CN115331864A

CN115331864A - Conductive material, conductive film and preparation method thereof

Info

Publication number: CN115331864A
Application number: CN202211017326.6A
Authority: CN
Inventors: 张立; 王昌顺; 许军
Original assignee: Ningbo Konojia New Materials Co ltd
Current assignee: Ningbo Konojia New Materials Co ltd
Priority date: 2022-08-23
Filing date: 2022-08-23
Publication date: 2022-11-11

Abstract

The application discloses a conductive material, a conductive film and a preparation method thereof. The conductive material comprises a copper wire, a coating layer and a conductive polymer; the coating layer is coated on the surface of the copper-copper wire to form a copper-copper wire core, and the copper-copper wire core-shell structure material of the wire shell is coated with the coating layer, wherein the coating layer comprises metal or metal oxide; the conducting polymer and the copper-copper wire core-shell structure material form a copolymer. On the basis of preparing the copper-copper nanowire core-shell structure material, the silane coupling and grafting conductive polymer is utilized, so that the preparation and synthesis method has the characteristics of simplicity, low cost, low temperature, environmental protection, safety and the like, and the prepared conductive film has excellent conductivity and light transmittance and has a very wide application prospect.

Description

Conductive material, conductive film and preparation method thereof

Technical Field

The application relates to the technical field of photoelectron, in particular to a conductive material, a conductive film and a preparation method thereof.

Background

Transparent Electrodes (TEs) play a crucial role in the development of electronics and photoelectron industry, are indispensable optoelectronic functional materials for preparing numerous electronic and photoelectron components, and are mainly applied to touch screens, solar cells, flat panel displays, light emitting diodes, sensors and the like. With the development of flexible, wearable, and portable electronic technologies, higher requirements are put on transparent electrodes. It is required not only to have excellent photoelectric properties and superior chemical stability but also to have high flexibility and to be fabricated at low cost and in a large area. Limited by the high price and low utilization rate of Indium Tin Oxide (ITO), various materials have been used to replace ITO, such as carbon nanotubes, graphene, metal grids and metal nanowires. The carbon nano tube has high mechanical strength, but the industrial production technology is not perfect, and the prepared film has poor conductivity; the performance of the graphene transparent electrode is closer to that of ITO, but the film making process is complex, so that the characteristics of low yield and high manufacturing cost are caused; the metal grid has excellent performance, but the regular structure of the metal grid is easy to generate Morie interference. The metal nanowire transparent electrode is a potential ITO alternative by virtue of its high flexibility resistance, excellent light transmittance and electrical conductivity. The performance of the transparent electrode prepared by silver Nanowires (Ag Nanowires, agNWs) is superior to that of ITO at present, but AgNWs still has the defect of high price. Copper is as conductive as silver, however, copper is only 1% as expensive as silver and is abundant. Therefore, the application prospect of preparing the transparent electrode by adopting the copper nanowire (Cu Nanowires, cuNWs) is wider, and the market competitiveness is higher.

CuNWs are widely spotlighted by researchers and industries as transparent conductive layers due to their excellent light transmittance, electrical conductivity, flexibility, and low cost characteristics. Currently, the mass-producible preparation of CuNWs has been achieved: the transparent electrode prepared by CuNWs has the resistance of 28-40 omega/sq under the condition of 90% transmittance, and the performance of the transparent electrode is comparable to that of ITO. The CuNWs transparent electrode has excellent performance and application prospect, but CuNWs are easy to oxidize, so that the application of the CuNWs in photoelectric devices is limited, namely CuNWs exposed in air are easy to react with water and oxygen in the air, and an oxide layer is spontaneously formed on the surface of the CuNWs, so that the conductivity is disabled. Therefore, how to obtain a flexible transparent electrode with lower sheet resistance and higher transmittance and realize the oxidation resistance of CuNWs becomes one of the hot spots and difficulties of the leading-edge research in the field. At present, researchers widely adopt a method for constructing a CuNWs composite film to improve the stability of the CuNWs composite film. Although the stability of CuNWs can be effectively improved by constructing the CuNWs composite film, certain conductivity and transmittance of the CuNWs are sacrificed. Therefore, there is a need to design and prepare a CuNWs composite film with high conductivity, high transmittance and excellent air stability.

