CN112071468B - Conductive slurry for HJT battery and preparation method thereof - Google Patents
Conductive slurry for HJT battery and preparation method thereof Download PDFInfo
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- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 claims description 3
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- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical group [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 claims description 2
- PQJKKINZCUWVKL-UHFFFAOYSA-N [Ni].[Cu].[Ag] Chemical compound [Ni].[Cu].[Ag] PQJKKINZCUWVKL-UHFFFAOYSA-N 0.000 claims description 2
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
- H01L31/074—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type comprising a heterojunction with an element of Group IV of the Periodic System, e.g. ITO/Si, GaAs/Si or CdTe/Si 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
Abstract
The invention provides a conductive paste for an HJT battery and a preparation method thereof, wherein the conductive paste comprises 55-70 parts by mass of flake silver powder, 15-25 parts by mass of silver alloy powder, 25-30 parts by mass of nano silver powder, 5-10 parts by mass of indium alloy powder, 2.5-5 parts by mass of organic resin and 8-12 parts by mass of solvent. The conductive paste is obtained by adding a predetermined conductive powder to an organic vehicle, and performing dispersion, vacuum defoaming and grinding. The conductive slurry can improve the mass ratio of the conductive powder and the compactness after curing and reduce the internal resistance by optimizing the composition of the conductive powder and matching with the selection of the organic carrier and the design of the preparation method; the curing time of the conductive paste is shortened, the performance is stable, and the conductive paste is suitable for production and preparation of the HJT battery.
Description
Technical Field
The invention relates to the field of solar cells and conductive paste, in particular to conductive paste for an HJT cell and a preparation method thereof.
Background
Solar power generation technology has a number of outstanding advantages over other renewable energy sources, and the solar cell industry is rapidly developing against this background. Among them, the crystalline silicon solar cell is still the most widely applied photovoltaic product in the industry at present due to lower cost of raw materials and relatively mature technology; in addition, as for the crystalline silicon solar cell, the industrialization technology is relatively mature, and the improvement of the cell efficiency by the conventional process improvement is more and more limited. Therefore, in order to meet the improvement of the requirements of domestic and foreign markets on the conversion efficiency and stability of the battery, more attention is paid to the research of the novel battery in the industry.
HJT cells (heterojunction cells, also called HIT cells) are mainly based on the deposition of intrinsic α -Si on the front/back side of an n-type silicon wafer: and depositing p-type alpha-Si: h layer and n-type α -Si: the H layer is metallized, and the solar cell has the advantages of high conversion efficiency, low light attenuation, low temperature coefficient and the like, and is an ideal battery product. At present, a plurality of manufacturers also carry out active research on the technology, materials and equipment of the HJT battery so as to occupy the dominant position of the industry. Compared with the conventional crystalline silicon solar cell,
the metallization of the HJT battery usually uses a corresponding low-temperature curing conductive paste, and the curing is performed at a temperature of about 200 ℃. The existing low-temperature curing conductive paste comprises silver powder, resin, solvent and additives, wherein the resin can be thermoplastic resin or thermosetting resin. The cured conductive paste realizes the bonding between the silver powder and the silicon substrate and between the silver powder particles through resin, and compared with high-temperature sintered silver paste, the conductive paste has relatively large volume resistance and poor adhesive force of electrode grid lines, and the curing process consumes long time, so that the productivity of curing equipment is greatly influenced. Therefore, in order to better meet the production requirements of the HJT battery, it is necessary to optimally design the composition, the proportion and the preparation process of the conductive paste, so as to improve the curing efficiency and the conductivity.
Disclosure of Invention
The invention aims to provide conductive paste for an HJT battery and a preparation method thereof, which can improve the conductivity and the process adaptability and meet the production requirement of the HJT battery.
