WO2020118781A1 - Composition de poudre de verre, pâte conductrice à base d'argent contenant la composition de poudre de verre et cellule solaire - Google Patents

Composition de poudre de verre, pâte conductrice à base d'argent contenant la composition de poudre de verre et cellule solaire Download PDF

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Publication number
WO2020118781A1
WO2020118781A1 PCT/CN2018/124222 CN2018124222W WO2020118781A1 WO 2020118781 A1 WO2020118781 A1 WO 2020118781A1 CN 2018124222 W CN2018124222 W CN 2018124222W WO 2020118781 A1 WO2020118781 A1 WO 2020118781A1
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Prior art keywords
glass frit
parts
silver paste
composition
frit composition
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PCT/CN2018/124222
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English (en)
Chinese (zh)
Inventor
周欣山
包娜
汪山
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苏州晶银新材料股份有限公司
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Publication of WO2020118781A1 publication Critical patent/WO2020118781A1/fr

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Classifications

    • 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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • 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
    • 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
    • C03C3/12—Silica-free oxide glass 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
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/122—Silica-free oxide glass compositions containing oxides of As, Sb, Bi, Mo, W, V, Te as glass formers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • 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
    • H01L31/022441—Electrode arrangements specially adapted for back-contact solar cells
    • H01L31/02245—Electrode arrangements specially adapted for back-contact solar cells for metallisation wrap-through [MWT] type 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

