CN113539548A - Preparation method of hollow silver nanotube conductive paste - Google Patents
Preparation method of hollow silver nanotube conductive paste Download PDFInfo
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- CN113539548A CN113539548A CN202110777554.2A CN202110777554A CN113539548A CN 113539548 A CN113539548 A CN 113539548A CN 202110777554 A CN202110777554 A CN 202110777554A CN 113539548 A CN113539548 A CN 113539548A
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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Abstract
The invention relates to the technical field of conductive materials, and provides a preparation method of hollow silver nanotube conductive slurry, which comprises the steps of dispersing gallium indium liquid metal in tetrahydrofuran and deionized water, carrying out surface modification treatment to obtain anion modified gallium indium liquid metal dispersion liquid, mixing the anion modified gallium indium liquid metal dispersion liquid with silver ammonia solution and pore-forming agent, dripping hydrazine hydrate to prepare nano silver-coated gallium indium alloy nanorods, adding a mixed solvent of deionized water and absolute ethyl alcohol, carrying out water bath heating and ultrasonic treatment to obtain porous hollow silver nanorods, and compounding the porous hollow silver nanorods with an organic binder phase, a curing agent, an accelerator, a diluent, a thickener and a solvent to prepare the conductive slurry. The method effectively reduces the consumption of silver, reduces the production cost, overcomes the defects of high shrinkage rate and difficult accumulation of spherical silver powder, overcomes the defects of low resolution and easy curling of flaky silver powder, and is favorable for promoting the industrial application of low-temperature cured conductive silver paste.
Description
Technical Field
The invention relates to the technical field of conductive materials, in particular to a preparation method of hollow silver nanotube conductive paste.
Background
The transparent conductive film has wide application fields, and the application fields include touch screens, flexible displays, OLED (organic light emitting diode) illumination, solar cells and the like. In photoelectric devices such as flexible displays, lighting, touch screens and the like, high-performance transparent electrodes are important components of the devices. As a semiconductor transparent film, a transparent conductive film ITO (indium tin oxide) contains about 30 percent of indium element, and indium ore belongs to rare mineral products, has rare sources and high price, the global estimated indium storage capacity is only about 5 ten thousand tons, wherein 50 percent of the available indium is accounted for, and the coating cost of the vacuum ITO sputtering technology is high; the required pattern is produced by etching with laser after film forming, a large part of raw materials are wasted in the etching link, the production process is complex, the production equipment investment is huge, and the energy consumption is very high. Meanwhile, with the rapid development of the technology level, flexible display or lighting, smart home and touch equipment become the mainstream direction of future development.
The existing high-temperature conductive silver paste is generally prepared into flowing slurry by silver powder, inorganic adhesive, organic phase carrier and the like. In the prior art, the high-conductivity silver paste and the preparation method thereof, the metal silver powder is a mixture of micron-sized flaky silver powder, submicron spherical silver powder and nanometer silver powder. The silver electrode slurry comprises 25-75% of spherical silver powder, 0-35% of flake silver powder, 2-18% of glass powder and 15-48% of organic phase carrier. The spherical silver powder particles are in point contact with each other, so that the spherical silver powder particles are easy to shrink during sintering, have large shrinkage rate after sintering, have the defects of large sintering shrinkage and large sintering stress and difficult accumulation of the nano silver powder, have low fine wire resolution of the flaky silver powder, and are likely to curl during sintering, thereby directly influencing the continuity and uniform compactness of the conductive film.