In order to achieve the above object, the present application provides a conductive paste for an HJT battery, comprising conductive powder and an organic vehicle, wherein the conductive powder comprises 55 to 70 parts by mass of flake silver powder, 15 to 25 parts by mass of silver alloy powder, 25 to 30 parts by mass of nano silver powder, and 5 to 10 parts by mass of indium alloy powder, and the median particle diameter of the flake silver powder is larger than that of the silver alloy powder; the organic carrier comprises 2.5-5 parts by mass of organic resin and 8-12 parts by mass of solvent.
As a further improvement of the embodiment of the present application, the silver content in the silver alloy powder is set to 85wt% to 95wt%.
As a further improvement of the embodiment of the application, the median particle diameter of the flake silver powder is 1-3 μm; the median particle diameter of the silver alloy powder is 0.5-1 mu m.
As a further improvement of the embodiment of the application, the median particle diameter of the silver nanoparticles is 20-80 nm.
As a further improvement of the embodiment of the application, the indium alloy powder is set to be indium tin alloy powder, and the median diameter of the indium alloy powder is set to be 0.3-5 μm.
As a further improvement of the embodiments of the present application, the organic resin is at least one selected from the group consisting of bisphenol a type epoxy resin, saturated polyester resin, hydroxylated acrylic resin, silicone resin; the solvent is a mixed solvent of at least one of diethylene glycol ethyl ether acetate and dibasic ester and dimethyl nylon acid.
As a further improvement of the embodiment of the application, the conductive paste further comprises a curing agent, a thixotropic agent and a leveling agent, wherein the thixotropic agent comprises one or more of fumed silica, organic bentonite, modified hydrogenated castor oil and polyamide wax; the leveling agent is polyether modified polydimethylsiloxane copolymer and the molecular weight of the polyether modified polydimethylsiloxane copolymer is 1000-2500.
The application also provides a preparation method of the conductive paste, which mainly comprises the following steps:
weighing organic resin and a solvent, adding the organic resin into the solvent, heating and stirring to obtain an organic carrier, and controlling the viscosity of the organic carrier to be 2800-6400 cP;
adding flaky silver powder, silver alloy powder, nano silver powder and indium alloy powder into an organic carrier, and performing dispersion and vacuum defoaming treatment in sequence to obtain mixed slurry;
and transferring the mixed slurry to a three-roller machine for grinding to obtain the conductive slurry.
As a further improvement of the embodiment of the application, the preparation of the silver alloy powder comprises the steps of simultaneously adding an aqueous solution of silver nitrate or silver fluoride or silver acetate and a metal salt solution containing at least one of gold, copper, nickel, aluminum and tin into a reaction solution, and keeping stirring and ultrasonic treatment; and then the silver alloy powder is obtained after separation, cleaning and drying.
As a further improvement of the embodiment of the application, the vacuum degree of the vacuum defoaming step is set to be 0.06-0.15 MPa, and the time is set to be 5-10 min.
The invention has the beneficial effects that: the conductive slurry and the preparation method thereof provided by the invention are suitable for metallization application of the HJT battery, and the composition of the conductive powder is optimally designed, so that the overall mass ratio of the conductive powder can be improved, the curing time can be shortened, the electrode form after curing can be improved, and the internal resistance can be reduced; and the process has wide adjustment window and stable performance, and is suitable for the production and preparation of the HJT battery.
Drawings
FIG. 1 is a schematic view of the main flow of the slurry preparation method of the present invention.
Detailed Description
The present invention will be described in detail below with reference to embodiments shown in the drawings. The present invention is not limited to the embodiment, and structural, methodological, or functional changes made by one of ordinary skill in the art according to the embodiment are included in the scope of the present invention.
The invention provides a conductive paste for an HJT cell, which can be used for printing a corresponding electrode pattern on the surface of the HJT cell by a screen printing process, and forming good ohmic contact with a Transparent Conductive Oxide (TCO) film layer on the surface of the HJT cell after solidification so as to realize the power output of the HJT cell.
