CN115312228A - Conductive silver paste for heterojunction battery, preparation method of conductive silver paste and product containing conductive silver paste - Google Patents
Conductive silver paste for heterojunction battery, preparation method of conductive silver paste and product containing conductive silver paste Download PDFInfo
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- 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
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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
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- H—ELECTRICITY
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- H01L31/02—Details
- H01L31/0224—Electrodes
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- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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Abstract
The invention discloses electrode paste, a preparation method of the electrode paste and a photovoltaic cell, relates to the technical field of solar cells, and aims to solve the problem that copper powder is easy to partially oxidize when silver-coated copper powder is used in the existing electrode paste. The electrode slurry comprises a silver-based conductive material and a carbon nano tube, wherein the silver-based conductive material is filled in a tube cavity of the carbon nano tube, the tube diameter of the carbon nano tube is 2-200 nm, and the specific surface area of the carbon nano tube is 60m 2 /g～1200m 2 (ii) in terms of/g. 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 oxidation resistance of the electrode paste and reducing the consumption of silver.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to conductive silver paste for a heterojunction battery, a preparation method of the conductive silver paste and a product containing the conductive silver paste.
Background
The theoretical efficiency of the heterojunction solar cell can reach 28%, which is much higher than that of the conventional PERC crystalline silicon solar cell, and thus the solar cell becomes one of the development directions of the next generation solar cell. At present, the content of silver in conductive silver paste for a heterojunction solar cell is generally more than 85%, and compared with a conventional PERC crystalline silicon solar cell, the usage amount of silver is increased by about 1 time, and the production cost is increased.
In view of the above problems, in the prior art, silver-coated copper powder is generally used to replace silver powder to prepare conductive silver paste for heterojunction solar cells. However, when the conductive silver paste is prepared by using the silver-coated copper powder, the copper powder is easily partially oxidized, so that the resistance of the heterojunction battery is obviously increased. Therefore, it is very critical to prepare an electrode paste having high oxidation resistance and capable of reducing the cost.
Disclosure of Invention
The invention aims to provide a conductive silver paste for a heterojunction battery, a preparation method thereof and a product containing the conductive silver paste, which can improve the oxidation resistance of electrode paste, reduce the consumption of silver and reduce the cost.
In a first aspect, the invention provides an electrode paste, which comprises a silver-based conductive material and a carbon nanotube, wherein the silver-based conductive material is filled in a tube cavity of the carbon nanotube, the tube diameter of the carbon nanotube is 2 nm-200 nm, and the specific surface area of the carbon nanotube is 60m 2 /g～1200m 2 /g。
Compared with the prior art, the electrode slurry provided by the invention has the following advantages:
the electrode slurry provided by the invention comprises the silver-based conductive material and the carbon nano tube, and the carbon nano tube mainly comprises a plurality of layers to tens of layers of coaxial circular tubes formed by the carbon atoms arranged in a hexagon shape, so that when the silver-based conductive material and the carbon nano tube are mixed, the silver-based conductive material can be filled in the tube diameter of the carbon nano tube. At this time, because the carbon nanotube has a high boiling point and good toughness, oxidation hardly occurs no matter under high temperature and high pressure or other severe conditions, so that when the silver-based conductive material is filled in the tube diameter of the carbon nanotube, the silver-based conductive material can be well protected under the action of the carbon nanotube, thereby making the electrodeThe slurry has a strong oxidation resistance. Meanwhile, the carbon nano tube has the same lamellar structure with the graphite, so the carbon nano tube has good electrical property, and when the silver-based conductive material is filled in the tube diameter of the carbon nano tube, the electrode slurry provided by the invention has good conductivity. Moreover, when the tube diameter of the carbon nano tube is 2 nm-200 nm, the specific surface area is 60m 2 /g～1200m 2 And when the conductive paste is used for coating the conductive material, the silver-based conductive material can be filled more fully, and the contact area of the silver-based conductive material and the surface of the carbon nano tube is larger, so that the conductivity of the electrode paste is enhanced. At this time, since the silver-based conductive material is filled in the carbon nanotube, the carbon nanotube can be used to replace a part of the silver-based conductive material, thereby reducing the usage amount of the silver-based conductive material and reducing the cost.
Therefore, the electrode paste provided by the invention can improve the oxidation resistance of the electrode paste and reduce the consumption of silver and the cost in the battery manufacturing process.
In a second aspect, the present invention also provides a method for preparing an electrode paste, comprising:
mixing a vinyl compound and a photoinitiator to obtain an organic carrier;
and mixing the organic carrier with a silver-based conductive material and carbon nanotubes 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 further provides an electrode plate, which comprises the electrode slurry provided by the invention.
