, but also reduces the content of silver in the formulation and reduces production
  • the glass powder with this content has a strong ability to dissolve silver, and has a low contact resistance. It is not easy to form a recombination center.
  • the solar cell prepared with it has a high opening pressure and improves the conversion efficiency of the cell.
  • the content of the aluminum-silicon alloy powder of the present invention is 1-10wt%, which can form effective aluminum doping at the silver-silicon alloy interface, reduce contact resistance and bulk resistance, and improve photoelectric conversion efficiency; the aluminum-silicon alloy of the present invention
  • the particle size of the powder is 0.5-5 ⁇ m, which will not increase the oxygen content and reduce oxidation. It can also form effective aluminum doping in the emitter, reduce the contact resistance, and facilitate the screen printing of narrow line width.
  • the sintering temperature of the silver-aluminum paste prepared by the present invention is lower at 700-750°C, and the surface recombination decreases during sintering at this temperature, thereby improving the photoelectric conversion efficiency.
  • a glass powder is prepared according to the formula A1 in Table 1.
  • PbO, BiO, B 2 O 3 , SiO 2 , Al 2 O 3 and ZnO are respectively weighed and prepared according to the proportions.
  • the compound includes 5% Na 2 O and 5% LiO.
  • the compound of main group II element includes 3% K 2 O, 3% CaO and 4% BaO.
  • the compound of main group I element and the compound of main group II The compounds of the main group elements are also weighed and prepared according to the proportions. Put the above-mentioned glass powder raw materials in a crucible and mix and stir evenly at room temperature. Place the crucible with the glass powder raw materials in a high-temperature furnace and heat to 1100°C for 1h.
  • a silver-aluminum paste for the front side of an N-type double-sided solar cell containing the above-mentioned glass powder Prepare the silver-aluminum paste according to the formula B1 in Table 2. Weigh the nano-silver powder, silver alloy powder, glass powder A1 and Si mass according to the ratio The 12% aluminum-silicon alloy powder and the organic carrier are mixed evenly with a disperser, and then ground to 0.1 ⁇ 1.5 ⁇ m with a three-roll mill to obtain the silver aluminum paste B1 for the front side of the solar cell. The formula of each group is repeated three times and the average is taken .
  • a glass powder is prepared according to the formula A2 in Table 1.
  • PbO, B 2 O 3 , SiO 2 , Al 2 O 3 and ZnO are respectively weighed and prepared according to the proportions.
  • the oxides of main group I elements Including 5% LiCl and 5% Cs 2 O
  • the compounds of main group II elements include 5% K 2 O and 5% CaO.
  • the compounds of main group I elements and the compounds of main group II elements are The ratio is also weighed and prepared. Put the above-mentioned glass powder raw materials in a crucible and mix and stir evenly at room temperature.
  • a silver-aluminum paste for the front side of an N-type double-sided solar cell containing the above glass powder Prepare the silver-aluminum paste according to the formula B2 in Table 2. Weigh the nano-silver powder, silver alloy powder, glass powder A2 and Si according to the proportions The 20% aluminum-silicon alloy powder and organic carrier are mixed evenly with a disperser, and then ground to 0.1 ⁇ 1.5 ⁇ m with a three-roll mill to obtain a silver-aluminum paste B2 for the front side of solar cells. Each group of formulas is repeated three times and averaged .
  • a glass powder is prepared according to the formula A3 in Table 1.
  • the BiO, B 2 O 3 , SiO 2 , Al 2 O 3 and ZnO are respectively weighed and prepared according to the proportions.
  • the compounds of the main group I elements include 5% K 2 O and 5% Cs 2 O.
  • the compound of the II main group element includes 3% SrO, 3% MgCO 3 and 4% BaO.
  • the compound of the first main group element and the second main group element The compound of the group element is also weighed and prepared according to the proportion. Put the above-mentioned glass powder raw material in a crucible and mix and stir evenly at room temperature. Place the crucible with the glass powder raw material in a high-temperature furnace and heat it to 1100°C for 1 hour.