To alleviate this problem, researchers turned their eyes to low temperature curing silver pastes. Due to the low curing temperature, the high-temperature-resistant and low-cost composite material can be printed on plastic or flexible boards with low glass transition temperature and low cost, and can be widely applied to the fields of touch screens, semiconductors, membrane switches and the like. The touch screen low-temperature curing conductive silver paste mainly adopts low-temperature curing conductive silver paste; the low-temperature curing conductive silver paste is mostly composed of silver powder, resin, solvent or diluent, auxiliary agent and the like; the silver has a high loading of about 70-80%. Under the market environment that the price of the silver paste is low and the price is low, the reduction of the silver content in the low-temperature curing conductive silver paste of the touch screen is urgently needed, so that the production cost of the low-temperature curing conductive silver paste is reduced. In addition, the low temperature curing conductive silver paste can partially shrink in the curing process, so that the silver paste is partially separated from the substrate after being cured, the overlap resistance is increased, and the performance of the low temperature curing conductive silver paste is not facilitated.
Chinese patent 201710136305.9 proposes a conductive silver paste, which comprises an organic carrier and silver particles with a surface modified with an organic compound, wherein the silver particles comprise submicron silver particles and nanometer silver particles, the particle size of the submicron silver particles is 100-1000nm, and the particle size of the nanometer silver particles is 2-50 nm. The conductive silver paste can decompose or desorb the surface-modified organic compound at a lower baking temperature, so that the organic compound is removed from the surfaces of silver particles in a gaseous state, and meanwhile, the nano-scale silver particles and the submicron-scale silver particles can be sintered together.
Chinese patent 201910571520.0 proposes a conductive silver paste and a preparation method thereof, belonging to the technical field of conductive silver paste. The conductive silver paste consists of metal powder and/or alloy powder, an organic phase carrier, silver nanowires and lead-free glass micro powder, wherein the melting point temperature of the metal powder and/or the alloy powder is 90-520 ℃, and the silver nanowires account for 56-80 percent, the metal powder and/or the alloy powder for 1-12 percent, the organic phase carrier for 10-34 percent and the lead-free glass micro powder for 1-8 percent in percentage by mass. According to the invention, the silver nanowires and the medium-low melting point metal or alloy (the melting point is 90-520 ℃) are adopted as the conductive phase, so that the conductive silver paste has high conductivity, high printing resolution and low silver content.
However, the method has the advantages that the consumption of the conductive silver powder is very large, and the method is not economical for industrial production, so that the consumption of the silver powder of the conductive silver paste is reduced, the cost is optimized, and the method has very important practical significance.
Disclosure of Invention
The invention provides a preparation method of hollow silver nanotube conductive paste, aiming at the problem of large silver consumption of the existing conductive silver paste.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing hollow silver nanotube conductive paste, said method comprises dispersing gallium indium liquid metal in tetrahydrofuran and deionized water, get anion modified gallium indium liquid metal dispersion through surface modification, then mix with silver ammonia solution, pore-forming agent, then drip hydrazine hydrate and make nanometer silver and cover gallium indium alloy nanorod, add deionized water and mixed solvent of absolute ethyl alcohol and water bath heating, ultrasonic treatment get porous hollow silver nanorod, then mix with organic binder phase, firming agent, accelerator, thinner, thickening agent, solvent to make conductive paste, the concrete preparation step is:
(1) dispersing gallium indium liquid metal in a mixed solution of tetrahydrofuran and deionized water, performing ultrasonic oscillation for 2-4h, and then adding 12- (2-bromoisobutylamine) dodecanoic acid for surface modification treatment to prepare an anion modified gallium indium liquid metal dispersion liquid;
(2) mixing the dispersion liquid prepared in the step (1) with a silver ammonia solution and a pore-forming agent, performing ultrasonic dispersion for 5-10min at 1-10 ℃, slowly dropwise adding hydrazine hydrate for 3-6h, standing and aging for 12h, performing centrifugal separation to obtain nano-silver-coated gallium-indium alloy nanorods, adding the obtained nanorods into a mixed solvent of deionized water and absolute ethyl alcohol for uniform mixing, then performing water bath heating at 60 ℃, simultaneously performing ultrasonic treatment, and performing centrifugal separation to obtain porous hollow silver nanorods;
(3) and (3) compounding the porous hollow silver nanorod obtained in the step (2) serving as a conductive phase with an organic binding phase, a curing agent, an accelerator, a diluent, a thickening agent and a solvent to prepare conductive slurry.
