CN116836421A - Conductive film and preparation method thereof - Google Patents

Conductive film and preparation method thereof Download PDF

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CN116836421A
CN116836421A CN202310406226.0A CN202310406226A CN116836421A CN 116836421 A CN116836421 A CN 116836421A CN 202310406226 A CN202310406226 A CN 202310406226A CN 116836421 A CN116836421 A CN 116836421A
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copper
weight
silver composite
coated carbon
graphene oxide
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CN116836421B (en
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汪晓霞
尹心恒
陈子俊
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Hubei Zhongyi Technology Co ltd
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Hubei Zhongyi Technology Co ltd
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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
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2409/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2409/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
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    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients

Abstract

The invention provides a conductive film and a preparation method thereof, and belongs to the technical field of battery materials. Adding a carbon nano tube into a graphene oxide ethanol aqueous solution, spray drying to obtain a wrinkled graphene oxide coated carbon nano tube, mixing the wrinkled graphene oxide coated carbon nano tube with a copper/silver composite nano wire modified by polydopamine, reducing to obtain a wrinkled graphene coated carbon nano tube-modified copper/silver composite nano wire mixture, adding the wrinkled graphene coated carbon nano tube-modified copper/silver composite nano wire mixture, a compatilizer, a plasticizer, a toughening agent and an antioxidant into molten high polymer resin, uniformly mixing, extruding, and preparing a film to obtain a conductive film.

Description

Conductive film and preparation method thereof
Technical Field
The invention relates to the technical field of battery materials, in particular to a conductive film and a preparation method thereof.
Background
The copper foil has low surface oxygen characteristic, can be attached to various base materials such as metal, insulating materials and the like, and has a wide temperature application range. The conductive copper foil is mainly applied to electromagnetic shielding and antistatic, is arranged on the substrate surface, is combined with a metal base material, has excellent conductivity, and provides an electromagnetic shielding effect. Meanwhile, an electronic grade copper foil (purity of 99.7% or more, thickness of 5-105 μm) is one of base materials for the electronic industry. There is an increasing demand for electronic grade copper foil, especially high performance electronic grade copper foil, in markets at home and abroad. With the rapid development of the electronic information industry, the use amount of electronic copper foil is increasing, and the product is widely applied to industrial calculators, communication equipment, lithium ion batteries, civil televisions, video recorders, CD players, copiers, telephones, cooling and heating air conditioners, electronic components for automobiles, game machines and the like.
The current manufacturing technology of pure copper foil is mainly divided into electrolysis and calendaring. The electrolytic method is a method that electrolytic copper or wire return materials with the same purity are taken as raw materials, dissolved in a solution containing copper sulfate, electrolyzed in an electrolytic tank with an insoluble material as an anode and a cathode roller immersed in the copper sulfate electrolyte at a constant speed at the bottom as a cathode, and copper in the solution is deposited on the surface of the cathode roller to form copper foil. The rolling method is a technique of forming a copper foil of a specific thickness by a roll. Pure copper, although having a relatively high electrical conductivity, still has a large relative mass. Therefore, the conductive film capable of replacing the copper foil is very important and has wide application prospect.
The traditional evaporation coating is a process method for evaporating coating materials (or film materials) by adopting a certain heating evaporation mode and gasifying the materials, and particles fly to the surface of a substrate to form a film by condensation. The physical process comprises the following steps: the deposition material is evaporated or sublimated into gaseous particles, the gaseous particles are quickly conveyed from an evaporation source to the surface of the substrate, the gaseous particles are adhered to the surface of the substrate to form nuclei and grow into a solid film, and the film atoms are reconstructed or chemical bonding is generated. The vapor deposition method can deposit thin films of metals, semiconductors, insulators, alloys with different composition ratios, compounds, partial organic polymers and the like on surfaces of metals, semiconductors, insulators, plastics, paper and fabrics. However, evaporation cannot achieve a coating with a large thickness, resulting in a limited process range. Electroplating is a process whereby a thin layer of other metals or alloys is plated onto some metal surfaces using the principles of electrolysis. Compared with the plating method, the plating method can enhance the corrosion resistance of metal, prevent abrasion, improve the conductivity, the lubricity, the heat resistance and the attractive surface. The electroplating mode can also realize the coating of a metal layer with large thickness, thereby widening the process range. However, most of the polymer films have very low conductivity, so that satisfactory bonding strength and electrical conductivity of the products cannot be achieved by direct electroplating.
Chinese patent CN103192074B discloses a highly dispersed silver powder and conductive silver paste for thin film batteries. The silver powder consists of polymer microspheres and nano silver layers coated on the surfaces of the polymer microspheres, wherein the polymer microspheres are formed by polymerizing methacrylic resin, photoinitiator 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide and polyvinyl alcohol through ultraviolet irradiation. The silver powder has good dispersion, reduces the consumption of the metal silver powder, reduces the cost and further improves the conductivity. However, the silver powder is complex in preparation steps, poor in repeatability and uneven in silver powder quality. The multi-element compound thin film solar cells in the market at present, such as gallium arsenide and cadmium sulfide thin film solar cells, and the like. Glass is used as an important component of a thin film solar cell, and glass with poor mechanical properties cannot resist the environment.
Disclosure of Invention
The invention aims to provide a conductive film and a preparation method thereof, which have the advantages of good conductive performance, good mechanical property, wear resistance and heat resistance stability, good durability, long service life, simple preparation method and low cost, and the obtained conductive film has high conductivity, low haze and high transmittance, and has wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of a conductive film, which comprises the steps of adding a carbon nano tube into a graphene oxide ethanol aqueous solution, spray drying to obtain a wrinkled graphene oxide coated carbon nano tube, mixing the wrinkled graphene oxide coated carbon nano tube with a polydopamine modified copper/silver composite nano wire, reducing to obtain a wrinkled graphene coated carbon nano tube-modified copper/silver composite nano wire mixture, adding the wrinkled graphene coated carbon nano tube-modified copper/silver composite nano wire mixture, a compatilizer, a plasticizer and an antioxidant into molten high polymer resin, uniformly mixing, extruding, and preparing a film to obtain the conductive film.
As a further improvement of the invention, the method comprises the following steps:
s1, preparing a pleated graphene oxide coated carbon nano tube: dissolving graphene oxide in an ethanol water solution, adding carbon nanotubes, uniformly dispersing, and carrying out spray drying and grinding to obtain the wrinkled graphene oxide coated carbon nanotubes;
s2, preparing copper/silver composite nanowires: dissolving polyvinylpyrrolidone in glycol, adding ethanol, sodium chloride, alum trioxide, silver nitrate and copper nitrate, carrying out microwave heating and stirring reaction, centrifuging, washing and drying to obtain a copper/silver composite nanowire;
s3, modifying polydopamine: dispersing the copper/silver composite nanowire prepared in the step S2 in water, adding dopamine hydrochloride and a catalyst, heating and stirring for reaction, centrifuging, washing and drying to obtain a modified copper/silver composite nanowire;
S4, preparation of a mixture: dispersing the pleated graphene oxide coated carbon nano tube prepared in the step S1 in ethanol, adding the modified copper/silver composite nano wire prepared in the step S3, stirring and mixing uniformly, and heating for reaction to prepare a pleated graphene oxide coated carbon nano tube-modified copper/silver composite nano wire mixture;
s5, reduction: adding the pleated graphene oxide coated carbon nanotube-modified copper/silver composite nanowire mixture prepared in the step S4 into water, uniformly dispersing, adding ammonia water and hydrazine hydrate, heating for reaction, filtering and washing to obtain the pleated graphene coated carbon nanotube-modified copper/silver composite nanowire mixture;
s6, mixing and dispersing the phase agent, the plasticizer, the toughening agent and the antioxidant to obtain the modifier;
s7, preparing a conductive film: adding high polymer resin into a double screw extruder, heating to melt, adding the wrinkled graphene coated carbon nano tube-modified copper/silver composite nano wire mixture prepared in the step S5 and the modifier prepared in the step S6, uniformly mixing, extruding to obtain conductive high polymer resin, and preparing a film to obtain the conductive film.