Definitions

  • the invention relates to a glass powder composition and conductive silver paste in a solar cell, belonging to the technical field of materials of solar cells.
  • the silver paste of the solar cell electrode is particularly important in improving the efficiency of the battery and reducing the cost.
  • the silver paste of the solar cell's light-receiving surface electrode is mainly composed of silver powder, inorganic glass powder composition and organic carrier, and silver powder is the main conductive matrix material;
  • the inorganic glass powder composition can passivate the SiO 2 , SiN x and Al 2 O 3 passivation of the battery surface Layer, and form a good ohmic contact with the silicon base to enhance the sintering effect with the silver particles;
  • the organic carrier is mainly used to disperse the silver powder and inorganic glass powder composition, and give the paste a certain rheological properties, suitable for screen printing process And form fine electrodes.
  • the glass frit compositions currently used mainly include leadate, tellurate and borosilicate glass frit compositions.
  • leadate, tellurate and borosilicate glass frit compositions With the development of solar cell technology, new high-efficiency batteries and new battery process technologies have been upgraded faster, and the performance requirements of electrode silver paste are becoming higher and higher. Among them, the requirements for glass powder, which is one of the main components of silver paste, have also increased accordingly.
  • the existing technology generally matches and develops different electrode pastes according to different battery technologies, especially glass powder that plays a central role.
  • the object of the present invention is to provide a solar cell having good corrosion ability to passivation layers such as silicon nitride, aluminum oxide, silicon oxide and the like, and having good wetting ability to silver and silicon substrates Front electrode silver paste.
  • the present invention first provides a glass frit composition, which is a Te-Pb-Ta-based glass frit composition, wherein, based on the weight of the corresponding oxide, the glass frit composition
  • the composition of the substance includes: Te(5-95): Pb(5-50): Ta(1-20).
  • the composition of the glass frit composition may be Te(10):Pb(20):Ta(9).
  • the composition of the glass frit composition may further contain Li, Na, K, Mg, Ca, Sr, Ba, Ti, V, Cr, Mn, Fe by weight of the oxide , Co, Ni, Cu, Zn, B, P, Bi, Si, Al, La, Ce, Nd, Eu, Er, Zr, Sn, Sb, Se, Mo and W one or a combination of several.
  • the glass frit composition may contain 1, 2, 3, 4, 5, 6 or 7 parts. 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts of Li, Na, K, Mg, Ca, Sr, Ba, Ti, V, Cr, Mn, Fe, Co, Ni, Cu , Zn, B, P, Bi, Si, Al, La, Ce, Nd, Eu, Er, Zr, Sn, Sb, Se, Mo and W one or a combination of several.
  • the composition of the glass frit composition may further contain 0.5-15 parts by weight of one of Li, Zn, Si, Al, Mg, B, Cr, P, and V or Several combinations.
  • the raw material composition of the glass frit composition includes oxides of Te, Pb, and Ta; or, a compound containing Te, Pb, and Ta; wherein, the compound containing Te, Pb, and Ta may Decomposed into oxides of Te, Pb and Ta.
  • the oxide of Te may be TeO 2 ; the oxide of Pb may be PbO or Pb 2 O 3 ; the oxide of Ta may be Ta 2 O 5 .
  • the raw material composition of the glass frit composition includes Te (5-95): Pb (5-50): Ta (1-20) based on the weight of the corresponding oxide.
  • the glass frit composition may be an amorphous glass frit composition, a crystallized glass frit composition, or an amorphous and crystal mixed glass frit composition.
  • the present invention also provides a solar cell including the above glass frit composition of the present invention.
  • the present invention also provides a method for preparing the above glass frit composition, which may include the following steps:
  • the raw material composition of the glass frit composition is mixed and melted at 750°C-1000°C for 30min-120min;
  • the glass powder composition fragments are further broken and then ball milled to obtain a glass powder composition with a desired particle size distribution.
  • heating and melting may be performed in a resistance furnace.
  • the roller machine can be cooled by water quenching, steel plate or stainless steel.
  • a planetary ball mill can be used for ball milling to obtain a Te-Pb-Ta-based glass powder composition with a desired particle size distribution.
  • the present invention also provides a conductive silver paste, which includes the Te-Pb-Ta-based glass powder composition of the present invention.
  • the raw material composition of the conductive silver paste may include: 70 parts to 90 parts of silver powder, 0.5 parts to 5 parts of the present invention Glass frit composition, 8-30 parts of organic carrier and 0.5-5 parts of auxiliary.
  • the content of the silver powder may be 72 parts, 75 parts, 80 parts, 82 parts, 85 parts, and 89 parts.
  • the content of the glass frit composition may be 0.7 parts, 1 part, 1.3 parts, 1.5 parts, 2 parts, 3 parts, 3.2 parts, 3.5 parts, 4 parts, 4.3 parts, 4.5 parts , 4.7 copies.
  • the content of the organic carrier may be 9, 10, 12, 15, 20, 22, 27, and 29 parts.
  • the content of the auxiliary agent may be 0.9 parts, 1.2 parts, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 2.5 parts, 4 parts, 4.2 parts, and 4.5 parts.
  • the silver powder used is modified silver powder. Modification can improve the dispersion stability of silver powder in conductive silver paste.
  • the modifiers used to modify the silver powder include oleic acid, linoleic acid, linolenic acid, silane coupling agent, hard fatty acid, fatty acid amine, polyvinylpyrrolidone, fatty alcohol polyoxygen One or a combination of vinyl ether and block macromolecular surfactants.
  • the modifier used when modifying the silver powder is a block macromolecular surfactant.
  • the block macromolecular surfactants used include alkyl vinyl-amine (hydroxy) vinyl ether block copolymers, acrylamide-surface active macromonomers-ionic monomers One or a combination of bulk copolymers, fluorine-containing acrylic block copolymers, and hydroxyethyl methacrylate block copolymers.
  • the organic carrier used includes resin and organic solvent.
  • the organic solvent used includes an organic solvent having a polarity of 2-5; even more preferably, the polarity of the organic solvent used is 2.5-4.
  • the polarities of the organic solvents used are 3 and 3.5.
  • the organic solvent used is one or a combination of terpineol, butyl carbitol acetate, and lauryl ester.
  • the resin used is a combination of one or more of cellulose, epoxy resin, and acrylic resin.
  • the additives used include one or a combination of thixotropic agents, dispersing agents, lubricants, humectants, and plasticizers.
  • the dispersant used is a macromolecular dispersant.
  • the macromolecular dispersant used may be polyether, polyester, polyamide or polysiloxane.
  • the lubricant used may be a surfactant, silicone oil, or the like.
