Water-based graphene coating solution as well as preparation method and application thereof

Abstract

The invention discloses a water-based graphene coating and plating solution and a preparation method and application thereof, and belongs to the technical field of high-conductivity metal wire materials, the water-based graphene coating and plating solution is composed of graphene or modified graphene, a dispersing agent, a binder, a coupling agent, an additive and solvent water; the application is to prepare a graphene / metal wire composite wire by adopting the aqueous graphene coating solution, and comprises the following steps: ultrasonically cleaning, washing and blow-drying a metal wire, and pre-treating the metal wire by dilute sulphuric acid, water or air plasma; and coating the surface of the pretreated metal wire with the water-based graphene coating solution by using a continuous coating machine, and drying in an inert atmosphere to obtain the water-based graphene metal wire. According to the prepared graphene coating solution, deionized water is used as a solvent, a large amount of harmful organic gas is not volatilized in the preparation process of the composite wire rod, and the graphene coating solution is environmentally friendly and wide in source; the preparation method is simple and efficient to operate, low in cost and easy to realize large-scale industrial production; and the graphene / metal wire composite material prepared by the invention shows excellent conductivity.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high-conductivity wire materials, and particularly relates to a water-based graphene plating solution, a preparation method and application thereof. BACKGROUND

[0002] High-conductivity wire materials are key basic materials in new-generation information technology, advanced rail transit equipment, aerospace equipment, energy-saving and new-energy vehicles, and other key high-tech fields in China, and are also key supporting materials in electronic information, power transmission, high-end equipment manufacturing, and national defense and military industries. With the rapid development of ultra-high voltage, 5G communication, the Internet of Things, and new-energy vehicles, higher requirements are placed on the conductivity of metal wire materials. How to further improve the high conductivity (electrical conductivity and thermal conductivity) of metal wire materials and develop functional and structural integrated advanced materials with excellent comprehensive properties such as electrical conductivity and oxidation resistance is a research problem in the technical field of metal wire materials.

[0003] Traditional metal wire materials (copper wire / aluminum wire) have reached their conductivity limit according to their own characteristics. Preparing composite materials by adding reinforcing materials with excellent electrical conductivity is a promising strategy to improve the electrical conductivity of metal wire materials. For example, graphene has a higher carrier mobility than metal, while metal (such as copper) has a higher carrier concentration than graphene. The effective combination of graphene and metal can significantly improve the carrier capacity of metal wire materials. Nano-carbon-metal wire composite materials are one of the most promising alternatives to traditional metal wire materials and are expected to break through the conductivity limit of metal wire materials. Currently, the preparation of graphene / copper wire composites mainly includes chemical vapor deposition, plasma sintering, and plating methods.

[0004] For example, the CVD method for preparing graphene / metal wire composite materials has a complex process and high cost, which severely limits its large-scale production. Plasma sintering can only handle a small amount of material at a time, and continuous operation is difficult. The spin coating method is complex and has not been realized in continuous production. In comparison, dispersing graphene in a solvent to form a dispersion liquid and directly coating it on the surface of a metal wire to prepare a graphene / copper composite material is more operable and has better economic benefits.

[0005] In the patents such as "Graphene coating liquid and preparation method thereof, composite wire and preparation method thereof", "A kind of graphene additive and preparation method of high-conductivity graphene / copper composite material", "Silver graphene conductive coating liquid and preparation method thereof", "Electrostatic attraction type graphene conductive coating liquid and preparation method thereof", etc., the inventors prepared an organic graphene dispersion liquid by mixing dispersant, coupling agent, film forming agent and graphene in organic solvent, and prepared graphene / copper wire composite material by coating, so that the electrical conductivity of copper wire is improved to a certain extent. However, the organic graphene conductive dispersion liquid, the organic component in the mixed solvent of the dispersion liquid can reach 90% and above, and a large amount of volatile organic solvents such as benzene, ethyl acetate, alcohol, ether and ketone are contained in the drying process, which not only increases the production cost, but also has great safety hidden dangers such as fire and explosion, which can easily cause poor working environment, harm workers' health, cause air pollution and other problems. SUMMARY

[0006] The purpose of the present application is to provide an environmentally friendly water-based graphene coating liquid, which can solve the problems of environmental unfriendliness and poor application safety of the current organic graphene coating liquid. The second purpose of the present application is to provide a preparation method of water-based graphene coating liquid, which solves the problems of poor dispersibility and stability of water-based graphene coating liquid. The third purpose of the present application is to provide a preparation method of graphene / metal wire composite material suitable for water-based graphene coating liquid coating, which solves the problem of poor stability in the preparation of graphene / metal wire composite material. The fourth purpose of the present application is to provide a graphene / metal composite wire, which solves the problem of high cost in the preparation of graphene / metal wire composite material.