As a further improvement of the invention, the mass ratio of the graphene oxide to the carbon nano tube in the step S1 is 5-10:3-5; the ethanol content in the ethanol water solution is 35-55wt%, the spray drying condition is that the air inlet temperature is 85-95 ℃, the air outlet temperature is 20-60 ℃, and the evaporation water amount is 1700-2200mL/h.
As a further improvement of the invention, the mass ratio of polyvinylpyrrolidone, ethylene glycol, ethanol, sodium chloride, alum trioxide, silver nitrate and copper nitrate in the step S2 is 0.2-0.3:70-90:2-5:0.0002-0.0003:0.0001-0.00015:0.12-0.17:0.10-0.12, wherein the temperature of the heating and stirring reaction is 175-185 ℃ and the time is 30-50min.
As a further improvement of the invention, the mass ratio of the copper/silver composite nanowire to the dopamine hydrochloride to the catalyst in the step S3 is 12-15:17-20:0.2-0.5, and the catalyst contains 3-5wt% of CoCl 2 The temperature of the heating and stirring reaction is 45-55 ℃ and the time is 2-3h.
As a further improvement of the invention, in the step S4, the mass ratio of the wrinkled graphene oxide coated carbon nano tube to the modified copper/silver composite nano wire is 20-25:3-5, the temperature of the heating reaction is 35-45 ℃, and the time is 20-40min.
As a further improvement of the present invention, the mass ratio of the wrinkled graphene oxide coated carbon nanotube-modified copper/silver composite nanowire, ammonia water and hydrazine hydrate in step S5 is 10:3-5:0.5-1.2; the concentration of the ammonia water is 15-25wt%, the temperature of the heating reaction is 80-100 ℃ and the time is 1-2h.
As a further improvement of the present invention, the mass ratio of the compatilizer, the plasticizer, the toughening agent and the antioxidant in the step S6 is 1-2:3-5:2-3:0.5-1, the compatilizer is at least one of ST-1, ST-2, ST-3, ST-4, ST-5, ST-6, ST-7, ST-8 and ST-9, the plasticizer is at least one of di (2-ethylhexyl) phthalate, dioctyl phthalate, di-n-octyl phthalate, butyl benzyl phthalate, di-sec-octyl phthalate, dicyclohexyl phthalate, dibutyl phthalate, diisobutyl phthalate, dimethyl phthalate, diethyl phthalate, diisononyl phthalate and diisodecyl phthalate, the toughening agent is at least one of liquid polysulfide rubber, liquid acrylate rubber, liquid polybutadiene rubber, nitrile rubber, ethylene propylene rubber and styrene-butadiene rubber, and the antioxidant is at least one of antioxidants 1010, antioxidants 1076, 168 and 1192.
As a further improvement of the invention, in the step S7, the mass ratio of the macromolecule resin, the wrinkled graphene coated carbon nano tube-modified copper/silver composite nano wire mixture and the modifier is 100:7-12:2-4; the polymer resin is at least one selected from polypropylene, polyethylene terephthalate, polyimide and polyethylene naphthalate.
The invention further provides the conductive film prepared by the preparation method.
The invention has the following beneficial effects: according to the preparation method, the carbon nano tube is added into graphene oxide ethanol aqueous solution, the graphene oxide aqueous solution forms small liquid beads which wrap the carbon nano tube through the air pressure effect of a nozzle, the solvent is quickly evaporated, the volume of the small liquid beads is quickly contracted, the folded graphene oxide coated carbon nano tube is obtained, the folded graphene oxide coated carbon nano tube is mixed with copper/silver composite nano wires modified by polydopamine, a polydopamine layer on the surface of the copper/silver composite nano wires contains abundant hydroxyl groups, carboxyl groups and amino groups, and can be fully bonded with the folded graphene oxide coated carbon nano tube, and after further reduction, the folded graphene coated carbon nano tube-modified copper/silver composite nano wire mixture is obtained.
According to the invention, graphene is a material with excellent conductivity, so that the conductivity of an electrode material can be improved, and the charge and discharge performance of the electrode material can be improved; meanwhile, the flexible two-dimensional layered structure of the graphene can effectively inhibit material pulverization of the electrode material caused by volume change in the charging and discharging process, and enhance conductive contact with a current collector.
In addition, after the surface of the copper/silver composite nanowire prepared by the method is modified by polydopamine, an insulating layer is formed, so that the problem that the surface is oxidized when copper and silver metals are contacted with air is effectively avoided, the durability of the conductive film can be improved, and the service life of the conductive film is prolonged.
The conductive film doped with the wrinkled graphene coated carbon nano tube-copper/silver composite nanowire has good transmittance, high conductivity, low cost, flexibility, bending property and comprehensive photoelectric property, meanwhile, the addition of copper further reduces silver doping, the preparation cost of the conductive film is greatly reduced, meanwhile, the copper and silver composite nanowire can further improve the electrical property of the film, the silver nanowire with higher length-diameter ratio can improve the construction efficiency of a conductive network, the addition of the copper nanowire can improve the length-diameter ratio of the silver nanowire, meanwhile, the construction of the conductive network is promoted, the addition amount of the copper/silver composite nanowire is further reduced, and the conductive film with high conductivity, low haze and high transmittance can be built.
Meanwhile, in the preparation process of the copper/silver composite nanowire, the higher temperature is favorable for improving the reaction rate of reactants, a large number of nanowires can be rapidly generated in a short time, the reduction of silver ions can be seriously influenced by the lower temperature, the growth speed of crystals is reduced, and the obtained product is mostly silver nanoparticles.
The invention controls the nucleation speed and the size of the product by adding the composite nucleation control agent (sodium chloride and alum trioxide), cl - The addition of (2) can promote the anisotropic growth of the crystal and the formation of silver nanowires, the alum trioxide and the sodium chloride can selectively etch out a plurality of twin Ag particles, and only single crystal grows into nano-level cubes and tetrahedra, and meanwhile Cl - Will be with Ag + Reacting to form AgCl colloid for buffering Ag + Thereby limiting the nucleation of Ag, promoting the growth of silver nanowires, improving the length-diameter ratio of silver nanowires, having synergistic effect and improving the conductivity of the conductive film.
