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WO2024254889A1 - Pâte d'argent-aluminium de face avant pour cellule solaire topcon, son procédé de préparation et utilisation de celle-ci - Google Patents

Pâte d'argent-aluminium de face avant pour cellule solaire topcon, son procédé de préparation et utilisation de celle-ci Download PDF

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Publication number
WO2024254889A1
WO2024254889A1 PCT/CN2023/100919 CN2023100919W WO2024254889A1 WO 2024254889 A1 WO2024254889 A1 WO 2024254889A1 CN 2023100919 W CN2023100919 W CN 2023100919W WO 2024254889 A1 WO2024254889 A1 WO 2024254889A1
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styrene
powder
silver
copolymer
solar cells
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PCT/CN2023/100919
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Chinese (zh)
Inventor
黄立夫
张洪旺
史卫利
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Wuxi Dk Electronic Materials Co Ltd
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Wuxi Dk Electronic Materials Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—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
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables

Definitions

  • the present invention relates to the field of solar cells, and in particular to a thin-line silver-aluminum conductive paste, a front silver-aluminum paste of a tunneling oxide passivated contact crystalline silicon solar cell (Tunnel Oxide Passivated Contact, TOPCon), and a preparation method and application thereof.
  • a thin-line silver-aluminum conductive paste a front silver-aluminum paste of a tunneling oxide passivated contact crystalline silicon solar cell (Tunnel Oxide Passivated Contact, TOPCon)
  • TOPCon Tunneling oxide passivated Contact
  • the front light-receiving surface of the silicon wafer of the solar cell has a conductive sub-grid electrode, which reduces the light-receiving area of the silicon wafer and affects the efficiency. Therefore, it is hoped that a finer electrode can be formed on the front light-receiving surface of the silicon wafer to increase the light-receiving area and thus improve the photovoltaic conversion efficiency of the cell.
  • the tendency is to use a narrower opening screen printing screen technology to produce electrodes in large quantities and quickly.
  • the fine-line grid electrode obtained by this technology has a relatively small light-shielding area on the silicon wafer, so it can obtain a higher photocurrent and further obtain better photovoltaic conversion efficiency.
  • the narrower opening screen design is also in line with the trend of overcoming the demand cost reduction, and can simultaneously meet the needs of reducing costs and improving efficiency in the industry, achieving the optimal price-performance ratio.
  • the new generation of TOPCon tunneling oxide passivated contact crystalline silicon solar cells has a back passivation achieved by an ultra-thin tunneling oxide layer and a doped polysilicon layer.
  • the electrode is only in contact with the polysilicon layer, and the carrier conduction uses the tunneling effect to avoid serious metal-semiconductor recombination, which can effectively improve the cell conversion efficiency.
  • the TOPCon front conductive paste uses two conductive powders, silver powder and aluminum powder.
  • the low-melting point silver-aluminum liquid phase diffuses with silicon to form silver-aluminum spikes, which form direct contact and conduction with the p+ emitter and the metal grid line body, greatly improving the contact resistance. It is the most critical material that dominates the conversion efficiency of the entire TOPCon cell. Compared with the traditional PERC conductive paste using pure silver, the solid content and viscosity tend to be higher, which is relatively unfavorable for the storage stability of the paste and the mass production yield and long-term printing on narrow line width screens.
  • the main purpose of the present invention is to provide a silver-aluminum conductive paste for the front side of a crystalline silicon solar cell with a fine line and good ink permeability through a tunneling oxide passivation contact, so as to solve the mass production problem of the conductive paste in the prior art, which has low cell conversion efficiency due to poor mesh permeability.
  • the present invention provides the following technical solutions:
  • a front silver-aluminum paste for TOPCon solar cells comprising 80-95wt% of conductive powder, 0.1-7wt% of glass powder and 1.5-15wt% of an organic vehicle paste composition, wherein the organic vehicle paste composition comprises a compounded resin, a compounded dispersant, an organic solvent and an additive.
  • the organic vehicle paste composition comprises a compounded resin, a compounded dispersant, an organic solvent and an additive.
  • the content of the compounded resin in the conductive paste is 0.2-5wt%, and the content of the compounded dispersant in the conductive paste is 0.01-2wt%.
  • the composite resin comprises at least two of cellulose acetate, cellulose acetate butyrate, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polyisobutyl acrylate, styrene-acrylate copolymer, acrylonitrile-styrene-acrylate copolymer, hydrogenated styrene-isoprene copolymer, styrene-butadiene-styrene copolymer and styrene-[ethylene-(ethylene-propylene)]-styrene copolymer.
