WO2020118781A1 - Glass powder composition, conductive silver paste containing glass powder composition, and solar cell - Google Patents

Glass powder composition, conductive silver paste containing glass powder composition, and solar cell 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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French (fr)
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/en

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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.

Abstract

A glass powder composition, a conductive silver paste containing glass powder composition, and a solar cell. The glass powder composition is a Te-Pb-Ta-based glass powder composition. According to the weight of a corresponding oxide, components of the glass powder composition comprise: Te(5-95):Pb(5-50):Ta(1-20). The conductive silver paste contains the glass powder composition, and the solar cell using the conductive silver paste has good corrosion capability for silicon nitride, aluminum oxide, and a silicon oxide passivation layer, and has good wetting capability for silver and silicon bases.

Description

一种玻璃粉组合物及含有其的导电银浆和太阳能电池Glass powder composition and conductive silver paste and solar cell containing the same 技术领域Technical field
本发明涉及一种太阳能电池中的玻璃粉组合物和导电银浆，属于太阳能电池的材料技术领域。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.
背景技术Background technique
光伏发电作为新型清洁能源的重要分支，近几年已经取得突飞猛进的发展，全产业链都在积极通过技术创新提升光伏电池转化效率并降低成本，替代传统高污染能源。As an important branch of new clean energy, photovoltaic power generation has achieved rapid development in recent years. The entire industrial chain is actively promoting the conversion efficiency of photovoltaic cells and reducing costs through technological innovation, replacing traditional high-pollution energy sources.
目前大规模产业化的光伏电池为晶硅太阳能电池。近年来，为了提升转化效率降低成本，高效太阳能电池技术迅速发展，细分类逐渐增多，如黑硅、PERC、双面氧化铝PERC、N型、P型等。At present, large-scale industrialized photovoltaic cells are crystalline silicon solar cells. In recent years, in order to improve conversion efficiency and reduce costs, high-efficiency solar cell technology has developed rapidly, and the fine classification has gradually increased, such as black silicon, PERC, double-sided alumina PERC, N-type, P-type and so on.
太阳能电池电极银浆作为电池电流导出的功能部分以及贵金属银的特点，在电池提高效率降低成本上显得尤为重要。太阳能电池受光面电极银浆主要由银粉、无机玻璃粉组合物和有机载体组成，银粉为主要导电基体材料；无机玻璃粉组合物起到腐蚀电池表面SiO 2、SiN x及Al 2O 3钝化层，并与硅基形成良好欧姆接触，增进与银颗粒间的烧结作用；有机载体主要是用来分散银粉和无机玻璃粉组合物，并赋予浆料一定的流变特性，适合丝网印刷工艺，并形成精细电极。 As a functional part of the battery current export and the characteristics of the precious metal silver, 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.
目前采用的玻璃粉组合物主要有铅酸盐、碲酸盐及硼硅酸盐类玻璃粉组合物。随着太阳能电池技术的发展，新高效电池及电池新工艺技术升级较快，对电极银浆性能要求也越来越高，其中，作为银浆主要成分之一的玻璃粉的要求也相应增高，现有技术一般会根据不同电池技术匹配开发不同电极浆料，尤其起核心作用的玻璃粉。The glass frit compositions currently used mainly include 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.
因此，开发出一种适配性能好的玻璃粉体系，能够应用于多种类型晶硅电池成为了本领域亟待解决的问题之一。Therefore, the development of a glass powder system with good adaptability, which can be applied to various types of crystalline silicon batteries, has become one of the problems to be solved in the art.
发明内容Summary of the invention
为了解决上述技术问题，本发明的目的在于提供一种对氮化硅、氧化铝、氧化硅等钝化层具有较好的腐蚀能力，并且对银和硅基具有很好的浸润能力的太阳能电池的正面电极银浆。In order to solve the above technical problems, 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.
为了实现上述技术目的，本发明首先提供了一种玻璃粉组合物，该玻璃粉组合物为Te-Pb-Ta基玻璃粉组合物，其中，以相应的氧化物的重量计，该玻璃粉组合物的组成包 括：Te(5-95)：Pb(5-50)：Ta(1-20)。In order to achieve the above technical object, 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).
