CN114822914A - Conductive material for constructing wireless communication functional circuit and preparation method thereof - Google Patents
Conductive material for constructing wireless communication functional circuit and preparation method thereof Download PDFInfo
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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Abstract
The invention provides a preparation method of a conductive material for constructing a wireless communication functional circuit, which comprises the following steps: preparing an MOF-derived porous carbon/carbon nanotube composite; placing a conductive metal filler in an ethanol solution of a silane coupling agent, stirring, adding the prepared MOF-derived porous carbon/carbon nanotube composite material, and continuously stirring to prepare a conductive composite material; mixing and stirring matrix resin and a solvent to prepare a resin solution, then adding the prepared conductive composite material, conductive filler, crosslinking agent and coupling agent, and continuously stirring and mixing to prepare the conductive material. The conductive material provided by the invention has high conductivity, strong binding force with a matrix and good mechanical property of a formed coating.
Description
The technical field is as follows:
the invention relates to the technical field of conductive materials, in particular to a conductive material for constructing a wireless communication functional circuit and a preparation method thereof.
Background art:
with the increasing attention paid to the technical innovations of wearable electronics, internet of things and the like, people put forward new requirements on devices related to human-computer interaction and sensing: the device needs to adapt to different working environments to a certain extent, can be effectively attached to the surfaces of objects in different shapes, has high mechanical flexibility, can bear deformation such as repeated bending, friction and the like, keeps the stability of electrical performance, and has biocompatibility and stretching with a wearable device attached to the skin. However, the conventional hard circuit board manufacturing technology cannot meet the requirements of flexibility, light weight, deformability and the like. Therefore, a method for preparing electronic devices and systems with certain functions by forming liquid conductive ink on a substrate by using a printing method has been proposed for the amplification of printed electronics. The process steps of printing the electronics mainly comprise printing and sintering, the preparation energy consumption is low, the efficiency is high, the environment is protected, the process is not limited by a substrate material, large-area batch manufacturing and digital personalized manufacturing can be realized, and the rapid development is realized.
The conductive ink is generally composed of conductive filler, functional assistant and solvent, and can be divided into inorganic and organic types according to the difference of the conductive filler, wherein the inorganic conductive ink has been widely paid attention and applied due to natural high conductivity and environmental stability, and mainly comprises carbon-series conductive ink, metal nano conductive ink and mixed conductive ink. The conductive filler adopted in the mixed conductive ink is the mixed conductive filler, and because different conductive materials have defects in the aspects of conductivity, oxidation resistance and mechanical stability, the effects of making up for deficiencies can be achieved by matching the conductive fillers. The key to current research on hybrid conductive inks is how to build a conductive network in the matrix resin to improve the conductivity of the ink.
The invention content is as follows:
the invention aims to solve the technical problem that the defects of the prior art are overcome, and the conductive material for constructing the wireless communication functional circuit and the preparation method thereof are provided.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method of making a conductive material useful in the construction of wireless communication function circuitry, comprising the steps of:
(1) adding the carbon nano tube into a methanol solution of polyvinylpyrrolidone to prepare a carbon nano tube dispersion liquid; adding a methanol solution of cobalt nitrate hexahydrate into a carbon nano tube dispersion liquid, carrying out primary stirring treatment, then adding a methanol solution of 2-methylimidazole, carrying out secondary stirring treatment, then carrying out centrifugal treatment, washing and drying a precipitate obtained by centrifugation, and placing a dried solid in a muffle furnace under a nitrogen atmosphere for carbonization treatment to obtain the MOF-derived porous carbon/carbon nano tube composite material;
(2) placing a conductive metal filler in an ethanol solution of a silane coupling agent, stirring, adding the prepared MOF-derived porous carbon/carbon nanotube composite material, and continuously stirring to prepare a conductive composite material;
(3) mixing and stirring matrix resin and a solvent to prepare a resin solution, then adding the prepared conductive composite material, conductive filler, crosslinking agent and coupling agent, and continuously stirring and mixing to prepare the conductive material.