Disclosure of Invention

The application provides a conductive material, a conductive film and a preparation method thereof, which have high light transmittance and conductivity and high stability.

The application provides a conductive material, which comprises a copper nanowire, a coating layer and a conductive polymer; the coating layer is coated on the surface of the copper nanowire to form a copper nanowire core-shell structure material taking the copper nanowire as a core and taking the coating layer as a shell, and the coating layer comprises metal or metal oxide; the conductive polymer and the copper nanowire core-shell structure material form a copolymer.

Optionally, in some embodiments of the present application, the conductive polymer is polymerized with the copper nanowire core-shell structure by radicals.

Optionally, in some embodiments of the present application, the diameter of the copper nanowire is 50 to 200nm.

Optionally, in some embodiments of the present application, the coating comprises one or more of silver, zinc, tin, nickel, titanium, silver oxide, zinc oxide, tin oxide, nickel oxide, or titanium dioxide.

Optionally, in some embodiments of the present application, the conductive polymer includes one or more of polyethylenedioxythiophene, polypyrazole, polythiophene, polyphenylene, polyphenylacetylene, or polyaniline.

Optionally, in some embodiments of the present application, the ratio between the copper nanowire, the cladding layer, and the conductive polymer is 1:1 to 1.5:10 to 1000.

Optionally, in some embodiments herein, the conducting polymer has a molecular weight of 10000 to 100000.

The application also provides a preparation method of the conductive material, which comprises the following steps: mixing an inorganic copper salt precursor, a reducing agent and a dispersing agent in an alkaline solution, and heating for reaction to obtain a copper nanowire; adding weak acid and polyvinylpyrrolidone into the copper nanowires, mixing, adding metal salt and an ion control agent, reacting and centrifuging to obtain a copper nanowire core-shell structure material; modifying the copper nanowire core-shell structure material by adopting acid, and adding a conductive polymer under the action of a silane coupling agent to obtain the conductive material.

Optionally, in some embodiments herein, the inorganic copper salt precursor comprises one or more of copper nitrate, copper chloride dihydrate, copper chloride, or copper bromide.

Optionally, in some embodiments of the present application, the reducing agent comprises one or more of glucose, sodium citrate, ascorbic acid, or borohydride.

Optionally, in some embodiments herein, the dispersant comprises one or more of polyvinylpyrrolidone, oleylamine, or octadecylamine.

Optionally, in some embodiments of the present application, the alkaline solution comprises one or more of ammonia, sodium hydroxide solution, or potassium hydroxide solution.

Optionally, in some embodiments of the present application, the metal salt comprises one or more of silver nitrate, zinc chloride, tin chloride, nickel acetylacetonate, titanium acetylacetonate, or silver acetylacetonate.

Optionally, in some embodiments herein, the ion control agent comprises one or more of sodium chloride, potassium chloride, sodium bromide, or potassium bromide.

Optionally, in some embodiments herein, the acid comprises one or more of hydrochloric acid, nitric acid, or sulfuric acid.

Optionally, in some embodiments herein, the silane coupling agent comprises one or more of vinyltriethoxysilane, vinyltrimethoxysilane, or vinyltrimethoxysilane.

Optionally, in some embodiments of the present application, the temperature of the heating reaction is from 100 to 200 ℃.

Optionally, in some embodiments of the present application, the heating reaction time is 4 to 6 hours.

Optionally, in some embodiments of the present application, the concentration of the inorganic copper salt precursor is 2.0 to 6.0g/L.

The application also provides a conductive film, and the conductive film comprises the conductive material or the conductive material prepared by the preparation method.

Optionally, in some embodiments of the present disclosure, the light transmittance of the conductive film may be 80% to 93%, or 83% to 90%, or 85% to 88%.

Optionally, in some embodiments of the present application, the sheet resistance of the conductive film may be 10 to 40 Ω/sq, may also be 15 to 35 Ω/sq, and may also be 20 to 30 Ω/sq.