[0007] In order to achieve the above purposes, the technical scheme adopted by the water-based graphene coating liquid of the present application is as follows: A water-based graphene coating liquid, which is composed of graphene or modified graphene, dispersant, binder, coupling agent, additive and solvent water; the graphene is prepared by mechanical exfoliation method, electrochemical exfoliation method, chemical vapor deposition method or reduction oxidation method; the modified graphene is surface modified by plasma treatment, or the modified graphene is synthesized by chemical oxidation method; the mass fraction of graphene or modified graphene in the water-based graphene coating liquid is 0.1-3%.

[0008] When the surface is modified by plasma treatment, the plasma atmosphere is one of air, nitrogen and ammonia or any combination thereof, the power is 80-120W, and the treatment time is 3-12min.

[0009] The modified graphene obtained by surface modification through a chemical oxidation method is conductive polyaniline functionalized graphene, conductive polypyrrole functionalized graphene, or conductive polythiophene functionalized graphene; the graphene modified through plasma treatment is carboxylated graphene, hydroxylated graphene, or aminated graphene.

[0010] The dispersant is selected from one or any of polyvinylpyrrolidone, polyacrylic acid, cetyltrimethylammonium bromide, sodium dodecylbenzenesulfonate, sodium polystyrene sulfonate, 1-pyrene butyric acid, 1-pyrene butyric acid sodium salt, and isopropyl alcohol; the mass fraction of the dispersant in the aqueous graphene coating solution is 0.1-0.5%; the binder is selected from one or any of sodium carboxymethyl cellulose, polystyrene butadiene copolymer, sodium alginate, and alkali-soluble acrylate emulsion; the mass fraction of the binder in the aqueous graphene coating solution is 0.1-0.6%; the coupling agent is selected from one or any of poly(3,4-ethylenedioxythiophene) / polystyrene sulfonate, dimethyl sulfoxide-doped poly(3,4-ethylenedioxythiophene) / polystyrene sulfonate, benzenesulfonic acid-doped conductive polyaniline, benzenesulfonic acid-doped conductive polypyrrole, polyvinylimidazole, mercaptoamino triazole pyrene monoquaternary ammonium salt, and diaminotriazole pyrene monoquaternary ammonium salt; the mass fraction of the coupling agent in the aqueous graphene coating solution is 0.1-1%.

[0011] The additive is selected from one or any of nano-silver, nano-gold, carbon nanotubes, and carbon black; the mass fraction of the additive in the aqueous graphene coating solution is 0.02-0.4%.

[0012] The preparation method of the aqueous graphene coating solution comprises the following steps: (1) mixing the formula amount of graphene or graphene modified by plasma or chemical oxidation with a dispersant, a coupling agent, a binder, an additive, and deionized water, and uniformly dispersing the mixture; (2) uniformly dispersing the aqueous graphene coating solution, dispersing for 3-12 h, high-shear dispersing for 10-45 min, ultrasonic dispersing for 10-60 min, ultrasonic power of 600-1000 W, and acoustic resonance dispersing acceleration of 10-80 g and dispersing time of 10 s-600 s.

[0013] The uniform dispersion of the aqueous graphene coating solution is achieved by using one or any combination of magnetic stirring, mechanical stirring, high-shear dispersion, ultrasonic dispersion, and acoustic resonance.

[0014] The application of the aqueous graphene coating solution is to prepare graphene / metal wire composite wire by using the aqueous graphene coating solution, which comprises the following steps: (1) the metal wire is pretreated by ultrasonic cleaning, water washing, drying, dilute sulfuric acid, water or air plasma, the diameter of the metal wire is 0.15-0.5mm, and the concentration of the dilute sulfuric acid is 1-8%; (2) the water-based graphene plating solution is coated on the surface of the pretreated metal wire by using a continuous plating machine, and dried in an inert atmosphere, thereby obtaining the graphene / metal wire composite material.

[0015] In step (2), the plating speed is 3-12m / min, the drying temperature is 100-240℃, and the drying time is 0.08-0.4min.

[0016] Compared with the prior art, the present application has obvious advantages and beneficial effects. By means of the above technical scheme, the present application can achieve considerable technical progress and practicability, and has wide practical application value, and at least has the following advantages: (1) under the action of the dispersant, coupling agent, additive and binder, the graphene plating solution enhances the uniform dispersion of graphene in solvent water, improves the stability of the plating solution, ensures the uniform plating of graphene on the surface of the metal wire, enhances the bonding force between graphene and the surface of the metal wire, builds an electronic transmission bridge between graphene and the metal wire substrate, and effectively improves the conductivity of the composite material.

[0017] (2) in the preparation process of the graphene / metal wire, a plurality of dispersion methods are combined to ensure the stable and efficient dispersion of graphene in solvent water, the pretreatment of the metal wire enhances the bonding force between graphene and the metal substrate, and the stability of the graphene coating structure is improved.

