CN115223746A - Electrode slurry, preparation method and photovoltaic cell - Google Patents
Electrode slurry, preparation method and photovoltaic cell Download PDFInfo
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- CN115223746A CN115223746A CN202210977393.6A CN202210977393A CN115223746A CN 115223746 A CN115223746 A CN 115223746A CN 202210977393 A CN202210977393 A CN 202210977393A CN 115223746 A CN115223746 A CN 115223746A
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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
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Sustainable Development (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Energy (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses electrode paste, a preparation method thereof and a photovoltaic cell, relates to the technical field of solar cells and aims to solve the problem that insufficient solder is easily generated between a silver layer and a solder strip of the existing electrode paste to cause low tension. The electrode paste comprises a first conductive material and a second conductive material, wherein the first conductive material at least comprises nano silver powder, the second conductive material is Sn-Zn-Ga-Nd alloy, and the melting point of the second conductive material is 176-198 ℃. The preparation method is used for preparing the electrode slurry, and the photovoltaic cell uses the electrode slurry. The electrode paste, the preparation method and the photovoltaic cell provided by the invention are used for improving the welding bonding force between the electrode paste and the welding strip of the assembly series welding when the main grid is printed in the cell manufacturing process.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to electrode slurry, a preparation method of the electrode slurry and a photovoltaic battery.
Background
The middle of the heterojunction cell HJT cell is N-type crystalline silicon, a double-sided cell structure is generally adopted, an intrinsic amorphous silicon film and a P-type film are sequentially deposited on one side of the crystalline silicon, and the intrinsic amorphous silicon film and the N-type film are sequentially deposited on the other side of the crystalline silicon, so that a P-N junction is formed. Due to the fact that the conductivity of amorphous silicon is poor, transparent conductive thin films (TCO) need to be deposited on two sides of the battery to conduct electricity, and finally the double-sided electrode is formed through the screen printing technology. Step printing is generally adopted to meet the requirements of the battery on electrical performance and welding tension, a main grid is mainly used for providing welding tension and collecting current, and a secondary grid is mainly used for collecting current with low contact resistance formed by a TCO layer.
The heterojunction cell main grid silver paste supplied on the market at present mainly depends on the crosslinking and curing of organic polymers to enable the contact between silver particles and between the silver particles and TCO to be formed and provide adhesion. However, the silver powder is coated by the organic polymer resin to a certain extent, so that the silver layer and the solder strip are prevented from being combined, cold solder is easily caused, and low tension is caused. Therefore, it is critical to prepare an electrode paste that enhances the bonding ability with the solder ribbon.
Disclosure of Invention
The invention aims to provide electrode paste, a preparation method thereof and a photovoltaic cell, which can improve the welding bonding force between the electrode paste and a welding strip for assembly series welding when a main grid is printed in the cell manufacturing process.
In a first aspect, the present invention provides an electrode paste comprising: the conductive material comprises a first conductive material and a second conductive material, wherein the first conductive material at least comprises nano silver powder, the second conductive material is Sn-Zn-Ga-Nd alloy, and the melting point of the second conductive material is 176-198 ℃.
Compared with the prior art, the electrode slurry provided by the invention has the following advantages:
the electrode paste provided by the invention comprises a first conductive material and a second conductive material, wherein the first conductive material at least comprises nano silver powder, the melting point of the nano silver powder is about 100 ℃, the second conductive material is Sn-Zn-Ga-Nd alloy, the melting point of the second conductive material is 176-198 ℃, and the nano silver powder and the second conductive material can be sequentially melted when a main grid is sintered and printed. On one hand, the sintering aid can play a role in sintering the first conductive material to promote the first conductive material to be sintered to form a compact bonding phase, so that a conductive path is increased, and the volume resistance of the main gate electrode is reduced. On the other hand, the Sn-Zn-Ga-Nd alloy can act on the surface of the transparent conductive film layer of the heterojunction battery through capillary force, and an anchoring effect can be formed after cooling, so that the welding force and the adhesive force of the film layer can be further improved. Meanwhile, ga in the Sn-Zn-Ga-Nd alloy is a surface active substance, and can play a role in reducing the surface tension of a melt and improving the wettability of the alloy in a system, so that the bonding force with a welding strip can be increased during welding, and the weldability and the peeling strength of a film layer are improved. Nd is uniformly dispersed in the alloy, so that the oxidation resistance of Sn-Zn can be effectively enhanced, and meanwhile, when the Nd is welded with a welding strip, an intermetallic compound can be generated with a welding flux on the welding strip and dispersed on a crystal boundary, so that the mechanical property of crystals can be improved, the solid solution strengthening effect is achieved, the welding resistance and the peeling strength of a film layer are improved, and the problems of aging failure and poor weldability caused by using a simple organic resin as a binding phase are solved. In addition, the second conductive material can replace part of the silver conductive material, so that the using amount of the silver conductive material is reduced, and the cost is reduced.
Therefore, the electrode paste provided by the invention can improve the welding bonding force between the electrode paste and the welding strip for assembly series welding when the main grid is printed in the manufacturing process of the battery.
In a second aspect, the present invention also provides a method for preparing an electrode paste, comprising:
uniformly mixing a curing agent, an organic solvent and an organic auxiliary agent, adding polymeric resin, and mixing to obtain an organic carrier;
and uniformly mixing the first conductive material, the second conductive material and the organic carrier to obtain the electrode slurry.
Compared with the prior art, the beneficial effects of the preparation method of the electrode slurry provided by the invention are the same as those of the electrode slurry in the first aspect, and the details are not repeated here.
In a third aspect, the invention also provides a photovoltaic cell, wherein the photovoltaic cell comprises the electrode paste provided by the invention.
Compared with the prior art, the photovoltaic cell provided by the invention comprises the electrode paste provided by the invention, so that the beneficial effects are the same as those of the electrode paste in the first aspect, and the details are not repeated here.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and do not limit the invention. In the drawings:
FIG. 1 is a schematic diagram of a battery according to an embodiment of the present invention;
fig. 2 is a flow chart illustrating the preparation of an electrode paste according to an embodiment of the present invention.