The application provides a conducting material, has following beneficial effect:

(1) The conductive material is coated with the metal or metal oxide coating layer, so that the stability of the conductive material is improved, and meanwhile, the conductive material is grafted with the conductive polymer and has excellent light transmittance and conductivity;

(2) The liquid phase synthesis method is adopted to prepare the conductive material, and the preparation process capable of producing the transparent conductive film with excellent photoelectric property and high stability in a large scale is formed under the conditions of low cost and low temperature (less than 200 ℃), so that the transparent conductive film has wider application prospect and benefits.

Detailed Description

The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

The application provides a conductive material, a conductive film and a preparation method thereof. The following are detailed below. It should be noted that the following description of the embodiments is not intended to limit the preferred order of the embodiments.

The embodiment of the application provides a conductive material, which comprises a copper nanowire, a coating layer and a conductive polymer; the coating layer is coated on the surface of the copper nanowire to form a copper nanowire core-shell structure material taking the copper nanowire as a core and taking the coating layer as a shell, and the coating layer comprises metal or metal oxide; the conductive polymer and the copper nanowire core-shell structure material form a copolymer.

At present, in order to improve the characteristic that CuNWs is easily oxidized, researchers generally adopt a coating method, that is, a protective layer is added on the surface of CuNWs to improve the stability of the CuNWs. Currently, chemical Vapor Deposition (CVD) graphene coating, graphene oxide coating, nickel, silver metal coating, oxide coating, polymer coating, and the like are commonly used as coating methods. Graphene has excellent conductivity and chemical stability, a layer of graphene is coated on the surface of CuNWs, so that oxidation and environmental corrosion of the CuNWs can be effectively prevented, a CVD (chemical vapor deposition) method is adopted to prepare the graphene-coated CuNWs transparent composite electrode at 400 ℃, the composite electrode has good oxygen resistance and stability, the resistance of the film is 23.2 omega/sq at 83.4% of transmittance, and the film is not suitable for a flexible substrate due to high preparation temperature; graphene Oxide (GO) is suitable for liquid phase membrane preparation, such as vacuum filtration, spin coating, spraying and the like, and can realize large-area continuous preparation. Close encapsulation of ultrafine CuNWs by GO nanoplates using ultrasound technology followed by 10% H ₂ GO is reduced by annealing at 260 ℃ for 30min under the atmosphere, and the photoelectric property of the CuNW-rGO composite transparent electrode can be found as follows: the film has the transmittance of 89.2 percent and the resistivity of 28.2 omega/sq, but has the defects of safety and preparation price because high temperature and hydrogen or helium gas protection are needed in the preparation process; nickel (Ni) has good mechanical strength and ductility, is resistant to high temperature, and has extremely high chemical stability, and is often used as a surface protective layer to prevent oxidation of metals; the light transmittance of the prepared film can be kept at about 80%, the sheet resistance is 62.4 omega/sq, and the light transmittance and the conductivity are lost; silver has stable chemical property, low activity, difficult corrosion by chemicals, good heat conduction and good electric conductivity. In CuNW by liquid phase reduction methodAnd a compact Ag coating layer is formed on the surface of the s, the Cu-Ag core-shell structure nanowire is prepared, and the sheet resistance and the light transmittance of the nanowire are maintained at 29 omega/sq and 84% through simple post-treatment. Although the oxidation resistance of the CuNWs transparent electrode can be improved by coating the CuNWs with Ag, the photoelectric property of the Ag-CuNWs film can be lost due to the fact that Ag is easily corroded by sulfide in air; zinc oxide (ZnO) and aluminum oxide (Al) ₂ O ₃ ) All are semiconductor materials with wide band gaps, and have high transmittance under visible light or good conductivity. Depositing AZO/Al on the surface of Cu nanofiber by adopting atomic deposition technology (ALD) ₂ O ₃ Protective layer, AZO/Al prepared after annealing at 250 ℃ for 1h ₂ O ₃ -a Cu composite transparent electrode with a low sheet resistance (< 20 Ω/sq) and a high transmittance (< 79%); the conductive polymer has both conductivity and light transmittance, is widely applied to the preparation of transparent functional films, and can be used as a hole transport layer or directly used as an electrode. The polypyrazole-coated CuNWs (Cu @ PPy) is prepared by a liquid phase reduction technology, the resistance is increased by 2-3 times after the polypyrazole-coated CuNWs are placed in the air for 1h, the stability is poor, hydrazine hydrate (with toxicity) can be used as a reducing agent in the preparation process, and the safety and the stability are to be improved.