[0018] (3) the graphene / metal wire composite material prepared by the present application exhibits excellent conductivity, for example, the conductivity of the composite wire material with a length of 1m and a diameter of 0.2mm reaches 106.5%IACS at room temperature.

[0019] (4) the graphene plating solution prepared by the present application uses deionized water as a solvent, and no large amount of harmful organic gas is volatilized during the preparation process of the composite wire material, which is environmentally friendly and has a wide source; the preparation method is simple, efficient, low in cost and easy to realize large-scale industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0020] The accompanying drawings are used to provide a further understanding of the present application, and constitute a part of the specification, together with the embodiments of the present application, to explain the present application, and do not constitute a limitation on the present application.

[0021] Figure 1 SEM and Raman spectrum analysis pictures of the copper wire / graphene composite material prepared in application example 1. DETAILED DESCRIPTION

[0022] The technical solutions of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative efforts belong to the protection scope of the present application. Embodiment 1

[0023] The present embodiment provides a water-based graphene coating solution, which is composed of the following components by mass percentage: graphene 1.5%, polyvinylpyrrolidone 0.2%, sodium carboxymethyl cellulose 0.3%, poly (3, 4-ethylenedioxythiophene) / polystyrene sulfonate 0.5%, nano-silver 0.2%, and the balance is deionized water; the graphene is prepared by mechanical exfoliation method.

[0024] The preparation method of the water-based graphene coating solution of the present embodiment includes the following steps: (1) Mix the formula amount of graphene with polyvinylpyrrolidone, sodium carboxymethyl cellulose, poly (3, 4-ethylenedioxythiophene) / polystyrene sulfonate, nano-silver and deionized water, and disperse uniformly; (2) Disperse the water-based graphene coating solution by magnetic stirring for 3h, and then by high shear dispersion for 4h. Embodiment 2

[0025] The present embodiment provides a water-based graphene coating solution, which is composed of the following components by mass percentage: graphene 0.1%, polyacrylic acid 0.5%, polystyrene butadiene copolymer 0.1%, polyaniline doped with benzenesulfonic acid 1%, nano-gold 0.02%, and the balance is water; the graphene is prepared by electrochemical exfoliation method. The preparation method of the water-based graphene coating solution of the present embodiment includes the following steps: (1) Mix the formula amount of graphene with polyacrylic acid, polystyrene butadiene copolymer, polyaniline doped with benzenesulfonic acid, nano-gold and deionized water, and disperse uniformly; (2) Disperse the water-based graphene coating solution by mechanical stirring for 1h, and then by high shear dispersion for 2h. Embodiment 3

[0026] The present embodiment provides a water-based graphene coating solution, which is composed of the following components by mass percentage: graphene 3%, cetyltrimethylammonium bromide 0.1%, sodium alginate 0.6%, polypyrrole doped with benzenesulfonic acid 0.1%, carbon nanotube 0.4%, and the balance is water; the graphene is prepared by chemical vapor deposition method.

[0027] The preparation method of the water-based graphene coating solution of the present embodiment includes the following steps: (1) The formula amount of graphene is mixed with dispersant, coupling agent, binder, additive and deionized water, and uniformly dispersed; (2) The aqueous graphene coating solution is dispersed by mechanical stirring for 2h, and the acceleration of acoustic resonance dispersion is 50g, and the time is 300s. Example 4

[0028] The aqueous graphene coating solution provided by the embodiment is composed of the following components by mass percentage: graphene 1%, sodium dodecyl benzene sulfonate 0.4%, sodium dodecyl benzene sulfonate 0.4%, polyvinylimidazole 0.8%, carbon black 0.08%, and the balance is water; the graphene is graphene prepared by reduction and oxidation.

[0029] The preparation method of the aqueous graphene coating solution of the embodiment includes the following steps: (1) The formula amount of graphene or modified graphene is mixed with sodium dodecyl benzene sulfonate, sodium dodecyl benzene sulfonate, polyvinylimidazole, carbon black and deionized water, and uniformly dispersed; (2) The aqueous graphene coating solution is mechanically stirred for 2h, and then ultrasonically dispersed uniformly, the ultrasonic dispersion time is 10min, and the ultrasonic power is 1000W. Example 5

[0030] The aqueous graphene coating solution provided by the embodiment is composed of the following components by mass percentage: modified graphene 2%, polystyrene sulfonate sodium 0.3%, polystyrene butadiene copolymer 0.5%, mercapto amino triazole pyrene one quaternary ammonium salt 0.3%, nano gold 0.1%, and the balance is water; the modified graphene is carboxylated graphene; The preparation method of the aqueous graphene coating solution of the embodiment includes the following steps: (1) The formula amount of modified graphene is mixed with polystyrene sulfonate sodium, polystyrene butadiene copolymer, mercapto amino triazole pyrene one quaternary ammonium salt, nano gold and deionized water, and uniformly dispersed; (2) The aqueous graphene coating solution is mechanically dispersed for 1h, and then ultrasonically dispersed uniformly, the ultrasonic dispersion time is 30min, and the ultrasonic power is 800W. Example 6

[0031] The aqueous graphene coating solution provided by the embodiment is composed of the following components by mass percentage: modified graphene 1.5%, 1-pyrene butyric acid 0.3%, sodium alginate 0.2%, diaminotriazole pyrene one quaternary ammonium salt 0.7%, carbon nanotube 0.3%, and the balance is water; the modified graphene is hydroxylated graphene.