Compared with the prior art, the electrode sheet provided by the invention comprises the electrode slurry provided by the invention, so that the beneficial effects are the same as those of the electrode slurry in the first aspect, and the details are not repeated here.
In a fourth aspect, the invention also provides a photovoltaic cell comprising 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 clearly apparent, the present invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not 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 implicitly indicating 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), 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 cell can reach 28%, which is much higher than that of the conventional crystalline silicon solar cell, the heterojunction cell becomes one of the development directions of the next generation solar cell.
The silver content of the conductive silver paste for the commercial heterojunction cell is generally more than 85%, and compared with the conventional PERC crystalline silicon solar cell, the usage amount of silver is increased by about 1 time. Therefore, reducing the silver consumption of the heterojunction battery is a research hotspot in the field, and the mainstream technology at present is to replace pure silver powder by silver-coated copper powder. However, when the conductive silver paste is prepared by using the silver-coated copper powder, the copper powder is easily oxidized partially, so that the resistance of the heterojunction battery is obviously increased, and the efficiency of the heterojunction battery is reduced.
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 oxidation resistance of an electrode paste, reduce the amount of silver used, and reduce cost. 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: silver-based conductive material and carbon nano tube, wherein the silver-based conductive material is filled in the tube cavity of the carbon nano tube, and the tube diameter of the carbon nano tube is 2 nm-200nm, the specific surface area of the carbon nano tube is 60m 2 /g～1200m 2 The length of the carbon nano tube is 1-5 mu m.
The electrode slurry provided by the invention comprises the silver-based conductive material and the carbon nano tubes, and the carbon nano tubes mainly comprise carbon atoms which are arranged in a hexagon to form a plurality of layers to dozens of layers of coaxial circular tubes, so when the silver-based conductive material and the carbon nano tubes are mixed, the silver-based conductive material can be filled in the tube diameters of the carbon nano tubes. At this time, because the carbon nanotube has a high boiling point and good toughness, oxidation hardly occurs no matter under high temperature and high pressure or other severe conditions, so that when the silver-based conductive material is filled in the tube diameter of the carbon nanotube, the silver-based conductive material can be well protected under the action of the carbon nanotube, thereby enabling the electrode paste to have strong oxidation resistance. Meanwhile, the carbon nano tube has the same lamellar structure as the graphite, so the carbon nano tube has good electrical property, and when the silver-based conductive material is filled in the tube diameter of the carbon nano tube, the electrode slurry provided by the invention has good conductivity. Moreover, when the tube diameter of the carbon nano tube is 2nm to 200nm, the specific surface area is 60m 2 /g～1200m 2 And g, when the length of the carbon nano tube is 1-5 mu m, the silver-based conductive material can be filled more fully, and the contact area of the silver-based conductive material and the surface of the carbon nano tube is larger, so that the conductivity of the electrode slurry is enhanced. At this time, since the silver-based conductive material is filled in the carbon nanotube, the carbon nanotube can be used to replace a part of the silver-based conductive material, thereby reducing the usage amount of the silver-based conductive material and reducing the cost.
Therefore, the electrode paste provided by the invention can improve the oxidation resistance of the electrode paste and reduce the consumption of silver and the cost in the battery manufacturing process.
In an optional manner, the electrode paste of the embodiment of the present invention further includes an organic carrier, the organic carrier is a liquid, the organic carrier includes a vinyl compound and a photoinitiator, and a mass ratio of the vinyl compound to the photoinitiator is (70 to 99): (1-30). The electrode slurry provided by the invention comprises an organic carrier, wherein the organic carrier is liquid, so that the carbon nano tubes can be uniformly dispersed in the organic carrier, the organic carrier comprises a vinyl compound and a photoinitiator, and the photoinitiator can absorb energy with a certain wavelength under the irradiation of ultraviolet light and then generates chemical change to generate free radicals or cations, so that the vinyl compound contained in the organic carrier is subjected to chain polymerization under the action of the free radicals or the cations to be rapidly crosslinked and cured. Meanwhile, when the organic carrier is crosslinked and cured, the carbon nano tubes and the silver-based conductive material filled in the carbon nano tubes can be crosslinked and cured at the same time as the carbon nano tubes are dispersed in the organic carrier, so that the oxidation resistance of the electrode slurry is improved. In the examples of the present invention, the mass ratio of the vinyl compound to the photoinitiator was (70 to 99): (1-30), the crosslinking curing reaction of the vinyl compound and the mercapto compound can be initiated by using a small amount of photoinitiator, so that the using amount of the photoinitiator is reduced, and the manufacturing cost is reduced.
