KR20160117671A - Preparation Method of Hybrid Materials composed of Carbon-Based Two-Dimensional Plate materials - Google Patents

Abstract

(A) preparing a first sheet material, which is a graphene oxide material having 10 layers or less; (b) preparing a second sheet-like material that is a carbon nanoplate material thicker than the first sheet-like material; (c) preparing a mixed solution obtained by mixing the first and second sheet materials in a liquid phase; And (d) adsorbing or coating the mixed liquid on the base material; Based two-dimensional hybrid material.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon-based two-dimensional hybrid material,

The present invention relates to a method of manufacturing a carbon-based two-dimensional hybrid material which can improve physical properties by solving the problem of the two-dimensional carbon-based plate-like material itself, the problem of the size of the material,

(Nano clay, ZnO nano plate, TiO ₂ nano plate, WS ₂ , MoS ₂ , oxide, clay shell, calcium carbonate, sulfide and the like), metal flake (silver flake, copper flake), graphite, carbon nano plate, Graphene, graphene nanoplate, and graphene oxide are plate materials. Composite compound, and organic or inorganic hybrid materials can be formed in a plate form. These sheet materials are very important in the fields of strength enhancement (flexural strength, tensile strength, etc.), electrical conductivity improvement, thermal conductivity improvement, filler material, gas permeation prevention, lubricant (solid or liquid) and liquid phase heat transfer material.

FIG. 1 is a conceptual diagram of a contact section between a 0-dimensional material (particle type), a 1-dimensional material (linear), and a 2-dimensional material (plate) for explaining excellent physical properties of 2-dimensional plate- It can be seen that the plate-like material of the 2D plate material can be brought into contact with a wafer, which is impossible in a zero-dimensional material or a one-dimensional material.

The conceptual diagram of FIG. 1 can be further considered through the case of incorporating 0-dimensional material (powder), 1-dimensional material (fiber, etc.) and 2-dimensional material (plate-like material) in a specific matrix. In the case of zero dimensional material, a considerably large amount should be added to induce point contact, and electric and heat transmitted through the point contact are minimized even if many point contacts are induced. In case of one-dimensional material, point contact is easily induced even in small amount, and line contact is also possible by using a large amount. Therefore, heat and electricity can be transferred through efficient contact rather than 0-dimensional powder-like particles. As a representative example, a silver nanowire transparent conductive film can be cited. However, the two-dimensional plate material is a key material that can be utilized in many fields because the interfacial contact easily occurs and the thermal conductivity and the electric conductivity are far superior to the one-dimensional material described above.

However, if the two-dimensional sheet material is thick, the adverse effect occurs. That is, when thick two-dimensional materials overlap each other, a step difference problem occurs as shown in the schematic diagram of FIG. Due to such a step difference, void spaces are generated between the two-dimensional sheet-like materials, and the contact surfaces are in line contact, and the electrical conductivity, thermal conductivity, filling rate, barrier properties, film density, thickness controllability, film uniformity, Are all lowered.

As a typical example, graphite is a very cheap material and very important in industry, but it is getting less and less used in industries such as electronics and IT that are growing everyday because the technology of improving the physical properties of graphite reaches its limit, It is impossible to satisfy the above-mentioned step difference problem seriously.

The carbon-based plate-like materials have basically a plate structure having a weak van der Waals bond such as graphite, and in the process of crushing the graphite, the van der Waals bond breaks preferentially and becomes thinner. However, it is difficult to make a material having a thickness of 200 nm or less from graphite. To this end, graphite oxide or graphene oxide (hereinafter referred to as "GO") is formed by using a specially processed material (graphite intercalated carbon And then reducing it to RGO (reduced graphene oxide).