[0032] The preparation method of the aqueous graphene coating solution of the embodiment includes the following steps: (1) the formula amount of modified graphene is mixed with 1-pyrene butyric acid, sodium alginate, carbon nanotube, diaminotriazole pyrene quaternary ammonium salt and deionized water, and is uniformly dispersed; (2) the aqueous graphite coating solution is stirred by magnetic force for 1h, and is uniformly dispersed by ultrasonic dispersion, the ultrasonic dispersion time is 60min, and the ultrasonic power is 600W. Example 7

[0033] The embodiment provides an aqueous graphene coating solution, which is composed of the following components in percentage by mass: modified graphene 2.5%, 1-pyrene butyric acid sodium salt 0.4%, carboxymethyl cellulose sodium 0.2%, 3,4-ethylenedioxythiophene / polystyrene sulfonate 0.7%, carbon nanotube 0.2%, and the balance is water; the modified graphene is amino-functionalized graphene.

[0034] The preparation method of the aqueous graphene coating solution in the embodiment comprises the following steps: (1) the formula amount of modified graphene is mixed with 1-pyrene butyric acid sodium salt, carboxymethyl cellulose sodium, 3,4-ethylenedioxythiophene / polystyrene sulfonate, carbon nanotube and deionized water, and is uniformly dispersed; (2) the aqueous graphite coating solution is stirred by mechanical stirring for 1h, and is uniformly dispersed by ultrasonic dispersion, the ultrasonic dispersion time is 30min, and the ultrasonic power is 800W. Example 8

[0035] The embodiment provides an aqueous graphene coating solution, which is composed of the following components in percentage by mass: modified graphene 1.2%, isopropyl alcohol 0.3%, sodium alginate 0.4%, polyvinylimidazole 0.7%, nano gold 0.3%, and the balance is water; the modified graphene is surface-modified by plasma treatment, the plasma atmosphere is air, the power is 100W, and the treatment time is 8min. The modified graphene is conductive polyaniline functionalized graphene.

[0036] The preparation method of the aqueous graphene coating solution in the embodiment comprises the following steps: (1) the formula amount of modified graphene is mixed with isopropyl alcohol, sodium alginate, polyvinylimidazole, nano gold and deionized water, and is uniformly dispersed; (2) the aqueous graphite coating solution is dispersed by magnetic stirring for 3h, and is dispersed by high shear for 7h. Example 9

[0037] The embodiment provides an aqueous graphene coating solution, which is composed of the following components in percentage by mass: modified graphene 1.5%, isopropyl alcohol 0.4%, sodium alginate 0.5%, polyvinylimidazole 0.6%, nano gold 0.1%, and the balance is water; the modified graphene is conductive polyaniline functionalized graphene.

[0038] The preparation method of the aqueous graphene coating solution of the embodiment comprises the following steps: (1) uniformly mix the modified graphene, isopropyl alcohol, sodium alginate, polyvinylimidazole, nano-gold and deionized water in the formula amount; (2) uniformly disperse the aqueous graphene coating solution by magnetic stirring for 3h, and then ultrasonic dispersion for 7h. Embodiment 10

[0039] The aqueous graphene coating solution of the embodiment comprises the following components by mass percentage: modified graphene 1.53%, isopropyl alcohol 0.3%, sodium alginate 0.4%, polyvinylimidazole 0.5%, nano-gold 0.2%, and the balance is water; the modified graphene is conductive polythiophene functionalized graphene.

[0040] The preparation method of the aqueous graphene coating solution of the embodiment comprises the following steps: (1) uniformly mix the modified graphene, isopropyl alcohol, sodium alginate, polyvinylimidazole, nano-gold and deionized water in the formula amount; (2) uniformly disperse the aqueous graphene coating solution by magnetic stirring for 4h, and then accelerate the dispersion by acoustic resonance of 80g for 60s.