In an achievable mode, the mass ratio of the silver-based conductive material, the carbon nanotubes and the organic carrier in the electrode paste of the embodiment of the invention is (30-75): (0.1-20): (10-69.9). Under the proportion, the silver-based conductive material can be fully filled in the carbon nano tube, and the carbon nano tube can be uniformly dispersed in the organic carrier, so that the carbon nano tube filled with the silver-based conductive material can be simultaneously cured when the organic carrier is crosslinked and cured. Meanwhile, the carbon nano tube has strong oxidation resistance, so that on one hand, when the silver-based conductive material is filled in the tube cavity of the carbon nano tube, the oxidation resistance of the silver-based conductive material can be improved. On the other hand, the carbon nanotubes dispersed in the organic vehicle may also improve the oxidation resistance of the electrode paste according to the embodiment of the present invention.
Illustratively, the carbon nanotubes of embodiments of the present invention may include at least one of single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes, among other types of carbon nanotubes.
In an alternative, the vinyl compound in the organic vehicle of the embodiment of the present invention includes at least two of modified epoxy resin, modified urethane resin, epoxy acrylate, methyl methacrylate, butyl methacrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate. The carbon-carbon double bonds contained in at least two vinyl compounds of the embodiment of the invention are subjected to chain polymerization under the action of the photoinitiator, so that the crosslinking and curing are rapid. The modified epoxy resin and polyurethane resin have good toughness and low-temperature curing performance, and the toughness and low-temperature curing performance of the organic carrier can be enhanced, so that the electrode slurry can be cured under a low-temperature condition without heating and sintering, and the cured electrode has strong toughness and is not easy to crack.
Illustratively, the photoinitiator of the embodiments of the present invention includes at least one of 1-hydroxy-cyclohexyl-phenyl-methanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and benzoin dimethyl ether.
In an optional mode, the silver-based conductive material implemented by the invention comprises spherical silver powder and flake silver powder, the particle size of the spherical silver powder is 0.1-5 μm, and the specific surface area of the spherical silver powder is less than 1.5m 2 The particle diameter of the flake silver powder is 0.1-4 mu m, and the specific surface area of the flake silver powder is less than 1m 2 The mass ratio of the spherical silver powder to the flake silver powder is (3-7): (7-3). The spherical silver powder in the embodiment of the invention is in point-to-point contact, the contact area is relatively small, the flaky silver powder contains a large amount of surface-to-surface contact or surface-to-surface contact, 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 flake silver powder is in the above range, the spherical silver powder can fill the gaps between the flake silver powders, so that the original adjacent flake silver powders which are not in contact are in contact with each other, a conductive path is increased, and the conductivity is improved.
Illustratively, the electrode paste of the examples of the present invention has a fineness of 5 μm or less and a viscosity of 100 to 300Pa · S. When the fineness and the viscosity of the electrode slurry are within the range, the problem of difficult stirring caused by excessive viscosity of the slurry can be avoided in the production and processing process, so that the good printing performance can be ensured, the problem that the viscosity is too low to cause sedimentation of suspended particles, the uniformity and the stability of the slurry are not facilitated can be avoided, and the curing rate is improved.
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 mixing the silver-based conductive material and the carbon nano tube to obtain the mixed conductive material.
For example: and mixing the silver-based conductive material and the carbon nano tube to enable the silver-based conductive material to be filled in the tube cavity of the carbon nano tube, so as to obtain the mixed conductive material.
Step 202: and mixing the mixed conductive material, a vinyl compound and a photoinitiator to obtain the electrode slurry.
For example: mixing the mixed conductive material, vinyl compound and photoinitiator, stirring, rolling on a three-roll mill, further dispersing and homogenizing, and obtaining the electrode slurry when the fineness of a scraper of the three-roll mill is less than 5 mu m. Meanwhile, the viscosity at a rotation speed of 10rmp is measured at room temperature of 25 ℃ using a Brookfield viscometer to be 100 Pa.S to 300 Pa.S.