Reference numerals are as follows:
100-cell, 101 a-anode, 101 b-cathode, 102 a-first amorphous silicon transparent conductive thin film layer, 102 b-second amorphous silicon transparent conductive thin film layer, 103 a-first intrinsic amorphous silicon thin film, 103 b-second intrinsic amorphous silicon thin film, 104-P type amorphous silicon thin film, 105-N type amorphous silicon thin film.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise. The meaning of "a number" is one or more unless specifically limited otherwise.
The conventional crystalline silicon solar cell is formed on a complete silicon wafer by different doping processes, wherein one side of the crystalline silicon solar cell forms an N-type semiconductor, the other side of the crystalline silicon solar cell forms a P-type semiconductor, and a PN junction is formed in a region near the interface of the two semiconductors. The Heterojunction solar cell is called an Intrinsic Thin film Heterojunction cell (HJT, heterojunction with Intrinsic Thin-layer), is a special PN junction, is formed by amorphous silicon and crystalline silicon materials, is formed by depositing an amorphous silicon Thin film on crystalline silicon, and belongs to one of N-type cells. Since the theoretical efficiency of the heterojunction solar cell can reach 28%, which is much higher than that of the conventional crystalline silicon solar cell, the heterojunction solar cell becomes one of the development directions of the next generation solar cell.
The heterojunction cell main grid silver paste supplied on the market at present mainly depends on the crosslinking and curing of organic polymers to enable the contact between silver particles and between the silver particles and TCO, so as to provide adhesive force. However, the silver powder is coated by the organic polymer resin to a certain extent, so that the silver layer and the solder strip are prevented from being combined, cold solder is easily caused, and low tension is caused.
In view of the above problems, embodiments of the present invention provide a photovoltaic cell, which may include an electrode material according to embodiments of the present invention, so as to improve a welding bonding force between an electrode paste and a solder strip for series welding of a component when a main grid is printed in a cell manufacturing process. It is to be understood that the photovoltaic cell may be a heterojunction cell, which may include an electrode material, a substrate, an amorphous silicon transparent conductive thin film layer, a P-type amorphous silicon thin film, an intrinsic amorphous silicon thin film, and an N-type amorphous silicon thin film. Fig. 1 shows a schematic structural diagram of a cell according to an embodiment of the present invention, and as shown in fig. 1, a heterojunction cell 100 according to an embodiment of the present invention includes, from top to bottom, a positive electrode 101a, a first amorphous silicon transparent conductive thin film layer 102a, a P-type amorphous silicon thin film 104, a first intrinsic amorphous silicon thin film 103a, a substrate 106, a second intrinsic amorphous silicon thin film 103b, an N-type amorphous silicon thin film 105, a second amorphous silicon transparent conductive thin film layer 102b, and a negative electrode 101b in this order from the front surface of the cell.
The electrode paste provided by the embodiment of the invention can be applied to the photovoltaic cell. The method comprises the following steps: the conductive material comprises a first conductive material and a second conductive material, wherein the first conductive material at least comprises nano silver powder, the second conductive material is Sn-Zn-Ga-Nd alloy, and the melting point of the second conductive material is 176-198 ℃.
The electrode paste provided by the invention comprises a first conductive material and a second conductive material, wherein the first conductive material at least comprises nano silver powder, the melting point of the nano silver powder is about 100 ℃, the second conductive material is Sn-Zn-Ga-Nd alloy, the melting point of the second conductive material is 176-198 ℃, and the nano silver powder and the second conductive material can be sequentially melted when a main grid is sintered and printed. On one hand, the sintering aid can play a role in sintering the first conductive material to promote the first conductive material to be sintered to form a compact bonding phase, so that a conductive path is increased, and the volume resistance of the main gate electrode is reduced. On the other hand, the Sn-Zn-Ga-Nd alloy can act on the surface of the transparent conductive film layer of the heterojunction cell through capillary force, and an anchoring effect can be formed after cooling, so that the welding force and the adhesive force of the film layer can be further improved. Meanwhile, ga in the Sn-Zn-Ga-Nd alloy is a surface active substance, and can play a role in reducing the surface tension of a melt and improving the wettability of the alloy in a system, so that the bonding force with a welding strip can be increased during welding, and the weldability and the peeling strength of a film layer are improved. Nd is uniformly dispersed in the alloy, so that the oxidation resistance of Sn-Zn can be effectively enhanced, and meanwhile, when the Nd is welded with a welding strip, an intermetallic compound can be generated with a welding flux on the welding strip and dispersed on a crystal boundary, so that the mechanical property of crystals can be improved, the solid solution strengthening effect is achieved, the welding resistance and the peeling strength of a film layer are improved, and the problems of aging failure and poor weldability caused by using a simple organic resin as a binding phase are solved. In addition, the second conductive material can replace part of the silver conductive material, so that the using amount of the silver conductive material is reduced, and the cost is reduced.
Therefore, the electrode paste provided by the invention can improve the welding bonding force between the electrode paste and the welding strip for assembly series welding when the main grid is printed in the manufacturing process of the battery.