[0041] Application Example 1 The application of the aqueous graphene coating solution of Embodiment 1 is to prepare graphene / metal wire composite wire by using the aqueous graphene coating solution, which comprises the following steps: (1) pretreat the metal wire by ultrasonic cleaning, water washing, blow drying, passing through dilute sulfuric acid, and passing through water, wherein the diameter of the metal wire is 0.3mm, and the concentration of the dilute sulfuric acid is 4%; (2) coat the aqueous graphene coating solution on the surface of the pretreated metal wire by using a continuous coating machine at a coating speed of 8m / min, and dry it in an inert atmosphere at a drying temperature of 160℃ for 0.2min.

[0042] Performance detection: take 5m of the graphene / copper wire composite wire prepared in Application Example 1, and test the conductivity of the composite wire by taking 1m length each time on a TX-1000 intelligent metal conductor resistance meter, a total of 5 times, and the conductivity of the graphene / copper wire composite wire is respectively: 105.1% IACS, 105.2% IACS, 105.2% IACS, 105.1% IACS, and 105.1% IACS.

[0043] Take the same diameter as Example 1 without graphene coating 5m length of pure copper wire, on TX-1000 intelligent metal conductor resistance meter each take 1m length of conductivity, pure copper wire conductivity results are: 99.8% IACS, 99.2% IACS, 99.5% IACS, 99.5% IACS, 99.3% IACS. Compared with pure copper wire, graphene / copper wire composite wire conductivity increased by about 5.7% IACS.

[0044] In addition, the SEM picture of the copper wire / graphene composite material prepared in Example 1 is shown in Figure 1 As can be seen from Figure 1 It can be seen that the graphene is uniformly distributed on the surface of the copper wire, and the graphene coating surface is smooth.

[0045] Example 2 Example 2 of the application of aqueous graphene coating solution is to prepare graphene / metal wire composite wire using aqueous graphene coating solution, which includes the following steps: (1) The metal wire is pretreated by ultrasonic cleaning, washing, drying, passing through dilute sulfuric acid, and passing through water. The diameter of the metal wire is 0.5mm, and the concentration of dilute sulfuric acid is 1%; (2) The aqueous graphene coating solution is coated on the surface of the pretreated metal wire by using a continuous coating machine, and the coating speed is 3m / min. Dry in an inert atmosphere, the drying temperature is 240℃, and the drying time is 0.08min.

[0046] Performance test: take 5m of graphene / copper wire composite wire prepared in Example 2, test the conductivity of the composite wire on TX-1000 intelligent metal conductor resistance meter every 1m length, a total of 5 times, the conductivity of graphene / copper wire composite wire is: 105.3% IACS, 105.1% IACS, 105.1% IACS, 105.2% IACS, 105.2% IACS.

[0047] Take the same diameter as Example 2 without graphene coating 5m length of pure copper wire, on TX-1000 intelligent metal conductor resistance meter each take 1m length of conductivity, pure copper wire conductivity results are: 99.4% IACS, 99.3% IACS, 99.6% IACS, 99.4% IACS, 99.3% IACS. Compared with pure copper wire, graphene / copper wire composite wire conductivity increased by about 5.8% IACS.

[0048] Example 3 Example 3 of the application of aqueous graphene coating solution is to prepare graphene / metal wire composite wire using aqueous graphene coating solution, which includes the following steps: (1) The metal wire is pretreated by ultrasonic cleaning, water washing, blow drying, passing through dilute sulfuric acid, and passing through water. The wire diameter of the metal wire is 0.5 mm, and the concentration of the dilute sulfuric acid is 1%. (2) The water-based graphene coating solution is coated on the surface of the pretreated metal wire by using a continuous coating machine at a coating speed of 12 m / min, and dried in an inert atmosphere at a drying temperature of 100°C for 0.4 min.

[0049] Performance detection: 5 m of the graphene / copper wire composite prepared in Example 3 is taken, and the conductivity of the composite wire is tested on a TX-1000 intelligent metal conductor resistance meter every 1 m in length, a total of 5 times. The conductivity of the graphene / copper wire composite is 105.3% IACS, 105.1% IACS, 105.3% IACS, 105.2% IACS, and 105.1% IACS, respectively.

[0050] 5 m of pure copper wire with the same diameter as in Example 3 is taken, and the conductivity of the pure copper wire is measured on a TX-1000 intelligent metal conductor resistance meter every 1 m in length. The conductivity of the pure copper wire is 99.6% IACS, 99.8% IACS, 99.4% IACS, 99.6% IACS, and 99.2% IACS, respectively. Compared with the pure copper wire, the conductivity of the graphene / copper wire composite is improved by about 5.7% IACS.

[0051] Example 4 Example 4 (1) The metal wire is pretreated by ultrasonic cleaning, water washing, blow drying, passing through dilute sulfuric acid, and passing through water. The wire diameter of the metal wire is 0.5 mm, and the concentration of the dilute sulfuric acid is 1%. (2) The water-based graphene coating solution is coated on the surface of the pretreated metal wire by using a continuous coating machine at a coating speed of 12 m / min, and dried in an inert atmosphere at a drying temperature of 100°C for 0.4 min.