The conductive paste mainly comprises conductive powder and an organic carrier, wherein the conductive powder comprises flaky silver powder, silver alloy powder, nano silver powder and indium alloy powder; the organic vehicle comprises an organic resin and a solvent. Specifically, the conductive powder comprises 55-70 parts by mass of flaky silver powder, 15-25 parts by mass of silver alloy powder, 25-30 parts by mass of nano silver powder and 5-10 parts by mass of indium alloy powder; the organic carrier comprises 2.5-5 parts by mass of organic resin and 8-12 parts by mass of solvent.
The median particle size of the flake silver powder is larger than that of the silver alloy powder, and the median particle size of the flake silver powder is 1-3 mu m; the median particle diameter of the silver alloy powder is 0.5-1 μm. In addition, the median particle size of the nano silver powder is between 20 and 80nm; the indium alloy powder is set to be indium tin alloy powder, and the median particle size of the indium alloy powder is set to be 0.3-5 mu m. Besides, the silver content in the silver alloy powder is set to be 85wt% -95 wt%. The silver alloy powder is preferably binary or ternary alloy powder, such as silver-copper alloy, silver-copper-nickel alloy and the like, and the silver alloy powder can adopt amorphous particles, preferably spherical or spheroidal particles.
The silver alloy powder can improve the activity of metal silver, the indium-tin alloy powder has the characteristics of soft texture, strong plasticity and the like, larger gaps among flaky silver powder and silver alloy powder particles can be filled well, and the bulk resistance after the conductive paste is reduced. The nano silver powder has good conductivity and a special surface effect, and the specification and the using amount of the nano silver powder are preferably designed by combining other compositions and process requirements of the conductive powder. The conductive powder is uniformly shrunk after being solidified, so that the current transmission performance is improved, the series resistance is reduced, and the corresponding electrode grid line is more uniform and attractive.
The organic resin is selected from at least one of bisphenol A epoxy resin, saturated polyester resin, hydroxylated acrylic resin and organic silicon resin; the solvent is a mixed solvent of at least one of diethylene glycol ethyl ether acetate and dibasic ester and dimethyl nylon acid (DBE). The preparation and application of the organic carrier are relatively friendly to environment and have small toxic and side pollution. The conductive paste further comprises a curing agent, a thixotropic agent and a leveling agent, and it should be noted that the curing agent, the thixotropic agent and the leveling agent can be used as components of the organic vehicle, and the organic vehicle can be added along with the conductive powder to prepare the conductive paste.
Specifically, the curing agent can adopt one of isocyanate, amine compounds and acid anhydride; the thixotropic agent comprises one or more of fumed silica, organic bentonite, modified hydrogenated castor oil and polyamide wax; the leveling agent is polyether modified polydimethylsiloxane copolymer, the molecular weight of the polyether modified polydimethylsiloxane copolymer is 1000-2500, and the using amount of the leveling agent is preferably 20-500 ppm. The optimization of the organic carrier and the application of the curing agent, the thixotropic agent and the leveling agent are beneficial to improving the printing performance of the conductive paste, and according to actual tests, the conductive paste can be used for printing uniform continuous grid lines with the width of 25-30 mu m, and the grid lines have a better height-width ratio.
To more clearly describe the conductive paste provided by the present application, we provide the results of comparing the following examples with comparative examples, wherein examples 1 and 2 employ the conductive paste of the present application, except that the curing time of example 1 is 25min, and the curing time of example 2 is 12min; the comparative example used the conventional conductive paste and the curing time was 12min. The test results of the above examples and comparative examples are shown in table 1 below, based on the conversion efficiency of HJT cells of the same specification obtained by curing the existing HJT conductive paste for 25 min:
| conversion efficiency (eff) | |
| Example 1 | Higher by 0.06% |
| Example 2 | Higher by 0.04 percent |
| Comparative example | Lower by 0.11 percent |
The above lists are average values obtained by testing a plurality of corresponding HJT batteries in examples 1 and 2 and a comparative example respectively, and as can be seen from comparison results, the conversion efficiency of the HJT battery can be improved by adopting the conductive paste, and when the curing time of the HJT battery is reduced from 25min to 12min, the conversion efficiency of the corresponding HJT battery is only slightly reduced, and the reduction of the series resistance Rs and the improvement of the filling factor FF are mainly caused by combining with analysis of various specific electrical parameters. In contrast, the conversion efficiency of the comparative example is significantly reduced, indicating that the existing conductive paste needs to ensure a sufficiently long curing time to avoid efficiency. In other words, the conductive paste can improve the conversion efficiency of the HJT battery, properly reduce the curing process time, has good process adaptability, is beneficial to improving the capacity of on-site curing production equipment, and optimizes the production process of the HJT battery.