Carbon nano-plates generally have a very thin structure rather than graphite, and their thickness is about 5 to 200 nm. Unlike carbon nanoparticles, graphene (GP) is a very thin carbon nanostructure new material that exhibits quantum mechanical properties. The graphene has electrical conductivity, thermal conductivity, strength, flexibility, gas permeation prevention The physical properties such as physical properties are known to be the most excellent materials that have been discovered or made to date. In particular, the flexibility and stretchability can be increased to 30% while maintaining strength, electrical conductivity and thermal conductivity properties. Such graphene typically has 1 to 20 layers of a single carbon atom layer having a honeycomb structure.

However, since the carbon nanolplate coating film without binder is hard to form, it is difficult to form, and graphene, which is expected to be a future innovative material, is easily wrinkled during coating liquid manufacturing due to its thin thickness and flexibility. Easily broken or very weakly formed. As a result, the physical properties of graphite become worse than those of graphite.

In order to solve this problem, a polymer binder is added to the coating film to solve the problem of the strength and uniformity of the film, but the polymer binder interferes between the nanoparticles and hinders electric conduction and thermal conductivity, so that it is still difficult to exhibit good physical properties .

The present invention relates to a carbon material for solving problems caused by carbon-based plate-like materials, such as a step, a wrinkle of a very thin plate-shaped material, a weakening or breakage of a film generated in the absence of a binder, and low physical properties (concrete conductivity, for example) Based two-dimensional hybrid material.

In order to solve the above-mentioned problems, the present invention intends to newly introduce the concept of carbon nanoflow material, which replaces graphite as a next generation material, as a main conductor and the concept of thermodynamically very unstable graphene as an additive.

The carbon nanoplate is thick and thermodynamically stable, so that it can not form a good quality coating film without a binder, and the problem of level difference is the next big problem after graphite. Graphene is thin, thermodynamically unstable, and can not form a good quality coating film because it has a wrinkled property by itself.

However, as shown in FIG. 3 (a), the present invention thermodynamically stabilizes the thermodynamically unstable graphene surface having a high specific surface area through bonding with the surface of the carbon nanoplate, and at the same time, By filling in the empty spaces generated from the problem and filling the space, it is possible to induce surface contact, so that the carbon nanoplate and the graphene can be hybridized with the carbon-based plate materials having the more stable property of electric conductivity and the like. .

Specifically, the present invention relates to a method for producing a graphene film, comprising the steps of: (a) preparing a first sheet material, which is a graphene oxide material having 10 layers or less; (b) preparing a second sheet-like material that is a carbon nanoplate material thicker than the first sheet-like material; (c) preparing a mixed solution obtained by mixing the first and second sheet materials in a liquid phase; And (d) adsorbing or coating the mixed liquid on the base material; Based two-dimensional hybrid material.

And the first plate-like material is made of a graphite raw material having an average diameter of 0.5 to 50 μm.

The second plate-shaped material may be manufactured by peeling Expanded Graphite, which is an expanded graphite intercalated compound (GIC). Further, the GIC may have a diameter of 0.5 to 5,000 mu m have.

The second plate-like material may have a thickness of 5 to 100 nm and a thickness of 60 wt% or more.

In the step (a), the first plate-shaped material may be prepared as a solid or a liquid.

The first and second plate-like materials may be characterized in that their surfaces are chemically modulated or doped.

The first and second plate-like materials may be characterized in that their surfaces are decorated with nanoparticles.

In the step (c), the first and second plate-like materials are put into a solvent to perform a liquid phase hybridization process, and the shock wave is provided to the solvent. At least one of an ultrasonic wave applying method, a molecular unit shearing force applying method, an ultrafast blading, an ultrafast stiring, a beads ball stuttering, a high pressure jetting method, and a high speed homogenizer method.

Further, the present invention provides a method for producing a carbon-based two-dimensional hybrid material, comprising: (e) further mixing an additive; And further comprising:

The additive may be graphene having 1 to 20 layers, or may be at least one of a zero-dimensional nanomaterial or a one-dimensional nanomaterial. The one-dimensional nanomaterial may be a metal nanowire or a carbon nanotube .