[0052] Performance detection: 5 m of the graphene / copper wire composite prepared in Example 3 is taken, and the conductivity of the composite wire is tested on a TX-1000 intelligent metal conductor resistance meter every 1 m in length, a total of 5 times. The conductivity of the graphene / copper wire composite is 105.3% IACS, 105.1% IACS, 105.3% IACS, 105.2% IACS, and 105.1% IACS, respectively.

[0053] Take the same diameter as Example 4 without graphene coating 5m length of pure copper wire, on TX-1000 intelligent metal conductor resistance meter each take 1m length of conductivity, pure copper wire conductivity results are: 99.7% IACS, 99.4% IACS, 99.3% IACS, 99.4% IACS, 99.4% IACS. Compared with pure copper wire, the conductivity of graphene / copper wire composite wire is increased by about 5.8% IACS.

[0054] Example 5 Example 5 of the application of aqueous graphene coating solution is to prepare graphene / metal wire composite wire by using aqueous graphene coating solution, which includes the following steps: (1) The metal wire is pretreated by ultrasonic cleaning, water washing, drying, passing through dilute sulfuric acid, and passing through water. The diameter of the metal wire is 0.25mm, and the concentration of dilute sulfuric acid is 6%; (2) The aqueous graphene coating solution is coated on the surface of the pretreated metal wire by using a continuous coating machine, and the coating speed is 5m / min. Dry in inert atmosphere, dry temperature is 220℃, dry time is 0.15min, get it.

[0055] Performance test: take 5m of graphene / copper wire composite wire prepared in Example 5, test the conductivity of the composite wire on TX-1000 intelligent metal conductor resistance meter each take 1m length, a total of 5 times, the conductivity of graphene / copper wire composite wire is: 105.4% IACS, 105.3% IACS, 105.3% IACS, 105.2% IACS, 105.2% IACS.

[0056] Take the same diameter as Example 5 without graphene coating 5m length of pure copper wire, on TX-1000 intelligent metal conductor resistance meter each take 1m length of conductivity, pure copper wire conductivity results are: 99.6% IACS, 99.5% IACS, 99.5% IACS, 99.3% IACS, 99.4% IACS. Compared with pure copper wire, the conductivity of graphene / copper wire composite wire is increased by about 5.8% IACS.

[0057] Example 6 Example 6 of the application of aqueous graphene coating solution is to prepare graphene / metal wire composite wire by using aqueous graphene coating solution, which includes the following steps: (1) The metal wire is pretreated by ultrasonic cleaning, water washing, drying, passing through dilute sulfuric acid, and passing through water. The diameter of the metal wire is 0.25mm, and the concentration of dilute sulfuric acid is 6%; (2) The water-based graphene coating solution is coated on the surface of the pretreated metal wire by using a continuous coating machine, the coating speed is 6 m / min, and the drying is performed in an inert atmosphere, the drying temperature is 190°C, and the drying time is 0.2 min, to obtain the graphene / metal wire composite wire.

[0058] Performance detection: 5 m of the graphene / copper wire composite wire prepared in Example 6 is taken, 1 m length of the composite wire is taken each time to test the conductivity on the TX-1000 intelligent metal conductor resistance meter, and the test is performed for 5 times, and the conductivity of the graphene / copper wire composite wire is 105.3% IACS, 105.3% IACS, 105.3% IACS, 105.1% IACS, and 105.2% IACS, respectively.

[0059] 5 m of pure copper wire with the same diameter as in Example 6 and without graphene coating is taken, 1 m length of the pure copper wire is taken each time to test the conductivity on the TX-1000 intelligent metal conductor resistance meter, and the conductivity of the pure copper wire is 99.4% IACS, 99.8% IACS, 99.6% IACS, 99.2% IACS, and 99.3% IACS, respectively. Compared with the pure copper wire, the conductivity of the graphene / copper wire composite wire is increased by about 5.8% IACS.

[0060] Example 7 Example 7 is the application of the water-based graphene coating solution to prepare a graphene / metal wire composite wire, which comprises the following steps: (1) The metal wire is pretreated by ultrasonic cleaning, water washing, blow drying, passing through dilute sulfuric acid, and passing through water, the diameter of the metal wire is 0.4 mm, and the concentration of the dilute sulfuric acid is 3%; (2) The water-based graphene coating solution is coated on the surface of the pretreated metal wire by using a continuous coating machine, the coating speed is 7 m / min, and the drying is performed in an inert atmosphere, the drying temperature is 150°C, and the drying time is 0.3 min, to obtain the graphene / metal wire composite wire.