在本发明的一具体实施方式中，玻璃粉组合物的组成可以为Te(10)：Pb(20)：Ta(9)。In a specific embodiment of the present invention, the composition of the glass frit composition may be Te(10):Pb(20):Ta(9).
在本发明的玻璃粉组合物中，按氧化物重量计，该玻璃粉组合物的组成中还可以含有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和W中的一种或几种的组合。In the glass frit composition of the present invention, 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.
在本发明的一具体实施方式中，以100重量份的玻璃粉组合物计，该玻璃粉组合物中可以含有1份、2份、3份、4份、5份、6份、7份、8份、9份、10份、11份、12份、13份、14份的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和W中的一种或几种的组合。In a specific embodiment of the present invention, based on 100 parts by weight of the glass frit composition, 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.
在本发明的进一步地具体实施方式中，该玻璃粉组合物的组成中还可以含有0.5-15重量份的Li、Zn、Si、Al、Mg、B、Cr、P和V中的一种或几种的组合。In a further specific embodiment of the present invention, 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.
在本发明的玻璃粉组合物中，该玻璃粉组合物的原料组成包括Te、Pb和Ta的氧化物；或，含有Te、Pb和Ta的化合物；其中，含有Te、Pb和Ta的化合物可以分解为Te、Pb和Ta的氧化物。In the glass frit composition of the present invention, 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.
在本发明的玻璃粉组合物中，Te的氧化物可以为TeO 2；Pb的氧化物可以为PbO或Pb 2O 3；Ta的氧化物可以为Ta 2O 5。 In the glass frit composition of the present invention, 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 .
在本发明的玻璃粉组合物中，以相应的氧化物的重量计，该玻璃粉组合物的原料组成包括Te(5-95)：Pb(5-50)：Ta(1-20)。In the glass frit composition of the present invention, 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.
在本发明的玻璃粉组合物中，该玻璃粉组合物可以为无定型玻璃粉组合物、结晶玻璃粉组合物或无定型与结晶混合的玻璃粉组合物。In the glass frit composition of the present invention, 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.
本发明还提供了一种太阳能电池，该太阳能电池包括本发明的上述玻璃粉组合物。The present invention also provides a solar cell including the above glass frit composition of the present invention.
为了实现上述技术目的，本发明还提供了上述玻璃粉组合物的制备方法，该制备方法可以包括以下步骤：In order to achieve the above technical objective, the present invention also provides a method for preparing the above glass frit composition, which may include the following steps:
将玻璃粉组合物的原料组成混合，在750℃-1000℃下熔融30min-120min；The raw material composition of the glass frit composition is mixed and melted at 750°C-1000°C for 30min-120min;
后经冷却，得到玻璃粉组合物碎片；After cooling, fragments of the glass frit composition are obtained;
将玻璃粉组合物碎片进一步破碎后进行球磨，得到所需粒径分布的玻璃粉组合物。The glass powder composition fragments are further broken and then ball milled to obtain a glass powder composition with a desired particle size distribution.
在本发明的制备方法中，进行加热熔融时，可以在电阻炉中进行。In the production method of the present invention, heating and melting may be performed in a resistance furnace.
在本发明的制备方法中，对冷却的操作没有特殊要求，可以通过水淬、钢板或不锈钢对辊机进行冷却。In the preparation method of the present invention, there is no special requirement for the cooling operation, and the roller machine can be cooled by water quenching, steel plate or stainless steel.
在本发明的制备方法中，球磨时只要可以获得所需粒径就可以，比如可以通过行星式球磨机进行球磨，得到所需粒径分布的Te-Pb-Ta基玻璃粉组合物。In the preparation method of the present invention, as long as the desired particle size can be obtained during ball milling, for example, 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.
为了实现上述技术目的，本发明又提供了一种导电银浆，该导电银浆包括本发明的Te-Pb-Ta基玻璃粉组合物。In order to achieve the above technical object, the present invention also provides a conductive silver paste, which includes the Te-Pb-Ta-based glass powder composition of the present invention.
在本发明的导电银浆中，以该导电银浆的总质量为100重量份计，该导电银浆的原料组成可以包括：70份-90份的银粉、0.5份-5份的本发明的玻璃粉组合物、8份-30份的有机载体和0.5份-5份的助剂。In the conductive silver paste of the present invention, based on the total mass of the conductive silver paste is 100 parts by weight, 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.