Referring to fig. 1, the present application also provides a method for preparing the conductive paste, including:
weighing organic resin and a solvent, adding the organic resin into the solvent, heating and stirring to obtain an organic carrier;
adding flaky silver powder, silver alloy powder, nano silver powder and indium alloy powder into an organic carrier, and performing dispersion and vacuum defoaming treatment in sequence to obtain mixed slurry;
and transferring the mixed slurry to a three-roller machine for grinding to obtain the conductive slurry.
Wherein, in the preparation process of the organic carrier, the viscosity of the organic carrier is controlled to be 2800-6400 cP; the vacuum degree of the vacuum defoaming step is set to be 0.06-0.15 Mpa, and the time is set to be 5-10 min. The dispersing step is to fully mix the flake silver powder, the silver alloy powder, the nano silver powder and the indium alloy powder with the organic carrier to obtain uniform mixed slurry, and the dispersing step can adopt a planetary mixer, preferably a high-speed disperser to realize more effective homogeneous dispersion effect. In actual production, the mixed slurry is ground twice or more in a three-roller machine according to the fineness requirement of the conductive slurry (preferably controlled at 6-14 μm). In addition, the ground conductive slurry can be subjected to vacuum defoaming again, so that the shape and quality of the slurry are improved.
The preparation of the silver alloy powder comprises the steps of simultaneously adding aqueous solution of silver nitrate or silver fluoride or silver acetate and metal salt solution containing at least one of gold, copper, nickel, aluminum and tin into reaction liquid, and keeping stirring and ultrasonic treatment; then the silver alloy powder is obtained after separation, cleaning and drying. The reaction solution is kept in an acid reaction environment with the pH value of 3.5-5, and a dispersing agent is usually added in the reaction solution to facilitate the reaction to generate the silver alloy. The stirring and the ultrasonic treatment are kept synchronous, and the maintaining time is set to be about 10 min; in addition, the separation step can be specifically realized by adopting a suction filtration method.
In another embodiment of the present invention, in order to further improve the quality of the conductive paste, the preparation process of the organic vehicle further comprises, after adding the organic resin into the solvent to melt, standing for a predetermined time, and then filtering to remove aggregates and impurities possibly existing in the organic vehicle, specifically, filtering with a polyester filter screen.
In conclusion, the conductive paste for the HJT battery can improve the overall mass ratio of the conductive powder by optimally designing the composition of the conductive powder, and can reduce the internal resistance and improve the conversion efficiency of the corresponding HJT battery by combining the improvement of the preparation process of the conductive paste; the method has wide process adjusting window, shortens the curing time, improves the electrode form after curing, has stable performance, is suitable for the production and preparation of the HJT battery, and has better application prospect.
It should be understood that although the present description refers to embodiments, not every embodiment contains only a single technical solution, and such description is for clarity only, and those skilled in the art should make the description as a whole, and the technical solutions in the embodiments can also be combined appropriately to form other embodiments understood by those skilled in the art.
The above-listed detailed description is only a specific description of a possible embodiment of the present invention, and they are not intended to limit the scope of the present invention, and equivalent embodiments or modifications made without departing from the technical spirit of the present invention should be included in the scope of the present invention.