The additive may be selected from the group consisting of a binder, a monomer, a polymer, a resin, a copolymer, a ceramic precursor, a polyimide precursor, a metal binder, a ceramic binder, a nanoparticle binder, a surfactant, a dispersant, a BYK, a functional material, And may be characterized by being at least one of acid, base, salt, ionic species, labeling agent, pressure-sensitive adhesive, oxide, ceramic, magnetic material, organic material and biomaterial.

Also, the present invention provides a method for producing a carbon-based two-dimensional hybrid material, comprising the steps of: (c-1) heat treating a product obtained after the step (c); And further comprising:

According to the present invention, the physical properties that could not be provided or separately provided can be expressed through a technique of hybridizing two types of carbonaceous plate materials having different thicknesses and thermodynamic properties. In particular, it is possible to replace graphite with a conventional two-dimensional plate-shaped material having improved properties in fields such as electric conduction, heat conduction, heat radiation, filler, and barrier.

[Fig. 1] is a conceptual diagram of a cross-section of a contact portion between zero dimensional, one dimensional and two dimensional materials.
[Fig. 2] is a conceptual diagram of a step difference problem occurring in a two-dimensional plate-like material.
[Fig. 3] is a conceptual view showing a step difference problem solving principle of the present invention.
[Fig. 4] is a FE-SEM photograph of a CNP-graphene hybrid material in which a step problem is overcome by the CNP having a single problem and the present invention.
[Fig. 5] is an FE-TEM photograph showing that nanoparticles can be dispersed and added to an empty space generated by a step difference problem.
FIG. 6 is an FE-SEM photograph of a material supplemented with disadvantages of a two-dimensional hybrid material by adding silver nanowires and silver nanoparticles.
[Fig. 7] is an FE-TEM photograph of an example in which the principle of the present invention is applied after decorating the surface of graphene and CNP with nanoparticles in advance.
[Fig. 8] is an FE-SEM photograph of a densified film obtained by adding a dispersant and a polymer binder.

Hereinafter, a method for manufacturing a carbon-based two-dimensional hybrid material according to the present invention will be described in detail.

In order to realize the present invention, it is necessary to adopt two materials having extremely different thicknesses and completely different thermodynamic properties. In the present invention, the first plate material having a thickness of 1 to 10 layers Pin and a carbon nanoplate, which is a second plate material having a thickness of 5 to 200 nm, can well realize the principle of the present invention in terms of thickness. In the present invention, it is essential that the first plate material and the second plate material are mutually dispersed in a liquid phase so that the graphene nanofibers are adsorbed on the surface of the graphene nanoplate in a state in which the graphenes are spread.

In addition, it was also confirmed that the principle of the present invention can be effectively operated when the carbon nanoflower exhibiting the main properties such as electrical conductors is relatively large and the graphene is smaller than the carbon nanoplate. It is also possible to measure the width and length of the plate- It is preferable that the GIC as a raw material of the carbon nanoplate is 0.5 to 5,000 mu m and the graphite raw material of the raw material GO of graphene RGO has a diameter of 0.5 to 50 mu m. Such a diameter standard is an important principle of the present invention, which is determined through consideration and experiment of the size of the space and the interface region caused by the step difference problem.

Specifically, the method for fabricating a carbon-based two-dimensional hybrid material according to the present invention includes the steps of: (a) preparing a first plate material, which is a graphene oxide material having 10 layers or less; (b) preparing a second sheet-like material that is a carbon nanoplate material thicker than the first sheet-like material; (c) preparing a mixed solution obtained by mixing the first and second sheet materials in a liquid phase; And (d) adsorbing or coating the mixed liquid on the base material.

The first plate material and the second plate material may be prepared as a solid or a liquid and may be hybridized. Solid phase hybridization can be realized by mechanical mixing or the like, and can be applied to solid phase molding, compression molding, powder molding, cast molding, powder deposition and the like. The plate-shaped material hybridized with solid phase can be supplied into a solvent to provide shock waves to maximize dispersion and hybridization. Liquid-phase dyeing is performed in a liquid state such as ink, paste, etc., and may be performed by adding a blending process and a shock wave providing process.