The electrode slurry provided by the invention comprises the silver-based conductive material and the carbon nano tube, and the carbon nano tube mainly comprises a plurality of layers to tens of layers of coaxial circular tubes formed by the carbon atoms arranged in a hexagon shape, so that when the silver-based conductive material and the carbon nano tube are mixed, the silver-based conductive material can be filled in the tube diameter of the carbon nano tube. At this time, because the carbon nanotube has a high boiling point and good toughness, oxidation hardly occurs no matter under high temperature and high pressure or other severe conditions, so that when the silver-based conductive material is filled in the tube diameter of the carbon nanotube, the silver-based conductive material can be well protected under the action of the carbon nanotube, thereby enabling the electrode paste to have strong oxidation resistance. Meanwhile, because the carbon nano tube has the same lamellar structure with the graphite, the carbon nano tube has good electrical property, when the silver-based conductive material is filled in the tube diameter of the carbon nano tube,therefore, the electrode slurry provided by the invention has good conductivity. Moreover, when the tube diameter of the carbon nano tube is 2nm to 200nm, the specific surface area is 60m 2 /g～1200m 2 And g, when the length of the carbon nano tube is 1-5 mu m, the silver-based conductive material can be filled more fully, and the contact area of the silver-based conductive material and the surface of the carbon nano tube is larger, so that the conductivity of the electrode slurry is enhanced. At this time, since the silver-based conductive material is filled in the carbon nanotube, the carbon nanotube can be used to replace a part of the silver-based conductive material, thereby reducing the usage amount of the silver-based conductive material and reducing the cost.
Therefore, the electrode slurry provided by the invention can improve the oxidation resistance of the electrode slurry and reduce the consumption of silver and the cost in the manufacturing process of the battery.
In the electrode slurry provided by the embodiment of the invention, a small amount of photoinitiator can be used for initiating the vinyl compound to generate a crosslinking curing reaction, so that the using amount of the photoinitiator is reduced, and the manufacturing cost is reduced. In addition, the electrode slurry provided by the embodiment of the invention can be cured without adding a solvent, so that the damage to the health of workers and the damage to the environment can be reduced in the production process of the heterojunction solar cell.
In order to verify the effects of the electrode paste provided in the examples of the present invention, the examples of the present invention were demonstrated by comparing the examples with comparative examples.
Example one
The electrode slurry provided by the embodiment of the invention comprises the following components in parts by weight: 30 parts by weight of spherical silver powder (average particle diameter D50=1.5 μm, specific surface area 0.2 m) 2 /g) 40 parts by weight of a plate-like silver powder (average particle diameter D50=3.5 μm, specific surface area 0.8m 2 Per g), 10 parts by weight of single-walled carbon nanotubes (5 nm in diameter and 100m in specific surface area) 2 G, average length 5 μm), 16 parts by weight of 1, 6-hexanediol diacrylate, 2 parts by weight of epoxy acrylate (type: CN104NS, manufactured by sartomer company) and 2 parts by weight of 1-hydroxy-cyclohexyl-phenyl-methanone.
The preparation method of the electrode slurry provided by the embodiment of the invention comprises the following steps:
firstly, preparing a mixed conductive material: and fully mixing 30 parts by weight of spherical silver powder, 40 parts by weight of flaky silver powder and 10 parts by weight of single-walled carbon nanotubes to obtain the mixed conductive material.
Step two, preparing an organic carrier: mixing 16 parts by weight of 1, 6-hexanediol diacrylate, 2 parts by weight of epoxy acrylate and 2 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone, and uniformly stirring to obtain the organic carrier.
Step three, preparing electrode slurry: and fully mixing and stirring the mixed conductive material and the organic carrier uniformly, and placing the mixed electrode slurry on a three-roll mill for dispersion grinding to prepare the electrode slurry.
And fourthly, performing viscosity test and resistivity test on the electrode slurry, and testing the viscosity value at 2 minutes by using a Brookfield viscometer at the rotating speed of 10 revolutions per minute. And testing the resistance at two ends of the solidified electrode body by adopting a four-probe ohmmeter. Then, using a solar simulator, at 25 deg.C, M1.5 spectrum, 1.000KW/M 2 The electrical properties of the electrode paste were tested under the conditions. Then the electrode slurry was irradiated with a mercury lamp with a power of 60W/cm for not more than 1min.
Example two
The electrode slurry provided by the embodiment of the invention comprises the following components in parts by weight: 60 parts by weight of spherical silver powder (average particle diameter D50=1.5 μm, specific surface area 0.2 m) 2 /g) 10 parts by weight of a plate-like silver powder (average particle diameter D50=3.5 μm, specific surface area 0.8m 2 Per g), 10 parts by weight of single-walled carbon nanotubes (tube diameter of 10nm, specific surface area of 200 m) 2 G, average length 5 μm), 16 parts by weight of 1, 6-hexanediol diacrylate, 2 parts by weight of epoxy acrylate (type: CN104NS, manufactured by sartomer corporation) and 1 part by weight of 1-hydroxy-cyclohexyl-phenyl-methanone.
The preparation method of the electrode slurry provided by the embodiment of the invention comprises the following steps:
firstly, preparing a mixed conductive material: and fully mixing 60 parts by weight of spherical silver powder, 10 parts by weight of flake silver powder and 10 parts by weight of single-walled carbon nanotubes to obtain the mixed conductive material.