The conductive film prepared by the invention has good conductive performance, good mechanical property, wear resistance and heat resistance stability, good durability, long service life, simple preparation method and low cost, and the conductive film with high conductivity, low haze and high transmittance is obtained, and has wide application prospect.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is an SEM image of a pleated graphene oxide coated carbon nanotube prepared in step S1 of example 1;
FIG. 2 is a graph showing comparison of mass change rates of each group in test example 1.
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 preparation method of the graphene oxide comprises the following steps:
firstly, weighing 10g of natural graphite powder, 4g of potassium persulfate and 10g of phosphorus pentoxide, adding into a three-neck flask filled with 25mL of sulfuric acid under the condition of stirring, reacting for 4 hours in a constant-temperature water bath at 60 ℃, then transferring the three-neck flask into the constant-temperature water bath at 25 ℃ for reacting for 5 hours, filtering, cleaning to neutrality, and drying in air to obtain pre-oxidized graphite;
weighing lg of pre-oxidized graphite, adding the pre-oxidized graphite into a three-neck flask filled with 25mL of sulfuric acid under stirring, placing the three-neck flask into an ice-water bath, adding 3g of potassium permanganate after the pre-oxidized graphite is completely dissolved, reacting for 2 hours, moving the three-neck flask into a constant-temperature water bath at 35 ℃ for reacting for 40 minutes, finally adding deionized water, continuing to react for 1 hour at 35 ℃, and finally dripping 30% of H 2 O 2 So that no more gas is generated, the solution turns bright yellow, is filtered centrifugally while hot, and is washed to neutrality with a large amount of 5% hydrochloric acid and deionized water. And (3) carrying out ultrasonic vibration on the final precipitate for 1h, pouring the precipitate into a culture dish, and drying the precipitate at 90 ℃ for 24h to obtain the flaky graphene oxide.
The carbon nanotubes are multi-walled carbon nanotubes, with an outer diameter: 4-6nm, purity of more than 98%, length of 10-20microns, specific surface area of 500-700m 2 And/g, purchased from the university of chinese academy of sciences, inc; nitrile rubber, nandi NBR1052, available from Shanghai rubber Inc.; ethylene propylene rubber, available from Fenyang Tang (Shanghai) Utility Co., ltd; styrene butadiene rubber, medium petrifaction SBR1712, purchased from Shanghai rubber industries, inc; polypropylene, medium petrochemical M800E, injection molded grade PP, was purchased from Shanghai Bib plasticizing technology Co.
Example 1
The embodiment provides a method for preparing a conductive film, which comprises the following steps:
s1, preparing a pleated graphene oxide coated carbon nano tube: dissolving 5 parts by weight of graphene oxide in 50 parts by weight of 35wt% ethanol aqueous solution, adding 3 parts by weight of carbon nano tubes, performing 1000W ultrasonic dispersion for 15min, and performing spray drying under the condition that the air inlet temperature is 85 ℃, the air outlet temperature is 40 ℃, the evaporation water amount is 1700mL/h, and grinding to obtain the pleated graphene oxide coated carbon nano tubes; fig. 1 is an SEM image of the produced pleated graphene oxide coated carbon nanotubes, and it can be seen from the figure that a pleated structure is formed.
S2, preparing copper/silver composite nanowires: dissolving 0.2 weight part of polyvinylpyrrolidone in 70 weight parts of ethylene glycol, adding 2 weight parts of ethanol, 0.0002 weight part of sodium chloride, 0.0001 weight part of alum trioxide, 0.12 weight part of silver nitrate and 0.10 weight part of copper nitrate, heating 1000W microwaves to a temperature of 175 ℃, stirring and reacting for 30min, centrifuging for 15min at 3000r/min, washing with deionized water, and drying at 105 ℃ for 1h to obtain the copper/silver composite nanowire;
s3, modifying polydopamine: dispersing 12 parts by weight of the copper/silver composite nanowire prepared in the step S2 in 100 parts by weight of water, adding 17 parts by weight of dopamine hydrochloride and 0.2 part by weight of catalyst, heating to 45 ℃, stirring and reacting for 2 hours, centrifuging for 15 minutes 3000r/min, washing with deionized water, and drying for 1 hour at 105 ℃ to obtain the modified copper/silver composite nanowire;
the catalyst was a catalyst containing 3wt% of CoCl 2 Tris-HCl solution at ph=5;
s4, preparation of a mixture: adding 20 parts by weight of the wrinkled graphene oxide coated carbon nano tube prepared in the step S1 into 50 parts by weight of ethanol, performing 1000W ultrasonic dispersion for 10min, adding 3 parts by weight of the modified copper/silver composite nano wire prepared in the step S3, uniformly stirring and mixing for 10min, heating to 35 ℃, and stirring and reacting for 20min to prepare a wrinkled graphene oxide coated carbon nano tube-modified copper/silver composite nano wire mixture;
S5, reduction: adding 10 parts by weight of the pleated graphene oxide coated carbon nanotube-modified copper/silver composite nanowire mixture prepared in the step S4 into 50 parts by weight of water, performing 1000W ultrasonic dispersion for 10min, adding 3 parts by weight of 15wt% ammonia water and 0.5 part by weight of hydrazine hydrate, heating to 80 ℃, stirring for reaction for 1h, filtering, washing with deionized water, and drying at 105 ℃ for 1h to obtain the pleated graphene coated carbon nanotube-modified copper/silver composite nanowire mixture;
s6, stirring and mixing 1 part by weight of a compatilizer ST-4, 3 parts by weight of di-n-octyl phthalate, 2 parts by weight of nitrile rubber and 0.5 part by weight of antioxidant 168 for 10min to obtain a modifier;
s7, preparing a conductive film: adding 100 parts by weight of polypropylene into a double-screw extruder, heating to melt, adding 7 parts by weight of the wrinkled graphene coated carbon nano tube-modified copper/silver composite nano wire mixture prepared in the step S5 and 2 parts by weight of the modifier prepared in the step S6, stirring and mixing for 1.5 hours, extruding into conductive high polymer resin, and preparing a film to obtain the conductive film.