Preferably, in the step (1), the concentration of the methanol solution of polyvinylpyrrolidone is 4-5mg/ml, the concentration of the methanol solution of cobalt nitrate hexahydrate is 10mg/ml, and the concentration of the methanol solution of 2-methylimidazole is 12-13 mg/ml; the dosage ratio of the carbon nano tube, the methanol solution of polyvinylpyrrolidone and the methanol solution of cobalt nitrate hexahydrate is 0.1-0.15 g: 20 ml: 20 ml: 35-45 ml.
In the above technical means, in the step (1), the time of the first stirring treatment is preferably 1 to 2 hours, and the time of the second stirring treatment is preferably 1 to 2 hours.
Preferably, the temperature of the carbonization treatment is 800 ℃, the temperature rise rate of the carbonization treatment is 3-5 ℃/min, and the time of the carbonization treatment is 3-4 h.
Preferably, in the step (2), the conductive metal filler is at least one of silver powder, copper powder, silver-coated nickel powder, and silver-coated alloy powder.
Preferably, in the above technical solution, the alloy powder in the silver-coated alloy powder is composed of any two or more metals selected from iron, chromium, nickel, copper, and niobium.
Preferably, in the step (3), the conductive filler is silver powder, the silver powder is formed by mixing flake silver powder and spherical silver powder in any proportion, and tap densities of the flake silver powder and the spherical silver powder are both 2-7g/cm 3 。
Preferably, in the step (2), the mass ratio of the conductive metal filler, the silane coupling agent and the MOF-derived porous carbon/carbon nanotube composite material is 1: (0.005-0.03): (0..005-0.5).
Preferably, in the step (3), the matrix resin is one of epoxy resin, phenoxy resin and polyurethane resin; the cross-linking agent is one or more of aluminum acetylacetonate, titanium acetylacetonate, cobalt acetylacetonate, zirconium acetylacetonate, zinc acetylacetonate, iron acetylacetonate and copper acetylacetonate; the coupling agent is one or a mixture of more of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, diamino silane coupling agent, 3-aminopropyl triethoxy silane, titanium coupling agent and aluminum coupling agent; the solvent comprises a mixture of diethylene glycol butyl ether acetate, ethanol and ethylene glycol.
Preferably, in the step (3), the amounts of the components in parts by weight are as follows: 5-20 parts of matrix resin, 5-25 parts of solvent, 40-90 parts of conductive filler, 0-0.5 part of conductive composite material, 0.001-2 parts of cross-linking agent and 0.1-2 parts of coupling agent.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
the conductive composite material in the conductive material is prepared by compounding the conductive metal filler and the MOF-derived porous carbon/carbon nanotube composite material, the MOF-derived porous carbon/carbon nanotube constructs a multi-path conductive network framework, and then the conductive metal filler is uniformly adhered to the framework to form an effective conductive bridge network.
The ZIF-67 metal organic framework material is synthesized in situ by taking carbon nano tubes as a basic framework, because of the chemical interaction between the functionalized carbon nano tubes and the metal center in the ZIF-67, ZIF-67 particles are uniformly interconnected through the carbon nano tubes to form a uniform three-dimensional interconnection structure, the calcined material takes MOF-derived porous carbon as a connecting node to connect the carbon nano tubes to form a multi-path network framework, the multi-path network framework is mixed with a modified conductive metal filler, the conductive metal filler is uniformly adsorbed in the multi-path network framework to form a conductive composite material with good dispersibility, the conductive composite material has good compatibility with a resin matrix, the prepared conductive material has good stability and excellent conductivity, the conductive circuit formed by spraying and sintering has good associativity with the matrix, and the enhanced interface interaction before the adjacent carbon nano tubes ensures the structural integrity and deformation adaptability of the conductive circuit under repeated mechanical deformation .
The specific implementation mode is as follows:
in order to better understand the present invention, the following examples further illustrate the invention, the examples are only used for explaining the invention, not to constitute any limitation of the invention.
The material properties in the following examples and comparative examples are as follows:
carbon nanotube: the average length is 1 μm, the average diameter is 0.83nm, and the specific surface area is not less than 700m 2 /g， Sigma-Aldrich；
Nano copper powder: the average particle size is 50nm, and the particle size is purchased from Beijing Deke island gold science and technology Co;
silver-coated copper powder: spherical, with an average particle size of 1-3 μm and a silver content of 20 wt%, available from Beijing Deke island gold technologies, Inc.;
silver-coated nickel powder: average particle size of 0.3 μm, silver content of 20 wt%, Jiangsu Bo Shi New Material Co., Ltd;
epoxy resin: and (3) epoxy resin E-20.