In a realizable manner, the particle size of the second conductive material of the embodiment of the invention is 1.5 μm to 3.5 μm, and the mass ratio of the Sn element, the Zn element, the Ga element, and the Nd element contained in the Sn-Zn-Ga-Nd alloy is (17.7 to 91.77): (8-80): (0.2-2): (0.03-0.3). In the electrode paste provided by the embodiment of the invention, the particle size of the second conductive material is controlled within the range of 1.5-3.5 microns, so that when a main grid is formed on a battery, the problem that the second conductive material with larger particle size is easy to block a net and cannot be normally printed when the main grid line is narrower is solved. Meanwhile, the embodiment of the invention adjusts the melting point of the alloy by controlling the content of the Ga element contained in the Sn-Zn-Ga-Nd alloy so as to meet the requirements of different curing processes. Ga is a surface active substance, can play a role in reducing the surface tension of a melt and improving the wettability of alloy in electrode slurry, can increase the bonding force with a welding strip during welding, and improves the weldability and the peel strength of a film layer. The trace rare earth element Nd is uniformly dispersed in the alloy, so that the oxidation resistance of Sn-Zn contained in the Sn-Zn-Ga-Nd alloy can be effectively enhanced, and meanwhile, when the Sn-Zn is welded with a welding strip, an intermetallic compound can be generated by the Sn-Zn contained in the Sn-Zn-Ga-Nd alloy and a welding flux on the welding strip and dispersed on a crystal boundary, so that the mechanical property of crystals is improved, a solid solution strengthening effect is achieved, and the welding resistance and the peeling strength of a film layer are further improved.
In an optional manner, the first conductive material of the embodiment of the present invention further includes microcrystalline silver powder and spherical silver powder, and a mass ratio of the nano silver powder, the microcrystalline silver powder, and the spherical silver powder is (1 to 5): (5-50): (50-80). According to the embodiment of the invention, a small amount of nano silver powder is added, and because the melting point of the nano silver powder is about 100 ℃, the nano silver powder can be firstly melted when the main gate is sintered and printed, so that the sintering aid effect on the first conductive material can be realized, the sintering of the first conductive material is promoted to form a compact bonding phase, the conductive path is increased, and the volume resistance of the main gate electrode is reduced. Meanwhile, the spherical silver powder in the embodiment of the invention is contacted in a point-to-point manner, the contact area is relatively small, a large amount of surface-to-surface contact or surface-to-surface contact is contained in the microcrystalline silver powder, the contact area is relatively large, and when the particle size and the specific surface area of the silver conductive material are in the ranges, the silver conductive material has larger internal friction during relative displacement, so that the viscosity of the prepared slurry is large, and the curing time is shortened. Meanwhile, when the mass ratio of the spherical silver powder to the microcrystalline silver powder is in the range, the spherical silver powder can fill gaps among the microcrystalline silver powder, so that the original non-contact microcrystalline silver powder is mutually contacted, a conductive path is increased, and the conductivity is improved.
Illustratively, the nano silver powder of the embodiment of the invention has the particle size of 20 nm-100 nm and the specific surface area of 4m 2 /g～12m 2 (ii)/g, tap density of 2.0g/cm 3 The above; the grain diameter of the microcrystalline silver powder is 0.8-2.5 mu m, and the specific surface area is 0.5m 2 /g～2m 2 (ii)/g, tap density 4.0g/cm 3 ～6.0g/cm 3 (ii) a The particle diameter of the spherical silver powder is 0.8-2.5 mu m, and the specific surface area is 0.2m 2 /g～1m 2 (ii)/g, tap density 4.5g/cm 3 ～7g/cm 3 . According to the embodiment of the invention, the nano silver powder, the microcrystalline silver powder and the spherical silver powder have different median particle diameters, so that the nano silver powder with a relatively small median particle diameter is firstly melted when the nano silver powder, the microcrystalline silver powder with a relatively large median particle diameter and the spherical silver powder are melted after being sintered to form the main grid, and thus, air holes generated during sintering can be reduced, a film layer of sintered electrode paste is more compact, the series resistance of a battery is reduced, the phenomenon that the resistance of a welding area is too high is avoided, and the welding tension is improved.
In an optional manner, the electrode paste of the embodiment of the present invention further includes an organic vehicle, and the mass ratio of the first conductive material, the second conductive material, and the organic vehicle is (30 to 70): (20 to 40): (8 to 20). At this ratio, the first conductive material and the second conductive material can be sufficiently well-matched with the organic vehicle and uniformly dispersed in the organic vehicle, so that the first conductive material and the second conductive material can be simultaneously cured while the organic vehicle is cured.
Illustratively, the organic vehicle of the embodiment of the present invention includes 1 to 10 parts of a polymerizable resin, 0.1 to 3 parts of a curing agent, 5 to 20 parts of an organic solvent, and 0.5 to 5 parts of an organic auxiliary agent. Wherein the curing agent comprises hexamethylene diisocyanate. The organic solvent comprises at least one of diethylene glycol butyl ether acetate, diethylene glycol butyl ether, alcohol ester dodeca, terpineol, ethylene glycol phenyl ether, diethylene glycol diethyl ether and dimethyl adipate. The organic auxiliary may include at least one of a dispersant, an emulsifier, a defoaming agent, and a leveling agent. The polymerizable resin may include at least one of polyester resin, vinyl chloride-vinyl acetate resin, polyurethane resin, epoxy resin, acrylic resin, and cellulose acetate butyrate resin.
For example: the polymerizable resin is preferably a vinyl chloride-vinyl acetate copolymer, and the vinyl chloride-vinyl acetate copolymer is preferably a carboxyl-modified vinyl chloride-vinyl acetate copolymer having an average molecular weight of 1000 to 30000 and a hydroxyl-modified vinyl chloride-vinyl acetate copolymer having an average molecular weight of 2000 to 100000. The vinyl chloride-vinyl acetate copolymer of the embodiment of the invention is straight-chain, so that the volume shrinkage rate is larger during curing, the distance between silver powders can be reduced, and the lower film sheet resistance can be obtained. Meanwhile, the carboxyl modified resin and the hydroxyl modified resin have more polar groups and are easy to form hydrogen bonds, so that the adhesive force is greatly enhanced after the carboxyl modified resin and the hydroxyl modified resin are crosslinked and cured with a curing agent, the chemical stability is good, the acetic acid and the water vapor are resistant, the aging resistance is strong, and the service life of the component can be greatly prolonged.