  • the thixotropic agent used may be hydrogenated castor oil, polyamide, fumed silica, and the like.
  • the humectant used may be diethylene glycol, triethylene glycol, PEG400, glycerin, ethylene glycol, sorbitol, 1,2-propylene glycol, diethylene glycol, diethylene glycol butyl Ether, monoethylene glycol, polyethylene glycol, N-methyl-2-pyrrolidone, condensate of polyhydric alcohol and ethylene oxide, xylitol, etc.
  • the plasticizer used may be aliphatic dibasic acid ester, phthalic acid ester, terephthalic acid ester, benzene polyester, benzoate ester, polyol ester Like epoxy, citrate, polyester and so on.
  • the conductive silver paste of the present invention can be prepared by the following steps:
  • Organic carrier preparation mix the resin and organic solvent evenly, stir evenly at room temperature or heating;
  • Preparation of slurry The silver powder, the glass powder composition and the organic carrier are mixed, stirred evenly, and the three-roller grinds and disperses, the average scraper fineness reaches 10 ⁇ m or less, preferably 5 ⁇ m or less, to obtain a conductive silver paste.
  • auxiliary agent may be added during the preparation of the organic carrier; it may also be added during the preparation of the slurry, or partly during the preparation of the organic carrier, and partly during the preparation of the silver paste.
  • the present invention further provides a solar cell including the conductive silver paste of the present invention.
  • the glass frit composition of the present invention and the silver paste formed by the glass frit composition can be used in crystalline silicon solar cells.
  • the formed solar cell has good corrosion ability to passivation layers such as silicon nitride, aluminum oxide, silicon oxide, etc., and has good infiltration to silver and silicon base, and has the ability to dissolve silver in an appropriate amount.
  • the Te-Pb-Ta-based glass powder composition of the present invention has a large glass forming range, good stability, and is easy to adjust the performance of the glass powder.
  • the solar cell formed from the glass frit composition of the present invention and the conductive silver paste has high photoelectric conversion efficiency, small series resistance, large short-circuit current, and high welding tension.
  • Solar cells are devices that directly convert light energy into electrical energy through the photoelectric effect or photochemical effect.
  • This example provides a glass frit composition, the specific composition of which is shown in Table 1.
  • Te-Pb-Ta-based glass frit composition Weigh the raw materials of the Te-Pb-Ta-based glass frit composition at a certain ratio, mix them and place them in a resistance furnace at 900°C for heating and melting for 50 minutes;
  • the fragments were further crushed and then ball-milled with a planetary ball mill to obtain a Te-Pb-Ta-based glass powder composition with a desired particle size distribution (D50: 0.1-5 ⁇ m).
  • the raw material composition (parts by weight) of the first type Te-Pb-Ta-based glass powder composition is: 10 parts tellurium trioxide, 45 parts lead monoxide, 20 parts tantalum pentoxide, 1 part aluminum trioxide, 3 parts magnesium oxide, 2 parts diboron trioxide, 0.5 parts titanium dioxide, 10 parts bismuth trioxide, 5 parts molybdenum trioxide, 3.5 parts zinc oxide.
  • the raw material composition (parts by weight) of the second type Te-Pb-Ta-based glass frit composition is: 30 parts tellurium trioxide, 40 parts lead monoxide, 4.5 parts tantalum dioxide, 1 part magnesium oxide, 1 part boron oxide, 5 parts bismuth trioxide, 6 parts tungsten trioxide, 5 parts zinc oxide, 7.5 parts lithium oxide.
  • the raw material composition (parts by weight) of the third type Te-Pb-Ta-based glass frit composition is: 38 parts tellurium dioxide, 31 parts lead dioxide, 5 parts tantalum pentoxide, 4.5 parts magnesium hydroxide, 2 parts three Chromium oxide, 8.5 parts sodium carbonate, 5 parts molybdenum trioxide, 3 parts silica, 3 parts vanadium pentoxide.
  • the raw material composition (parts by weight) of the fourth type Te-Pb-Ta-based glass frit composition is: 45 parts of tellurium trioxide, 30 parts of lead monoxide, 12 parts of tantalum pentoxide, 2 parts of silica, 1.5 parts of three Aluminum oxide, 2 parts boric acid, 3 parts chromium trioxide, 0.5 parts titanium dioxide, 1 part phosphoric acid, 1 part sodium oxide, 1 part vanadium pentoxide, 1 part zinc molybdate.
  • This embodiment provides a conductive silver paste, which is prepared by the following steps:
  • Organic carrier preparation Weigh and mix the organic matter in proportion, stir evenly at room temperature or under heating;
  • This embodiment provides a solar cell, which is prepared by the following steps:
  • the P-type silicon substrate doped with boron is selected for the semiconductor substrate.
  • the P-type silicon substrate is a silicon wafer with a thickness of 125-125mm or 156x156mm or other typical sizes of 180-250 ⁇ m;
  • the first step is to use an alkaline solution to etch one side of the silicon substrate.
  • the title is pyramidal (single crystal) or uneven (polycrystalline) anti-reflective suede.
  • Wet or dry black silicon technology can also be used to make black silicon nanofleece surface;
  • an N-type diffusion layer is formed on the other side of the P-type silicon substrate to form a PN junction.
  • the N-type diffusion layer may be a gas phase thermal diffusion method using gaseous phosphorus oxychloride as a diffusion source, or a phosphorus ion implantation method, or Slurry coating with phosphorus pentoxide coating thermal diffusion method, etc.;
  • the third step is to deposit a layer of SiNx anti-reflection layer on the fleece side of the silicon substrate, or add a layer of aluminum oxide passivation, or other similar coatings with good anti-reflection effect;
  • the fourth step is to print or coat the Al electrode layer and the main gate silver electrode layer on the side of the P or N-type silicon substrate.
  • SiNx and aluminum oxide or silicon oxide can also be used to form a passivation layer on the back of the battery as a back reflection To increase the absorption of long-wave light.
  • the fifth step is to form the vertical and horizontal main grids and fine grids by screen printing, coating or inkjet printing on the anti-reflective film on the N-type silicon substrate side of the conductive silver paste in Table 2, at a certain sintering temperature program Next, co-firing to form an electrode body.
  • the peak sintering temperature is 600°C-950°C.
  • the series resistance of the solar cell is low, the short-circuit current is large, the photoelectric conversion efficiency is high, and the welding tension is large.
  • the glass powder component in the silver paste can moderately erode the passivation layer during sintering, such as the passivation layer of silicon nitride, aluminum oxide or silicon oxide, etc., and form a good ohmic contact with the silicon base, and have contact with the silver and silicon base Good wettability, improve electrode density after sintering to improve electrical conductivity, and improve welding tension.