Preferably, the pore-forming agent is hydroxypropyl methyl cellulose.
Preferably, the organic binder phase is an epoxy resin.
Preferably, the curing agent is an acid anhydride curing agent.
Preferably, the accelerator is methylimidazole.
Preferably, the diluent is butyl acetate.
Preferably, the thickener is a polyamide wax.
Preferably, the solvent is terpineol.
Preferably, the melting point of the gallium indium liquid metal is 15-25 ℃.
Preferably, in the step (1), the mass ratio of the gallium indium liquid metal, the tetrahydrofuran, the deionized water and the 12- (2-bromoisobutylamine) dodecanoic acid is 5-10: 80-100: 30-50: 10-20.
Preferably, in the step (2), the mass ratio of the dispersion liquid, the silver ammonia solution and the pore-forming agent is 1: 1-3: 0.01-0.03.
Preferably, in the step (2), the addition amount of hydrazine hydrate is 5-10% of the total mass of the dispersion liquid and the silver ammonia solution.
Preferably, in the step (2), the mass ratio of the deionized water to the absolute ethyl alcohol is 1: 5.
Preferably, in the conductive silver paste in the step (3), the mass ratio of the conductive phase to the organic binder phase to the curing agent to the accelerator to the diluent to the thickener to the solvent is 50-60: 6-8: 0.5-1: 0.5-1: 4-6: 0.5-1: 30-40.
At present, the content of silver in the low-temperature curing conductive silver paste of the touch screen is high and reaches 70-80wt%, and the popularization and application of the low-temperature curing conductive silver paste are affected due to high production cost. The invention takes gallium-indium liquid metal as a template to prepare the silver nanorod, and the liquid metal is amorphous and flowable metal and can be regarded as a mixture consisting of positive ion fluid and free electron gas. The gallium indium liquid metal can be broken under the action of ultrasonic waves, and can be spontaneously changed into a nano rod shape from a nano sphere shape in the further standing and aging process. After the surface anion modification is carried out on the gallium-indium liquid metal, the silver-ammonia solution can be effectively adsorbed, silver nano particles are reduced on the surface of the silver-ammonia solution for coating, and the silver coating layer is induced to form a nano rod structure.
Further, hydroxypropylmethylcellulose is one of nonionic cellulose mixed ethers, is a semi-synthetic, inactive, viscoelastic polymer, has good support properties in the solid state and good solubility in water, and is useful as a pore-forming agent. According to the invention, a hydroxypropyl methyl cellulose pore forming agent is added into a silver ammonia solution, after the nano silver is coated with a gallium-indium alloy nanorod to form the nano silver-indium-coated gallium-indium alloy nanorod, the pore forming agent is dissolved in water through the mixed water bath of deionized water and absolute ethyl alcohol and the ultrasonic action, so that more pores appear on the surface of the silver nanotube, and meanwhile, gallium-indium liquid metal is crushed again and separated out under the ultrasonic action, so that the silver nanotube with a hollow and porous structure is obtained. The structure of the hollow porous silver nanotube realizes effective reduction of the using amount of silver, and the conductive paste with good performance can be obtained while the generation cost is reduced.
Furthermore, the spherical silver powder particles are in point contact with each other, so that the spherical silver powder particles are easy to shrink during sintering, have large shrinkage rate after sintering, and have the defects of large sintering shrinkage and large sintering stress and difficult accumulation. And the fine line resolution of the flake silver powder is low, and the flake silver powder is likely to curl during sintering, so that the continuity and uniform compactness of the conductive film are directly influenced. According to the invention, gallium indium liquid metal is used for effectively adsorbing the silver ammonia solution, the silver coating layer is induced to form a nanorod structure, then pore forming and liquid metal precipitation are further carried out to form a hollow porous silver nanotube, and the conductive slurry is filled with the silver nanotube with a linear structure, so that the defects of high shrinkage rate and difficulty in accumulation of a spherical structure and low resolution and easiness in curling of a sheet structure are overcome.