Illustratively, the organic auxiliary of the embodiment of the present invention may include 0.2 to 2 parts of a dispersant, 0.2 to 2 parts of an emulsifier, 0.1 to 1 part of an antifoaming agent, and 0.1 to 1 part of a leveling agent. Wherein the dispersant comprises at least one of stearic acid, stearic acid derivatives, unsaturated fatty acids or alkylamines. The emulsifier comprises at least one of hydroxymethyl cellulose and sodium carboxymethyl cellulose. The leveling agent comprises at least one of isophorone and diacetone alcohol. The defoaming agent comprises at least one of fatty acid, fatty acid ester and phosphate.
Fig. 2 shows a flow chart of preparing an electrode paste according to an embodiment of the present invention, and as shown in fig. 2, the present invention further provides a method for preparing the electrode paste, including:
step 201: and (3) uniformly mixing the organic solvent and the organic auxiliary agent, adding the polymeric resin, mixing, and adding the curing agent to obtain the organic carrier.
For example: weighing the curing agent, the organic solvent and the organic auxiliary agent according to the formula, stirring at room temperature for 10-30 min, heating to 60-80 ℃, adding the vinyl chloride-vinyl acetate copolymer in batches according to the proportion while stirring, keeping the temperature for 30-90 min, cooling to room temperature, finally adding the curing agent, and stirring at room temperature for 30-60 min.
Step 202: and uniformly mixing the first conductive material, the second conductive material and the organic carrier to obtain the electrode slurry.
For example: weighing the first conductive material, the second conductive material and the organic carrier according to the proportion, uniformly mixing the materials by a high-speed centrifugal stirrer, stirring and dispersing the materials for 10-30 min at room temperature, and grinding the materials by a three-roll mill to obtain the electrode slurry with the fineness of less than or equal to 6um and the viscosity of 80Pa.s-140Pa.s (5 RPM, 25 ℃, CP52 rotor). The second conductive material is Sn-Zn-Ga-Nd alloy, the second conductive material is prepared by adopting a two-flow atomization method, the atomization medium is high-purity argon, and the high-purity argon is used for protecting the whole process of alloy melting, pipeline transmission, airflow injection and powder cooling to discharge, so that the oxidation of alloy powder is avoided.
The electrode paste provided by the invention comprises a first conductive material and a second conductive material, wherein the first conductive material at least comprises nano silver powder, the melting point of the nano silver powder is about 100 ℃, the second conductive material is Sn-Zn-Ga-Nd alloy, the melting point of the second conductive material is 176-198 ℃, and the nano silver powder and the second conductive material can be sequentially melted when a main grid is sintered and printed. On one hand, the sintering aid can play a role in sintering the first conductive material to promote the first conductive material to be sintered to form a compact bonding phase, so that a conductive path is increased, and the volume resistance of the main gate electrode is reduced. On the other hand, the Sn-Zn-Ga-Nd alloy can act on the surface of the transparent conductive film layer of the heterojunction battery through capillary force, and an anchoring effect can be formed after cooling, so that the welding force and the adhesive force of the film layer can be further improved. Meanwhile, ga in the Sn-Zn-Ga-Nd alloy is a surface active substance, and can play a role in reducing the surface tension of a melt and improving the wettability of the alloy in a system, so that the bonding force with a welding strip can be increased during welding, and the weldability and the peeling strength of a film layer are improved. Nd is uniformly dispersed in the alloy, so that the oxidation resistance of Sn-Zn can be effectively enhanced, and meanwhile, when the Nd is welded with a welding strip, an intermetallic compound can be generated with a welding flux on the welding strip and dispersed on a crystal boundary, so that the mechanical property of crystals can be improved, the solid solution strengthening effect is achieved, the welding resistance and the peeling strength of a film layer are improved, and the problems of aging failure and poor weldability caused by using a simple organic resin as a binding phase are solved. In addition, the second conductive material can replace part of the silver conductive material, so that the using amount of the silver conductive material is reduced, and the cost is reduced.
Therefore, the electrode paste provided by the invention can improve the welding bonding force between the electrode paste and the welding strip for assembly series welding when the main grid is printed in the manufacturing process of the battery.
In order to verify the effect of the electrode paste provided by the embodiment of the present invention, the embodiment of the present invention is demonstrated by comparing the embodiment with the comparative example.
Example one
The electrode slurry provided by the embodiment of the invention comprises the following components in percentage by mass: 60.5% of a first conductive material, 29.2% of fine Sn-Zn-Ga-Nd alloy powder (average particle diameter D50=1.5 to 3.5 μm), and 10.3% of an organic vehicle.
The preparation method of the electrode slurry provided by the embodiment of the invention comprises the following steps:
the first step is as follows: preparing a first conductive material: 1% of nano silver powder (particle diameter D50=50 nm) and 19% of microcrystalline silver powder (particle diameter D50=1.10um, specific surface area 1.3 m) 2 (ii)/g, tap density 4.5g/cm 3 ) 80% of spherical silver powder (particle diameter D50=1.20um, specific surface area 0.8 m) 2 (ii)/g, tap density 5.3g/cm 3 ) And mixing to obtain the first conductive material.
Secondly, preparing the Sn-Zn-Ga-Nd alloy: by mass%, 0.1% of Nd,1.5% of Ga, 20% of Zn and 78.4% of Sn were mixed to prepare an Sn-Zn-Ga-Nd alloy.
Thirdly, preparing an organic carrier: according to the mass percentage, 24 percent of diethylene glycol butyl ether, 12 percent of dimethyl adipate and 13 percent of ethylene glycol phenyl ether are uniformly mixed, 3.0 percent of stearic acid and 3.0 percent of isophorone are added at the same time and are uniformly stirred, 15 percent of hexamethylene diisocyanate is added at the same time when the mixture is stirred to form a uniform solution, then 15 percent of vinyl chloride-vinyl acetate copolymer and 15 percent of acrylic resin are continuously added according to the proportion while stirring, and the mixture is heated and stirred to 80 ℃. And after complete dissolution, continuing stirring for 60 minutes, standing and cooling to room temperature to obtain the organic carrier.