  • the above-mentioned glass liquid is water-quenched with deionized water to form irregular glass flakes, and the above-mentioned glass flakes are crushed in a ball mill for 6 hours, and the rotation speed is set to 250r/min.
  • the fine glass powder is sieved with a mesh number of 200-250 meshes.
  • the sieved glass powder is dried in a dryer for 3 hours and the temperature is set to 55°C to obtain silver-aluminum paste glass Powder A3, each formula is repeated three times and averaged.
  • a silver-aluminum paste for the front side of an N-type double-sided solar cell containing the above glass powder Prepare the silver-aluminum paste according to the formula B3 in Table 2. Weigh the nano-silver powder, silver alloy powder, glass powder A3, and Si according to the proportions The 25% aluminum-silicon alloy powder and organic carrier are mixed evenly with a disperser, and then ground to 0.1 ⁇ 1.5 ⁇ m with a three-roll mill to obtain a silver-aluminum paste B3 for the front side of solar cells. Repeat the formula for each group three times and take the average value. .
  • the silver-aluminum pastes B1, B2 and B3 for the front side of an N-type double-sided solar cell prepared in Examples 1 to 3 were printed on a single crystal (156 ⁇ 156mm, square resistance 60 ⁇ /sq), dried and sintered The crystalline silicon solar cell was prepared, and the electrical performance was tested. The results were averaged and listed in Table 4:
  • the present invention is not limited to the above-mentioned best embodiments.
  • anyone can derive other products in various forms under the enlightenment of the present invention, but regardless of any changes in its shape or structure, any products that are the same or similar to those of this application Approximate technical solutions fall within the protection scope of the present invention.