在本发明的一具体实施方式中，银粉的含量可以为72份、75份、80份、82份、85份、89份。In a specific embodiment of the present invention, the content of the silver powder may be 72 parts, 75 parts, 80 parts, 82 parts, 85 parts, and 89 parts.
在本发明的一具体实施方式中，玻璃粉组合物的含量可以为0.7份、1份、1.3份、1.5份、2份、3份、3.2份、3.5份、4份、4.3份、4.5份、4.7份。In a specific embodiment of the present invention, 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.
在本发明的一具体实施方式中，有机载体的含量可以为9份、10份、12份、15份、20份、22份、27份、29份。In a specific embodiment of the present invention, the content of the organic carrier may be 9, 10, 12, 15, 20, 22, 27, and 29 parts.
在本发明的一具体实施方式中，助剂的含量可以为0.9份、1.2份、1.5份、2份、2.5份、3份、2.5份、4份、4.2份、4.5份。In a specific embodiment of the present invention, 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.
在本发明的导电银浆中，采用的银粉为经过改性的银粉。通过改性可以提高银粉在导电银浆中的分散稳定性。In the conductive silver paste of the present invention, the silver powder used is modified silver powder. Modification can improve the dispersion stability of silver powder in conductive silver paste.
在本发明的导电银浆中，对银粉进行改性时采用的改性剂包括油酸、亚油酸、亚麻酸、硅烷偶联剂、硬脂肪酸、脂肪酸胺、聚乙烯吡咯烷酮、脂肪醇聚氧乙烯醚和嵌段大分子表面活性剂中的一种或几种的组合。In the conductive silver paste of the present invention, 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.
在本发明的导电银浆中，对银粉进行改性时采用的改性剂为嵌段大分子表面活性剂。In the conductive silver paste of the present invention, the modifier used when modifying the silver powder is a block macromolecular surfactant.
在本发明的一具体实施方式中，采用的嵌段大分子表面活性剂包含烷基乙烯基-胺(羟)基乙烯基醚嵌段共聚物、丙烯酰胺-表面活性大单体-离子型单体共聚物、含氟丙烯酸嵌段共聚物、甲基丙烯酸羟乙酯嵌段共聚物中的一种或几种的组合。In a specific embodiment of the present invention, 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.
在本发明的导电银浆中，采用的有机载体包括树脂和有机溶剂。In the conductive silver paste of the present invention, the organic carrier used includes resin and organic solvent.
在本发明的导电银浆中，优选地，采用的有机溶剂包含极性为2-5的有机溶剂；更进一步优选地，采用的有机溶剂的极性为2.5-4。比如，采用的有机溶剂的极性为3、3.5。In the conductive silver paste of the present invention, preferably, 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. For example, the polarities of the organic solvents used are 3 and 3.5.
在本发明的一具体实施方式中，采用的有机溶剂为松油醇、丁基卡必醇醋酸酯、十二醇酯中的一种或几种的组合。In a specific embodiment of the present invention, the organic solvent used is one or a combination of terpineol, butyl carbitol acetate, and lauryl ester.
在本发明的导电银浆中，采用的树脂为纤维素、环氧树脂和丙烯酸树脂中的一种或 多种的组合。In the conductive silver paste of the present invention, the resin used is a combination of one or more of cellulose, epoxy resin, and acrylic resin.
在本发明的导电银浆中，采用的助剂包括触变剂、分散剂、润滑剂、保湿剂和增塑剂中的一种或几种的组合。In the conductive silver paste of the present invention, the additives used include one or a combination of thixotropic agents, dispersing agents, lubricants, humectants, and plasticizers.
在本发明的导电银浆中，采用的分散剂为大分子分散剂。In the conductive silver paste of the present invention, the dispersant used is a macromolecular dispersant.
在本发明的一具体实施方式中，采用的大分子分散剂可以为聚醚、聚酯、聚酰胺或聚有机硅。In a specific embodiment of the present invention, the macromolecular dispersant used may be polyether, polyester, polyamide or polysiloxane.
在本发明的导电银浆中，采用的润滑剂可以为表面活性剂、硅油等。In the conductive silver paste of the present invention, the lubricant used may be a surfactant, silicone oil, or the like.