  • the composite resin is selected from at least two of cellulose acetate, cellulose acetate butyrate, ethyl cellulose, polybutyl acrylate, styrene-acrylate copolymer, hydrogenated styrene-isoprene copolymer or styrene-butadiene-styrene copolymer.
  • the compounded resin can be used to more completely coat conductive powders such as silver powder and aluminum powder, which is beneficial to the grinding and dispersion effect in the subsequent slurry process, reduces the proportion of silver flakes, and helps the high-solid content conductive slurry to have good ink-passing properties.
  • the compounded resin has a cohesive effect on the silver-aluminum conductive slurry, which can prevent the powder from collapsing or flowing significantly under high-temperature sintering, maintain the height morphology of the grid line, and thus effectively control the thinning ability of the secondary grid.
  • the compounded resin also has an adhesive effect, which can respond to the different velvet polishing degrees on the silicon wafer, avoid the grid line from falling off due to the rapid shrinkage of the organic carrier and the volatilization of the solvent during high-temperature drying and sintering, and further improve the bonding strength between the slurry and the substrate.
  • the compound dispersant comprises at least two of TDO, oleic acid, ED120, ED350, ED420, isomeric decanol polyoxyethylene ether, isomeric undecanol polyoxyethylene ether and isomeric tridecanol polyoxyethylene ether.
  • Compound dispersants can promote better dispersion of inorganic powder in conductive paste, balance the performance of various components in the paste, avoid powder agglomeration, and achieve the lowest viscosity under high solid content paste formula design to meet the mass production process requirements of screen printing. Especially, compared with other combinations of resins and dispersants.
  • the organic solvent accounts for 1 to 10 wt % of the conductive paste.
  • the organic solvent is selected from the group consisting of ethyl cellosolve, butyl cellosolve, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, monobutyl ether acetate, propylene glycol monomethyl ether, diethylene glycol butyl ether acetate, alcohol ester dodeca, tripropylene glycol monomethyl ether, triacetin, triethylene glycol dibenzoate and terpineol.
  • the conductive powder comprises at least one conductive inorganic powder; preferably, the inorganic powder is silver powder and aluminum powder, the average particle size D50 of the silver powder is 0.1-5 ⁇ m, and the average particle size D50 of the aluminum powder is 0.3-8 ⁇ m.
  • the silver-aluminum conductive paste comprises 84.7-92.6wt% of conductive powder, 1.3-4wt% of glass powder, 2.7-9wt% of organic solvent, 2-4wt% of additive, 0.7-3wt% of compound resin and 0.05-1.6wt% of compound dispersant, wherein the resin is composed of cellulose acetate, polybutyl acrylate and styrene-acrylate copolymer; preferably, in the composition of the resin, the weight ratio of cellulose acetate, polybutyl acrylate and styrene-acrylate copolymer is (1-1.6):(1-2.3):(3-5.5); wherein the dispersant is ED350 and isomeric decanol polyoxyethylene ether; preferably, in the dispersant, the weight ratio of ED350 and isomeric decanol polyoxyethylene ether is (1-1.35):(1-1.6);
  • the silver-aluminum conductive paste comprises 87-94wt% of conductive powder, 2.5-5wt% of glass powder, 3.5-9.3wt% of organic solvent, 2.5-4.2wt% of additives, 0.45-2.8wt% of compound resin and 0.1-1.3wt% of compound dispersant, wherein the resin is composed of polybutyl acrylate, styrene-acrylate copolymer or styrene-butadiene-styrene copolymer; preferably, in the composition of the resin, the weight ratio of polybutyl acrylate, styrene-acrylate copolymer or styrene-butadiene-styrene copolymer is (1-2):(1-3):(2-4); wherein the dispersant is oleic acid and isotridecyl alcohol polyoxyethylene ether; preferably, in the dispersant, the weight ratio of oleic acid and isotridecyl alcohol poly
  • the silver-aluminum conductive paste comprises 85-94.7wt% of conductive powder, 3.5-6wt% of glass powder, 2.5-8.6wt% of organic solvent, 2-4.5wt% of additives, 0.5-2.9wt% of compound resin and 0.2-1wt% of compound dispersant, wherein the resin is composed of polybutyl acrylate, styrene-acrylate copolymer and hydrogenated styrene-isoprene copolymer; preferably, in the composition of the resin, the weight ratio of polybutyl acrylate, styrene-acrylate copolymer and hydrogenated styrene-isoprene copolymer is (1-3.4):(1-2.2):(3-5.5); wherein the dispersant is TDO and isomeric undecyl alcohol polyoxyethylene ether; preferably, in the dispersant, the weight ratio of TDO and isomeric undecyl alcohol polyoxyethylene ether is (1-1.8):(1-2
  • the silver-aluminum conductive paste of the present invention is widely applicable when applied to screen printing, and can be applied to mesh counts of 480/500/520, wire diameters of 9 to 11um, yarn thicknesses of 12.5 to 15um, film thicknesses of 3.5 to 7um, and screen openings of 11 to 18 ⁇ m. In addition, within this opening range, the requirements for thinning can be maintained while taking into account better ink passing capabilities.
  • a solar cell electrode is provided, which is prepared from the silver-aluminum conductive paste, and preferably, the width of the solar cell electrode is 15 to 35 ⁇ m.