Example 2
The embodiment provides a method for preparing a conductive film, which comprises the following steps:
s1, preparing a pleated graphene oxide coated carbon nano tube: dissolving 10 parts by weight of graphene oxide in 50 parts by weight of 55wt% ethanol aqueous solution, adding 5 parts by weight of carbon nano tubes, performing 1000W ultrasonic dispersion for 15min, and performing spray drying, wherein the spray drying condition is that the air inlet temperature is 95 ℃, the air outlet temperature is 60 ℃, the evaporation water amount is 2200mL/h, and grinding to obtain the pleated graphene oxide coated carbon nano tubes;
S2, preparing copper/silver composite nanowires: dissolving 0.3 part by weight of polyvinylpyrrolidone in 90 parts by weight of ethylene glycol, adding 5 parts by weight of ethanol, 0.0003 part by weight of sodium chloride, 0.00015 part by weight of alum trioxide, 0.17 part by weight of silver nitrate and 0.12 part by weight of copper nitrate, heating 1200W microwaves to 185 ℃, stirring and reacting for 50min, centrifuging for 15min 3000r/min, washing with deionized water, and drying for 1h at 105 ℃ to obtain copper/silver composite nanowires;
s3, modifying polydopamine: dispersing 15 parts by weight of the copper/silver composite nanowire prepared in the step S2 in 100 parts by weight of water, adding 20 parts by weight of dopamine hydrochloride and 0.5 part by weight of catalyst, heating to 55 ℃, stirring and reacting for 3 hours, centrifuging for 15 minutes 3000r/min, washing with deionized water, and drying for 1 hour at 105 ℃ to obtain the modified copper/silver composite nanowire;
the catalyst was a catalyst containing 5wt% of CoCl 2 Tris-HCl solution at ph=6;
s4, preparation of a mixture: adding 25 parts by weight of the wrinkled graphene oxide coated carbon nano tube prepared in the step S1 into 50 parts by weight of ethanol, performing 1000W ultrasonic dispersion for 10min, adding 5 parts by weight of the modified copper/silver composite nano wire prepared in the step S3, uniformly stirring and mixing for 10min, heating to 45 ℃, and stirring and reacting for 40min to prepare a wrinkled graphene oxide coated carbon nano tube-modified copper/silver composite nano wire mixture;
S5, reduction: adding 10 parts by weight of the pleated graphene oxide coated carbon nanotube-modified copper/silver composite nanowire mixture prepared in the step S4 into 50 parts by weight of water, performing 1000W ultrasonic dispersion for 10min, adding 5 parts by weight of 25wt% ammonia water and 1.2 parts by weight of hydrazine hydrate, heating to 100 ℃, stirring for reacting for 2h, filtering, washing with deionized water, and drying at 105 ℃ for 1h to obtain the pleated graphene coated carbon nanotube-modified copper/silver composite nanowire mixture;
s6, stirring and mixing 2 parts by weight of a compatilizer ST-1, 5 parts by weight of diisononyl phthalate, 3 parts by weight of ethylene propylene rubber and 1 part by weight of an antioxidant 1010 for 10min to obtain a modifier;
s7, preparing a conductive film: adding 100 parts by weight of polypropylene into a double-screw extruder, heating to melt, adding 12 parts by weight of the wrinkled graphene coated carbon nano tube-modified copper/silver composite nano wire mixture prepared in the step S5 and 4 parts by weight of the modifier prepared in the step S6, stirring and mixing for 1.5 hours, extruding into conductive high polymer resin, and preparing a film to obtain the conductive film.
Example 3
The embodiment provides a method for preparing a conductive film, which comprises the following steps:
s1, preparing a pleated graphene oxide coated carbon nano tube: dissolving 7 parts by weight of graphene oxide in 50 parts by weight of 45wt% ethanol aqueous solution, adding 4 parts by weight of carbon nano tubes, performing 1000W ultrasonic dispersion for 15min, and performing spray drying under the condition that the air inlet temperature is 90 ℃, the air outlet temperature is 50 ℃, the evaporation water amount is 2000mL/h, and grinding to obtain the pleated graphene oxide coated carbon nano tubes;
S2, preparing copper/silver composite nanowires: dissolving 0.25 weight part of polyvinylpyrrolidone in 80 weight parts of ethylene glycol, adding 3.5 weight parts of ethanol, 0.00025 weight parts of sodium chloride, 0.00012 weight parts of alum trioxide, 0.15 weight parts of silver nitrate and 0.11 weight parts of copper nitrate, heating 1100W microwaves to 180 ℃, stirring and reacting for 40min, centrifuging for 15min 3000r/min, washing with deionized water, and drying at 105 ℃ for 1h to obtain the copper/silver composite nanowire;
s3, modifying polydopamine: dispersing 13.5 parts by weight of the copper/silver composite nanowire prepared in the step S2 in 100 parts by weight of water, adding 18.5 parts by weight of dopamine hydrochloride and 0.35 part by weight of catalyst, heating to 50 ℃, stirring and reacting for 2.5 hours, centrifuging for 15 minutes at 3000r/min, washing with deionized water, and drying for 1 hour at 105 ℃ to obtain the modified copper/silver composite nanowire;
the catalyst was a catalyst containing 4wt% CoCl 2 Tris-HCl solution at ph=5.5;
s4, preparation of a mixture: adding 22 parts by weight of the wrinkled graphene oxide coated carbon nano tube prepared in the step S1 into 50 parts by weight of ethanol, performing 1000W ultrasonic dispersion for 10min, adding 4 parts by weight of the modified copper/silver composite nano wire prepared in the step S3, uniformly stirring and mixing for 10min, heating to 40 ℃, and stirring and reacting for 30min to prepare a wrinkled graphene oxide coated carbon nano tube-modified copper/silver composite nano wire mixture;
S5, reduction: adding 10 parts by weight of the wrinkled graphene oxide coated carbon nano tube-modified copper/silver composite nano wire mixture prepared in the step S4 into 50 parts by weight of water, performing 1000W ultrasonic dispersion for 10min, adding 4 parts by weight of 20wt% ammonia water and 0.9 part by weight of hydrazine hydrate, heating to 90 ℃, stirring for reacting for 1.5h, filtering, washing with deionized water, and drying at 105 ℃ for 1h to obtain the wrinkled graphene coated carbon nano tube-modified copper/silver composite nano wire mixture;
s6, stirring and mixing 1.5 parts by weight of a compatilizer ST-2, 4 parts by weight of di-sec-octyl phthalate, 2.5 parts by weight of styrene-butadiene rubber and 0.7 part by weight of an antioxidant 1192 for 10 minutes to obtain a modifier;
s7, preparing a conductive film: adding 100 parts by weight of polypropylene into a double-screw extruder, heating to melt, adding 10 parts by weight of the wrinkled graphene coated carbon nano tube-modified copper/silver composite nano wire mixture prepared in the step S5 and 3 parts by weight of the modifier prepared in the step S6, stirring and mixing for 1.5 hours, extruding into conductive high polymer resin, and preparing a film to obtain the conductive film.
Comparative example 1
The difference from example 3 is that no carbon nanotubes were added in step S1.
The method comprises the following steps:
s1, dissolving 11 parts by weight of graphene oxide in 50 parts by weight of 45wt% ethanol aqueous solution, performing 1000W ultrasonic dispersion for 15min, performing spray drying, wherein the spray drying condition is that the air inlet temperature is 90 ℃, the air outlet temperature is 50 ℃, the evaporation water amount is 2000mL/h, and grinding to obtain the wrinkled graphene oxide.
Comparative example 2
In comparison with example 3, the difference is that graphene oxide is not added in step S1.
The method comprises the following steps:
s1, adding 50 parts by weight of 45wt% ethanol water solution into 11 parts by weight of carbon nano tubes, performing 1000W ultrasonic dispersion for 15min, performing spray drying, wherein the spray drying condition is that the air inlet temperature is 90 ℃, the air outlet temperature is 50 ℃, the evaporation water amount is 2000mL/h, and grinding to obtain the carbon nano tubes.
Comparative example 3
In comparison with example 3, the difference is that in step S1, spray drying is not performed, and direct drying is employed.