Fourthly, preparing electrode slurry: mixing and stirring the 60.5 percent of the first conductive material, 29.2 percent of Sn-Zn-Ga-Nd alloy micro powder and 10.3 percent of organic carrier uniformly, and dispersing and grinding on a three-roll mill to prepare the electrode slurry.
And fifthly, testing the electrode slurry: the viscosity values were measured at constant temperature 25 ℃ using a rotary viscometer (CP 52 spindle viscometer). After the slurry is printed, drying and curing the slurry at the low temperature of 250 ℃, welding the slurry by adopting a phi-0.35 mm tin-lead welding strip and performing tension test by using a KJ-1065E semi-automatic tension machine. Then, the battery piece is subjected to an IV electrical property test by using a HALM, IV tester.
Example two
The electrode slurry provided by the embodiment of the invention comprises the following components in percentage by mass: 60.5% of a first conductive material, 29.2% of fine Sn-Zn-Ga-Nd alloy powder (average particle diameter D50=1.5 to 3.5 μm), and 10.3% of an organic vehicle.
The preparation method of the electrode slurry provided by the second embodiment of the invention comprises the following steps:
the first step is as follows: preparing a first conductive material: 1% of nano silver powder (particle diameter D50=50 nm) and 28% of microcrystalline silver powder (particle diameter D50=1.10um, specific surface area 1.3 m) 2 (ii)/g, tap density 4.5g/cm 3 ) 71% of spherical silver powder (particle diameter D50=1.20um, specific surface area 0.8 m) 2 (ii)/g, tap density 5.3g/cm 3 ) And mixing to obtain the first conductive material.
Secondly, preparing the Sn-Zn-Ga-Nd alloy: by mass%, 0.1% of Nd,1.5% of Ga, 20% of Zn and 78.4% of Sn were mixed to prepare an Sn-Zn-Ga-Nd alloy.
Thirdly, preparing an organic carrier: according to the mass percent, 13 percent of diethylene glycol monobutyl ether, 26 percent of dimethyl adipate and 13 percent of ethylene glycol phenyl ether are uniformly mixed, 4.0 percent of stearic acid and 4.0 percent of isophorone are added at the same time and are uniformly stirred, 15 percent of hexamethylene diisocyanate is added at the same time of stirring to form a uniform solution, 15 percent of vinyl chloride-vinyl acetate copolymer and 10 percent of acrylic resin are continuously added according to the proportion in the stirring, and the mixture is heated and stirred to 80 ℃. And after complete dissolution, continuing stirring for 60 minutes, standing and cooling to room temperature to obtain the organic carrier.
Step four, preparing electrode slurry: 60.5 percent of first conductive material, 29.2 percent of Sn-Zn-Ga-Nd alloy micro powder and 10.3 percent of organic carrier are mixed and stirred uniformly, and are placed on a three-high mill for dispersion grinding to prepare electrode slurry.
And fifthly, testing the electrode slurry: the viscosity values were measured at constant temperature of 25 ℃ using a rotary viscometer (CP 52 spindle viscometer). After the slurry is printed, the slurry is dried and cured at the low temperature of 250 ℃, tin-lead welding strips with the diameter of phi-0.35 mm are adopted for welding, and a KJ-1065E semi-automatic tensile machine is used for carrying out tensile test. And then, carrying out an IV electrical property test on the battery piece by using a HALM, IV tester.
EXAMPLE III
The electrode slurry provided by the embodiment of the invention comprises the following components in percentage by mass: 60.5% of a first conductive material, 29.2% of fine powder of Sn-Zn-Ga-Nd alloy (average particle diameter D50=1.5 to 3.5 μm), and 10.3% of an organic vehicle.
The preparation method of the electrode slurry provided by the third embodiment of the invention comprises the following steps:
the first step is as follows: preparing a first conductive material: 1% of nano silver powder (particle diameter D50=50 nm) and 37% of microcrystalline silver powder (particle diameter D50=1.10um, specific surface area 1.3 m) 2 (ii)/g, tap density 4.5g/cm 3 ) 62% of spherical silver powder (particle diameter D50=1.20um, specific surface area 0.8 m) 2 (ii)/g, tap density 5.3g/cm 3 ) And mixing to obtain the first conductive material.
Secondly, preparing the Sn-Zn-Ga-Nd alloy: 0.1% of Nd,1.5% of Ga, 20% of Zn and 78.4% of Sn are mixed by mass percent to prepare Sn-Zn-Ga-Nd alloy.
Step three, preparing an organic carrier: according to the mass percentage, 24 percent of diethylene glycol butyl ether, 12 percent of dimethyl adipate and 13 percent of ethylene glycol phenyl ether are uniformly mixed, 3.0 percent of stearic acid and 3.0 percent of isophorone are added at the same time and are uniformly stirred, 15 percent of hexamethylene diisocyanate is added at the same time when the mixture is stirred to form a uniform solution, then 15 percent of vinyl chloride-vinyl acetate copolymer and 15 percent of acrylic resin are continuously added according to the proportion while stirring, and the mixture is heated and stirred to 80 ℃. And after complete dissolution, continuing stirring for 60 minutes, standing and cooling to room temperature to obtain the organic carrier.
Fourthly, preparing electrode slurry: 60.5 percent of first conductive material, 29.2 percent of Sn-Zn-Ga-Nd alloy micro powder and 10.3 percent of organic carrier are mixed and stirred uniformly, and are placed on a three-high mill for dispersion grinding to prepare electrode slurry.
And fifthly, testing the electrode slurry: the viscosity values were measured at constant temperature 25 ℃ using a rotary viscometer (CP 52 spindle viscometer). After the slurry is printed, the slurry is dried and cured at the low temperature of 250 ℃, tin-lead welding strips with the diameter of phi-0.35 mm are adopted for welding, and a KJ-1065E semi-automatic tensile machine is used for carrying out tensile test. Then, the battery piece is subjected to an IV electrical property test by using a HALM, IV tester.