Therefore, the current coating modification methods of metals, oxides, conductive polymers and the like have the defects of high temperature, high energy consumption, poor stability and general conductive light transmittance, so that the conductive material with the novel structure is prepared by adopting a simple, safe and high-efficiency-yield liquid-phase synthesis method, and has high light transmittance, high conductivity and high stability.

Further, the conductive polymer is polymerized with the core-shell structure of the copper nanowire through free radicals.

Specifically, the diameter of the copper nanowire can be 50-200 nm, 80-180 nm, or 100-150 nm.

Specifically, the coating layer includes one or more of silver, zinc, tin, nickel, titanium, silver oxide, zinc oxide, tin oxide, nickel oxide, or titanium dioxide. The conductive material is coated with a metal or metal oxide coating layer, so that the stability of the conductive material is improved.

Specifically, the conductive polymer includes one or more of Polyethylenedioxythiophene (PEDOT), polypyrazole, polythiophene, polyphenylene, polyphenylacetylene, or polyaniline. The conductive polymer has both conductivity and light transmittance, is widely applied to the preparation of transparent functional films, and can be used as a hole transport layer or directly used as an electrode. The conductive material is grafted with a conductive polymer, thereby having excellent light transmittance and conductivity.

Specifically, the mass ratio of the copper nanowire, the coating layer and the conductive polymer is 1: 1-1.5: 10-1000.

Specifically, the molecular weight of the conductive polymer may be 10000 to 100000, 20000 to 90000, or 50000 to 80000.

The embodiment of the application also provides a preparation method of the conductive material, which comprises the following steps: mixing an inorganic copper salt precursor, a reducing agent and a dispersing agent in an alkaline solution, and heating for reaction to obtain a copper nanowire; adding weak acid and polyvinylpyrrolidone into the copper nanowires, mixing, adding metal salt and an ion control agent, reacting and centrifuging to obtain a copper nanowire core-shell structure material; modifying the copper nanowire core-shell structure material by adopting acid, and adding a conductive polymer under the action of a silane coupling agent to obtain the conductive material. The liquid phase synthesis method is a hydrothermal liquid phase synthesis method, and the conductive material can be produced in a large scale under the conditions of low cost and low temperature.

Further, the inorganic copper salt precursor comprises one or more of copper nitrate, copper chloride dihydrate, copper chloride or copper bromide.

Further, the reducing agent includes one or more of glucose, sodium citrate, ascorbic acid, or borohydride.

Further, the dispersant includes one or more of polyvinylpyrrolidone (PVP), oleylamine, or octadecylamine.

Further, the alkaline solution comprises one or more of ammonia, sodium hydroxide solution or potassium hydroxide solution.

Further, the metal salt comprises one or more of silver nitrate, zinc chloride, tin chloride, nickel acetylacetonate, titanium acetylacetonate or silver acetylacetonate.

Further, the ion control agent includes one or more of sodium chloride, potassium chloride, sodium bromide, or potassium bromide. The ion control agent functions to control the aspect ratio of growth of the conductive material.

Further, the acid comprises one or more of hydrochloric acid, nitric acid or sulfuric acid, and preferably, dilute hydrochloric acid is used for modifying the copper nanowire core-shell structure material. The concentration of hydrochloric acid was 0.1mol/L.

Further, the silane coupling agent includes one or more of vinyltriethoxysilane, vinyltrimethoxysilane, or vinyltrimethoxysilane.

Further, the conductive polymer includes one or more of polyethylenedioxythiophene, polypyrazole, polythiophene, polyphenylene, polyphenylacetylene, or polyaniline.

