CN115910422B - Conductive silver paste and preparation method and application thereof - Google Patents
Conductive silver paste and preparation method and application thereof Download PDFInfo
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- CN115910422B CN115910422B CN202211624190.5A CN202211624190A CN115910422B CN 115910422 B CN115910422 B CN 115910422B CN 202211624190 A CN202211624190 A CN 202211624190A CN 115910422 B CN115910422 B CN 115910422B
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Abstract
The application discloses a conductive silver paste, a preparation method and application thereof, wherein the conductive silver paste comprises the following components: silver powder, glass powder, silicon-containing organic high polymer and organic carrier; the glass frit comprises the following components ：Bi2O3、SnO、SiO2、B2O3、Nb2O5、CuO、MnO2、 alkali metal oxides. The glass powder adopted by the application can reduce the resistivity of a glass system, reduce the contact resistance of a silver-aluminum area, stabilize the glass state and reduce the reactivity of the silver-aluminum area; the silicon-containing organic polymer added in the silver powder is sintered to deposit a silver-aluminum region, so that the aluminum paste is prevented from being corroded in an enlarged manner, and the recombination of the silver-aluminum region can be obviously reduced; the organic carrier provides good dispersion for glass powder and silicon-containing organic high polymer, so that silver paste is more uniform, organic residue in the sintering process is less, and contact resistance of silver-aluminum areas is lower.
Description
Technical Field
The invention relates to the technical field of conductive silver paste, in particular to conductive silver paste and a preparation method and application thereof.
Background
In recent years, the gradual downward adjustment of photovoltaic patches is reducing the cost and enhancing the efficiency of enterprises, the price of photovoltaic cells is one-way landslide, and the photovoltaic enterprises face new challenges. As the market grows to mature and then declines, the 'cost reduction and effect improvement' is a necessary requirement for market development, and is also in agreement with the final goal of future low-price surfing of photovoltaic power generation. The cost is reduced mainly by the way of reducing solid content and unit consumption. For the silver paste on the back side, the reduction of the solid content ensures good welding effect, but the corrosion to the passivation film is improved, and the composition is larger, which causes the risk of reducing the electrical performance. However, if the corrosion of the silver-aluminum region is reduced, the recombination is reduced, which causes the contact resistance of the region to increase, so that the series resistance Rs increases, the fill factor FF decreases, and the electrical performance is lost.
Disclosure of Invention
The primary purpose of the present invention is to overcome the disadvantages and shortcomings of the prior art and provide a conductive silver paste.
Another object of the present invention is to provide a method for preparing the above conductive silver paste.
It is still another object of the present invention to provide the use of the above conductive silver paste.
The aim of the invention is achieved by the following technical scheme: the conductive silver paste comprises the following components in parts by weight: 40 to 70 parts of silver powder, 0.1 to 5 parts of glass powder, 0.1 to 1 part of silicon-containing organic high polymer and 20 to 40 parts of organic carrier;
The glass powder comprises the following components in parts by weight: 20 to 60 parts of Bi 2O3, 1 to 10 parts of SnO, 10 to 40 parts of SiO 2, 1 to 10 parts of B 2O3, 0.1 to 5 parts of Nb 2O5, 5 to 15 parts of CuO, 5 to 10 parts of MnO 2 and 0.1 to 5 parts of alkali metal oxide.
Preferably, the silver powder is microcrystalline silver powder.
Preferably, the particle size D50 of the silver powder is 0.1-5 μm.
Preferably, the silicon-containing organic high polymer is at least one of polysiloxane and modified polysiloxane. The modified polysiloxane can be amino, polyether, epoxy, carboxyl, alcoholic hydroxyl and thio modified.
Preferably, the viscosity of the silicon-containing organic high polymer is 5 to 8,000,000cps.
The organic carrier is a mixture of resin, solvent and thixotropic agent; preferably, the resin is at least one of acrylic resin, modified acrylic resin, ethyl cellulose, cellulose acetate butyrate, cellulose acetate propionate, polyvinyl butyral, polyvinyl pyrrolidone; the solvent is at least one of diethylene glycol monobutyl ether, diethylene glycol butyl ether acetate, alcohol ester-12, alcohol ester-16, terpineol, tributyl citrate, acetyl tributyl citrate and turpentine.