Secondly, preparing an organic carrier: mixing 16 parts by weight of 1, 6-hexanediol diacrylate, 2 parts by weight of epoxy acrylate and 1 part by weight of 1-hydroxy-cyclohexyl-phenyl-methanone, and stirring the mixture uniformly to obtain the organic carrier.
Step three, preparing electrode slurry: and adding the mixed conductive material into the organic carrier, fully and uniformly stirring, and placing the mixed electrode slurry on a three-roll mill for dispersion and grinding to prepare the electrode slurry.
And fourthly, performing viscosity test and resistivity test on the electrode slurry, and testing the viscosity value at 2 minutes by using a Brookfield viscometer at a rotating speed of 10 revolutions per minute. And testing the resistance at two ends of the solidified electrode body by adopting a four-probe ohmmeter. Then, using a solar simulator, at 25 deg.C, M1.5 spectrum, 1.000KW/M 2 The electrical properties of the electrode paste were tested under the conditions. Then the electrode slurry was irradiated with a mercury lamp with a power of 60W/cm for not more than 1min.
EXAMPLE III
The electrode slurry provided by the embodiment of the invention comprises the following components in parts by mass: 30 parts by weight of spherical silver powder (average particle diameter D50=1.5 μm, specific surface area 0.2 m) 2 /g) 30 parts by weight of a plate-like silver powder (average particle diameter D50=3.5 μm, specific surface area 0.8m 2 G) 15 parts by weight of single-walled carbon nanotubes (the tube diameter is 5nm, and the specific surface area is 100m 2 G, average length 5 μm), 20 parts by weight of 1, 6-hexanediol diacrylate, 4 parts by weight of epoxy acrylate (type: CN104NS, manufactured by sartomer) and 1 part by weight of 1-hydroxy-cyclohexyl-phenyl-methanone.
The preparation method of the electrode slurry provided by the third embodiment of the invention comprises the following steps:
firstly, preparing a mixed conductive material: and fully mixing 30 parts by weight of spherical silver powder, 30 parts by weight of flaky silver powder and 15 parts by weight of single-walled carbon nanotubes to obtain the mixed conductive material.
Secondly, preparing an organic carrier: mixing 20 parts by weight of 1, 6-hexanediol diacrylate, 4 parts by weight of epoxy acrylate and 1 part by weight of 1-hydroxy-cyclohexyl-phenyl-ketone, and uniformly stirring to obtain the organic carrier.
Step three, preparing electrode slurry: and adding the mixed conductive material into the organic carrier, fully and uniformly stirring, and placing the mixed electrode slurry on a three-roll mill for dispersion grinding to prepare the electrode slurry.
And fourthly, performing viscosity test and resistivity test on the electrode slurry, and testing the viscosity value at 2 minutes by using a Brookfield viscometer at the rotating speed of 10 revolutions per minute. And testing the resistance at two ends of the solidified electrode body by adopting a four-probe ohmmeter. Then, using a solar simulator, at 25 deg.C, M1.5 spectrum, 1.000KW/M 2 The electrical properties of the electrode paste were tested under the conditions. Then the electrode slurry was irradiated with a mercury lamp with a power of 60W/cm for not more than 1min.
Example four
The electrode slurry provided by the embodiment of the invention comprises the following components in parts by weight: 60 parts by weight of spherical silver powder (average particle diameter D50=1.5 μm, specific surface area 0.2 m) 2 /g) 40 parts by weight of a plate-like silver powder (average particle diameter D50=3.5 μm, specific surface area 0.8m 2 /g) 20 parts by weight of single-walled carbon nanotubes (tube diameter of 2nm, specific surface area of 60 m) 2 G, average length 1 μm), 25 parts by weight of methyl methacrylate, 6 parts by weight of epoxy acrylate (type: CN104NS, manufactured by sartomer corporation) and 2 parts by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone.
The preparation method of the electrode slurry provided by the fourth embodiment of the invention comprises the following steps:
firstly, preparing a mixed conductive material: and fully mixing 60 parts by weight of spherical silver powder, 40 parts by weight of flaky silver powder and 20 parts by weight of single-walled carbon nanotubes to obtain the mixed conductive material.
Secondly, preparing an organic carrier: mixing 25 parts by weight of methyl methacrylate, 6 parts by weight of epoxy acrylate and 2 parts by weight of 2-hydroxy-2-methyl-1-phenyl-1-acetone, and uniformly stirring to obtain the organic carrier.