Example four
The electrode slurry provided by the embodiment of the invention comprises the following components in percentage by mass: 60.5% of a first conductive material, 29.2% of fine Sn-Zn-Ga-Nd alloy powder (average particle diameter D50=1.5 to 3.5 μm), and 10.3% of an organic vehicle.
The preparation method of the electrode slurry provided by the fourth embodiment of the invention comprises the following steps:
the first step is as follows: preparing a first conductive material: 3% of nano silver powder (particle diameter D50=50 nm) and 28% of microcrystalline silver powder (particle diameter D50=1.10um, specific surface area 1.3 m) 2 (ii)/g, tap density 4.5g/cm 3 ) 69% of spherical silver powder (particle diameter D50=1.20um, specific surface area 0.8 m) 2 (g) tap densityThe degree is 5.3g/cm 3 ) And mixing to obtain the first conductive material.
Secondly, preparing the Sn-Zn-Ga-Nd alloy: 0.1% of Nd,1.5% of Ga, 20% of Zn and 78.4% of Sn are mixed by mass percent to prepare Sn-Zn-Ga-Nd alloy.
Step three, preparing an organic carrier: according to the mass percentage, 24 percent of diethylene glycol butyl ether, 12 percent of dimethyl adipate and 13 percent of ethylene glycol phenyl ether are uniformly mixed, 3.0 percent of stearic acid and 3.0 percent of isophorone are added at the same time and are uniformly stirred, 15 percent of hexamethylene diisocyanate is added at the same time when the mixture is stirred to form a uniform solution, then 15 percent of vinyl chloride-vinyl acetate copolymer and 15 percent of acrylic resin are continuously added according to the proportion while stirring, and the mixture is heated and stirred to 80 ℃. And after complete dissolution, continuing stirring for 60 minutes, standing and cooling to room temperature to obtain the organic carrier.
Step four, preparing electrode slurry: mixing and stirring 60.5% of first conductive material, 29.2% of Sn-Zn-Ga-Nd alloy micro powder and 10.3% of organic carrier uniformly, and placing the mixture on a three-roll mill for dispersion and grinding to prepare electrode slurry.
And step five, testing the electrode slurry: the viscosity values were measured at constant temperature of 25 ℃ using a rotary viscometer (CP 52 spindle viscometer). After the slurry is printed, the slurry is dried and cured at the low temperature of 250 ℃, tin-lead welding strips with the diameter of phi-0.35 mm are adopted for welding, and a KJ-1065E semi-automatic tensile machine is used for carrying out tensile test. Then, the battery piece is subjected to an IV electrical property test by using a HALM, IV tester.
EXAMPLE five
The electrode slurry provided by the embodiment of the invention comprises the following components in percentage by mass: 50% of a first conductive material, 30% of a fine powder of an Sn-Zn-Ga-Nd alloy (average particle diameter D50=1.5 to 3.5 μm), and 20% of an organic vehicle.
The preparation method of the electrode slurry provided by the fifth embodiment of the invention comprises the following steps:
the first step is as follows: preparing a first conductive material: 1% of nano silver powder (particle diameter D50=50 nm) and 28% of microcrystalline silver powder (particle diameter D50=1.10um, specific surface area 1.3 m) 2 The tap density is 4.5g/cm 3 ) 71% of spherical silver powder (particle diameter)D50=1.20um, specific surface area 0.8m 2 G, tap density of 5.3g/cm 3 ) And mixing to obtain the first conductive material.
Secondly, preparing the Sn-Zn-Ga-Nd alloy: 0.1% of Nd,1.5% of Ga, 20% of Zn and 78.4% of Sn are mixed by mass percent to prepare Sn-Zn-Ga-Nd alloy.
Step three, preparing an organic carrier: according to the mass percentage, 13 percent of diethylene glycol butyl ether, 26 percent of dimethyl adipate and 13 percent of ethylene glycol phenyl ether are uniformly mixed, 4.0 percent of stearic acid and 4.0 percent of isophorone are added at the same time and are uniformly stirred, 15 percent of hexamethylene diisocyanate is added at the same time when the mixture is stirred to form a uniform solution, then 15 percent of vinyl chloride-vinyl acetate copolymer and 10 percent of acrylic resin are continuously added according to the proportion while stirring, and the mixture is heated and stirred to 80 ℃. And after complete dissolution, continuously stirring for 60 minutes, standing and cooling to room temperature to obtain the organic carrier.
Fourthly, preparing electrode slurry: mixing and stirring uniformly 50% of first conductive material, 30% of Sn-Zn-Ga-Nd alloy micro powder and 20% of organic carrier, and placing the mixture on a three-roll mill for dispersion grinding to prepare electrode slurry.
And step five, testing the electrode slurry: the viscosity values were measured at constant temperature of 25 ℃ using a rotary viscometer (CP 52 spindle viscometer). After the slurry is printed, the slurry is dried and cured at the low temperature of 250 ℃, tin-lead welding strips with the diameter of phi-0.35 mm are adopted for welding, and a KJ-1065E semi-automatic tensile machine is used for carrying out tensile test. And then, carrying out an IV electrical property test on the battery piece by using a HALM, IV tester.
Example six
The electrode slurry provided by the embodiment of the invention comprises the following components in percentage by mass: 50% of a first conductive material, 40% of fine powder of an Sn-Zn-Ga-Nd alloy (average particle diameter D50=1.5 to 3.5 μm), and 10% of an organic vehicle.
The preparation method of the electrode slurry provided by the sixth embodiment of the invention comprises the following steps:
the first step is as follows: preparing a first conductive material: 1% of nano silver powder (particle diameter D50=50 nm) and 28% of microcrystalline silver powder (particle diameter D50=1.10um, specific surface area 1.3 m) 2 Per g, tap density of4.5g/cm 3 ) 71% of spherical silver powder (particle diameter D50=1.20um, specific surface area 0.8 m) 2 G, tap density of 5.3g/cm 3 ) And mixing to obtain the first conductive material.