在本发明的导电银浆中，采用的触变剂可以为氢化蓖麻油、聚酰胺、气相二氧化硅等。In the conductive silver paste of the present invention, the thixotropic agent used may be hydrogenated castor oil, polyamide, fumed silica, and the like.
在本发明的导电银浆中，采用的保湿剂可以为二甘醇，三甘醇，PEG400，甘油，乙二醇，山梨醇，1,2-丙二醇、二乙二醇、二乙二醇丁醚，一缩乙二醇，聚乙二醇，N-甲基-2-吡咯烷酮，多元醇与环氧乙烷的缩合物、木糖醇等。In the conductive silver paste of the present invention, 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.
在本发明的导电银浆中，采用的增塑剂可以为脂肪族二元酸酯、邻苯二甲酸酯、对苯二甲酸酯、苯多酸酯、苯甲酸酯、多元醇酯类环氧、柠檬酸酯、聚酯等。In the conductive silver paste of the present invention, 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.
本发明的导电银浆可以通过以下步骤制备得到：The conductive silver paste of the present invention can be prepared by the following steps:
有机载体制备：将树脂和有机溶剂混合均匀，室温或加热搅拌均匀；Organic carrier preparation: mix the resin and organic solvent evenly, stir evenly at room temperature or heating;
浆料制备：将银粉、玻璃粉组合物、有机载体混合，搅拌均匀，三辊机研磨分散，平均刮板细度达到10μm以下，优选5μm以下，得到导电银浆。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 μm or less, preferably 5 μm or less, to obtain a conductive silver paste.
这里需要说明的是，助剂可以在制备有机载体时加入；也可以在浆料制备时加入，或者部分在制备有机载体时加入、部分在银浆制备时加入。It should be noted here that the 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.
本发明进而又提供了一种太阳能电池，该太阳能电池包括本发明的导电银浆。The present invention further provides a solar cell including the conductive silver paste of the present invention.
本发明的玻璃粉组合物及该玻璃粉组合物形成的银浆，可以用于晶硅太阳能电池中。形成的太阳能电池对氮化硅、氧化铝、氧化硅等钝化层都具有较好的腐蚀能力，并且对银和硅基有很好的浸润，同时具有适量溶银能力。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.
本发明的Te-Pb-Ta基玻璃粉组合物的成玻范围大，稳定性好，易于调节玻璃粉的性能。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.
由本发明的玻璃粉组合物和导电银浆形成的太阳能电池的光电转化效率高、串联电阻小、短路电流大、焊接拉力高。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.
具体实施方式detailed description
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，现对本发明的技术方案进行以下详细说明，但不能理解为对本发明的可实施范围的限定。In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solutions of the present invention will now be described in detail below, but it cannot be understood as limiting the scope of the present invention.
太阳能电池是通过光电效应或者光化学效应直接把光能转化成电能的装置。Solar cells are devices that directly convert light energy into electrical energy through the photoelectric effect or photochemical effect.
实施例1Example 1
本实施例提供了一种玻璃粉组合物，其具体组成如表1所示。This example provides a glass frit composition, the specific composition of which is shown in Table 1.
表1Table 1
Figure PCTCN2018124222-appb-000001
Figure PCTCN2018124222-appb-000001
实施例2Example 2
本实施例提供了一种玻璃粉组合物，该玻璃粉组合物通过以下步骤制备得到：This embodiment provides a glass frit composition prepared by the following steps:
将Te-Pb-Ta基玻璃粉组合物原料按一定比例称取，混合后置于电阻炉中900℃加热熔融50min；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;
经水淬、钢板冷却，得到玻璃粉组合物碎片；After water quenching and steel plate cooling, fragments of glass frit composition are obtained;
将碎片进一步破碎后用行星式球磨机球磨，得到所需粒径分布(D50：0.1-5μm)的Te-Pb-Ta基玻璃粉组合物。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 μm).
其中，第一类Te-Pb-Ta基玻璃粉组合物的原料组成(重量份)为：10份三氧化碲、45份一氧化铅、20份五氧化二钽、1份三氧二铝、3份氧化镁、2份三氧化二硼、0.5份二氧化钛、10份三氧化二铋、5份三氧化钼、3.5份氧化锌。Among them, 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.