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Abstract

一种玻璃粉及包括该玻璃粉的N型双面太阳能电池正面用银铝浆，包括导电银粉、硅铝合金粉、玻璃粉和有机载体，其中玻璃粉的包括如下组分的重量含量：0～50％的PbO、0～50％的BiO、5～15％的B 2O 3、8～9％的SiO 2、2～3％的Al 2O 3和5～15％ZnO，玻璃粉中硅和铝的质量之比为4～5:1，导电银粉的含量为80～90wt％，导电银粉包括纳米银粉和银合金粉，该纳米银粉和银合金粉的质量比为1：18～90。制备的玻璃粉既保证了SiN x的腐蚀，也不会造成较强的金属化复合，用该玻璃粉制备得到的银铝浆解决了N型晶硅太阳能电池正面印刷银铝浆接触电阻和开路电压的矛盾问题。

Description

一种玻璃粉及包括该玻璃粉的N型双面太阳能电池正面用银铝浆 技术领域
本发明属于太阳能电池领域，尤其涉及一种玻璃粉及包括该玻璃粉的N型双面太阳能电池正面用银铝浆。
背景技术
太阳能电池领域一直追逐的目标是：提高转换效率跟降低成本，目前P型晶硅电池占据晶硅电池市场的绝对份额，N型单晶硅较常规的P型单晶硅具有少子寿命高、光致衰减小等优点，具有更大的效率提升空间，同时，N型单晶组件具有弱光响应好、温度系数低等优点。因此，N型单晶系统具有发电量高和可靠性高的双重优势。随着电池新技术和工艺的引入，N型单晶电池的效率优势会越来越明显，且N型单晶电池市场份额将从2014年的5％左右提高到2025年的35％左右。目前研究的N型单晶高效电池主要有：PERT电池、HIT电池和IBC电池，其中PERT与现有产线兼容性高，引起很多一流制造厂商和市场的密切关注。PERT是一种典型的双面电池，双面太阳电池是指硅片的正面和反面都可以接受光照并能产生光生电压和电流的太阳电池。
目前科研人员在研究银铝浆时主要是通过以下几个方面进行改进的：
(1)降低银铝浆的制造成本：主要是通过降低浆料中成本比较高的组分的使用，从而降低浆料的成本，如中国专利CN200710042439.0制备得到的浆料制备降低了高价格银浆的使用量，降低制造成本的同时，避免了银铝烧结不同步，避免了印烧过程产生铝珠的现象，欧姆接触良好，提高光电转化率，但是该技术方案制备得到的银铝浆接烧结温度较高，会导致表面复合增加，光电转化效率会有所降低。
(2)提高银铝浆导电电极的光电转化率：主要集中在增加欧姆接触、减少复合、增加开压以及减少接触电阻等方面，如中国专利专利CN201610264780.X的银铝浆料中包含了银粉和铝粉作为基础导致金属成分，其中应用的铝和银共同作为导电金属粉料，由于铝粉代替了部分的银粉，所以导电浆料的成本得到很好的降低。同时本发明加入了石墨烯增加了银铝浆料烧结后的导电性能，但是在银铝浆中使用金属铝粉，制备得到的银铝浆印刷时线电阻会偏高，从而使串联电阻变大，尤其在细栅印刷线框小于30μm时，银铝浆中导电铝的量对线电阻的影响更大。
(3)减少导电银铝浆的环境污染：主要集中在减少Pb等重金属在浆料中的应用，如中国专利CN201010294275.2的浆料以不含有害物质的环保玻璃粉作为粘结剂，环保型有机试剂作为溶剂和稀释剂，制备的银铝浆不含欧盟RoHS指令所禁止的六项物质(Pb、Cd、Hg、Cr(VI)、多溴联苯PBB、多溴联苯醚PBDE)，做到了真正意义上的环保，但是该浆料不适合低温烧结浆料的使用，且不含有Pb的玻璃粉不适合钝化层SiN x的烧结，不能满足低温烧结要求。
发明内容
发明目的：为了解决现有技术的不足，本发明提供了一种玻璃粉及包括该玻璃粉的N型双面太阳能电池正面用银铝浆。