Specifically, the temperature of the heating reaction may be 100 to 200 ℃, 120 to 180 ℃, or 150 to 160 ℃. The temperature mainly affects the reduction rate of the precursor in the reaction process and the growth thermodynamic equilibrium of the nanowire seed crystal. When the reaction temperature is low, the reduction rate of the precursor in the solution in the reaction process is low, and the growth rate of the nanowire is reduced, so that the required reaction time is long, and the obtained nanowire is low in length and low in yield. The temperature rise can accelerate the reaction rate and reduce the required reaction time, thereby increasing the length and yield of the nanowire. Meanwhile, the growth of the nanowire seed crystal needs energy, and the energy needed by the growth of the one-dimensional seed crystal of the nanowire seed crystal cannot be provided under the low-temperature condition; the temperature rise can promote the growth of the nanowires, but when the reaction is too high, the nanowires can be broken, and the length-diameter ratio of the required nanowires is reduced. Meanwhile, the reduction rate of the precursor is too high due to too high reaction, and the nanowire is not easy to form. The relatively high temperature thus facilitates the synthesis of nanowires of conductive material.

Specifically, the heating reaction time may be 4 to 6 hours, or may be 5 hours. At a relatively high reaction temperature, the precursor in the solution has a fast reduction rate in the reaction process, so that nanowire crystal nuclei with a required size can be generated, and then the nanowire crystal nuclei grow to one-dimensional crystal seeds along with the increase of the reaction time. Meanwhile, the reaction time is too long, and the length of the nanowire cannot be infinitely increased. Therefore, the nanowire material with a certain length-diameter ratio can be prepared by controlling the reaction time.

Specifically, the concentration of the inorganic copper salt precursor can be 2.0-6.0 g/L, can also be 3.O-5.0 g/L, and can also be 4.0g/L. The functional group acyl of PVP can coordinate with copper and silver ions, and is adsorbed on a specific crystal face through coordination, so that the nanowire seed crystal grows into the nanowire in an anisotropic mode. Therefore, the growth of the nanowire is influenced by the molar ratio of PVP (polyvinyl pyrrolidone) to the precursor, when the average molecular weight and the reaction addition amount of PVP (K30) are fixed (the viscosity of a reaction solution system can be caused by the increase of the addition amount of PVP, and the difficulty of a synthesis experiment is increased), when the concentration of the inorganic copper salt precursor is too low, the PVP can coat the nanowire seed crystal in a large area, the growth selectivity of different crystal faces is reduced, and the final product can be a mixture of nanoparticles or a small amount of nanowire products; the concentration of the precursor is increased, the coating area of PVP on the nanowire seed crystal can be reduced, the anisotropic growth of the nanowire seed crystal is promoted, and the required nanowire material is obtained; when the concentration of the current driver is too high, PVP can not absorb and coat a specific crystal face of the nanowire seed crystal, so that the seed crystal is difficult to grow anisotropically, and the nanowire material can not be generated.

In specific implementation, the preparation method of the conductive material comprises the following steps:

(1) Firstly, taking inorganic copper salt as a precursor, adding a reducing agent and a dispersing agent into an alkaline aqueous solution, heating at constant temperature, and after the reaction is finished, obtaining a copper nanowire through a centrifugal process;

(2) Adding a proper amount of mixed solution of diluted weak acid and a small amount of polyvinylpyrrolidone solution into the prepared solution of the copper nanowires, transferring the mixed solution into a reaction bottle, stirring at constant temperature by magnetic force, adding inorganic salt or organic metal salt solution, ion control agent and the like, continuously stirring and adjusting a proper temperature, and forming a layer of metal or metal oxide coating layer on the surface of CuNWs by adopting a liquid phase reduction method to prepare the copper nanowire core-shell structure material; transferring the reaction product solution to a centrifuge tube and placing the centrifuge tube into a centrifuge for centrifugal treatment, and centrifuging for three times to obtain the copper nanowire core-shell structure material deposited at the bottom;

(3) And then carrying out hydroxylation modification on the copper nanowire core-shell structure material by using dilute acid, diluting the material to a proper concentration, and adding a conductive polymer material under the action of a silane coupling agent to synthesize and prepare the conductive material with the novel copper nano core-shell structure of the conjugated polymer.