Secondly, preparing the Sn-Zn-Ga-Nd alloy: by mass%, 0.1% of Nd,1.5% of Ga, 20% of Zn and 78.4% of Sn were mixed to prepare an Sn-Zn-Ga-Nd alloy.
Step three, preparing an organic carrier: according to the mass percent, 13 percent of diethylene glycol butyl ether, 26 percent of dimethyl adipate and 13 percent of ethylene glycol phenyl ether are uniformly mixed, 4.0 percent of unsaturated fatty acid and 4.0 percent of diacetone alcohol are added and uniformly stirred, 15 percent of hexamethylene diisocyanate is added while stirring to form a uniform solution, 15 percent of vinyl chloride-vinyl acetate copolymer and 10 percent of acrylic resin are continuously added in proportion while stirring, and the mixture is heated and stirred to 80 ℃. And after complete dissolution, continuing stirring for 60 minutes, standing and cooling to room temperature to obtain the organic carrier.
Fourthly, preparing electrode slurry: mixing and stirring uniformly 50% of first conductive material, 40% of Sn-Zn-Ga-Nd alloy micro powder and 10% of organic carrier, and placing the mixture on a three-roll mill for dispersion grinding to prepare electrode slurry.
And fifthly, testing the electrode slurry: the viscosity values were measured at constant temperature of 25 ℃ using a rotary viscometer (CP 52 spindle viscometer). After the slurry is printed, the slurry is dried and cured at the low temperature of 250 ℃, tin-lead welding strips with the diameter of phi-0.35 mm are adopted for welding, and a KJ-1065E semi-automatic tensile machine is used for carrying out tensile test. Then, the battery piece is subjected to an IV electrical property test by using a HALM, IV tester.
EXAMPLE seven
The electrode slurry provided by the embodiment of the invention comprises the following components in percentage by mass: 60.5% of a first conductive material, 29.2% of fine powder of Sn-Zn-Ga-Nd alloy (average particle diameter D50=1.5 to 3.5 μm), and 10.3% of an organic vehicle.
The preparation method of the electrode slurry provided by the seventh embodiment of the invention comprises the following steps:
the first step is as follows: preparing a first conductive material: 1% of nano silver powder (particle diameter D50=50 nm) and 19% of microcrystalline silver powder (particles)Diameter D50=1.10um, specific surface area 1.3m 2 (ii)/g, tap density 4.5g/cm 3 ) 80% of spherical silver powder (particle diameter D50=1.20um, specific surface area 0.8 m) 2 (ii)/g, tap density 5.3g/cm 3 ) And mixing to obtain the first conductive material.
Secondly, preparing the Sn-Zn-Ga-Nd alloy: 0.2% of Nd,2% of Ga, 20% of Zn and 77.8% of Sn are mixed by mass percent to prepare Sn-Zn-Ga-Nd alloy.
Step three, preparing an organic carrier: according to the mass percentage, 24 percent of diethylene glycol butyl ether, 12 percent of dimethyl adipate and 13 percent of ethylene glycol phenyl ether are uniformly mixed, 3.0 percent of stearic acid and 3.0 percent of isophorone are added at the same time and are uniformly stirred, 15 percent of hexamethylene diisocyanate is added at the same time when the mixture is stirred to form a uniform solution, then 15 percent of vinyl chloride-vinyl acetate copolymer and 15 percent of acrylic resin are continuously added according to the proportion while stirring, and the mixture is heated and stirred to 80 ℃. And after complete dissolution, continuing stirring for 60 minutes, standing and cooling to room temperature to obtain the organic carrier.
Fourthly, preparing electrode slurry: mixing and stirring the 60.5 percent of the first conductive material, 29.2 percent of Sn-Zn-Ga-Nd alloy micro powder and 10.3 percent of organic carrier uniformly, and dispersing and grinding on a three-roll mill to prepare the electrode slurry.
And step five, testing the electrode slurry: the viscosity values were measured at constant temperature of 25 ℃ using a rotary viscometer (CP 52 spindle viscometer). After the slurry is printed, the slurry is dried and cured at the low temperature of 250 ℃, tin-lead welding strips with the diameter of phi-0.35 mm are adopted for welding, and a KJ-1065E semi-automatic tensile machine is used for carrying out tensile test. And then, carrying out an IV electrical property test on the battery piece by using a HALM, IV tester.
Example eight
The electrode slurry provided by the embodiment of the invention comprises the following components in percentage by mass: 60.5% of a first conductive material, 29.2% of fine Sn-Zn-Ga-Nd alloy powder (average particle diameter D50=1.5 to 3.5 μm), and 10.3% of an organic vehicle.
The preparation method of the electrode slurry provided by the eighth embodiment of the invention comprises the following steps:
the first step is as follows: preparing a first conductive material: mixing the raw materials by weight percentSilver powder (particle diameter D50=50 nm) and 19% of microcrystalline silver powder (particle diameter D50=1.10um, specific surface area 1.3 m) 2 The tap density is 4.5g/cm 3 ) 80% of spherical silver powder (particle diameter D50=1.20um, specific surface area 0.8 m) 2 G, tap density of 5.3g/cm 3 ) And mixing to obtain the first conductive material.
Secondly, preparing the Sn-Zn-Ga-Nd alloy: by mass percent, 0.5% of Nd,5% of Ga, 20% of Zn and 74.5% of Sn are mixed to prepare Sn-Zn-Ga-Nd alloy.