  • the present invention uses a specific type of resin carrier and dispersant combination to form a better match with other components such as conductive powder, and the components have a better synergistic effect as a whole, and will not bring any negative effects on the subsequent electrode production or application under high temperature sintering in solar cells, such as electrode conductivity, electrode aspect ratio and battery conversion efficiency.
  • such a combination of resin and dispersant can effectively reduce the viscosity of the slurry with a high solid content, thereby improving the processing performance of the slurry in the subsequent printing process, such as: improving the ink-passing performance of the slurry, having better ink penetration ability, thereby promoting lower electrode resistance, avoiding the phenomenon of grid line breaking in electrode production or uneven ink return caused by adhesion to processing devices such as printing scrapers, and thus improving battery conversion efficiency.
  • the above-mentioned conductive slurry has a relatively wide printing operation window, which is more suitable for advanced narrow line width opening printing screen operation, obtaining a finer line electrode, reducing the light-receiving area of the silicon wafer, and improving the generation of photocurrent, thereby obtaining a higher battery conversion efficiency.
  • Fig. 1 is one schematic diagram of the preparation process of the present invention
  • Fig. 2 is one schematic diagram of the preparation process of the present invention.
  • FIG4 is a schematic diagram of a preparation process of the present invention.
  • FIG5 is a schematic diagram of a preparation process of the present invention.
  • FIG6 is a schematic diagram of a preparation process of the present invention.
  • FIG7 is a schematic diagram of a preparation process of the present invention.
  • FIG8 is a schematic diagram of a preparation process of the present invention.
  • FIG9 is a schematic diagram of a preparation process of the present invention.
  • N-type silicon substrate 20, P layer; 30, front passivation layer; 40, back passivation layer; 50, back main grid silver electrode (after high-temperature sintering); 60, back auxiliary grid silver electrode (after high-temperature sintering); 70, front main grid silver electrode (after high-temperature sintering); 80, front auxiliary grid silver electrode (after high-temperature sintering).
  • FIG. 1 shows an N-type silicon substrate 10 .
  • the crystalline silicon substrate is composed of an N-type silicon substrate 10 and a P layer 20 to form a PN junction.
  • An anti-corrosion agent is used to protect the surface of the P layer 20 , and the surrounding and bottom layers of the P layer 20 are removed by etching, leaving only the main surface, and then an organic solvent is used to remove excess anti-corrosion agent, as shown in FIG. 3 .
  • a passivation layer 30 is formed on the P layer 20 by plasma chemical vapor deposition (PECVD) using Al 2 O 3 and SiN x as passivation layer materials, and a passivation layer 40 is formed on the back of the N layer 10 using SiN x as passivation layer material.
  • PECVD plasma chemical vapor deposition
  • the back main grid silver paste 50 is printed onto the passivation layer 40 by screen printing and then dried.
  • the back side sub-gate silver paste 60 is printed onto the passivation layer 40 by screen printing and then dried.
  • the dried back silver paste after high temperature sintering forms a back silver main grid electrode 50 and a back silver sub-grid 60, and the front part forms a front silver main grid electrode 70 and a back silver sub-grid 80.
  • a good ohmic contact is formed at the front silver aluminum/silicon interface and the back silver/silicon interface to achieve electrical connection.
  • the front silver-aluminum conductive silver paste in the present invention can realize the expected narrow line width of the front silver-aluminum electrode through advanced screen printing screen design. With different screen opening designs, the electrode width after sintering in different embodiments is 17 to 30 um.
  • the present invention takes N-type silicon-based solar cells as an example, but is not limited thereto and may also be applicable to P-type silicon-based solar cells, back-contact solar cells, or other solar cell technologies formed using conductive pastes.
  • the present invention also provides a solar cell, comprising an electrode, wherein the electrode is the solar cell electrode as described above.
  • the battery of the present invention has a better battery conversion rate.
  • the conductive pastes in the embodiments and comparative examples are made of the following materials.
  • Conductive powder Spherical silver powder, particle size (D50) is 1.2-2.1 ⁇ m.
  • the particle size D50 of aluminum powder is 0.3-8 ⁇ m.
  • the brand of silver powder is Japan DOWA4-8FD, and the brand of aluminum powder is ToyalTFH-A02P.
  • Glass powder Glass powder based on lead oxide-tellurium oxide-bismuth oxide-zinc oxide. Particle size (D50) is 1.5-2.0 ⁇ m, brand name BASS T2.
  • Resins including cellulose acetate butyrate, ethyl cellulose, hydroxyethyl cellulose from EastmanTM; polyethyl acrylate and polybutyl acrylate from Shanghai MacLean Biochemical Technology Co., Ltd.; synthetic latex AT-928 styrene-acrylate copolymer from Andes; and at least two of styrene-butadiene-styrene copolymers from Taiwan Rubber Corporation.
  • Dispersants including TDO from AkzoNobelDuomeen®; oleic acid from Shanghai Yuanji Chemical Co., Ltd. and two types of isomeric undecanol polyoxyethylene ether and isomeric tridecanol polyoxyethylene ether provided by BASF.