The graphene material may be RGO (Reduced Graphene Oxide) obtained by reduction from GO (Graphene Oxide). Further, the GO may be manufactured from a graphite raw material having an average diameter of 0.5 to 50 μm. You may. Further, the second plate-shaped material may be manufactured by peeling Expanded Graphite, which is an expanded Graphite Intercalated Compound (GIC). Further, the GIC may have a diameter of 50 to 5,000 mu m It is possible. On the other hand, the graphenes of the present invention may have surface modified, doped, or some oxidized groups. In the graphenes synthesized, small or small amounts of doping and surface oxidizing groups are present.

The carbon-based two-dimensional hybrid material produced by the present invention may have a main weight content of 60% or more of the carbon nano plate. Specifically, the second plate material may have a thickness of 5 to 200 nm Is at least 60 wt%.

The first and second plate-like materials may be characterized in that the surface is chemically modulated. Specifically, the graphene and the carbon nanoplate may be surface-oxidized or modified in order to ensure dispersibility, functionality, ease of mixing, applicability with other materials, and ease of compounding with other materials . At this time, examples of the functional group that can occur after oxidation or modify-is _{-OH, -COOH, -CONH 2, -NH} 2, -COO-, -SO 3 -, -NR 3+, -CH = O, C-OH , ≫ O, CX, and the like.

The first and second plate-like materials may be characterized in that their surfaces are decorated with nanoparticles. Both types of sheet materials can be decorated with nanoparticles (metals, oxides, ceramics, semiconductors, quantum dots, nanoparticles, etc.) using conventional chemical process technology. These nanomaterials adhered directly to the surface of the graphene and carbon nanoplates to induce a new electronic structure by the chemical bonding of heterogeneous materials, and the new electronic structure expresses new properties. For example, it is very difficult to coat quantum dots on a substrate with a single layer. However, if a monolayer film can be formed on graphenes and carbon nanoplates, which are two-dimensional plate structures of the present invention, And can exhibit unique quantum properties easily. Therefore, nanostructured materials such as magnetic materials, metals, and oxides can also exhibit new physical properties. Specifically, graphene and carbon nanoparticles were prepared by liquid phase chemical reduction, thermal decomposition, heat treatment, and electrical reduction using metal precursors, which are well mixed in a liquid phase and can be easily interfaced with each other. It is possible to apply the principle of the present invention after decorating the surface.

In the step (c), a shock wave is provided to the solvent while the mixture of the first and second plate-like materials is mixed in a liquid phase. The two-dimensional plate- When a molecular shock wave is applied to disperse the material, gaps between the same sheet materials spread and the sheet material or the different sheet materials having different thicknesses can be evenly dispersed in the gap. Therefore, the shock wave providing process can be minimized in solutions, inks, pastes, etc. in which nano plate materials are well dispersed.

The shock wave can be performed by a physical energy application method, such as a micro cavity explosion induction method, an ultrasonic wave application method, a molecular unit shear force application method (a high pressure ejection method using a fine nozzle, a high speed homogenizer, etc.) , High-speed blading, ultra-high-speed stirling, bead ball stirling (a method of stuttering with fine bead balls), a high-pressure spraying method (squeezing / spraying into fine gaps), and a high-speed homogenizer method. For example, a method of applying a high energy shear force while applying ultrasonic waves can be adopted.

Meanwhile, the method for producing a carbon-based two-dimensional hybrid material provided by the present invention comprises the steps of: (c-1) heat treating a product obtained after the step (c); And further comprising: The heat treatment is for shortening the natural drying time, inducing chemical bonding between the added materials, annealing for improving the arrangement among the nanostructures, curing of the thermosetting material, and inducing local surface melting among the nanostructures. To improve the physical properties of the carbon-based two-dimensional hybrid material produced by the present invention.