The glass powder adopted in the application is lead-free glass powder, bi 2O3 is matched with SnO which also has a metal bridge effect, and the Bi 2O3 and the SnO are matched according to a certain proportion, so that the high-temperature viscosity of the glass is reduced, the softening fluidity of the glass powder is regulated, and the contact resistance of the glass is lower; siO 2 and B 2O3 are taken as frameworks of the glass structure, and the two are compounded in a certain proportion to realize the adjustment of the stability of the glass structure, so that lower corrosiveness is ensured; the welding tension and corrosiveness of the glass are regulated by the CuO, the MnO 2 and the Bi 2O3、SnO、SiO2 and the B 2O3 together, and the welding performance and corrosiveness of the glass are balanced, so that the glass has good welding performance and low corrosiveness; nb 2O5 and alkali metal oxide provide free charged particles for the glass structure, and add more non-bridging oxygen structures (NBO), so that the glass structure is looser, the resistivity of the glass system can be reduced after sintering, and the contact resistance of silver-aluminum areas can be further reduced; meanwhile, nb 2O5 is taken as a two-dimensional transition element, and reacts with alkali metal ions in an intercalation manner to jointly adjust the structural stability of the glass and properly reduce the reactivity of the glass.
The preparation method of the conductive silver paste comprises the following steps:
(1) Uniformly dispersing the components of the glass powder, smelting, carrying out water quenching, carrying out air flow grinding treatment on the obtained glass fragments, and sieving to obtain the glass powder;
(2) And (3) pre-dispersing the glass powder, silver powder, the silicon-containing organic high polymer and the organic carrier in the step (1), and grinding the glass powder, the silver powder and the silicon-containing organic high polymer until the fineness of the slurry is less than 5 mu m to obtain the conductive silver slurry.
Preferably, the smelting in the step (1) is to smelt the dispersed components at 1200-1500 ℃ for 60-90 min.
The application of the conductive silver paste in preparing a crystalline silicon solar cell.
Compared with the prior art, the invention has the following beneficial effects:
According to the application, bi 2O3、SnO、SiO2、B2O3、Nb2O5、CuO、MnO2 and alkali metal oxide are used as glass powder components, so that the resistivity of a glass system is reduced, the contact resistance of a silver-aluminum area is reduced, the glass state is stabilized, and the reactivity of the silver-aluminum area is reduced; by adding the silicon-containing organic high polymer into the conductive silver paste, the silver-aluminum area is deposited after sintering, so that the aluminum paste is prevented from being corroded in an expanding way, and the compounding of the silver-aluminum area can be obviously reduced; the organic carrier provides good dispersion effect for glass powder and silicon-containing organic high polymer, so that silver paste is more uniform, organic residue is less in the sintering process, and contact resistance of silver-aluminum areas is lower.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The experimental methods used in the examples and comparative examples are conventional methods unless otherwise specified, and materials, reagents and the like used, unless otherwise specified, are commercially available.
Example 1
The conductive silver paste comprises the following components in parts by weight: 40 parts of microcrystalline silver powder, 0.1 part of glass powder, 0.1 part of silicon-containing organic high polymer and 20 parts of organic carrier.
The glass powder comprises the following components in parts by weight: 20 parts of Bi 2O3, 1 part of SnO, 10 parts of SiO 2, 1 part of B 2O3, 0.1 part of Nb 2O5, 5 parts of CuO, 5 parts of MnO 2 and 0.1 part of K 2 O.
The D50 of the microcrystalline silver powder is 5 μm.
The silicon-containing organic high polymer is polysiloxane and has a viscosity of 6,000,000cps.
The organic carrier is a mixture of cellulose acetate butyrate, terpineol and thixotropic agent polyamide wax, and the mass ratio of the cellulose acetate butyrate, terpineol and thixotropic agent polyamide wax is 12:87:1.
The preparation method of the conductive silver paste comprises the following steps:
(1) Weighing the components of the glass powder according to the proportion, uniformly dispersing, and carrying out water quenching after high-temperature smelting to obtain glass fragments; and carrying out jet milling treatment on the fragments, and sieving to obtain the glass powder. The specific smelting process comprises the following steps: and (3) placing the dispersed components into an alumina crucible, and placing the alumina crucible into a resistance furnace for smelting for 70min at 1500 ℃.