The existing conductive silver paste has the problem of large silver consumption, so that the application of the conductive silver paste is limited. In view of the above, the invention provides a preparation method of a hollow silver nanotube conductive paste, which comprises the steps of dispersing gallium indium liquid metal in a mixed solution of tetrahydrofuran and deionized water, performing ultrasonic oscillation, and then adding 12- (2-bromoisobutylamine) dodecanoic acid for surface modification treatment to obtain an anion modified gallium indium liquid metal dispersion liquid; mixing the obtained dispersion with a silver ammonia solution and a pore-forming agent, performing ultrasonic dispersion, keeping slowly dropwise adding hydrazine hydrate for reaction, standing, aging, performing centrifugal separation to obtain nano-silver-coated gallium-indium alloy nanorods, adding the obtained nanorods into a mixed solvent of deionized water and absolute ethyl alcohol for uniform mixing, heating in a water bath, performing ultrasonic treatment simultaneously, and performing centrifugal separation to obtain porous hollow silver nanorods; the obtained porous hollow silver nano-rod is used as a conductive phase and compounded with an organic binding phase, a curing agent, an accelerant, a diluent, a thickening agent and a solvent to prepare conductive slurry. The method effectively reduces the consumption of silver, reduces the production cost, overcomes the defects of high shrinkage rate and difficult accumulation of spherical silver powder, overcomes the defects of low resolution and easy curling of flaky silver powder, and is favorable for promoting the industrial application of low-temperature cured conductive silver paste.
Compared with the prior art, the preparation method of the hollow silver nanotube conductive paste has the outstanding characteristics and excellent effects that:
1. according to the invention, the silver nano-tube is prepared and then is prepared into the conductive silver paste with the organic solvent and the auxiliary agent, so that the defects of high shrinkage rate and difficult accumulation of spherical silver powder are overcome, and the defects of low resolution and easy curling of flaky silver powder are overcome.
2. According to the invention, the silver-ammonia solution is adsorbed by adopting the surface-modified gallium-indium liquid metal, silver nanoparticles are reduced to be coated, the silver coating layer is induced to form a nanorod structure, and then the hollow porous silver nanotube is formed by separating out the pore-forming agent and the liquid metal, so that the using amount of silver is effectively reduced.
3. The liquid metal used by the invention can be recycled by simple hydrothermal and ultrasonic treatment, and the production cost is effectively reduced.
Drawings
FIG. 1 is a photograph of a slurry of a sample of example 1;
fig. 2 is a photograph of the slurry of the sample of comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Dispersing 7kg of gallium indium liquid metal in a mixed solution of 85 kg of tetrahydrofuran and 40kg of deionized water, carrying out ultrasonic oscillation for 2h, and then adding 12kg of 12- (2-bromoisobutylamine) dodecanoic acid for surface modification treatment to prepare an anion modified gallium indium liquid metal dispersion;
(2) mixing 1kg of dispersion liquid prepared in the step (1) with 2kg of silver ammonia solution and 0.02kg of hydroxypropyl methyl cellulose, performing ultrasonic dispersion for 7min at the temperature of 5 ℃, keeping slowly dropwise adding kg of hydrazine hydrate for 5h, standing, aging for 12h, performing centrifugal separation to obtain nano-silver-coated gallium-indium alloy nanorods, adding the obtained nanorods into a mixed solvent of deionized water and absolute ethyl alcohol (the mass ratio is 1: 5) to be uniformly mixed, then performing water bath heating at the temperature of 60 ℃, performing ultrasonic treatment at the same time, and performing centrifugal separation to obtain porous hollow silver nanorods;
(3) and (3) compounding 50kg of porous hollow silver nanorods obtained in the step (2) serving as a conductive phase with 6kg of epoxy resin organic binding phase, 1kg of anhydride curing agent, 0.5kg of methylimidazole accelerator, 6kg of butyl acetate diluent, 0.5kg of polyamide wax thickener and 35kg of terpineol solvent to prepare conductive slurry.