The method comprises the following steps:
s1, preparing a pleated graphene oxide coated carbon nano tube: after 7 parts by weight of graphene oxide is dissolved in 50 parts by weight of 45wt% ethanol aqueous solution, 4 parts by weight of carbon nanotubes are added, 1000W is subjected to ultrasonic dispersion for 15min, drying is carried out at 105 ℃ for 4h, and grinding is carried out, so that the graphene oxide coated carbon nanotubes are obtained.
Comparative example 4
The difference from example 3 is that no silver nitrate was added in step S2.
The method comprises the following steps:
s2, dissolving 0.25 part by weight of polyvinylpyrrolidone in 80 parts by weight of ethylene glycol, adding 3.5 parts by weight of ethanol, 0.00025 parts by weight of sodium chloride, 0.00012 parts by weight of alum trioxide and 0.26 part by weight of copper nitrate, heating by 1100W microwaves to 180 ℃, stirring and reacting for 40min, centrifuging for 15min at 3000r/min, washing by deionized water, and drying for 1h at 105 ℃ to obtain the copper nanowire.
Comparative example 5
The difference from example 3 is that copper nitrate is not added in step S2.
The method comprises the following steps:
s2, dissolving 0.25 part by weight of polyvinylpyrrolidone in 80 parts by weight of ethylene glycol, adding 3.5 parts by weight of ethanol, 0.00025 parts by weight of sodium chloride, 0.00012 parts by weight of alum trioxide and 0.26 part by weight of silver nitrate, heating by 1100W microwaves to 180 ℃, stirring and reacting for 40min, centrifuging for 15min 3000r/min, washing by deionized water, and drying for 1h at 105 ℃ to obtain the copper/silver composite nanowire.
Comparative example 6
In comparison with example 3, the difference is that sodium chloride is not added in step S2.
The method comprises the following steps:
s2, preparing copper/silver composite nanowires: dissolving 0.25 weight part of polyvinylpyrrolidone in 80 weight part of ethylene glycol, adding 3.5 weight parts of ethanol, 0.00037 weight parts of alum trioxide, 0.15 weight parts of silver nitrate and 0.11 weight part of copper nitrate, heating by 1100W microwaves to 180 ℃, stirring and reacting for 40min, centrifuging for 15min at 3000r/min, washing with deionized water, and drying at 105 ℃ for 1h to obtain the copper/silver composite nanowire.
Comparative example 7
In comparison with example 3, the difference is that no alum trioxide is added in step S2.
The method comprises the following steps:
S2, preparing copper/silver composite nanowires: dissolving 0.25 weight part of polyvinylpyrrolidone in 80 weight part of ethylene glycol, adding 3.5 weight parts of ethanol, 0.00037 weight parts of sodium chloride, 0.15 weight part of silver nitrate and 0.11 weight part of copper nitrate, heating by 1100W microwaves to 180 ℃, stirring for reaction 40min, centrifuging for 15min at 3000r/min, washing by deionized water, and drying for 1h at 105 ℃ to obtain the copper/silver composite nanowire.
Comparative example 8
The difference from comparative example 3 is that sodium chloride and alum trioxide are not added in step S2.
The method comprises the following steps:
s2, dissolving 0.25 part by weight of polyvinylpyrrolidone in 80 parts by weight of ethylene glycol, adding 3.5 parts by weight of ethanol, 0.15 parts by weight of silver nitrate and 0.11 part by weight of copper nitrate, heating by 1100W microwaves to 180 ℃, stirring for reaction 40min, centrifuging for 15min at 3000r/min, washing by deionized water, and drying for 1h at 105 ℃ to obtain the copper/silver composite nanowire.
Comparative example 9
In comparison with example 3, the difference is that step S3 is not performed.
The method comprises the following steps:
s1, preparing a pleated graphene oxide coated carbon nano tube: dissolving 7 parts by weight of graphene oxide in 50 parts by weight of 45wt% ethanol aqueous solution, adding 4 parts by weight of carbon nano tubes, performing 1000W ultrasonic dispersion for 15min, and performing spray drying under the condition that the air inlet temperature is 90 ℃, the air outlet temperature is 50 ℃, the evaporation water amount is 2000mL/h, and grinding to obtain the pleated graphene oxide coated carbon nano tubes;
S2, preparing copper/silver composite nanowires: dissolving 0.25 weight part of polyvinylpyrrolidone in 80 weight parts of ethylene glycol, adding 3.5 weight parts of ethanol, 0.00025 weight parts of sodium chloride, 0.00012 weight parts of alum trioxide, 0.15 weight parts of silver nitrate and 0.11 weight parts of copper nitrate, heating 1100W microwaves to 180 ℃, stirring and reacting for 40min, centrifuging for 15min 3000r/min, washing with deionized water, and drying at 105 ℃ for 1h to obtain the copper/silver composite nanowire;
s3, preparing a mixture: adding 22 parts by weight of the wrinkled graphene oxide coated carbon nano tube prepared in the step S1 into 50 parts by weight of ethanol, performing 1000W ultrasonic dispersion for 10min, adding 4 parts by weight of the copper/silver composite nano wire prepared in the step S2, uniformly stirring and mixing for 10min, heating to 40 ℃, and stirring and reacting for 30min to prepare a wrinkled graphene oxide coated carbon nano tube-copper/silver composite nano wire mixture;
s4, reduction: adding 10 parts by weight of the wrinkled graphene oxide coated carbon nano tube-copper/silver composite nano wire mixture prepared in the step S3 into 50 parts by weight of water, performing 1000W ultrasonic dispersion for 10min, adding 4 parts by weight of 20wt% ammonia water and 0.9 part by weight of hydrazine hydrate, heating to 90 ℃, stirring and reacting for 1.5h, filtering, washing with deionized water, and drying at 105 ℃ for 1h to obtain the wrinkled graphene coated carbon nano tube-copper/silver composite nano wire mixture;
S5, stirring and mixing 1.5 parts by weight of a compatilizer ST-2, 4 parts by weight of di-sec-octyl phthalate, 2.5 parts by weight of styrene-butadiene rubber and 0.7 part by weight of an antioxidant 1192 for 10 minutes to obtain a modifier;
s6, preparing a conductive film: and (2) adding 100 parts by weight of polypropylene into a double-screw extruder, heating to melt, adding 10 parts by weight of the wrinkled graphene-coated carbon nano tube-copper/silver composite nanowire mixture prepared in the step (S4) and 3 parts by weight of the modifier prepared in the step (S5), stirring and mixing for 1.5 hours, extruding into conductive high polymer resin, and preparing a film to obtain the conductive film.
Test example 1
The modified copper/silver composite nanowires prepared in examples 1 to 3 of the present invention and the copper/silver composite nanowire prepared in comparative example 9 were stored in a dry box at room temperature of 25 ℃ for 60 days, one record was made every ten days, the mass of the sample was measured before and after each other, and the mass change rate was calculated, and the result was shown in fig. 2.
As can be seen from fig. 2, the copper/silver composite nanowire of the present invention has better oxidation resistance after being modified by polydopamine coating. After the surface of the copper/silver composite nanowire prepared by the method is modified by polydopamine, an insulating layer is formed, so that the problem that the surface is oxidized when copper and silver metals are contacted with air is effectively avoided, the durability of the conductive film can be improved, and the service life of the conductive film is prolonged.