The embodiment of the application also provides a conductive film, and the conductive film comprises the conductive material or the conductive material prepared by the preparation method.

In some embodiments of the present disclosure, the light transmittance of the conductive film may be 85% to 93%, or 85% to 90%.

In some embodiments of the present application, the sheet resistance of the conductive film may be 10 to 40 Ω/sq, may be 15 to 35 Ω/sq, and may be 20 to 30 Ω/sq.

In specific implementation, a film forming material is added into the prepared conductive material, and then a coating method is adopted to prepare the conductive film. Specifically, the film forming material comprises one or more of nitrocellulose, cellulose acetate, carboxymethyl cellulose, resin-modified hydroxyethyl cellulose, ethyl cellulose, nitrile ethyl cellulose, or hydroxyethyl cellulose.

The following description will be given with reference to specific examples.

The first embodiment,

The preparation method of the conductive film provided by the embodiment comprises the following steps:

(1) Diluting the conductive material: diluting 1.0wt% of conductive material in an alcohol/water solution (the volume ratio of ethanol to water is 1: 5-1: 10) to prepare 100g of solution, adding 0.10g of sodium dodecyl benzene sulfonate as a dispersion stabilizer, adding 2g of high molecular resin modified carboxymethyl cellulose with the molecular weight of about 10000, performing ultrasonic dispersion for 10-20 minutes, performing centrifugal separation for 10min at the rotating speed of 1000rpm, and taking supernatant to obtain the composite conductive coating of the conductive material;

(2) Selecting a substrate, washing the substrate with ethanol, washing the substrate with deionized water for 2 times, and drying the substrate for later use;

(3) The composite conductive coating solution is coated on a substrate (the substrate is made of a PET transparent base material, the light transmittance is 91%, the haze is 0.3%, and the thickness is 0.1 mm) in a coating mode, and the conductive film is prepared by heating for 2min at the temperature of 70 ℃.

The preparation method of the conductive material in step (1) of this embodiment includes:

a) Adding 0.2g of copper chloride, 1.0g of PVP, 0.5g of ascorbic acid and 60mL of ethylene glycol into a 150mL three-neck flask, adjusting the pH value to be alkalescent by using 0.5% ammonia water, then putting the mixture into an oil bath kettle, stirring and mixing the mixture uniformly at 160-180 ℃, reacting for 4-5 hours, and after the reaction is finished, obtaining the copper nanowire through a centrifugal process;

b) And then mixing the copper nanowire solution prepared by the reaction with the diluted weak acid and the polyvinylpyrrolidone aqueous solution according to the ratio of 4:11:4, mixing and injecting into a reaction bottle, magnetically stirring at constant temperature for 3min, adding 0.26g of silver nitrate solution and an ion control agent, and continuously stirring for 10-30 min to finish the reaction;

c) Transferring the reaction product solution to a centrifugal tube, adding ethylene glycol as a cleaning solvent, placing the centrifugal tube in a centrifuge for centrifugal treatment to remove excessive organic matters, and centrifuging for three times to obtain a copper nanowire core-shell structure material deposited at the bottom;

d) Carrying out hydroxylation modification on the copper nanowire core-shell structure material by using dilute hydrochloric acid, diluting the modified copper nanowire core-shell structure material to a proper concentration, adding 2.5g of conductive polymer polyethylene dioxythiophene under the action of 0.2g of silane coupling agent, and heating and reacting at a constant temperature of 50-70 ℃ for 1-2 h under the protection of nitrogen to synthesize the conductive material.