Example 1
(1) Adding 0.1g of carbon nano tube into 20ml of methanol solution of polyvinylpyrrolidone with the concentration of 4mg/ml to prepare carbon nano tube dispersion liquid; adding 20ml of methanol solution of cobalt nitrate hexahydrate with the concentration of 10mg/ml into carbon nano tube dispersion liquid, carrying out primary stirring treatment for 1h, then adding 35ml of methanol solution of 2-methylimidazole with the concentration of 12mg/ml, carrying out secondary stirring treatment for 1h, then carrying out centrifugal treatment, washing and drying the precipitate obtained by centrifugation, placing the dried solid in a muffle furnace under nitrogen atmosphere, heating to 800 ℃ at the heating rate of 3 ℃/min, and carrying out carbonization treatment for 3h to obtain the MOF-derived porous carbon/carbon nano tube composite material;
(2) placing 6g of silver powder, 2g of nano-copper powder, 1g of silver-coated copper powder and 1g of silver-coated nickel powder in an ethanol solution containing 0.1g of silane coupling agent, stirring, adding 2g of the prepared MOF-derived porous carbon/carbon nanotube composite material, and continuing stirring to prepare a conductive composite material;
(3) mixing and stirring 10 parts of epoxy resin, 5 parts of diethylene glycol butyl ether acetate, 1 part of ethanol and 1 part of ethylene glycol by weight to prepare a resin solution, adding 50 parts of silver powder, 0.5 part of the prepared conductive composite material, 1 part of aluminum acetylacetonate and 0.5 part of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, and continuously stirring and mixing to prepare the conductive material.
Example 2
(1) Adding 0.15g of carbon nano tube into 20ml of methanol solution of polyvinylpyrrolidone with the concentration of 5mg/ml to prepare carbon nano tube dispersion liquid; adding 20ml of methanol solution of cobalt nitrate hexahydrate with the concentration of 10mg/ml into carbon nano tube dispersion liquid, carrying out primary stirring treatment for 2 hours, then adding 45ml of methanol solution of 13mg/ml of 2-methylimidazole, carrying out secondary stirring treatment for 2 hours, then carrying out centrifugal treatment, washing and drying the precipitate obtained by centrifugation, placing the dried solid in a muffle furnace under nitrogen atmosphere, heating to 800 ℃ at the heating rate of 5 ℃/min, and carrying out carbonization treatment for 4 hours to obtain the MOF-derived porous carbon/carbon nano tube composite material;
(2) placing 6g of silver powder, 2g of nano-copper powder, 1g of silver-coated copper powder and 1g of silver-coated nickel powder in an ethanol solution containing 0.3g of silane coupling agent, stirring, adding 5g of the prepared MOF-derived porous carbon/carbon nanotube composite material, and continuing stirring to prepare a conductive composite material;
(3) mixing and stirring 11 parts of epoxy resin, 5 parts of diethylene glycol butyl ether acetate, 1 part of ethanol and 1 part of ethylene glycol by weight to prepare a resin solution, adding 60 parts of silver powder, 0.5 part of the prepared conductive composite material, 1 part of cobalt acetylacetonate and 0.5 part of bisaminosilane coupling agent, and continuously stirring and mixing to prepare the conductive material.