Comparative example 10
The difference from example 3 is that the pleated graphene oxide coated carbon nanotubes are not added in step S4.
The method comprises the following steps:
s1, preparing a copper/silver composite nanowire: dissolving 0.25 weight part of polyvinylpyrrolidone in 80 weight parts of ethylene glycol, adding 3.5 weight parts of ethanol, 0.00025 weight parts of sodium chloride, 0.00012 weight parts of alum trioxide, 0.15 weight parts of silver nitrate and 0.11 weight parts of copper nitrate, heating 1100W microwaves to 180 ℃, stirring and reacting for 40min, centrifuging for 15min 3000r/min, washing with deionized water, and drying at 105 ℃ for 1h to obtain the copper/silver composite nanowire;
s2, modifying polydopamine: dispersing 13.5 parts by weight of the copper/silver composite nanowire prepared in the step S2 in 100 parts by weight of water, adding 18.5 parts by weight of dopamine hydrochloride and 0.35 part by weight of catalyst, heating to 50 ℃, stirring and reacting for 2.5 hours, centrifuging for 15 minutes at 3000r/min, washing with deionized water, and drying for 1 hour at 105 ℃ to obtain the modified copper/silver composite nanowire;
the catalyst was a catalyst containing 4wt% CoCl 2 Tris-HCl solution at ph=5.5;
s3, stirring and mixing 1.5 parts by weight of a compatilizer ST-2, 4 parts by weight of di-sec-octyl phthalate, 2.5 parts by weight of styrene-butadiene rubber and 0.7 part by weight of an antioxidant 1192 for 10 minutes to obtain a modifier;
S4, preparation of a conductive film: adding 100 parts by weight of polypropylene into a double-screw extruder, heating to melt, adding 10 parts by weight of the modified copper/silver composite nanowire prepared in the step S2 and 3 parts by weight of the modifier prepared in the step S3, stirring and mixing for 1.5 hours, extruding to obtain conductive high polymer resin, and preparing a film to obtain the conductive film.
Comparative example 11
The difference compared to example 3 is that the modified copper/silver composite nanowire is not added in step S4.
The method comprises the following steps:
s1, preparing a pleated graphene oxide coated carbon nano tube: dissolving 7 parts by weight of graphene oxide in 50 parts by weight of 45wt% ethanol aqueous solution, adding 4 parts by weight of carbon nano tubes, performing 1000W ultrasonic dispersion for 15min, and performing spray drying under the condition that the air inlet temperature is 90 ℃, the air outlet temperature is 50 ℃, the evaporation water amount is 2000mL/h, and grinding to obtain the pleated graphene oxide coated carbon nano tubes;
s2, reduction: adding 10 parts by weight of the pleated graphene oxide coated carbon nanotube prepared in the step S1 into 50 parts by weight of water, performing 1000W ultrasonic dispersion for 10min, adding 4 parts by weight of 20wt% ammonia water and 0.9 part by weight of hydrazine hydrate, heating to 90 ℃, stirring and reacting for 1.5h, filtering, washing with deionized water, and drying at 105 ℃ for 1h to obtain the pleated graphene coated carbon nanotube;
S3, stirring and mixing 1.5 parts by weight of a compatilizer ST-2, 4 parts by weight of di-sec-octyl phthalate, 2.5 parts by weight of styrene-butadiene rubber and 0.7 part by weight of an antioxidant 1192 for 10 minutes to obtain a modifier;
s4, preparation of a conductive film: and (3) adding 100 parts by weight of polypropylene into a double-screw extruder, heating to melt, adding 10 parts by weight of the wrinkled graphene-coated carbon nanotube mixture prepared in the step (S2) and 3 parts by weight of the modifier prepared in the step (S3), stirring and mixing for 1.5 hours, extruding into conductive high polymer resin, and preparing a film to obtain the conductive film.
Comparative example 12
In comparison with example 3, the difference is that step S5 is not performed.
The method comprises the following steps:
s1, preparing a pleated graphene oxide coated carbon nano tube: dissolving 7 parts by weight of graphene oxide in 50 parts by weight of 45wt% ethanol aqueous solution, adding 4 parts by weight of carbon nano tubes, performing 1000W ultrasonic dispersion for 15min, and performing spray drying under the condition that the air inlet temperature is 90 ℃, the air outlet temperature is 50 ℃, the evaporation water amount is 2000mL/h, and grinding to obtain the pleated graphene oxide coated carbon nano tubes;
s2, preparing copper/silver composite nanowires: dissolving 0.25 weight part of polyvinylpyrrolidone in 80 weight parts of ethylene glycol, adding 3.5 weight parts of ethanol, 0.00025 weight parts of sodium chloride, 0.00012 weight parts of alum trioxide, 0.15 weight parts of silver nitrate and 0.11 weight parts of copper nitrate, heating 1100W microwaves to 180 ℃, stirring and reacting for 40min, centrifuging for 15min 3000r/min, washing with deionized water, and drying at 105 ℃ for 1h to obtain the copper/silver composite nanowire;
S3, modifying polydopamine: dispersing 13.5 parts by weight of the copper/silver composite nanowire prepared in the step S2 in 100 parts by weight of water, adding 18.5 parts by weight of dopamine hydrochloride and 0.35 part by weight of catalyst, heating to 50 ℃, stirring and reacting for 2.5 hours, centrifuging for 15 minutes at 3000r/min, washing with deionized water, and drying for 1 hour at 105 ℃ to obtain the modified copper/silver composite nanowire;
the catalyst was a catalyst containing 4wt% CoCl 2 Tris-HCl solution at ph=5.5;
s4, preparation of a mixture: adding 22 parts by weight of the wrinkled graphene oxide coated carbon nano tube prepared in the step S1 into 50 parts by weight of ethanol, performing 1000W ultrasonic dispersion for 10min, adding 4 parts by weight of the modified copper/silver composite nano wire prepared in the step S3, uniformly stirring and mixing for 10min, heating to 40 ℃, and stirring and reacting for 30min to prepare a wrinkled graphene oxide coated carbon nano tube-modified copper/silver composite nano wire mixture;
s5, stirring and mixing 1.5 parts by weight of a compatilizer ST-2, 4 parts by weight of di-sec-octyl phthalate, 2.5 parts by weight of styrene-butadiene rubber and 0.7 part by weight of an antioxidant 1192 for 10 minutes to obtain a modifier;
s6, preparing a conductive film: adding 100 parts by weight of polypropylene into a double-screw extruder, heating to melt, adding 10 parts by weight of the wrinkled graphene oxide coated carbon nano tube-modified copper/silver composite nano wire mixture prepared in the step S5 and 3 parts by weight of the modifier prepared in the step S6, stirring and mixing for 1.5 hours, extruding into conductive high polymer resin, and preparing a film to obtain the conductive film.
Test example 2
The conductive films prepared in examples 1 to 3 and comparative examples 1 to 12 were subjected to sheet resistance test according to "sheet resistance measurement by noble metal paste test method for microelectronics technology of GB/T17473.3-2008".
The results are shown in Table 1.