Thirdly, preparing an organic carrier: according to the mass percent, 24 percent of diethylene glycol monobutyl ether, 12 percent of dimethyl adipate and 13 percent of ethylene glycol phenyl ether are uniformly mixed, 3.0 percent of stearic acid and 3.0 percent of isophorone are added at the same time and are uniformly stirred, 15 percent of hexamethylene diisocyanate is added at the same time of stirring to form a uniform solution, 15 percent of vinyl chloride-vinyl acetate copolymer and 15 percent of acrylic resin are continuously added according to the proportion in the stirring, and the mixture is heated and stirred to 80 ℃. And after complete dissolution, continuing stirring for 60 minutes, standing and cooling to room temperature to obtain the organic carrier.
Fourthly, preparing electrode slurry: mixing and stirring the 60.5 percent of the first conductive material, 29.2 percent of Sn-Zn-Ga-Nd alloy micro powder and 10.3 percent of organic carrier uniformly, and dispersing and grinding on a three-roll mill to prepare the electrode slurry.
And fifthly, testing the electrode slurry: the viscosity values were measured at constant temperature 25 ℃ using a rotary viscometer (CP 52 spindle viscometer). After the slurry is printed, drying and curing the slurry at the low temperature of 250 ℃, welding the slurry by adopting a phi-0.35 mm tin-lead welding strip and performing tension test by using a KJ-1065E semi-automatic tension machine. And then, carrying out an IV electrical property test on the battery piece by using a HALM, IV tester.
Comparative example 1
Comparative example I of the invention adopts outsourcing main grid silver paste, and does not contain Sn-Zn-Ga-Nd alloy and nano silver powder in the invention example.
The results of testing the electrode slurry provided in the examples and comparative examples are shown in the following table:
as can be seen from the above table, the welding tension in examples one to eight was much higher than that of comparative example one, and the efficiency was better than that of the battery in comparative example one. Therefore, the electrode paste provided by the embodiment of the invention uses the nano silver powder and the Sn-Zn-Ga-Nd alloy, the melting point of the Sn-Zn-Ga-Nd alloy is 176-198 ℃, the nano silver powder and the Sn-Zn-Ga-Nd alloy can be sequentially melted when the printing main gate is sintered, the sintering assisting effect can be exerted on the first conductive material, the first conductive material is promoted to be sintered to form a compact adhesive phase, so that the conductive path is increased, the volume resistance of the main gate electrode is reduced, and the welding tension is improved. Meanwhile, the fifth embodiment and the sixth embodiment reduce the usage amount of the first conductive material, and the welding tension and the battery conversion efficiency of the fifth embodiment and the sixth embodiment are still higher than those of the first embodiment, that is, the second conductive material can replace part of the silver conductive material, so that the usage amount of the first conductive material can be reduced, and the cost is reduced.
While the foregoing is directed to embodiments of the present invention, it will be apparent that various modifications and combinations can be made without departing from the spirit and scope of the invention. Accordingly, the specification and figures are merely exemplary of the invention as defined in the appended claims and are intended to cover any and all modifications, variations, combinations, or equivalents within the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. Those skilled in the art can easily conceive of changes and substitutions within the technical scope of the present disclosure, and all such changes and substitutions are intended to be included within the scope of the present disclosure. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. An electrode paste, comprising: the conductive material comprises a first conductive material and a second conductive material, wherein the first conductive material at least comprises nano silver powder, the second conductive material is Sn-Zn-Ga-Nd alloy, and the melting point of the second conductive material is 176-198 ℃.
2. The electrode paste according to claim 1, wherein the particle size of the second conductive material is 1.5 to 3.5 μm, and the Sn-Zn-Ga-Nd alloy contains Sn, zn, ga, and Nd elements in a mass ratio of (17.7 to 91.77): (8-80): (0.2-2): (0.03-0.3).
3. The electrode slurry according to claim 1, wherein the first conductive material further comprises microcrystalline silver powder and spherical silver powder, and the mass ratio of the nanocrystalline silver powder, the microcrystalline silver powder, and the spherical silver powder is (1-5): (5-50): (50-80).
4. The electrode slurry according to claim 3, wherein the nano silver powder has a particle size of 20 to 100nm and a specific surface area of 4m 2 /g～12m 2 The tap density is 2.0g/cm 3 The above; the grain diameter of the microcrystalline silver powder is 0.8-2.5 mu m, and the specific surface area is 0.5m 2 /g～2m 2 (ii)/g, tap density 4.0g/cm 3 ～6.0g/cm 3 (ii) a The particle diameter of the spherical silver powder is 0.8-2.5 mu m, and the specific surface area is 0.2m 2 /g～1m 2 (ii)/g, tap density 4.5g/cm 3 ～7g/cm 3 。
5. The electrode paste according to any one of claims 1 to 4, further comprising an organic vehicle, wherein the mass ratio of the first conductive material, the second conductive material, and the organic vehicle is (30 to 70): (20 to 40): (8 to 20).
6. The electrode slurry according to claim 5, wherein the organic vehicle comprises, by mass, 1 to 10 parts of the polymerizable resin, 0.1 to 3 parts of the curing agent, 5 to 20 parts of the organic solvent, and 0.5 to 5 parts of the organic auxiliary agent.
7. The electrode slurry according to claim 6, wherein the polymerizable resin comprises at least one of a polyester resin, a vinyl chloride-acetate resin, a polyurethane resin, an epoxy resin, an acrylic resin, and a cellulose acetate butyrate resin.
8. The electrode slurry according to claim 6, wherein the molecular structure of the vinyl chloride-vinyl acetate copolymer is linear, and the vinyl chloride-vinyl acetate copolymer includes a carboxyl-modified resin and a hydroxyl-modified resin.
9. A method for preparing the electrode slurry according to any one of claims 1 to 8, comprising:
uniformly mixing an organic solvent and an organic auxiliary agent, adding polymeric resin, mixing, and adding a curing agent to obtain an organic carrier;
and uniformly mixing the first conductive material, the second conductive material and the organic carrier to obtain the electrode slurry.
10. A photovoltaic cell, characterized in that the surface of the photovoltaic cell is provided with grid lines, and the material of the grid lines is the electrode paste of any one of claims 1 to 8.
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