Example 3
(1) Adding 0.11g of carbon nano tube into 20ml of methanol solution of polyvinylpyrrolidone with the concentration of 4.5mg/ml to prepare carbon nano tube dispersion liquid; adding 20ml of methanol solution of cobalt nitrate hexahydrate with the concentration of 10mg/ml into carbon nano tube dispersion liquid, carrying out primary stirring treatment for 1h, then adding 40ml of methanol solution of 2-methylimidazole with the concentration of 12mg/ml, carrying out secondary stirring treatment for 2h, then carrying out centrifugal treatment, washing and drying the precipitate obtained by centrifugation, placing the dried solid in a muffle furnace under nitrogen atmosphere, heating to 800 ℃ at the heating rate of 4 ℃/min, and carrying out carbonization treatment for 3h to obtain the MOF-derived porous carbon/carbon nano tube composite material;
(2) placing 6g of silver powder, 2g of nano-copper powder, 1g of silver-coated copper powder and 1g of silver-coated nickel powder in an ethanol solution containing 0.2g of silane coupling agent, stirring, adding 3g of the prepared MOF-derived porous carbon/carbon nanotube composite material, and continuing stirring to prepare a conductive composite material;
(3) mixing and stirring 12 parts of epoxy resin, 5 parts of diethylene glycol butyl ether acetate, 1 part of ethanol and 1 part of ethylene glycol by weight to prepare a resin solution, adding 70 parts of silver powder, 0.5 part of the prepared conductive composite material, 1 part of zirconium acetylacetonate and 0.5 part of 3-aminopropyltriethoxysilane, and continuously stirring and mixing to prepare the conductive material.
Example 4
(1) Adding 0.12g of carbon nano tube into 20ml of methanol solution of polyvinylpyrrolidone with the concentration of 4.5mg/ml to prepare carbon nano tube dispersion liquid; adding 20ml of methanol solution of cobalt nitrate hexahydrate with the concentration of 10mg/ml into carbon nano tube dispersion liquid, carrying out primary stirring treatment for 1h, then adding 40ml of methanol solution of 2-methylimidazole with the concentration of 12mg/ml, carrying out secondary stirring treatment for 1h, then carrying out centrifugal treatment, washing and drying the precipitate obtained by centrifugation, placing the dried solid in a muffle furnace under the nitrogen atmosphere, heating to 800 ℃ at the heating rate of 4 ℃/min, and carrying out carbonization treatment for 3h to obtain the MOF-derived porous carbon/carbon nano tube composite material;
(2) placing 6g of silver powder, 2g of nano-copper powder, 1g of silver-coated copper powder and 1g of silver-coated nickel powder in an ethanol solution containing 0.15g of silane coupling agent, stirring, adding 3g of the prepared MOF-derived porous carbon/carbon nanotube composite material, and continuing stirring to prepare a conductive composite material;
(3) mixing and stirring 10 parts of epoxy resin, 5 parts of diethylene glycol butyl ether acetate, 1 part of ethanol and 1 part of ethylene glycol by weight to prepare a resin solution, adding 60 parts of silver powder, 0.5 part of the prepared conductive composite material, 1 part of zirconium acetylacetonate and 0.5 part of titanium coupling agent, and continuously stirring and mixing to prepare the conductive material.
Example 5
(1) Adding 0.1g of carbon nano tube into 20ml of methanol solution of polyvinylpyrrolidone with the concentration of 4mg/ml to prepare carbon nano tube dispersion liquid; adding 20ml of methanol solution of cobalt nitrate hexahydrate with the concentration of 10mg/ml into carbon nano tube dispersion liquid, carrying out primary stirring treatment for 1h, then adding 40ml of methanol solution of 2-methylimidazole with the concentration of 12mg/ml, carrying out secondary stirring treatment for 1h, then carrying out centrifugal treatment, washing and drying the precipitate obtained by centrifugation, placing the dried solid in a muffle furnace under the nitrogen atmosphere, heating to 800 ℃ at the heating rate of 3 ℃/min, and carrying out carbonization treatment for 4h to obtain the MOF-derived porous carbon/carbon nano tube composite material;
(2) placing 6g of silver powder, 2g of nano-copper powder, 1g of silver-coated copper powder and 1g of silver-coated nickel powder in an ethanol solution containing 0.1g of silane coupling agent, stirring, adding 2g of the prepared MOF-derived porous carbon/carbon nanotube composite material, and continuing stirring to prepare a conductive composite material;
(3) mixing and stirring 10 parts of epoxy resin, 5 parts of diethylene glycol butyl ether acetate, 1 part of ethanol and 1 part of ethylene glycol by weight to prepare a resin solution, adding 70 parts of silver powder, 0.5 part of the prepared conductive composite material, 1 part of titanium acetylacetonate and 0.5 part of aluminum coupling agent, and continuously stirring and mixing to prepare the conductive material.