第二类Te-Pb-Ta基玻璃粉组合物的原料组成(重量份)为：30份三氧化碲、40份一氧化铅、4.5份二氧化钽、1份氧化镁、1份氧化硼、5份三氧化二铋、6份三氧化钨、5份氧化锌、7.5份氧化锂。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.
第三类Te-Pb-Ta基玻璃粉组合物的原料组成(重量份)为：38份二氧化碲、31份二氧化铅、5份五氧化二钽、4.5份氢氧化镁、2份三氧化二铬、8.5份碳酸钠、5份三氧化钼、3份二氧化硅、3份五氧化二钒。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.
第四类Te-Pb-Ta基玻璃粉组合物的原料组成(重量份)为：45份三氧化碲、30份一氧化铅、12份五氧化二钽、2份二氧化硅、1.5份三氧化二铝、2份硼酸、3份三氧化二铬、0.5份二氧化钛、1份磷酸、1份氧化钠、1份五氧化二钒、1份钼酸锌。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.
实施例3Example 3
本实施例提供了一种导电银浆，其是通过以下步骤制备得到的：This embodiment provides a conductive silver paste, which is prepared by the following steps:
有机载体制备：将有机物按比例称取混合，室温或加热下搅拌均匀；Organic carrier preparation: Weigh and mix the organic matter in proportion, stir evenly at room temperature or under heating;
将85重量份的银粉、3重量份的表1中的序号10的玻璃粉组合物、12重量份的有机载体按比例混合搅拌均匀，三辊机研磨分散，平均刮板细度达到10μm以下，优选5μm以下。Mix 85 parts by weight of silver powder, 3 parts by weight of the glass powder composition of serial number 10 in Table 1 and 12 parts by weight of organic vehicle in proportion, stir and disperse evenly, grind and disperse with a three-roller, and the average scraper fineness reaches 10 μm or less. It is preferably 5 μm or less.
实施例4Example 4
本实施例提供了一种太阳能电池，其是通过以下步骤制备得到的：This embodiment provides a solar cell, which is prepared by the following steps:
半导体衬底选择掺杂硼的P型硅基底，P型硅基底为180-250μm厚的125×125mm或156×156mm或其它典型尺寸的硅片；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 180-250μm;
第一步，用碱溶液对硅基底一侧进行腐蚀职称金字塔形(单晶)或凹凸不平(多晶)减反射绒面，也可以用湿法或干法黑硅技术制成黑硅纳米绒面；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;
第二步，在P型硅基底另一侧形成N型扩散层制成PN结，N型扩散层可以是以气 态三氯氧磷作为扩散源的气相热扩散法，或者磷离子注入法，或者含有五氧化二磷的浆料涂覆热扩散法等；In the second step, 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.;
第三步，在硅基底绒面一侧沉覆一层SiNx减反层，或再加一层氧化铝钝化层，也可以是相近的其它具有良好减反射效果的涂层；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;
第四步，在P或N型硅基底一侧印刷或涂覆Al电极层和主栅银电极层，另外，也可以利用SiNx和氧化铝或氧化硅在电池背面形成钝化层，作为背反射器，增加长波光的吸收。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. In addition, 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.
第五步，将表2中的导电银浆在N型硅基底一侧减反膜上通过丝网印刷、涂覆或喷墨打印等方式形成纵横的主栅和细栅，在一定烧结温度程序下，共烧形成电极体。烧结峰值温度为600℃-950℃。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℃-950℃.
对上述太阳能电池进行电性能测试，具体是：The electrical performance test of the above solar cells, specifically:
使用太阳能模拟电效率测试仪，在标准条件下测试(大气质量AM1.5，光照强度1000W/m 2，测试温度25℃)，结果如表2所示。 Using a solar simulated electrical efficiency tester, the test was conducted under standard conditions (atmospheric mass AM1.5, light intensity 1000W/m 2 , test temperature 25°C). The results are shown in Table 2.
对上述太阳能电池进行焊接拉力测试方法，具体是：Welding tensile test method for the above solar cells, specifically:
选用1.2×0.25mm焊条，电烙铁设置温度350℃，用拉力测试机180°匀速测试，取平均值为本次测试拉力值。每个配方测试5片电池片，然后取平均值，结果如表2所示。Use 1.2×0.25mm electrode, set the temperature of the electric iron at 350℃, use the tensile tester to test at 180° uniform speed, and take the average value as the test tensile value. Each formula tested 5 batteries, and then averaged, the results are shown in Table 2.