(2) Adding microcrystalline silver powder, glass powder, a silicon-containing organic polymer premix and an organic carrier according to a formula, pre-dispersing by a planetary mixer, and grinding by a three-roller grinder until the fineness of the slurry is 3 mu m to obtain the conductive silver slurry.
The following examples were prepared by the same procedure as in example 1.
Example 2
The conductive silver paste comprises the following components in parts by weight: 70 parts of microcrystalline silver powder, 5 parts of glass powder, 1 part of silicon-containing organic high polymer and 40 parts of organic carrier;
The glass powder comprises the following components in parts by weight: 60 parts of Bi 2O3, 10 parts of SnO, 40 parts of SiO 2, 10 parts of B 2O3, 5 parts of Nb 2O5, 15 parts of CuO, 10 parts of MnO 2 and 5 parts of K 2 O.
The D50 of the microcrystalline silver powder is 0.1 μm.
The silicon-containing organic high polymer is polysiloxane and has a viscosity of 5,000,000cps.
The organic carrier is a mixture of ethyl cellulose, diethylene glycol butyl ether acetate and thixotropic agent polyamide wax, and the mass ratio of the ethyl cellulose to the diethylene glycol butyl ether acetate to the thixotropic agent polyamide wax is 5:88:7.
Example 3
The conductive silver paste comprises the following components in parts by weight: 50 parts of microcrystalline silver powder, 3 parts of glass powder, 0.5 part of silicon-containing organic high polymer and 30 parts of organic carrier;
The glass powder comprises the following components in parts by weight: 36 parts of Bi 2O3, 5 parts of SnO, 25 parts of SiO 2, 7 parts of B 2O3, 3 parts of Nb 2O5, 10 parts of CuO, 8 parts of MnO 2 and 3 parts of K 2 O.
The D50 of the microcrystalline silver powder is 0.5 μm.
The silicon-containing organic high polymer is polysiloxane and has a viscosity of 8,000,000cps.
The organic carrier is a mixture of acrylic resin, diethylene glycol monobutyl ether and thixotropic polyamide wax, and the mass ratio of the acrylic resin to the diethylene glycol monobutyl ether to the thixotropic polyamide wax is 25:70:5.
Examples 4 to 5
Examples 4 and 5 differ from example 3 in that the parts of the silicon-containing organic high polymer are 0.1 part and 1 part, respectively.
Examples 6 to 9
Examples 6-9 differ from example 3 in that the parts of Nb 2O5 are 0.1 part, 0.5 part, 1 part, 5 parts, respectively.
Comparative example 1
Comparative example 1 differs from example 3 in that the parts of Bi 2O3 and SnO are 65 parts, 15 parts, respectively.
Comparative examples 2 to 4
Comparative examples 2 to 4 differ from example 3 in that the parts of the silicon-containing organic high polymer are 0 part, 3 parts, 5 parts, respectively.
Comparative example 5
Comparative example 5 is different from example 3 in that the part of Nb 2O5 in the glass frit is 0 part.
Performance testing
The testing method comprises the following steps:
(1) Glass softening point test: taking a certain amount (about 1 g) of glass powder from an alumina substrate, slightly flattening the glass powder into a cake shape, putting the cake shape into a constant temperature box with a set temperature for heat preservation for 3min, taking out and cooling the cake shape, turning over the alumina substrate, and observing whether the glass powder is stuck to the substrate or not, wherein the lowest temperature of the glass powder stuck to the substrate is the softening point. Test temperature range: 400-700 ℃, starting from 400 ℃, increasing every 10 ℃ and ending at 700 ℃.
(2) Silver aluminum contact resistance: rectangular transmission line model (Transmission Line Method, TLM method) is used, a method common in the industry. Reference test methods "methods for measuring and calculating metal-semiconductor contact resistivity", authors Li Hongjian;
(3) Silver-aluminum region compounding: tested by PL tester.
(4) Efficiency is that: tested by a photovoltaic I-V tester.
2. Test results
TABLE 1
Note that: the silver-aluminum region composition is expressed in terms of absolute gray scale values of PL, with larger compositions being smaller.