Comparative example 1
(1) Putting 6g of silver powder, 2g of nano-copper powder, 1g of silver-coated copper powder and 1g of silver-coated nickel powder into an ethanol solution containing 0.1g of silane coupling agent, stirring, adding 2g of carbon nano-tube, and continuing stirring to prepare the conductive composite material;
(2) mixing and stirring 10 parts of epoxy resin, 5 parts of diethylene glycol butyl ether acetate, 1 part of ethanol and 1 part of ethylene glycol by weight to prepare a resin solution, adding 70 parts of silver powder, 0.5 part of the prepared conductive composite material, 1 part of titanium acetylacetonate and 0.5 part of aluminum coupling agent, and continuously stirring and mixing to prepare the conductive material.
Comparative example 2
(1) Stirring 20ml of methanol solution of cobalt nitrate hexahydrate with the concentration of 10mg/ml and 40ml of methanol solution of 2-methylimidazole with the concentration of 12mg/ml for 1 hour, then performing centrifugal treatment, washing and drying the precipitate obtained by centrifugation, putting the dried solid in a muffle furnace under the nitrogen atmosphere, heating to 800 ℃ at the heating rate of 3 ℃/min, performing carbonization for 4 hours to prepare an MOF (metal organic framework) derivative porous carbon material, and directly grinding and mixing the MOF derivative porous carbon material and 0.1g of carbon nano tubes to prepare a composite material;
(2) putting 6g of silver powder, 2g of nano-copper powder, 1g of silver-coated copper powder and 1g of silver-coated nickel powder into an ethanol solution containing 0.1g of silane coupling agent, stirring, adding 2g of the prepared composite material, and continuing stirring to prepare the conductive composite material;
(3) mixing and stirring 10 parts of epoxy resin, 5 parts of diethylene glycol butyl ether acetate, 1 part of ethanol and 1 part of ethylene glycol by weight to prepare a resin solution, adding 70 parts of silver powder, 0.5 part of the prepared conductive composite material, 1 part of titanium acetylacetonate and 0.5 part of aluminum coupling agent, and continuously stirring and mixing to prepare the conductive material.
The conductive material obtained above was subjected to a performance test as follows.
1. Resistance (RC)
The conductive materials prepared in the above examples and comparative examples were uniformly coated on PET substrates, respectively, and the printing thickness was 15 μm, and after drying, the resistivity of the coating film was measured by a four-probe method, and the volume resistivity of the coating film was calculated.
2. Hardness and adhesion
After the conductive materials prepared in the above examples and comparative examples were printed on a glass slide by screen printing and cured, the adhesion of the cured film was tested by astm d3359 paint film cross-cut experimental method. The hardness of the cured film is tested by A QHQ-A pencil scratch hardness tester, according to the GB/T6739 + 1996 standard, the surface of the pencil and the film is kept at 45 degrees and slides forwards at the speed of 1mm/s, the film layer is scratched by the pencil point, the pencil of each grade is subjected to 5 times from the pencil of the grade with the highest hardness, the pencil which cannot scratch the film layer for at least 4 times is found, and the pencil hardness is the film layer hardness.
3. Bending resistance test
The conductive material printed circuit obtained as described above was tested for bending resistance using a model TOS-817 swing tester, taiwan tostada test equipment ltd. The length of the conductive wire is 2.4cm, the width is 0.9mm, the thickness is 3 μm, 5 parallel values are measured, and the average value is taken. The experimental parameters were as follows: the swinging angle is as follows: 180 degrees; the swinging speed is as follows: 60 times per min -1 (ii) a The swinging times are as follows: 10000 times; temperature: 28 ℃, relative humidity: 80 percent. The characterization is carried out by the resistance change of the conductive lines before and after bending.
The test results are shown in table 1.
TABLE 1
The test results show that the conductive material prepared by the invention has excellent conductivity, good binding force with a substrate, and high hardness and good flexibility of a film formed by the film.
Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Claims (10)
1. A method for preparing a conductive material used for constructing a wireless communication functional circuit, comprising the steps of:
(1) adding the carbon nano tube into a methanol solution of polyvinylpyrrolidone to prepare a carbon nano tube dispersion liquid; adding a methanol solution of cobalt nitrate hexahydrate into a carbon nano tube dispersion liquid, carrying out primary stirring treatment, then adding a methanol solution of 2-methylimidazole, carrying out secondary stirring treatment, then carrying out centrifugal treatment, washing and drying a precipitate obtained by centrifugation, and placing a dried solid in a muffle furnace under a nitrogen atmosphere for carbonization treatment to obtain the MOF-derived porous carbon/carbon nano tube composite material;
(2) placing a conductive metal filler in an ethanol solution of a silane coupling agent, stirring, adding the prepared MOF-derived porous carbon/carbon nanotube composite material, and continuously stirring to prepare a conductive composite material;
(3) mixing and stirring matrix resin and a solvent to prepare a resin solution, adding the prepared conductive composite material, conductive filler, crosslinking agent and coupling agent, continuously stirring and mixing, and uniformly stirring to prepare the conductive material.
2. The method according to claim 1, wherein in the step (1), the concentration of the methanol solution of polyvinylpyrrolidone is 4-5mg/ml, the concentration of the methanol solution of cobalt nitrate hexahydrate is 10mg/ml, and the concentration of the methanol solution of 2-methylimidazole is 12-13 mg/ml; the dosage ratio of the carbon nano tube to the methanol solution of the polyvinylpyrrolidone to the methanol solution of the cobalt nitrate hexahydrate is 0.1-0.15 g: 20 ml: 20 ml: 35-45 ml.
3. The method for preparing a conductive material used for constructing a wireless communication functional circuit according to claim 1, wherein in the step (1), the time of the first stirring treatment is 1-2h, and the time of the second stirring treatment is 1-2 h.
4. The method for preparing a conductive material used for constructing a circuit with wireless communication function according to claim 1, wherein in the step (1), the temperature of the carbonization treatment is 800 ℃, the temperature rise rate of the carbonization treatment is 3-5 ℃/min, and the time of the carbonization treatment is 3-4 h.
5. The method according to claim 1, wherein in the step (2), the conductive metal filler is at least one of silver powder, copper powder, silver-coated nickel powder and silver-coated alloy powder; the alloy powder in the silver-coated alloy powder is composed of any two or more than two of iron, chromium, nickel, copper and niobium.
6. The method according to claim 1, wherein in the step (3), the conductive filler is silver powder, the silver powder is a mixture of flake silver powder and spherical silver powder in any proportion, and the tap densities of the flake silver powder and the spherical silver powder are both 2-7g/cm 3 。
7. The method for preparing the conductive material used for constructing the wireless communication functional circuit according to claim 1, wherein in the step (2), the mass ratio of the conductive metal filler, the silane coupling agent and the MOF-derived porous carbon/carbon nanotube composite material is 1: (0.005-0.03): (0.005-0.5).
8. The method for preparing the conductive material used for constructing the wireless communication functional circuit according to claim 1, wherein in the step (3), the matrix resin is one of epoxy resin, phenoxy resin, polyester and polyurethane resin; the cross-linking agent is one or more of aluminum acetylacetonate, titanium acetylacetonate, cobalt acetylacetonate, zirconium acetylacetonate, zinc acetylacetonate, iron acetylacetonate and copper acetylacetonate; the coupling agent is one or a mixture of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, a diamino silane coupling agent, 3-aminopropyl triethoxy silane, a titanium coupling agent and an aluminum coupling agent, and the solvent comprises a mixture of diethylene glycol butyl ether acetate, ethanol and ethylene glycol.
9. The method for preparing the conductive material used for constructing the wireless communication functional circuit according to claim 1, wherein in the step (3), the amounts of the components are respectively as follows by weight: 2-20 parts of matrix resin, 10-25 parts of solvent, 40-90 parts of conductive filler, 0-0.5 part of conductive composite material, 0.001-1 part of cross-linking agent and 0.1-2 parts of coupling agent.
10. An electrically conductive material useful for constructing a circuit for wireless communication functions, prepared by the method of any one of claims 1 to 9.
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| CN115602357A (en) * | 2022-10-24 | 2023-01-13 | 浙江振有电子股份有限公司（Cn） | Through hole copper paste with strong stability and high conductivity and preparation method thereof |
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| CN115602357A (en) * | 2022-10-24 | 2023-01-13 | 浙江振有电子股份有限公司（Cn） | Through hole copper paste with strong stability and high conductivity and preparation method thereof |
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