TABLE 1
Group of Square resistance (omega)
Example 1 51.7
Example 2 51.2
Implementation of the embodimentsExample 3 49.8
Comparative example 1 145.2
Comparative example 2 152.7
Comparative example 3 122.4
Comparative example 4 422.1
Comparative example 5 405.5
Comparative example 6 344.2
Comparative example 7 305.7
Comparative example 8 367.7
Comparative example 9 178.2
Comparative example 10 459.7
Comparative example 11 578.2
Comparative example 12 210.4
As is clear from the above table, the conductive films prepared in examples 1 to 3 of the present invention have low resistivity and good conductive properties.
Test example 3 Oxidation resistance analysis
The conductive films prepared in examples 1 to 3 and comparative examples 1 to 12 were placed in a dry box and stored at room temperature of 25 ℃ for 60 days, the mass and conductivity of the conductive film samples were measured respectively before and after, and the oxidation resistance of the conductive film was analyzed by measuring the change of the mass and conductivity of the conductive film during the test period, the smaller the change of the mass and conductivity was, the better the oxidation resistance was.
TABLE 2
As can be seen from the above table, the conductive films prepared in examples 1 to 3 of the present invention have good oxidation resistance.
Test example 4
The conductive films prepared in examples 1 to 3 and comparative examples 1 to 12 were subjected to mechanical property test, and the results are shown in Table 3.
Tensile strength: determination of tensile Properties of plastics according to GB/T1040.3-2006 section 3: test conditions for thin plastics and flakes.
Notched impact strength: the test was carried out according to GB/T1843-2008 "determination of impact Strength of Plastic cantilever".
Flexural strength: the test was carried out according to GB/T9341-2008 "determination of Plastic flexural Properties".
TABLE 3 Table 3
As can be seen from the above table, the conductive films prepared in examples 1 to 3 of the present invention have good mechanical properties.
In comparative examples 1 and 2, no carbon nanotubes or graphene oxide was added in step S1, as compared with example 3. Comparative example 3 in contrast to example 3, no spray drying was performed in step S1, and direct drying was employed. The sheet resistance is improved, and the mechanical property is reduced. According to the invention, the carbon nano tube is added into the graphene oxide ethanol water solution, the graphene oxide solution forms small liquid beads which wrap the carbon nano tube through the air pressure action of a nozzle, the solvent is quickly evaporated, the volume of the small liquid beads is quickly contracted, the folded graphene oxide coated carbon nano tube is obtained, and the stacked agglomeration of the composite in the high polymer matrix is reduced due to the folded structure of the graphene in the composite, so that uniform dispersion is realized, the modification effect is fully exerted, and the mechanical property, the electric conductivity, the wear resistance, the heat resistance stability and the lubricating property of the high polymer matrix are obviously improved.
In comparative examples 4 and 5, no silver nitrate or copper nitrate was added in step S2, as compared with example 3. The sheet resistance is obviously improved. The conductive film doped with the wrinkled graphene coated carbon nano tube-copper/silver composite nanowire has good transmittance, high conductivity, low cost, flexibility, bending property and comprehensive photoelectric property, meanwhile, the addition of copper further reduces silver doping, the preparation cost of the conductive film is greatly reduced, meanwhile, the copper and silver composite nanowire can further improve the electrical property of the film, the silver nanowire with higher length-diameter ratio can improve the construction efficiency of a conductive network, the addition of the copper nanowire can improve the length-diameter ratio of the silver nanowire, meanwhile, the construction of the conductive network is promoted, the addition amount of the copper/silver composite nanowire is further reduced, and the conductive film with high conductivity, low haze and high transmittance can be built.
Comparative examples 6 and 7 compared with example 3, sodium chloride was not added in step S2Or the vanadium trioxide, the sheet resistance is obviously improved, and the oxidation resistance is reduced. Comparative example 8 in comparison with comparative example 3, sodium chloride and alum trioxide were not added in step S2. The invention controls the nucleation speed and the size of the product by adding the composite nucleation control agent (sodium chloride and alum trioxide), cl - The addition of (2) can promote the anisotropic growth of the crystal and the formation of silver nanowires, the alum trioxide and the sodium chloride can selectively etch out a plurality of twin Ag particles, and only single crystal grows into nano-level cubes and tetrahedra, and meanwhile Cl - Will be with Ag + Reacting to form AgCl colloid for buffering Ag + Thereby limiting the nucleation of Ag, promoting the growth of silver nanowires, improving the length-diameter ratio of silver nanowires, having synergistic effect and improving the conductivity of the conductive film.
In comparative example 9, compared with example 3, the sheet resistance was improved and the oxidation resistance was remarkably reduced without performing step S3. The invention mixes the wrinkled graphene oxide coated carbon nano-tube with the copper/silver composite nano-wire modified by polydopamine, the polydopamine layer on the surface of the copper/silver composite nano-wire contains abundant hydroxyl, carboxyl and amino, can be fully adhered with the wrinkled graphene oxide coated carbon nano-tube, and can obtain the wrinkled graphene coated carbon nano-tube-modified copper/silver composite nano-wire mixture after further reduction, thereby obviously improving the mechanical property, the electrical conductivity, the wear resistance, the heat resistance stability and the lubricating property of a high polymer matrix,
in comparative example 10, in comparison with example 3, the pleated graphene oxide coated carbon nanotubes were not added in step S4. The sheet resistance is obviously improved, the oxidation resistance is reduced, and the mechanical property is obviously reduced. Comparative example 11 compared with example 3, the modified copper/silver composite nanowire was not added in step S4. The sheet resistance is obviously improved.
In comparative example 12, compared with example 3, the sheet resistance was significantly improved and the mechanical properties were reduced without performing step S5. According to the invention, graphene is a material with excellent conductivity, so that the conductivity of an electrode material can be improved, and the charge and discharge performance of the electrode material can be improved; meanwhile, the flexible two-dimensional layered structure of the graphene can effectively inhibit material pulverization of the electrode material caused by volume change in the charging and discharging process, and enhance conductive contact with a current collector.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (10)

1. The preparation method of the conductive film is characterized by adding carbon nanotubes into graphene oxide ethanol aqueous solution, spray drying to obtain wrinkled graphene oxide coated carbon nanotubes, mixing the wrinkled graphene oxide coated carbon nanotubes with polydopamine modified copper/silver composite nanowires, reducing to obtain a wrinkled graphene coated carbon nanotube-modified copper/silver composite nanowire mixture, adding the wrinkled graphene coated carbon nanotube-modified copper/silver composite nanowire mixture, a compatilizer, a plasticizer and an antioxidant into molten high polymer resin, uniformly mixing, extruding, and preparing the film to obtain the conductive film.