技术方案：本发明的第一个创新点在于：提供了一种玻璃粉，所述玻璃粉的包括如下组分的重量含量：0～50％的PbO、0～50％的BiO、5～15％的B 2O 3、8～9％的SiO 2、2～3％的Al 2O 3和5～15％ZnO，其中，所述玻璃粉中硅和铝的质量之比为4～5:1，所述玻璃粉中还包括5～15％的第Ⅰ主族元素的氧化物和5～15％第Ⅱ主族元素的氧化物。
在有的实施例中，所述第Ⅰ主族元素的氧化物是LiO、K 2O、Na 2O、Cs 2O、 Li 2CO 3、K 2CO 3、NaCl和KCl中的一种或者几种第Ⅰ主族元素的化合物制备得到的。
在有的实施例中，所述第Ⅱ主族元素的氧化物是MgO、CaO、BaO、SrO、CaCO 3、MgCO 3和BaCO 3中的一种或者几种第Ⅱ主族元素的化合物制备得到的。
在有的实施例中，所述玻璃粉的软化温度为300～400℃，所述玻璃粉的平均粒径D50为0.5～5μm。
本发明的第二个创新点在于：还提供了一种包含所述玻璃粉的一种N型双面太阳能电池正面用银铝浆，包括导电银粉、硅铝合金粉、玻璃粉和有机载体，其特征在于：所述导电银粉的含量为80～90wt％，所述导电银粉包括平均粒径为50～100nm的纳米银粉和平均粒径为1～10μm的银合金粉，所述纳米银粉和银合金粉的质量比为1：18～90，所述玻璃粉的含量为5～10wt％。
在有的实施例中，所述纳米银粉的含量大于99.9％，所述纳米银粉的松装密度为1.4～1.90g/cm 3，所述纳米银粉的振实密度为2.6～4.1g/cm 3，所述纳米银粉的方阻为0～0.002Ω/sq。
在有的实施例中，所述铝硅合金粉的含量为1～10wt％，所述硅铝合金粉的平均粒径为0.5～5μm，所述铝硅合金粉的熔点为450～650℃，所述铝硅合金粉中的Si的质量分数为12～25％。
在有的实施例中，所述铝硅合金粉的熔点为500～600℃，所述硅铝合金粉为包括Si质量分数为12％的铝硅合金粉、Si质量分数为20％铝硅合金粉及Si质量分数为25％铝硅合金粉三者中的至少一种。
在有的实施例中，所述有机载体含量为5～10wt％，所述有机载体包括有机粘结剂、表面分散剂和触变剂，所述有机粘结剂包括1～3质量份的有机树脂和7～9质量份的有机溶剂。
在有的实施例中，所述有机树脂选自乙基纤维素、醋酸丁基纤维素中的一种或几种，所述有机溶剂选自松油醇、醇酯十二、丁基卡必醇、丁基卡必醇乙酸酯、甘油中的一种或几种，所述表面分散剂选硬脂酸、硬脂酸衍生物和不饱和脂肪酸中的一种或多种，所述的触变剂选自改性氢化蓖麻油、聚酰胺蜡中的一种或多种。
在有的实施例中，所述银铝浆的烧结温度为700～750℃。
有益效果：本发明的具体优势如下：
(1)本发明的提供的一种玻璃粉软化温度低、玻璃化程度高，高温熔融状态下对钝化层及银粉有良好的浸润性，能够穿透减反射膜层形成良好的欧姆接触。本发明的玻璃粉中引入第Ⅰ主族和第Ⅱ主族元素的氧化物，既增加玻璃粉对钝化层的腐蚀，又不会造成比较严重的金属复合；本发明的玻璃粉引入第三主族元素增加掺杂；本发明的玻璃粉在制作的过程中调节硅铝比例合适，因此可以改善玻璃粉的粘度，从而改进银颗粒的大小，降低复合和接触电阻。
(2)本发明含有该玻璃粉的银铝浆，本发明的银铝浆是将纳米银粉跟普通银粉复配的导电金属，加入的纳米银粉减少了接触电阻；本发明中还添加了硅铝合金，减少了硼的析出，保证了欧姆接触，提高开压。
(3)本发明的银铝浆中玻璃粉的含量为5～10wt％，本发明的银铝浆中玻璃粉的含量高，既对SiNx破坏小，又可以降低配方中银的含量，降低了生产成本，且该含量的玻璃粉溶解银的能力较强，且接触电阻较小，还不容易形成复合中心，用其制备得到的太阳能电池的开压高，提高电池的转换效率。
(4)本发明的铝硅合金粉的含量为1～10wt％，既能在银硅合金界面形成有效的铝掺杂，减少接触电阻和体电阻，提高光电转换效率；本发明的铝硅合金粉的粒径为0.5～5μm，既不会使含氧量偏高，减少氧化，还可以在发射极形成 有效的铝掺杂，接触电阻降低，又利于窄线宽的丝网印刷。