Example 2
(1) Dispersing 10kg of gallium indium liquid metal into a mixed solution of 80 kg of tetrahydrofuran and 30kg of deionized water, carrying out ultrasonic oscillation for 3h, and then adding 15kg of 12- (2-bromoisobutylamine) dodecanoic acid for surface modification treatment to prepare an anion modified gallium indium liquid metal dispersion;
(2) mixing 1kg of dispersion liquid prepared in the step (1) with 3kg of silver ammonia solution and 0.01kg of hydroxypropyl methyl cellulose, performing ultrasonic dispersion for 10min at 10 ℃, keeping slowly dropwise adding kg of hydrazine hydrate for 6h, standing, aging for 12h, performing centrifugal separation to obtain nano-silver-coated gallium-indium alloy nanorods, adding the obtained nanorods into a mixed solvent of deionized water and absolute ethyl alcohol (the mass ratio is 1: 5) to be uniformly mixed, then heating in a water bath at 60 ℃, performing ultrasonic treatment at the same time, and performing centrifugal separation to obtain porous hollow silver nanorods;
(3) and (3) compounding 52kg of porous hollow silver nanorods obtained in the step (2) serving as a conductive phase with 7kg of epoxy resin organic binding phase, 0.7kg of anhydride curing agent, 0.5kg of methylimidazole accelerator, 6kg of butyl acetate diluent, 0.6kg of polyamide wax thickener and 38kg of terpineol alcohol solvent to prepare conductive paste.
Example 3
(1) Dispersing 7kg of gallium indium liquid metal in a mixed solution of 90 kg of tetrahydrofuran and 35kg of deionized water, carrying out ultrasonic oscillation for 3h, and then adding 12kg of 12- (2-bromoisobutylamine) dodecanoic acid for surface modification treatment to prepare an anion modified gallium indium liquid metal dispersion liquid;
(2) mixing 1kg of dispersion liquid prepared in the step (1) with 1kg of silver ammonia solution and 0.01kg of hydroxypropyl methyl cellulose, performing ultrasonic dispersion for 8min at the temperature of 8 ℃, keeping slowly dropwise adding kg of hydrazine hydrate for 3h, standing and aging for 12h, performing centrifugal separation to obtain nano-silver-coated gallium-indium alloy nanorods, adding the obtained nanorods into a mixed solvent of deionized water and absolute ethyl alcohol (the mass ratio is 1: 5) to be uniformly mixed, then performing water bath heating at the temperature of 60 ℃, performing ultrasonic treatment at the same time, and performing centrifugal separation to obtain porous hollow silver nanorods;
(3) and (3) compounding 55kg of porous hollow silver nanorods obtained in the step (2) serving as a conductive phase with 7kg of epoxy resin organic binding phase, 0.5kg of anhydride curing agent, 1kg of methylimidazole accelerator, 4kg of butyl acetate diluent, 1kg of polyamide wax thickener and 40kg of terpineol solvent to prepare conductive slurry.