Claims (6)
1. A conductive paste for an HJT battery comprises conductive powder and an organic carrier, and is characterized in that: the conductive powder comprises 55-70 parts by mass of flake silver powder, 15-25 parts by mass of silver alloy powder, 25-30 parts by mass of nano silver powder and 5-10 parts by mass of indium alloy powder, the median particle size of the flake silver powder is larger than that of the silver alloy powder, and the median particle size of the flake silver powder is 1-3 mu m; the silver alloy powder is silver-copper alloy or silver-copper-nickel alloy, the silver content in the silver alloy powder is 85wt% -95 wt%, and the median particle size of the silver alloy powder is 0.5-1 μm; the median particle size of the nano silver powder is 20-80 nm; the indium alloy powder is indium tin alloy powder, and the median particle size of the indium alloy powder is set to be 0.3-5 mu m; the organic carrier comprises 2.5-5 parts by mass of organic resin and 8-12 parts by mass of solvent.
2. The conductive paste according to claim 1, wherein: the organic resin is selected from at least one of bisphenol A epoxy resin, saturated polyester resin, hydroxylated acrylic resin and organic silicon resin; the solvent is a mixed solvent of at least one of diethylene glycol ethyl ether acetate and dibasic ester and dimethyl nylon acid.
3. The electroconductive paste according to claim 1 or 2, characterized in that: the conductive paste also comprises a curing agent, a thixotropic agent and a leveling agent, wherein the thixotropic agent comprises one or more of fumed silica, organic bentonite, modified hydrogenated castor oil and polyamide wax; the leveling agent is polyether modified polydimethylsiloxane copolymer and the molecular weight of the polyether modified polydimethylsiloxane copolymer is 1000-2500.
4. A method for producing the electroconductive paste according to any one of claims 1 to 3, characterized in that:
weighing organic resin and a solvent, adding the organic resin into the solvent, heating and stirring to obtain an organic carrier, and controlling the viscosity of the organic carrier to be 2800-6400 cP;
adding the flake silver powder, the silver alloy powder, the nano silver powder and the indium alloy powder into an organic carrier, and sequentially performing dispersion and vacuum defoamation treatment to obtain mixed slurry;
and transferring the mixed slurry to a three-roller machine for grinding to obtain the conductive slurry.
5. The method of claim 4, wherein: the preparation of the silver alloy powder comprises the steps of simultaneously adding aqueous solution of silver nitrate or silver fluoride or silver acetate and metal salt solution containing copper into reaction liquid, or simultaneously adding aqueous solution of silver nitrate or silver fluoride or silver acetate and metal salt solution containing copper and nickel into the reaction liquid, and keeping stirring and ultrasonic treatment; then the silver alloy powder is obtained after separation, cleaning and drying.
6. The method of manufacturing according to claim 4, characterized in that: the vacuum degree of the vacuum defoaming step is set to be 0.06-0.15 Mpa, and the time is set to be 5-10 min.
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| CN112562885B (en) * | 2020-12-29 | 2022-06-17 | 四川东树新材料有限公司 | High-welding-tension main grid low-temperature silver paste for solar heterojunction battery and preparation method thereof |
| CN112863733B (en) * | 2021-02-05 | 2022-04-26 | 苏州思尔维纳米科技有限公司 | Low-temperature silver paste for HIT solar cell and preparation method thereof |
| CN113436782B (en) * | 2021-04-29 | 2023-01-24 | 哈工大机器人集团(无锡)科创基地研究院 | Light high-conductivity aqueous conductive slurry and preparation method thereof |
| CN113257456A (en) * | 2021-05-12 | 2021-08-13 | 浙江奕成科技有限公司 | Low-cost conductive paste for heterojunction solar cell and preparation method thereof |
| CN114023487A (en) * | 2021-10-26 | 2022-02-08 | 苏州市贝特利高分子材料股份有限公司 | HJT photovoltaic silver paste and preparation method thereof |
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| CN106229026B (en) * | 2016-07-12 | 2018-08-28 | 常州聚和新材料股份有限公司 | Alloy silver powder and preparation method thereof and solar energy electrocondution slurry prepared therefrom |
| CN109065217A (en) * | 2018-08-10 | 2018-12-21 | 深圳市思迈科新材料有限公司 | HJT solar low-temperature conductive silver paste and the preparation method and application thereof |
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