(5)本发明制备的银铝浆烧结温度较低为700～750℃，该温度烧结时表面复合降低，从而提高光电转换效率。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，以使本领域的技术人员能够更好的理解本发明的优点和特征，从而对本发明的保护范围做出更为清楚的界定。本发明所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例，基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
一种玻璃粉，按照表1中A1配方，制备玻璃粉，将PbO、BiO、B 2O 3、SiO 2、Al 2O 3和ZnO按比例分别称取准备好，其中第Ⅰ主族元素的化合物包括5％的Na 2O和5％的LiO，第Ⅱ主族元素的化合物包括3％的K 2O、3％的CaO和4％的BaO，将第Ⅰ主族元素的化合物和第Ⅱ主族元素的化合物按照比例也称取准备好，将上述玻璃粉原料置于坩埚中在常温下混合搅拌均匀，将承载有玻璃粉原料的坩埚置于高温熔炉中加热至1100℃，持续1h，熔炼成均匀的玻璃液，将上述玻璃液用去离子水进行水淬，形成不规则的玻璃碎薄片，将上述玻璃碎薄片置于球磨机中粉碎，持续6h，转速设置为250r/min，将上述球磨好的玻璃粉过筛，筛网目数为200～250目，将上述过筛后的玻璃粉置于烘干机中烘干，持续3h，温度设置为55℃，制得银铝浆用玻璃粉A1，每组配方重复三次取平均值。
一种含有上述玻璃粉的一种N型双面太阳能电池正面用银铝浆，按照表2中B1配方，制备银铝浆，按照比例称取纳米银粉、银合金粉、玻璃粉A1、Si质量分数为12％的铝硅合金粉和有机载体，使用分散机混合均匀后，用三辊研 磨机研磨至0.1～1.5μm，得到太阳能电池正面用银铝浆B1，每组配方重复三次取平均值。
实施例2
一种玻璃粉，按照表1中A2配方，制备玻璃粉，将PbO、B 2O 3、SiO 2、Al 2O 3和ZnO按比例分别称取准备好，其中第Ⅰ主族元素的氧化物包括5％的LiCl和5％的Cs 2O，第Ⅱ主族元素的化合物包括5％的K 2O和5％的CaO，将第Ⅰ主族元素的化合物和第Ⅱ主族元素的化合物按照比例也称取准备好，将上述玻璃粉原料置于坩埚中在常温下混合搅拌均匀，将承载有玻璃粉原料的坩埚置于高温熔炉中加热至1100℃，持续1h，熔炼成均匀的玻璃液，将上述玻璃液用去离子水进行水淬，形成不规则的玻璃碎薄片，将上述玻璃碎薄片置于球磨机中粉碎，持续6h，转速设置为250r/min，将上述球磨好的玻璃粉过筛，筛网目数为200～250目，将上述过筛后的玻璃粉置于烘干机中烘干，持续3h，温度设置为55℃，制得银铝浆用玻璃粉A2，每组配方重复三次取平均值。
一种含有上述玻璃粉的一种N型双面太阳能电池正面用银铝浆，按照表2中B2配方，制备银铝浆，按照比例称取纳米银粉、银合金粉、玻璃粉A2、Si质量分数为20％的铝硅合金粉和有机载体，使用分散机混合均匀后，用三辊研磨机研磨至0.1～1.5μm，得到太阳能电池正面用银铝浆B2，每组配方重复三次取平均值。
实施例3
一种玻璃粉，按照表1中A3配方，制备玻璃粉，将BiO、B 2O 3、SiO 2、Al 2O 3和ZnO按比例分别称取准备好，其中第Ⅰ主族元素的化合物包括5％的K 2O和5％的Cs 2O，第Ⅱ主族元素的化合物包括3％的SrO、3％的MgCO 3和4％的BaO，将第Ⅰ主族元素的化合物和第Ⅱ主族元素的化合物按照比例也称取准备好，将 上述玻璃粉原料置于坩埚中在常温下混合搅拌均匀，将承载有玻璃粉原料的坩埚置于高温熔炉中加热至1100℃，持续1h，熔炼成均匀的玻璃液，将上述玻璃液用去离子水进行水淬，形成不规则的玻璃碎薄片，将上述玻璃碎薄片置于球磨机中粉碎，持续6h，转速设置为250r/min，将上述球磨好的玻璃粉过筛，筛网目数为200～250目，将上述过筛后的玻璃粉置于烘干机中烘干，持续3h，温度设置为55℃，制得银铝浆用玻璃粉A3，每组配方重复三次取平均值。
一种含有上述玻璃粉的一种N型双面太阳能电池正面用银铝浆，按照表2中B3配方，制备银铝浆，按照比例称取纳米银粉、银合金粉、玻璃粉A3、Si质量分数为25％的铝硅合金粉和有机载体，使用分散机混合均匀后，用三辊研磨机研磨至0.1～1.5μm，得到太阳能电池正面用银铝浆B3，每组配方重复三次取平均值。