  • the brand name of the thixotropic agent is Kusumoto DISPARLON® 6500.
  • the brand name of the plasticizer is Dow Corning 200 Fluid 50 cSt.
  • the conductive paste in the above embodiments and comparative examples was printed onto the SiN layer of the silicon wafer substrate (182 ⁇ 182mm) by screen printing technology.
  • the electrical properties (electrode printing screen for testing the conversion efficiency of the battery) and printing screen specifications used were respectively 500 mesh without mesh/9 ⁇ m wire diameter/total thickness 18-18.5 ⁇ m/opening 13 ⁇ m (narrow opening) and 500 mesh without mesh/9 ⁇ m wire diameter/total thickness 18-18.5 ⁇ m/openings 16 ⁇ m, 14 ⁇ m, 12, 10 ⁇ m (narrow opening).
  • the battery cell was dried in an infrared drying furnace and then sintered in a belt sintering furnace at 920-930°C for 40 seconds.
  • the sintered conductive paste was cooled to form an electrode.
  • the width of the electrode was measured using an optical microscope and a micro-imaging inspection instrument.
  • the resistance values at different screen openings (16 ⁇ m, 14 ⁇ m, 12, 10 ⁇ m) are directly measured by a resistance tester.
  • the ink passing performance (printability test) of the slurry under different screen openings is expressed by resistance value. The higher the resistance, the worse the ink passing ability.
  • the formed solar cell is placed in a Berger solar cell tester under a light source condition for efficiency measurement.
  • the xenon arc lamp in the solar cell tester simulates sunlight with a known intensity and radiates it on the light-receiving front surface of the cell.
  • the voltage (V) and current (I) are measured under a load resistance setting of approximately 400 using the four-point contact method to determine the voltage-current curve of the cell, and then the cell conversion efficiency (EFF) is calculated based on this curve.
  • Examples 1 to 6 The difference between Examples 1 to 6 is that when the ratio of other raw materials is fixed, when comparing the additive combination with the addition amount of 0.55%, Examples 3, 4, and 5 all have lower slurry viscosity at 50rpm and lower resistance values at different line width openings, which respectively use TDO/isotridecyl alcohol polyoxyethylene ether, oleic acid/isoundecyl alcohol polyoxyethylene ether, and oleic acid/isotridecyl alcohol polyoxyethylene ether. These three dispersant combinations are subsequently selected to further adjust the addition ratio of other raw materials.
  • Example 7 increases the silver powder by 0.25wt%, reduces the additive by 0.15wt% and the solvent by 0.1%;
  • Example 8 increases the silver powder by 0.5wt%, reduces the additive by 0.2wt% and the solvent by 0.3%.
  • Example 11 increases the silver powder by 0.25wt%, reduces the additive by 0.15wt% and the solvent by 0.1%;
  • Example 12 increases the silver powder by 0.5wt%, reduces the additive by 0.2wt% and the solvent by 0.3%.
  • oleic acid/isomeric undecanol polyoxyethylene ether can provide the widest printing window, less viscosity improvement, narrow electrode width and optimal printability resistance value performance, and can be further matched with the adjustment of organic carriers or inorganic powders to provide efficiency gains and find the critical value of raw material addition.
  • Example 13 increases 0.75wt% of silver powder, reduces 0.25wt% of additives and 0.5% of solvents;
  • Example 14 increases 1wt% of silver powder, reduces 0.3wt% of additives and 0.7% of solvents.
  • Example 13 with 0.75wt% of silver powder has further efficiency gains compared to Examples 4, 9, and 10, and the viscosity and line resistivity are still within the controllable range.
  • Example 14 with 1wt% of silver powder the overall viscosity and line resistivity have exceeded the theoretical standard, and there is no efficiency gain, which is already within the adjustment range of the outlier value.
  • Example 15 reduces 0.15wt% of cellulose acetate butyrate and increases 0.15wt% of styrene-butadiene-styrene copolymer
  • Example 16 increases 0.15wt% of cellulose acetate butyrate and reduces 0.15wt% of styrene-butadiene-styrene copolymer.
  • Example 15 which reduces the high-polarity resin cellulose acetate butyrate and increases the low-polarity resin styrene-butadiene-styrene copolymer, can reduce the overall slurry viscosity, further improve the efficiency by 0.03% and have a lower line resistivity.
  • Example 16 which increases the high-polarity resin cellulose acetate butyrate and reduces the low-polarity resin styrene-butadiene-styrene copolymer, has a slightly worse printability due to the higher viscosity, the line resistivity increases, and the overall grid line height decreases instead of increases, thus having no efficiency advantage.
  • Example 17 fixes the total amount of dispersant at 0.55wt%, increases the proportion of oleic acid to be higher than isomeric undecyl alcohol polyoxyethylene ether;
  • Example 18 fixes the ratio of oleic acid to isomeric undecyl alcohol polyoxyethylene ether, and reduces the overall addition amount by 0.25wt%.
  • Example 17 which increases the proportion of dispersant oleic acid
  • Example 18 which fixes the proportion of dispersant and reduces the addition amount, can provide lower viscosity and lower line resistance than Example 13 at the same silver content, and better ink permeability also further contributes to a slight increase in efficiency, and has better adaptability for mass production.