Example 4
(1) Dispersing 10kg of gallium indium liquid metal into a mixed solution of 100 kg of tetrahydrofuran and 30kg of deionized water, carrying out ultrasonic oscillation for 2h, and then adding 10kg of 12- (2-bromoisobutylamine) dodecanoic acid for surface modification treatment to prepare an anion modified gallium indium liquid metal dispersion;
(2) mixing 1kg of dispersion liquid prepared in the step (1) with 2kg of silver ammonia solution and 0.02kg of hydroxypropyl methyl cellulose, performing ultrasonic dispersion for 8min at 10 ℃, keeping slowly dropwise adding kg of hydrazine hydrate for 4h, standing, aging for 12h, performing centrifugal separation to obtain nano-silver-coated gallium-indium alloy nanorods, adding the obtained nanorods into a mixed solvent of deionized water and absolute ethyl alcohol (the mass ratio is 1: 5) to be uniformly mixed, then heating in a water bath at 60 ℃, performing ultrasonic treatment at the same time, and performing centrifugal separation to obtain porous hollow silver nanorods;
(3) and (3) taking 60kg of porous hollow silver nanorods obtained in the step (2) as a conductive phase, and compounding the conductive phase with 8kg of epoxy resin organic binding phase, 0.5kg of anhydride curing agent, 1kg of methylimidazole accelerator, 4kg of butyl acetate diluent, 0.9kg of polyamide wax thickener and 32kg of terpineol solvent to prepare conductive paste.
Example 5
(1) Dispersing 7kg of gallium indium liquid metal in a mixed solution of 80 kg of tetrahydrofuran and 50kg of deionized water, carrying out ultrasonic oscillation for 2h, and then adding 20kg of 12- (2-bromoisobutylamine) dodecanoic acid for surface modification treatment to prepare an anion modified gallium indium liquid metal dispersion;
(2) mixing 1kg of dispersion liquid prepared in the step (1) with 3kg of silver ammonia solution and 0.01kg of hydroxypropyl methyl cellulose, performing ultrasonic dispersion for 10min at 4 ℃, keeping slowly dropwise adding kg of hydrazine hydrate for 3h, standing and aging for 12h, performing centrifugal separation to obtain nano-silver-coated gallium-indium alloy nanorods, adding the obtained nanorods into a mixed solvent of deionized water and absolute ethyl alcohol (the mass ratio is 1: 5) to be uniformly mixed, then heating in a water bath at 60 ℃, performing ultrasonic treatment at the same time, and performing centrifugal separation to obtain porous hollow silver nanorods;
(3) and (3) compounding 58kg of porous hollow silver nanorods obtained in the step (2) serving as a conductive phase with 7kg of epoxy resin organic binding phase, 0.7kg of anhydride curing agent, 0.8kg of methylimidazole accelerator, 5kg of butyl acetate diluent, 0.5kg of polyamide wax thickener and 30kg of terpineol alcohol solvent to prepare conductive paste.
Comparative example 1
70kg of solid silver nanowires are used as a conductive phase, and compounded with 6kg of epoxy resin organic binding phase, 1kg of anhydride curing agent, 0.5kg of methylimidazole accelerator, 6kg of butyl acetate diluent, 0.5kg of polyamide wax thickener and 35kg of terpineol solvent to prepare conductive slurry.
Comparative example 1 compared to example 1, solid silver nanowires were used as the conductive phase in an amount of 70kg, and the rest was identical to example 1.
The test method comprises the following steps:
and (3) observing the state of the slurry: by adopting naked eye observation, the method can be seen: example 1 the sample slurry was relatively fine, as shown in fig. 1; comparative example 1 is a solid silver nanowire that settles more easily during slurry formulation, resulting in less uniformity than example 1, as shown in fig. 2;
and (3) testing the conductivity: examples 1 to 5 and comparative example 1 were drawn on the surface of a substrate to form a film, and the surface resistivity of the film was measured by the four-probe method, and the results are shown in table 1, in which: the resistivity of the film prepared by the embodiment is low, which shows that the hollow silver nanotubes used in the slurry can obtain more excellent performance under the condition of less using amount; comparative example 1 is a solid silver nanowire that settles more easily during slurry formulation, resulting in a less uniform and relatively higher resistivity.