Step three, preparing electrode slurry: and adding the mixed conductive material into the organic carrier, fully and uniformly stirring, and placing the mixed electrode slurry on a three-roll mill for dispersion grinding to prepare the electrode slurry.
And fourthly, performing viscosity test and resistivity test on the electrode slurry, and testing the viscosity value at 2 minutes by using a Brookfield viscometer at the rotating speed of 10 revolutions per minute. And testing the resistance at two ends of the solidified electrode body by adopting a four-probe ohmmeter. Then, using a solar simulator, at 25 deg.C, M1.5 spectrum, 1.000KW/M 2 The electrical properties of the electrode paste were tested under the conditions. Then the electrode slurry was irradiated with a mercury lamp with a power of 60W/cm for not more than 1min.
EXAMPLE five
The electrode slurry provided by the embodiment of the invention comprises the following components in parts by mass: 70 parts by weight of spherical silver powder (average particle diameter D50=1.5 μm, specific surface area 0.2 m) 2 /g) 30 parts by weight of a plate-like silver powder (average particle diameter D50=3.5 μm, specific surface area 0.8m 2 /g) 18 parts by weight of single-walled carbon nanotubes (tube diameter of 2nm, specific surface area of 60 m) 2 G, average length 1 μm), 20 parts by weight of methyl methacrylate, 6 parts by weight of epoxy acrylate (type: CN104NS, manufactured by sartomer) and 2 parts by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone.
The preparation method of the electrode slurry provided by the fifth embodiment of the invention comprises the following steps:
firstly, preparing a mixed conductive material: and fully mixing 70 parts by weight of spherical silver powder, 30 parts by weight of flake silver powder and 18 parts by weight of single-walled carbon nanotubes to obtain the mixed conductive material.
Secondly, preparing an organic carrier: mixing 20 parts by weight of butyl methacrylate, 6 parts by weight of epoxy acrylate and 2 parts by weight of 2-hydroxy-2-methyl-1-phenyl-1-acetone, and uniformly stirring to obtain the organic carrier.
Step three, preparing electrode slurry: and adding the mixed conductive material into the organic carrier, fully and uniformly stirring, and placing the mixed electrode slurry on a three-roll mill for dispersion and grinding to prepare the electrode slurry.
Fourthly, the electrode slurry is subjected to viscosity test and resistivity test by using Brookfield viscometer at 10 rpmRotational speed, viscosity value at 2 minutes was measured. And testing the resistance at two ends of the solidified electrode body by adopting a four-probe ohmmeter. Then, using a solar simulator, at 25 deg.C, M1.5 spectrum, 1.000KW/M 2 The electrical properties of the electrode paste were tested under the conditions. Then the electrode slurry was irradiated with a mercury lamp with a power of 60W/cm for not more than 1min.
Example six
The electrode slurry provided by the embodiment of the invention comprises the following components in parts by weight: 70 parts by weight of spherical silver powder (average particle diameter D50=1.5 μm, specific surface area 0.2 m) 2 (g)/g) 30 parts by weight of a plate-like silver powder (average particle diameter D50=3.5 μm, specific surface area 0.8m 2 (g)) 15 parts by weight of double-walled carbon nanotubes (20 nm in diameter and 200m in specific surface area 2 G, average length 2 μm), 20 parts by weight of a modified urethane resin, 8 parts by weight of an epoxy acrylate (type: CN104NS, manufactured by sartomer company) and 2 parts by weight of benzoin dimethyl ether.
The preparation method of the electrode slurry provided by the sixth embodiment of the invention comprises the following steps:
firstly, preparing a mixed conductive material: and (3) fully mixing 70 parts by weight of spherical silver powder, 30 parts by weight of flake silver powder and 15 parts by weight of double-walled carbon nano tube to obtain the mixed conductive material.
Secondly, preparing an organic carrier: and (3) mixing 20 parts by weight of modified polyurethane resin and 8 parts by weight of benzoin dimethyl ether of epoxy acrylate, and uniformly stirring to obtain the organic carrier.
Step three, preparing electrode slurry: and adding the mixed conductive material into the organic carrier, fully and uniformly stirring, and placing the mixed electrode slurry on a three-roll mill for dispersion grinding to prepare the electrode slurry.
And fourthly, performing viscosity test and resistivity test on the electrode slurry, and testing the viscosity value at 2 minutes by using a Brookfield viscometer at a rotating speed of 10 revolutions per minute. And testing the resistance at two ends of the solidified electrode body by adopting a four-probe ohmmeter. Then, using a solar simulator, at 25 deg.C, M1.5 spectrum, 1.000KW/M 2 The electrical properties of the electrode slurry were tested under the conditions. Then using power of 60W/cmThe mercury lamp irradiates the electrode slurry for no more than 1min.