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Abstract

L'invention concerne une composition de poudre de verre, une pâte conductrice à base d'argent contenant la composition de poudre de verre et une cellule solaire. La composition de poudre de verre est une composition de poudre de verre à base de Te-Pb-Ta. Selon le poids d'un oxyde correspondant, les constituants de la composition de poudre de verre comprennent : Te (5-95) : Pb (5-50) : Ta (1-20). La pâte conductrice à base d'argent contient la composition de poudre de verre et la cellule solaire utilisant la pâte conductrice à base d'argent présente une bonne aptitude à la corrosion pour le nitrure de silicium, l'oxyde d'aluminium et une couche de passivation d'oxyde de silicium et présente une bonne aptitude au mouillage pour des bases d'argent et de silicium.
PCT/CN2018/124222 2018-12-11 2018-12-27 Composition de poudre de verre, pâte conductrice à base d'argent contenant la composition de poudre de verre et cellule solaire WO2020118781A1 (fr)

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CN201811508995.7 2018-12-11
CN201811508995.7A CN111302636A (zh) 2018-12-11 2018-12-11 一种玻璃粉组合物及含有其的导电银浆和太阳能电池

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CN114315159A (zh) * 2021-12-16 2022-04-12 浙江光达电子科技有限公司 TOPCon电池主栅电极银浆料用玻璃粉及其制备方法与应用

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CN114394754B (zh) * 2021-12-31 2023-05-23 广州市儒兴科技股份有限公司 一种应用窗口宽的玻璃粉与高性能的导电银浆
CN114702240B (zh) * 2022-04-15 2023-12-22 北京大学深圳研究生院 一种玻璃组合物及其制备方法和应用
CN115036056B (zh) * 2022-08-11 2022-11-01 西安拓库米电子科技有限公司 一种高可焊性厚膜导体浆料

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