Example II,

(1) Diluting the conductive material: diluting 1.5wt% of conductive material in an alcohol/water solution (the volume ratio of ethanol to water is 1: 5-1: 10) to prepare 100g of solution, adding 0.15g of sodium dodecyl benzene sulfonate as a dispersion stabilizer, adding 2g of macromolecular resin modified carboxymethyl cellulose with the molecular weight of about 10000, performing ultrasonic dispersion for 10-20 minutes, performing centrifugal separation for 10min at the rotating speed of 1000rpm, and taking supernatant to obtain the composite conductive coating of the conductive material;

b) Mixing the copper nanowire solution prepared by the reaction with the diluted weak acid and the polyvinylpyrrolidone aqueous solution according to the ratio of 4:11:4, injecting the mixture into a reaction bottle, magnetically stirring at constant temperature for 3min, adding 0.26g of silver nitrate solution and an ion control agent, and continuously stirring for 10-30 min to complete the reaction;

Example III,

(1) Diluting the conductive material: diluting 2.0wt% of conductive material in an alcohol/water solution (the volume ratio of ethanol to water is 1: 5-1: 10) to prepare 100g of solution, adding 0.2g of sodium dodecyl benzene sulfonate as a dispersion stabilizer, adding 2g of high molecular resin modified carboxymethyl cellulose with the molecular weight of about 10000, performing ultrasonic dispersion for 10-20 minutes, performing centrifugal separation for 10min at the rotating speed of 1000rpm, and taking supernatant to obtain the composite conductive coating of the conductive material;

(3) The composite conductive coating solution is coated on a substrate (the substrate is made of a PET transparent base material, the light transmittance is 91%, the haze is 0.3%, and the thickness is 0.1 mm) by adopting a coating mode, and the conductive film is prepared by heating for 2min at the temperature of 70 ℃.

d) Carrying out hydroxylation modification on the copper nanowire core-shell structure material by using dilute hydrochloric acid, diluting the modified copper nanowire core-shell structure material to a proper concentration, adding 2.5g of conductive polymer polyethylene dioxythiophene under the action of 0.2g of silane coupling agent, and carrying out constant-temperature heating reaction for 1-2 h at 50-70 ℃ under the protection of nitrogen to synthesize the conductive material.

Example four,

(1) Diluting the conductive material: diluting 1.5wt% of conductive material in an alcohol/water solution (the volume ratio of ethanol to water is 1: 5-1: 10) to prepare 100g of solution, adding 0.2g of sodium polyacrylate as a dispersion stabilizer, adding 2g of polymer resin modified carboxymethyl cellulose with the molecular weight of about 10000, performing ultrasonic dispersion for 10-20 minutes, performing centrifugal separation for 10min at the rotating speed of 1000rpm, and taking supernatant to obtain the composite conductive coating of the conductive material;

(3) The composite conductive coating solution is coated on a substrate (the substrate is made of a PET transparent base material, the light transmittance is 91%, the haze is O.3%, and the thickness is 0.1 mm) in a coating mode, and the conductive film is prepared by heating for 2min at the temperature of 70 ℃.

The preparation method of the conductive material in the step (1) of the embodiment includes:

a) Adding 0.2g of copper chloride, 1.0g of PVP, 0.5g of ascorbic acid and 60mL of ethylene glycol into a 150mL three-neck flask, adjusting the pH to be alkalescent by using 0.5% ammonia water, then putting the mixture into an oil bath kettle, stirring and mixing the mixture uniformly at 160-180 ℃, reacting for 2-3 hours, and obtaining the copper nanowire through a centrifugal process after the reaction is finished;

Performance testing

Comparative example 1: the conductive polymer polyethylenedioxythiophene in the conductive material system of example 1 was removed, and the amounts of other components and their synthetic agents were kept unchanged, and the transparent conductive film was prepared according to the method for preparing a conductive film in the examples.

For the conductive film products of examples 1 to 4 and comparative example 1, the sheet resistance of the patterned transparent conductive film was measured using a four-probe tester, the light transmittance and haze of the patterned transparent conductive film were measured using a photoelectric haze meter, and the adhesion was measured using a 3M610 adhesive tape, and the results are shown in table 1.

TABLE 1 Performance test results

From the above table, when the same base material is adopted, the transparent conductive film prepared by adding the conductive liquid material of polyethylenedioxythiophene has better optical transmittance, lower haze and lower sheet resistance.