2. The method of manufacturing according to claim 1, comprising the steps of:
s1, preparing a pleated graphene oxide coated carbon nano tube: dissolving graphene oxide in an ethanol water solution, adding carbon nanotubes, uniformly dispersing, and carrying out spray drying and grinding to obtain the wrinkled graphene oxide coated carbon nanotubes;
s2, preparing copper/silver composite nanowires: dissolving polyvinylpyrrolidone in glycol, adding ethanol, sodium chloride, alum trioxide, silver nitrate and copper nitrate, carrying out microwave heating and stirring reaction, centrifuging, washing and drying to obtain a copper/silver composite nanowire;
s3, modifying polydopamine: dispersing the copper/silver composite nanowire prepared in the step S2 in water, adding dopamine hydrochloride and a catalyst, heating and stirring for reaction, centrifuging, washing and drying to obtain a modified copper/silver composite nanowire;
s4, preparation of a mixture: dispersing the pleated graphene oxide coated carbon nano tube prepared in the step S1 in ethanol, adding the modified copper/silver composite nano wire prepared in the step S3, stirring and mixing uniformly, and heating for reaction to prepare a pleated graphene oxide coated carbon nano tube-modified copper/silver composite nano wire mixture;
S5, reduction: adding the pleated graphene oxide coated carbon nanotube-modified copper/silver composite nanowire mixture prepared in the step S4 into water, uniformly dispersing, adding ammonia water and hydrazine hydrate, heating for reaction, filtering and washing to obtain the pleated graphene coated carbon nanotube-modified copper/silver composite nanowire mixture;
s6, mixing and dispersing the phase agent, the plasticizer, the toughening agent and the antioxidant to obtain the modifier;
s7, preparing a conductive film: adding high polymer resin into a double screw extruder, heating to melt, adding the wrinkled graphene coated carbon nano tube-modified copper/silver composite nano wire mixture prepared in the step S5 and the modifier prepared in the step S6, uniformly mixing, extruding to obtain conductive high polymer resin, and preparing a film to obtain the conductive film.
3. The preparation method according to claim 2, wherein the mass ratio of graphene oxide to carbon nanotubes in step S1 is 5-10:3-5; the ethanol content in the ethanol water solution is 35-55wt%, the spray drying condition is that the air inlet temperature is 85-95 ℃, the air outlet temperature is 20-60 ℃, and the evaporation water amount is 1700-2200mL/h.
4. The preparation method according to claim 2, wherein the mass ratio of polyvinylpyrrolidone, ethylene glycol, ethanol, sodium chloride, alum trioxide, silver nitrate and copper nitrate in the step S2 is 0.2-0.3:70-90:2-5:0.0002-0.0003:0.0001-0.00015:0.12-0.17:0.10-0.12, wherein the temperature of the heating and stirring reaction is 175-185 ℃ and the time is 30-50min.
5. The preparation method according to claim 2, wherein the mass ratio of the copper/silver composite nanowire, the dopamine hydrochloride and the catalyst in the step S3 is 12-15:17-20:0.2-0.5, and the catalyst is 3-5wt% of CoCl 2 The temperature of the heating and stirring reaction of the Tris-HCl solution with the pH of between 5 and 6 is 45 and 55 DEG CThe time is 2-3h.
6. The preparation method according to claim 2, wherein in the step S4, the mass ratio of the wrinkled graphene oxide coated carbon nanotubes to the modified copper/silver composite nanowires is 20-25:3-5, the temperature of the heating reaction is 35-45 ℃, and the time is 20-40min.
7. The preparation method according to claim 2, wherein in step S5, the mass ratio of the wrinkled graphene oxide coated carbon nanotube-modified copper/silver composite nanowire, ammonia water and hydrazine hydrate is 10:3-5:0.5-1.2; the concentration of the ammonia water is 15-25wt%, the temperature of the heating reaction is 80-100 ℃ and the time is 1-2h.
8. The preparation method according to claim 2, wherein the mass ratio of the compatilizer, the plasticizer, the toughening agent and the antioxidant in the step S6 is 1-2:3-5:2-3:0.5-1, the compatilizer is at least one of ST-1, ST-2, ST-3, ST-4, ST-5, ST-6, ST-7, ST-8 and ST-9, the plasticizer is at least one of di (2-ethylhexyl) phthalate, dioctyl phthalate, di-n-octyl phthalate, butyl benzyl phthalate, di-sec-octyl phthalate, dicyclohexyl phthalate, dibutyl phthalate, diisobutyl phthalate, dimethyl phthalate, diethyl phthalate, diisononyl phthalate and diisodecyl phthalate, and the plasticizer is at least one of antioxidant 1010, antioxidant 1196, antioxidant 168 and antioxidant 1192.
9. The preparation method according to claim 2, wherein in the step S7, the mass ratio of the polymer resin, the wrinkled graphene-coated carbon nanotube-modified copper/silver composite nanowire mixture and the modifier is 100:7-12:2-4; the polymer resin is at least one selected from polypropylene, polyethylene terephthalate, polyimide and polyethylene naphthalate.
10. A conductive film produced by the production method according to any one of claims 1 to 9.
CN202310406226.0A 2023-04-11 2023-04-11 Conductive film and preparation method thereof Active CN116836421B (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170028081A (en) * 2015-09-03 2017-03-13 한국과학기술원 Nano composites, flexible and stretchable composites comprising the nano composites and methods for the manufacturing thereof
KR101742593B1 (en) * 2016-12-20 2017-06-01 한국지질자원연구원 Manufacturing method of crumpled graphene-carbon nanotube-polymer composite, the composite manufactured thereby and supercapacitor containing the composite
WO2018110776A1 (en) * 2016-12-12 2018-06-21 한국지질자원연구원 Method for manufacturing crumpled graphene composite, composite manufactured thereby, and supercapacitor including composite
KR101973997B1 (en) * 2017-11-10 2019-05-02 한국전력공사 A process of preparing three dimensional graphene composite, three dimensional graphene composite prepared thereby, and supercapacitor electrode comprising the same
WO2021232597A1 (en) * 2020-05-21 2021-11-25 电子科技大学中山学院 Near-infrared thermal repair flexible conductive film and preparation method therefor
CN114163712A (en) * 2021-12-27 2022-03-11 杭州耕鑫生物科技有限公司 Graphene composite PE material and preparation method thereof
CN115223758A (en) * 2022-05-26 2022-10-21 江苏怡丽科姆新材料股份有限公司 Processing technology of transparent conductive film containing silver nanowires

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170028081A (en) * 2015-09-03 2017-03-13 한국과학기술원 Nano composites, flexible and stretchable composites comprising the nano composites and methods for the manufacturing thereof
WO2018110776A1 (en) * 2016-12-12 2018-06-21 한국지질자원연구원 Method for manufacturing crumpled graphene composite, composite manufactured thereby, and supercapacitor including composite
KR101742593B1 (en) * 2016-12-20 2017-06-01 한국지질자원연구원 Manufacturing method of crumpled graphene-carbon nanotube-polymer composite, the composite manufactured thereby and supercapacitor containing the composite
KR101973997B1 (en) * 2017-11-10 2019-05-02 한국전력공사 A process of preparing three dimensional graphene composite, three dimensional graphene composite prepared thereby, and supercapacitor electrode comprising the same
WO2021232597A1 (en) * 2020-05-21 2021-11-25 电子科技大学中山学院 Near-infrared thermal repair flexible conductive film and preparation method therefor
CN114163712A (en) * 2021-12-27 2022-03-11 杭州耕鑫生物科技有限公司 Graphene composite PE material and preparation method thereof
CN115223758A (en) * 2022-05-26 2022-10-21 江苏怡丽科姆新材料股份有限公司 Processing technology of transparent conductive film containing silver nanowires

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