[0061] Performance detection: 5 m of the graphene / copper wire composite wire prepared in Example 7 is taken, 1 m length of the composite wire is taken each time to test the conductivity on the TX-1000 intelligent metal conductor resistance meter, and the test is performed for 5 times, and the conductivity of the graphene / copper wire composite wire is 105.3% IACS, 105.3% IACS, 105.2% IACS, 105.1% IACS, and 105.2% IACS, respectively.

[0062] Take the same diameter as Example 7 without graphene coating 5m length of pure copper wire, on TX-1000 intelligent metal conductor resistance meter each take 1m length of conductivity, pure copper wire conductivity results are: 99.3% IACS, 99.6% IACS, 99.6% IACS, 99.4% IACS, 99.4% IACS. Compared with pure copper wire, the conductivity of graphene / copper wire composite wire is increased by about 5.8% IACS.

[0063] Example 8 Example 8 of aqueous graphene coating solution is used to prepare graphene / metal wire composite wire, including the following steps: (1) the metal wire is pretreated by ultrasonic cleaning, water washing, drying, passing through dilute sulfuric acid, and passing through water. The diameter of the metal wire is 0.3mm, and the concentration of dilute sulfuric acid is 4%; (2) the aqueous graphene coating solution is coated on the surface of the pretreated metal wire by using a continuous coating machine, the coating speed is 8m / min, and the drying is carried out in an inert atmosphere, the drying temperature is 200℃, and the drying time is 0.3min.

[0064] Performance test: take 5m of graphene / copper wire composite wire prepared in Example 8, test the conductivity of the composite wire on TX-1000 intelligent metal conductor resistance meter every 1m length, a total of 5 times, the conductivity of graphene / copper wire composite wire is: 105.3% IACS, 105.1% IACS, 105.3% IACS, 105.3% IACS, 105.2% IACS.

[0065] Take the same diameter as Example 8 without graphene coating 5m length of pure copper wire, on TX-1000 intelligent metal conductor resistance meter each take 1m length of conductivity, pure copper wire conductivity results are: 99.4% IACS, 99.2% IACS, 99.4% IACS, 99.6% IACS, 99.3% IACS. Compared with pure copper wire, the conductivity of graphene / copper wire composite wire is increased by about 5.9% IACS.

[0066] Example 9 Example 9 of aqueous graphene coating solution is used to prepare graphene / metal wire composite wire, including the following steps: (1) the metal wire is pretreated by ultrasonic cleaning, water washing, drying, passing through dilute sulfuric acid, and passing through water. The diameter of the metal wire is 0.3mm, and the concentration of dilute sulfuric acid is 4%; (2) using a continuous coating machine to coat the water-based graphene coating solution on the surface of the pretreated metal wire, the coating speed is 8 m / min, and dried in an inert atmosphere, the drying temperature is 200°C, and the drying time is 0.3 min, to obtain.

[0067] Performance detection: take 5m of graphene / copper wire composite wire prepared in application example 9, test the conductivity of the composite wire on TX-1000 intelligent metal conductor resistance meter every 1m length, a total of 5 times, the conductivity of graphene / copper wire composite wire is: 105.4% IACS, 105.5% IACS, 105.5% IACS, 105.3% IACS, 105.2% IACS.

[0068] Take 5m length of pure copper wire with the same diameter as application example 9 without graphene coating, test the conductivity on TX-1000 intelligent metal conductor resistance meter every 1m length, the conductivity of pure copper wire is: 99.2% IACS, 99.1% IACS, 99.4% IACS, 99.5% IACS, 99.3% IACS. Compared with pure copper wire, the conductivity of graphene / copper wire composite wire is improved by about 6.1% IACS.

[0069] Application example 10 Application of water-based graphene coating solution in example 10 is to prepare graphene / metal wire composite wire using water-based graphene coating solution, including the following steps: (1) the metal wire is pretreated by ultrasonic cleaning, washing, drying, passing through dilute sulfuric acid, and passing through water, the diameter of the metal wire is 0.3mm, and the concentration of dilute sulfuric acid is 4%; (2) using a continuous coating machine to coat the water-based graphene coating solution on the surface of the pretreated metal wire, the coating speed is 8 m / min, and dried in an inert atmosphere, the drying temperature is 200°C, and the drying time is 0.3 min, to obtain.

[0070] Performance detection: take 5m of graphene / copper wire composite wire prepared in application example 10, test the conductivity of the composite wire on TX-1000 intelligent metal conductor resistance meter every 1m length, a total of 5 times, the conductivity of graphene / copper wire composite wire is: 105.6% IACS, 105.4% IACS, 105.3% IACS, 105.2% IACS, 105.2% IACS.

[0071] Take the same diameter of pure copper wire without graphene coating 5m length, take 1m length on TX-1000 intelligent metal conductor resistance meter each time to measure conductivity, the conductivity results of pure copper wire are: 99.2% IACS, 99.3% IACS, 99.2% IACS, 99.1% IACS, 99.3% IACS. Compared with pure copper wire, the conductivity of graphene / copper wire composite wire is increased by about 6.1% IACS.