以单晶硅太阳能电池为例，电性能及焊接拉力数据如下：Taking monocrystalline silicon solar cells as an example, the electrical properties and welding tensile data are as follows:
表2Table 2
Figure PCTCN2018124222-appb-000002
Figure PCTCN2018124222-appb-000002
表2可以看出，该太阳能电池的串联电阻低，短路电流大，光电转化效率高，焊接拉力大。这是由于银浆中玻璃粉组分在烧结中可以适度腐蚀钝化层，如氮化硅、氧化铝或氧化硅等钝化层，与硅基形成良好欧姆接触，并且与银和硅基有良好浸润性，提高烧结后电极致密度从而提高导电能力，提高焊接拉力。It can be seen from Table 2 that 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. This is because 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.

Claims (16)

  1. 一种玻璃粉组合物，其特征在于，该玻璃粉组合物为Te-Pb-Ta基玻璃粉组合物，其中，以相应的氧化物的重量计，该玻璃粉组合物的组成包括：Te(5-95)：Pb(5-50)：Ta(1-20)。A glass frit composition, characterized in that the glass frit composition is a Te-Pb-Ta-based glass frit composition, wherein, based on the weight of the corresponding oxide, the composition of the glass frit composition includes: Te( 5-95): Pb(5-50): Ta(1-20).
  2. 根据权利要求1所述的玻璃粉组合物，其特征在于，按氧化物重量计，该玻璃粉组合物的组成中还含有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和W中的一种或几种的组合。The glass frit composition according to claim 1, wherein the composition of the glass frit composition further contains Li, Na, K, Mg, Ca, Sr, Ba, Ti, V, based on the weight of the oxide One of Cr, Mn, Fe, Co, Ni, Cu, Zn, B, P, Bi, Si, Al, La, Ce, Nd, Eu, Er, Zr, Sn, Sb, Se, Mo and W or Several combinations.
  3. 根据权利要求1所述的玻璃粉组合物，其特征在于，该玻璃粉组合物的原料组成包括Te、Pb和Ta的氧化物；或，含有Te、Pb和Ta的化合物，所述化合物可分解为Te、Pb和Ta的氧化物。The glass frit composition according to claim 1, wherein the raw material composition of the glass frit composition includes oxides of Te, Pb, and Ta; or, a compound containing Te, Pb, and Ta, the compound being decomposable It is an oxide of Te, Pb and Ta.
  4. 根据权利要求1所述的玻璃粉组合物，其特征在于，所述Te的氧化物为TeO 2；所述Pb的氧化物为PbO或Pb 2O 3；所述Ta的氧化物为Ta 2O 5。 The glass frit composition according to claim 1, wherein the oxide of Te is TeO 2 ; the oxide of Pb is PbO or Pb 2 O 3 ; the oxide of Ta is Ta 2 O 5 .
  5. 根据权利要求1所述的玻璃粉组合物，其特征在于，以相应的氧化物的重量计，该玻璃粉组合物的原料组成包括：Te(5-95):Pb(5-50):Ta(1-20)。The glass frit composition according to claim 1, characterized in that, based on the weight of the corresponding oxide, the raw material composition of the glass frit composition includes: Te(5-95):Pb(5-50):Ta (1-20).
  6. 根据权利要求1所述的玻璃粉组合物，其特征在于，该玻璃粉组合物为无定型玻璃粉组合物和/或结晶玻璃粉组合物。The glass frit composition according to claim 1, wherein the glass frit composition is an amorphous glass frit composition and/or a crystallized glass frit composition.
  7. 权利要求1所述的玻璃粉组合物的制备方法，其特征在于，该制备方法包括以下步骤：The method for preparing a glass frit composition according to claim 1, wherein the method includes the following steps:
    将玻璃粉组合物的原料组成混合，在750℃-1000℃下熔融30min-120min；The raw material composition of the glass frit composition is mixed and melted at 750°C-1000°C for 30min-120min;
    经冷却，得到玻璃粉组合物碎片；After cooling, fragments of the glass frit composition are obtained;
    将所述玻璃粉组合物碎片进一步破碎后进行球磨，得到所需粒径分布的玻璃粉组合物。The glass powder composition fragments are further broken and then ball milled to obtain a glass powder composition with a desired particle size distribution.