Table 1:
| performance index | State of slurry | Film surface resistivity (omega. cm) |
| Example 1 | Fineness of fineness | 32.7×10-6 |
| Example 2 | Fineness of fineness | 31.5×10-6 |
| Example 3 | Fineness of fineness | 32.3×10-6 |
| Example 4 | Fineness of fineness | 32.1×10-6 |
| Example 5 | Fineness of fineness | 31.8×10-6 |
| Comparative example 1 | Is relatively fine and smooth | 62.3×10-6 |
Claims (8)
1. A preparation method of hollow silver nanotube conductive paste is characterized in that gallium indium liquid metal is dispersed in tetrahydrofuran and deionized water, anion modified gallium indium liquid metal dispersion liquid is obtained through surface modification treatment, then the dispersion liquid is mixed with silver ammonia solution and pore-forming agent, hydrazine hydrate is dripped to prepare nano silver coated gallium indium alloy nano rods, then deionized water and absolute ethyl alcohol mixed solvent is added for water bath heating and ultrasonic treatment to obtain porous hollow silver nano rods, and then the porous hollow silver nano rods are compounded with organic binder phase, curing agent, accelerant, diluent, thickening agent and solvent to prepare the conductive paste, wherein the preparation method specifically comprises the following steps:
(1) dispersing gallium indium liquid metal in a mixed solution of tetrahydrofuran and deionized water, performing ultrasonic oscillation for 2-4h, and then adding 12- (2-bromoisobutylamine) dodecanoic acid for surface modification treatment to prepare an anion modified gallium indium liquid metal dispersion liquid;
(2) mixing the dispersion liquid prepared in the step (1) with a silver ammonia solution and a pore-forming agent, performing ultrasonic dispersion for 5-10min at 1-10 ℃, slowly dropwise adding hydrazine hydrate for 3-6h, standing and aging for 12h, performing centrifugal separation to obtain nano-silver-coated gallium-indium alloy nanorods, adding the obtained nanorods into a mixed solvent of deionized water and absolute ethyl alcohol for uniform mixing, then performing water bath heating at 60 ℃, simultaneously performing ultrasonic treatment, and performing centrifugal separation to obtain porous hollow silver nanorods;
(3) and (3) compounding the porous hollow silver nanorod obtained in the step (2) serving as a conductive phase with an organic binding phase, a curing agent, an accelerator, a diluent, a thickening agent and a solvent to prepare conductive slurry.
2. The method for preparing the hollow silver nanotube conductive paste according to claim 1,
the pore-forming agent is hydroxypropyl methyl cellulose;
the organic binding phase is epoxy resin;
the curing agent is an anhydride curing agent;
the accelerant is methylimidazole;
the diluent is butyl acetate;
the thickening agent is polyamide wax;
the solvent is terpineol.
3. The method for preparing the hollow silver nanotube conductive paste according to claim 1, wherein the melting point of the gallium indium liquid metal is 15-25 ℃.
4. The method for preparing the hollow silver nanotube conductive paste according to claim 1, wherein in the step (1), the mass ratio of the gallium indium liquid metal, the tetrahydrofuran, the deionized water and the 12- (2-bromoisobutylamine) dodecanoic acid is 5-10: 80-100: 30-50: 10-20.
5. The preparation method of the hollow silver nanotube conductive paste according to claim 1, wherein in the step (2), the mass ratio of the dispersion liquid to the silver-ammonia solution to the pore-forming agent is 1: 1-3: 0.01-0.03.
6. The method for preparing the hollow silver nanotube conductive paste according to claim 1, wherein in the step (2), the addition amount of hydrazine hydrate is 5-10% of the total mass of the dispersion liquid and the silver ammonia solution.
7. The method for preparing the hollow silver nanotube conductive paste according to claim 1, wherein in the step (2), the mass ratio of the deionized water to the absolute ethyl alcohol is 1: 5.
8. The preparation method of the hollow silver nanotube conductive paste according to claim 1, wherein in the conductive silver paste obtained in the step (3), the mass ratio of the conductive phase to the organic binder phase to the curing agent to the accelerator to the diluent to the thickener to the solvent is 50-60: 6-8: 0.5-1: 0.5-1: 4-6: 0.5-1: 30-40.
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