EXAMPLE seven
The electrode slurry provided by the embodiment of the invention comprises the following components in parts by weight: 40 parts by weight of spherical silver powder (average particle diameter D50=1.5 μm, specific surface area 0.2 m) 2 (g)/g) 60 parts by weight of a plate-like silver powder (average particle diameter D50=3.5 μm, specific surface area 0.8m 2 Per gram) 16 parts by weight of multi-walled carbon nanotubes (the tube diameter is 50nm, the specific surface area is 500m 2 G, average length 5 μm), 30 parts by weight of butyl methacrylate, 10 parts by weight of epoxy acrylate (type: CN104NS, manufactured by sartomer corporation) and 1 part by weight of benzoin dimethyl ether.
The preparation method of the electrode slurry provided by the seventh embodiment of the invention comprises the following steps:
step one, preparing a mixed conducting material: and (2) fully mixing 40 parts by weight of spherical silver powder, 60 parts by weight of flaky silver powder and 16 parts by weight of multi-wall carbon nano tubes to obtain the mixed conductive material.
Secondly, preparing an organic carrier: and mixing 30 parts by weight of butyl methacrylate, 10 parts by weight of epoxy acrylate and 1 part by weight of benzoin dimethyl ether, and uniformly stirring to obtain the organic carrier.
Step three, preparing electrode slurry: and adding the mixed conductive material into the organic carrier, fully and uniformly stirring, and placing the mixed electrode slurry on a three-roll mill for dispersion and grinding to prepare the electrode slurry.
And fourthly, performing viscosity test and resistivity test on the electrode slurry, and testing the viscosity value at 2 minutes by using a Brookfield viscometer at the rotating speed of 10 revolutions per minute. And testing the resistance at two ends of the solidified electrode body by adopting a four-probe ohmmeter. Then, using a solar simulator, at 25 deg.C, M1.5 spectrum, 1.000KW/M 2 The electrical properties of the electrode slurry were tested under the conditions. Then the electrode slurry was irradiated with a mercury lamp with a power of 60W/cm for not more than 1min.
Example eight
The electrode slurry provided by the embodiment of the invention comprises the following components in parts by mass: 50 parts by weight of a spherical silver powder (average particle diameter D50=1.5 μm,specific surface area 0.2m 2 /g) of silver flakes, 50 parts by weight of a plate-like silver powder (average particle diameter D50=3.5 μm, specific surface area 0.8m 2 (g) 8 parts by weight of multi-walled carbon nanotubes (the tube diameter is 50nm, the specific surface area is 500 m) 2 /g, average length 2.5 μm), 25 parts by weight of trimethylolpropane triacrylate, 6 parts by weight of methyl methacrylate and 1 part by weight of benzoin bismethyl ether.
The preparation method of the electrode slurry provided by the eighth embodiment of the invention comprises the following steps:
firstly, preparing a mixed conductive material: and fully mixing 50 parts by weight of spherical silver powder, 50 parts by weight of flaky silver powder and 15 parts by weight of multi-wall carbon nano tube to obtain the mixed conductive material.
Step two, preparing an organic carrier: mixing 25 parts by weight of trimethylolpropane triacrylate, 6 parts by weight of methyl methacrylate and 1 part by weight of benzoin dimethyl ether, and stirring uniformly to obtain the organic vehicle.
Step three, preparing electrode slurry: and adding the mixed conductive material into the organic carrier, fully and uniformly stirring, and placing the mixed electrode slurry on a three-roll mill for dispersion and grinding to prepare the electrode slurry.
And fourthly, performing viscosity test and resistivity test on the electrode slurry, and testing the viscosity value at 2 minutes by using a Brookfield viscometer at the rotating speed of 10 revolutions per minute. And testing the resistance at two ends of the solidified electrode body by adopting a four-probe ohmmeter. Then, using a solar simulator, at 25 deg.C, M1.5 spectrum, 1.000KW/M 2 The electrical properties of the electrode paste were tested under the conditions. Then the electrode slurry was irradiated with a mercury lamp with a power of 60W/cm for not more than 1min.
Comparative example 1
Comparative example one of the present invention, using a uv-cured high silver conductive silver-containing paste as a comparative electrode paste, comprises: 30 parts by weight of spherical silver powder (average particle diameter D50=1.5 μm, specific surface area 0.2 m) 2 (g)/g) and 60 parts by weight of a plate-like silver powder (average particle diameter D50=3.5 μm, specific surface area 0.8m 2 (g)), 6 parts by weight of 1, 6-hexanediol diacrylate, 3 parts by weight of epoxy acrylate (type: CN104NS, saedoma CorpProduction), 1 part by weight of 1-hydroxy-cyclohexyl-phenyl-methanone.