The results in table 1 show that: 1. the mass ratio of Bi 2O3 and SnO in the glass powder influences the high-temperature fluidity and stability of the glass, promotes rearrangement densification in the silver powder sintering process, and simultaneously promotes mutual expansion between silver and aluminum; 2. the amount of the silicon-containing organic high polymer is adjusted and optimized, so that the recombination of silver-aluminum areas can be reduced, but the overlap resistance of silver-aluminum is obviously increased, and the electrical property is not good; 3. under the condition of adding the silicon-containing organic high polymer, adding a proper amount of Nb 2O5 can reduce the contact resistance of silver and aluminum, and at the same time, the glass activity is not improved, and the silver and aluminum regional recombination is not increased.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, such changes and modifications are also intended to be within the scope of the invention.
Claims (7)
1. The conductive silver paste is characterized by comprising the following components in parts by weight: 40 to 70 parts of silver powder, 0.1 to 5 parts of glass powder, 0.1 to 1 part of silicon-containing organic high polymer and 20 to 40 parts of organic carrier;
The glass powder consists of the following components in parts by weight: 20 to 60 parts of Bi 2O3, 1 to 10 parts of SnO, 10to 40 parts of SiO 2, 1 to 10 parts of B 2O3, 0.1 to 5 parts of Nb 2O5, 5 to 15 parts of CuO, 5 to 10 parts of MnO 2 and 0.1 to 5 parts of alkali metal oxide;
the organic carrier is a mixture of resin, solvent and thixotropic agent;
the resin is at least one of acrylic resin, modified acrylic resin, ethyl cellulose, cellulose acetate butyrate, cellulose acetate propionate, polyvinyl butyral and polyvinylpyrrolidone;
the solvent is at least one of diethylene glycol monobutyl ether, diethylene glycol butyl ether acetate, alcohol ester-12, alcohol ester-16, terpineol, tributyl citrate, acetyl tributyl citrate and turpentine.
2. The conductive silver paste according to claim 1, wherein the silicon-containing organic polymer is at least one of polysiloxane and modified polysiloxane.
3. The conductive silver paste of claim 1, wherein the silver powder is microcrystalline silver powder.
4. The conductive silver paste according to claim 1, wherein the particle size D50 of the silver powder is 0.1 to 5 μm.
5. The method for preparing the conductive silver paste according to any one of claims 1 to 4, comprising the steps of:
(1) Uniformly dispersing the components of the glass powder, smelting, carrying out water quenching, carrying out air flow grinding treatment on the obtained glass fragments, and sieving to obtain the glass powder;
(2) And (3) pre-dispersing the glass powder, silver powder, the silicon-containing organic high polymer and the organic carrier in the step (1), and grinding the glass powder, the silver powder and the silicon-containing organic high polymer until the fineness of the slurry is less than 5 mu m to obtain the conductive silver slurry.
6. The method of producing a conductive silver paste according to claim 5, wherein the melting in the step (1) is melting the dispersed components at 1200 to 1500 ℃ for 60 to 90 minutes.
7. Use of the conductive silver paste of any one of claims 1-4 in the preparation of a crystalline silicon solar cell.
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| US20170092788A1 (en) * | 2015-09-25 | 2017-03-30 | Heraeus Precious Metals North America Conshohocken Llc | Poly-siloxane containing organic vehicle for electroconductive pastes |
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| WO2010011430A1 (en) * | 2008-06-26 | 2010-01-28 | E. I. Du Pont De Nemours And Company | Glass compositions used in conductors for photovoltaic cells |
| US9574091B2 (en) * | 2012-10-19 | 2017-02-21 | Namics Corporation | Conductive paste |
| US10217876B2 (en) * | 2015-09-25 | 2019-02-26 | Heraeus Precious Metals North America Conshohocken Llc | Poly-siloxane containing organic vehicle for electroconductive pastes |
| CN105679400B (en) * | 2016-01-22 | 2018-05-08 | 四川银河星源科技有限公司 | Conductive paste for solar cell and preparation method thereof |
| CN106297956A (en) * | 2016-11-10 | 2017-01-04 | 北京市合众创能光电技术有限公司 | A kind of crystal silicon solar energy battery positive silver paste and preparation method thereof |
| CN110663087A (en) * | 2018-04-28 | 2020-01-07 | 深圳市首骋新材料科技有限公司 | Front conductive silver paste of crystalline silicon solar cell and preparation method thereof and solar cell |
| CN114360766B (en) * | 2021-12-31 | 2024-03-19 | 广东南海启明光大科技有限公司 | Front electrode silver paste of high-silver-content crystalline silicon solar cell and preparation method |
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