表1
Figure PCTCN2019086561-appb-000001
表2
Figure PCTCN2019086561-appb-000002
测试例1
对实施例1～3得到的一种玻璃粉A1、A2和A3进行性能测试结果如表3所示：
表3
Figure PCTCN2019086561-appb-000003
测试例2
将实施例1～3制备得到的一种N型双面太阳能电池正面用银铝浆，B1、B2和B3，印刷在单晶(156×156mm，方阻60Ω/sq)，经烘干、烧结制得晶硅太阳能电池，测试电性能，结果取平均值，且列于表4中：
表4
Figure PCTCN2019086561-appb-000004
本发明不局限于上述最佳实施方式，任何人在本发明的启示下都可得出其他各种形式的产品，但不论在其形状或结构上作任何变化，凡是具有与本申请相同或相近似的技术方案，均落在本发明的保护范围之内。

Claims (10)

  1. 一种玻璃粉，其特征在于：所述玻璃粉的包括如下组分的重量含量：0～50％的PbO、0～50％的BiO、5～15％的B 2O 3、8～9％的SiO 2、2～3％的Al 2O 3和5～15％ZnO，其中，所述玻璃粉中硅和铝的质量之比为4～5:1，所述的玻璃粉中还包括5～15％的第Ⅰ主族元素的氧化物和5～15％第Ⅱ主族元素的氧化物。
  2. 根据权利要求1所述的玻璃粉，其特征在于：所述的第Ⅰ主族元素的氧化物是LiO、K 2O、Na 2O、Cs 2O、Li 2CO 3、K 2CO 3、NaCl和KCl中的一种或者几种第Ⅰ主族元素的化合物制备得到的。
  3. 根据权利要求1所述的玻璃粉，其特征在于：所述的第Ⅱ主族元素的氧化物是MgO、CaO、BaO、SrO、CaCO 3、MgCO 3和BaCO 3中的一种或者几种第Ⅱ主族元素的化合物制备得到的。
  4. 根据权利要求1所述的玻璃粉，其特征在于：所述的玻璃粉的软化温度为300～400℃，所述的玻璃粉的平均粒径D50为0.5～5μm。
  5. 一种包含权利要求1所述的玻璃粉的N型双面太阳能电池正面用银铝浆，包括导电银粉、硅铝合金粉、玻璃粉和有机载体，其特征在于：所述导电银粉的含量为80～90wt％，所述导电银粉包括平均粒径为50～100nm的纳米银粉和平均粒径为1～10μm的银合金粉，所述纳米银粉和银合金粉的质量比为1：18～90，所述玻璃粉的含量为5～10wt％。
  6. 根据权利要求5所述的N型双面太阳能电池正面用银铝浆，其特征在于：所述纳米银粉的纯度大于99％，所述纳米银粉的松装密度为1.4～1.90g/cm 3，所述纳米银粉的振实密度为2.6～4.1g/cm 3。
  7. 根据权利要求5所述的N型双面太阳能电池正面用银铝浆，其特征在于：所述铝硅合金粉的含量为1～10wt％，所述硅铝合金粉的平均粒径为0.5～5μm，所述铝硅合金粉的熔点为450～650℃，所述铝硅合金粉中的Si的质量分数为12～ 25％。
  8. 根据权利要求6所述的N型双面太阳能电池正面用银铝浆，其特征在于：所述铝硅合金粉的熔点为500～600℃，所述硅铝合金粉为包括Si质量分数为12％的铝硅合金粉、Si质量分数为20％铝硅合金粉及Si质量分数为25％铝硅合金粉三者中的至少一种。
  9. 根据权利要求5所述的N型双面太阳能电池正面用银铝浆，其特征在于：所述有机载体含量为5～10wt％，所述有机载体包括有机粘结剂、表面分散剂和触变剂，所述有机粘结剂包括1～3质量份的有机树脂和7～9质量份的有机溶剂；所述的有机树脂选自乙基纤维素、醋酸丁基纤维素中的一种或几种，所述的有机溶剂选自松油醇、醇酯十二、丁基卡必醇、丁基卡必醇乙酸酯、甘油中的一种或几种，所述的表面分散剂选硬脂酸、硬脂酸衍生物和不饱和脂肪酸中的一种或多种，所述的触变剂选自改性氢化蓖麻油、聚酰胺蜡中的一种或多种。
  10. 根据权利要求8所述的N型双面太阳能电池正面用银铝浆，其特征在于：所述银铝浆的烧结温度为700～750℃。
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