The preparation process of the heterojunction battery formed by the electrode paste provided by the first comparative example of the invention is as follows:
firstly, cleaning a silicon wafer for texturing.
Step two, amorphous silicon deposition: the intrinsic amorphous silicon film and the P-type amorphous silicon film are prepared by adopting an amorphous silicon front PECVD method, and the intrinsic amorphous silicon film and the N-type amorphous silicon film are prepared by adopting a back PECVD method.
And thirdly, depositing a transparent conductive film, and depositing transparent conductive oxide films on two sides by a sputtering method.
Fourthly, screen printing low-temperature curing electrode paste.
Fifthly, irradiating the electrode slurry for no more than 1min by using a mercury lamp with the power of 60W/cm to obtain the heterojunction cell.
The test results of the electrode pastes provided in the present example and comparative example are as follows:
as can be seen from the above table, the silver conductive material, the carbon nanotubes, and the organic vehicle, which contains at least two vinyl compounds and the photoinitiator, were uniformly mixed in the examples one to six, while the comparative example one did not contain the carbon nanotubes of the inventive examples. The silver content of the first to eighth examples is much lower than that of the first comparative example, the oxidation resistance is better than that of the electrode paste of the first comparative example, and the cell conversion efficiency is higher than that of the electrode paste of the first comparative example. Therefore, in the electrode paste provided by the embodiment of the invention, the photoinitiator is used for initiating at least two vinyl compounds to carry out curing crosslinking reaction, the silver-based conductive material is filled in the carbon nano tubes, and the carbon nano tubes are uniformly dispersed in the organic carrier, so that the vinyl compounds contained in the organic carrier are subjected to chain polymerization under the action of free radicals or cations, and thus, the rapid crosslinking curing can be realized, the curing time is less than 1min, the curing temperature is less than 50 ℃, and the silver content in the electrode paste is greatly reduced. Moreover, the carbon nanotube has good oxidation resistance and electrical property, and when the silver-based conductive material is filled in the pipe diameter of the carbon nanotube, the carbon nanotube can be used for replacing part of the silver-based conductive material, so that the electrode slurry provided by the invention has good conductivity, the oxidation resistance of the electrode slurry can be improved, the consumption of silver can be reduced, and the cost can be 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. The electrode slurry is characterized by comprising a silver-based conductive material and carbon nano tubes, wherein the silver-based conductive material is filled in tube cavities of the carbon nano tubes, the tube diameters of the carbon nano tubes are 2-200 nm, and the specific surface areas of the carbon nano tubes are 60m 2 /g～1200m 2 /g。
2. The electrode slurry according to claim 1, further comprising an organic vehicle, wherein the organic vehicle is a liquid, and the organic vehicle comprises a vinyl compound and a photoinitiator.
3. The electrode slurry according to claim 2, wherein the mass ratio of the vinyl compound to the photoinitiator is (70 to 99): (1-30), the mass ratio of the silver-based conductive material, the carbon nano tube and the organic carrier is (30-75): (0.1-20): (10-69.9).
4. The electrode slurry of claim 1, wherein the carbon nanotubes comprise at least one of single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes.
5. The electrode slurry according to claim 1, wherein the vinyl compound includes at least two of a vinyl resin and an acrylate compound.
6. The electrode slurry according to claim 5, wherein the vinyl resin comprises a modified epoxy resin and a modified polyurethane resin; the acrylate compound includes epoxy acrylate, methyl methacrylate, butyl methacrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate.
7. The electrode slurry of claim 1, wherein the photoinitiator comprises at least one of 1-hydroxy-cyclohexyl-phenyl-methanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and benzoin dimethyl ether.
8. The electrode slurry according to any one of claims 1 to 7, wherein the silver-based conductive material comprises spherical silver powder having a particle diameter of 0.1 to 5 μm and flake silver powder having a specific surface area of less than 1.5m 2 The particle diameter of the flake silver powder is 0.1-4 mu m, and the specific surface area of the flake silver powder is less than 1m 2 The mass ratio of the spherical silver powder to the flake silver powder is (3-7): (7-3), the fineness of the electrode slurry is less than 5 μm, and the viscosity is 100Pa & S-300 Pa & S.
9. A method for preparing the electrode slurry according to any one of claims 1 to 8, comprising:
mixing the silver-based conductive material and the carbon nano tube to obtain a mixed conductive material;
and mixing the mixed conductive material, a vinyl compound and a photoinitiator 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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