The novel conductive material is synthesized and prepared by adopting a liquid phase synthesis method, the whole preparation scheme is simple to operate, the reaction temperature is lower (less than 200 ℃), and the synthesis cost is low; the conductive material and the conductive film are easy to expand production, and the prepared transparent conductive film is uniform in dispersion, controllable in conductivity and light transmittance and good in oxidation resistance, and can keep long-time stability at high temperature (less than 200 ℃) and high humidity.

The above detailed descriptions of the conductive material and the conductive film and the preparation method thereof provided by the present application, and the specific examples are applied herein to illustrate the principles and embodiments of the present application, and the descriptions of the above examples are only used to help understand the method and the core ideas of the present application; meanwhile, for those skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.

Claims

1. The conductive material is characterized by comprising copper wires, a coating layer and a conductive polymer; the coating layer is coated on the surface of the copper-copper wire to form a copper-copper wire core, and the coating layer is made of a copper-copper wire core-shell structure material of the coating layer wire shell and comprises metal or metal oxide; the conducting polymer and the copper-copper rice noodle core-shell structure material form a copolymer.

2. The conductive material as claimed in claim 1, wherein the conductive polymer is coupled with the copper-copper nanowire core-shell structure material by silane coupling to form a copolymer.

3. The conductive material as claimed in claim 1, wherein the copper wire has a diameter of 50-200 nm.

4. The conductive material of claim 1, wherein the coating comprises one or more of silver, zinc, tin, nickel, titanium, silver oxide, zinc oxide, tin oxide, nickel oxide, or titanium dioxide; and/or the conducting polymer comprises one or more of polyethylene dioxythiophene, polypyrrole, polythiophene, polyphenylene, polyphenylacetylene or polyaniline.

5. The conductive material as claimed in claim 1, wherein the mass ratio of the copper-copper wire, the cladding layer and the conductive polymer is 1:1-1.5: 10 to 1000.

6. The conductive material of claim 4, wherein the conductive polymer has a molecular weight of 10000-100000.

7. A preparation method of a conductive material is characterized by comprising the following steps: mixing an inorganic copper precursor, a reduction union and a dispersion union in an alkaline solution, and heating for reaction to obtain a copper wire; adding weak acid and polyvinylpyrrolidone into the copper-copper rice noodle, mixing, adding metal copper and ion control unit, reacting and centrifuging to obtain a copper-copper rice noodle core-shell structure material; and modifying the copper-copper nanowire core-shell structure material by adopting acid, and adding a conductive polymer under the action of silane coupling to obtain the conductive material.

8. The method of claim 7, wherein the inorganic copper precursor comprises one or more of copper nitrate, copper chloride dihydrate, copper chloride, or copper bromide; and/or the reducing union comprises one or more of glucose, sodium citrate, ascorbic acid or borohydride; and/or, the dispersing couple comprises one or more of polyvinylpyrrolidone, oleylamine or octadecylamine; and/or the alkaline solution comprises one or more of ammonia water, sodium hydroxide solution or potassium hydroxide solution; and/or the metallic copper comprises one or more of silver nitrate, zinc chloride, tin chloride, nickel acetylacetonate, titanium acetylacetonate or silver acetylacetonate; and/or, the ion control combination comprises one or more of sodium chloride, potassium chloride, sodium bromide or potassium bromide; and/or, the acid comprises one or more of copper acid, nitric acid or sulfuric acid; and/or, the silane coupling group comprises one or more of vinyltriethoxysilane, vinyltrimethoxysilane or vinyltrimethoxysilane; and/or the conducting polymer comprises one or more of polyethylene dioxythiophene, polypyrrole, polythiophene, polyphenylene, polyphenylacetylene or polyaniline.

9. The method for preparing the conductive material as claimed in claim 7, wherein the temperature line of the heating reaction is 100-200 ℃. The time line of the heating reaction is 4-6 h. The concentration line of the inorganic copper precursor is 2.0-6.0 g/L.

10. A conductive film comprising the conductive material according to any one of claims 1 to 6 or the conductive material produced by the production method according to any one of claims 7 to 9.

11. The conductive film of claim 10, wherein the light transmittance of the conductive film is 85% to 93%; and/or the sheet resistance line of the guide film is 10-40 omega/sq.