  8. 一种导电银浆，其特征在于，该导电银浆包括权利要求1所述的玻璃粉组合物。A conductive silver paste, characterized in that the conductive silver paste comprises the glass frit composition of claim 1.
  9. 根据权利要求8所述的导电银浆，其特征在于，以该导电银浆的总质量为100重量份计，该导电银浆的原料组成包括：70份-90份的银粉、0.5份-5份的权利要求1-5任一项所述玻璃粉组合物、8份-30份的有机载体和0.5份-5份的助剂。The conductive silver paste according to claim 8, characterized in that, based on the total mass of the conductive silver paste is 100 parts by weight, the raw material composition of the conductive silver paste includes: 70 parts-90 parts of silver powder, 0.5 parts -5 1 part of the glass frit composition according to any one of claims 1 to 5, 8 parts to 30 parts of an organic vehicle and 0.5 parts to 5 parts of an auxiliary agent.
  10. 根据权利要求9所述的导电银浆，其特征在于，所述银粉为经过改性的银粉改性采用的改性剂包括油酸、亚油酸、亚麻酸、硅烷偶联剂、硬脂肪酸、脂肪酸胺、聚乙烯吡咯烷酮、脂肪醇聚氧乙烯醚和嵌段大分子表面活性剂中的一种或几种的组合。The conductive silver paste according to claim 9, wherein the silver powder is a modified silver powder. Modifiers used in the modification include oleic acid, linoleic acid, linolenic acid, silane coupling agent, hard fatty acid, One or a combination of fatty acid amine, polyvinylpyrrolidone, fatty alcohol polyoxyethylene ether and block macromolecular surfactant.
  11. 根据权利要求10所述的导电银浆，其特征在于，改性采用的改性剂为嵌段大分子表面活性剂。The conductive silver paste according to claim 10, wherein the modifier used for modification is a block macromolecular surfactant.
  12. 根据权利要求9所述的导电银浆，其特征在于，所述有机载体包括树脂和有机溶剂；所述有机溶剂为极性为2-5的有机溶剂。The conductive silver paste according to claim 9, wherein the organic vehicle includes a resin and an organic solvent; the organic solvent is an organic solvent having a polarity of 2-5.
  13. 根据权利要求12所述的导电银浆，其特征在于，所述有机溶剂为极性为2.5-4的有机溶剂；The conductive silver paste according to claim 12, wherein the organic solvent is an organic solvent having a polarity of 2.5-4;
    所述有机溶剂为松油醇、丁基卡必醇醋酸酯、十二醇酯中的一种或几种的组合。The organic solvent is one or a combination of terpineol, butyl carbitol acetate, and dodecanol ester.
  14. 根据权利要求12所述的导电银浆，其特征在于，所述树脂为纤维素、环氧树脂和丙烯酸树脂中的一种或多种的组合。The conductive silver paste according to claim 12, wherein the resin is a combination of one or more of cellulose, epoxy resin and acrylic resin.
  15. 根据权利要求9所述的导电银浆，其特征在于，所述助剂包括触变剂、分散剂、保湿剂、润滑剂和增塑剂中一种或几种的组合；The conductive silver paste according to claim 9, characterized in that the auxiliary agent comprises one or a combination of thixotropic agent, dispersing agent, moisturizing agent, lubricant and plasticizer;
    所述分散剂为大分子分散剂；The dispersant is a macromolecular dispersant;
    所述大分子分散剂为聚醚、聚酯、聚酰胺或聚有机硅。The macromolecular dispersant is polyether, polyester, polyamide or polyorganosilicon.
  16. 一种太阳能电池，其特征在于，该太阳能电池包括权利要求1所述的玻璃粉组合物和/或权利要求8所述的导电银浆。A solar cell, characterized in that the solar cell comprises the glass frit composition of claim 1 and/or the conductive silver paste of claim 8.
PCT/CN2018/124222 2018-12-11 2018-12-27 Glass powder composition, conductive silver paste containing glass powder composition, and solar cell WO2020118781A1 (en)

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