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Conductive Materials (AREA)

Abstract

La présente invention se rapporte au domaine technique des cellules solaires. Sont divulgués spécifiquement une pâte d'argent-aluminium de face avant pour une cellule solaire TOPCon, son procédé de préparation et l'utilisation de celle-ci. La pâte conductrice d'argent-aluminium contient de 80 à 95% en poids de poudre conductrice, de 0,1 à 7% en poids de poudre de verre et de 1,5 à 15% en poids d'une composition de pâte de support organique, la composition de pâte de support organique comprenant une résine composite, un dispersant composite, un solvant organique et un additif. La résine composite et le dispersant composite peuvent résoudre efficacement les problèmes suivants : faible rendement de production de masse et faible efficacité de conversion de cellules sur des plaques de sérigraphie à largeur de raie étroite en raison de la teneur élevée en matières solides et de la viscosité élevée, et faible perméabilité à l'encre de la pâte conductrice d'argent-aluminium.
PCT/CN2023/100919 2023-06-15 2023-06-18 Pâte d'argent-aluminium de face avant pour cellule solaire topcon, son procédé de préparation et utilisation de celle-ci Pending WO2024254889A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202310710627.5A CN116779212B (zh) 2023-06-15 2023-06-15 一种用于TOPCon太阳能电池的正面银铝浆料及其制备方法和应用
CN202310710627.5 2023-06-15

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WO2024254889A1 true WO2024254889A1 (fr) 2024-12-19

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CN119361212A (zh) * 2024-12-26 2025-01-24 西安宏星电子浆料科技股份有限公司 一种非烧穿型太阳能电池导电浆料、方法、电极和电池
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