[0072] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. An aqueous graphene coating solution, characterized by: The water-based graphene coating solution is composed of graphene or modified graphene, dispersant, binder, coupling agent, additive, and solvent water; the graphene is prepared by mechanical exfoliation, electrochemical exfoliation, chemical vapor deposition, or reduction of graphene oxide; the modified graphene is surface-modified by plasma treatment or synthesized by chemical oxidation method; and the mass fraction of graphene or modified graphene in the water-based graphene coating solution is 0.1-3%.

2. The aqueous graphene coating solution of claim 1, wherein: When the surface is modified by plasma treatment, the plasma atmosphere is one or any combination of air, nitrogen, and ammonia, the power is 80-120 W, and the treatment time is 3-12 min.

3. The aqueous graphene coating solution of claim 1, wherein: The modified graphene obtained by surface modification by chemical oxidation method is conductive polyaniline functionalized graphene, conductive polypyrrole functionalized graphene, or conductive polythiophene functionalized graphene; and the graphene modified by plasma treatment is carboxylated graphene, hydroxylated graphene, or aminated graphene.

4. The aqueous graphene coating solution of claim 1, wherein: The dispersant is selected from one or any combination of polyvinylpyrrolidone, polyacrylic acid, cetyltrimethylammonium bromide, sodium dodecylbenzenesulfonate, sodium polystyrene sulfonate, 1-pyrene butyric acid, 1-pyrene butyric acid sodium salt, and isopropyl alcohol; the mass fraction of the dispersant in the water-based graphene coating solution is 0.1-0.5%; the binder is selected from one or any combination of sodium carboxymethyl cellulose, polystyrene butadiene copolymer, sodium alginate, and alkali-soluble acrylate emulsion; the mass fraction of the binder in the water-based graphene coating solution is 0.1-0.6%; the coupling agent is selected from one or any combination of poly(3,4-ethylenedioxythiophene) / polystyrene sulfonate, dimethyl sulfoxide-doped poly(3,4-ethylenedioxythiophene) / polystyrene sulfonate, benzene sulfonic acid-doped conductive polyaniline, benzene sulfonic acid-doped conductive polypyrrole, polyvinylimidazole, mercaptoamino triazole pyrene monoquaternary ammonium salt, and diaminotriazole pyrene monoquaternary ammonium salt; and the mass fraction of the coupling agent in the water-based graphene coating solution is 0.1-1%.

5. The aqueous graphene coating solution of claim 1, wherein: The additive is selected from one or any combination of nano-silver, nano-gold, carbon nanotube, and carbon black; and the mass fraction of the additive in the water-based graphene coating solution is 0.02-0.4%.

6. The method of claim 1-5, wherein the aqueous graphene coating solution is prepared by the steps of: a) mixing the graphene oxide and the dispersant to form a mixture; b) adding the reducing agent to the mixture; and c) adding the water to the mixture. The method comprises the following steps: (1) mixing the graphene or graphene modified by plasma or chemical oxidation method with the dispersant, coupling agent, binder, additive, and deionized water in a formula amount, and uniformly dispersing the mixture; (2) uniformly dispersing the water-based graphene coating solution, wherein the dispersion time is 3-12 h, the high-shear dispersion time is 10-45 min, the ultrasonic dispersion time is 10-60 min, the ultrasonic power is 600-1000 W, the acoustic resonance dispersion acceleration is 10-80 g, and the dispersion time is 10 s-600 s.

7. The method of claim 6, wherein the aqueous graphene coating solution is prepared by the steps of: a) mixing the graphene oxide and the dispersant in the water to form a mixture; b) adding the reducing agent to the mixture; and c) stirring the mixture to form the aqueous graphene coating solution. The uniform dispersion of the water-based graphene coating solution is achieved by one or any combination of magnetic stirring, mechanical stirring, high-shear dispersion, ultrasonic dispersion, and acoustic resonance dispersion.

8. Use of the aqueous graphene coating solution according to any one of claims 1 to 5, characterized in that: The water-based graphene coating solution is used to prepare graphene / metal wire composite wire, which comprises the following steps: (1) The metal wire is pretreated by ultrasonic cleaning, water washing, blow drying, dilute sulfuric acid, water or air plasma, the diameter of the metal wire is 0.15-0.5mm, and the concentration of the dilute sulfuric acid is 1-8%; (2) The water-based graphene plating solution is coated on the surface of the pretreated metal wire by using a continuous plating machine, and dried in an inert atmosphere, thereby obtaining the graphene coated metal wire.

9. The use of the aqueous graphene coating solution according to claim 8, characterized in that: In step (2), the plating speed is 3-12m / min, the drying temperature is 100-240℃, and the drying time is 0.08-0.4min.

Images