The heat treatment may be performed by a direct heating method using electricity, thermal energy, a flame, or the like, a light non-contact heating method using IR, radiation, mild wave, radiant heat, convection heat or the like.

Further, the present invention provides a method for producing a carbon-based two-dimensional hybrid material, comprising: (e) further mixing an additive; And further comprising:

The additive may be a third plate material having a different thickness depending on required physical properties, or may be a zero-dimensional nanomaterial or a one-dimensional nanomaterial. The one-dimensional nanomaterial may be silver nanowire A metal nanowire such as a copper nanowire, or a carbon nanotube. As the third plate material, a ceramic nano plate (nano clay, ZnO nano plate, TiO ₂ nano plate, WS ₂ , MoS ₂ , oxide, clam shell, calcium carbonate, sulfide, complex compound, organic hybrid material, etc.) Metal flakes (silver flakes, copper flakes), graphite, carbon nanoplates, graphene nanoplates, graphene, graphene oxides, and the like. That is, not only the first plate material or the second plate material but also the plate material of the same kind as that of the first and second plate materials may be applied as the third plate material, Two or more of the above-mentioned plate materials may be mixed and applied as a third plate material.

The zero-dimensional nanomaterial, the one-dimensional nanomaterial, and the third plate material having different thickness serve for the supplementation of the step difference occurring when the plate materials overlap each other (additional expansion of the interface, filling of the void space, etc.). Specifically, the zero-dimensional nanomaterial refers to spherical (powdery) nanoparticles, and these fill the space generated at the step corresponding to the interplanar confinement of the sheet material as shown in FIG. 3 (b). The one-dimensional nanomaterial extends the interface length (not the interfacial area) of the stepped portion. The third plate material having a thickness different from that of the first plate material or the flexible plate material widens the interface of the stepped portion. They maximize the contact area between materials and increase the density. In particular, metal nanoparticles, metal nanowires (such as silver nanowires and copper nanowires), metal nanoflakes, and carbon nanotubes (CNTs) improve the electrical conductivity of the coating.

The additives may also be selected from the group consisting of binders, monomers (thermosetting, UV-curable, chemically curable), polymers, resins, copolymers, ceramic precursors (siloxanes, polycarboxylic acids, etc.), polyimide precursors (such as polyamic acid), metal binders, , Nanoparticle binders, surfactants (BYK series, etc.), dispersants, BYK, functional materials, solvents (organic solvents, amphoteric solvents, aqueous solutions and hydrophilic solvents), oils, dispersants, acids, bases The present invention may be characterized in that the additive is at least one of a salt, an ionic species, a labeling agent, a pressure-sensitive adhesive, an oxide, a ceramic, a magnetic substance, an organic substance and a biomaterial. Labeling properties, viscosity properties, physical properties of the coating film, and drying properties. In particular, metal binders, ceramic binders, nanoparticle binders, oxides, ceramics, magnetic materials, carbon nanotubes and the like are applied to further enhance the functionality of the two-dimensional hybrid sheet material coatings.

Hereinafter, various materials that can be applied as additives will be described in detail.

1. Binder

The binder may be added in an amount of 1 to 50,000 parts by weight based on 100 parts by weight of the carbon-based two-dimensional hybrid material. For example, it is preferable that 20 to 600 parts by weight of binder is added to 100 parts by weight of graphene in the non-aqueous graphene coating solution for producing a film. As such a binder, any one or more of (1) a thermosetting resin, (2) a photocurable resin, (3) a silane compound which causes hydrolysis and condensation reaction, (4) a thermoplastic resin, and .

(1) Thermosetting resin

The thermosetting resin may be at least one of urethane resin, epoxy resin, melamine resin and polyimide.

(2) Photocurable resin

The photocurable resin may be at least one selected from the group consisting of epoxy resin, polyethylene oxide, urethane resin, reactive oligomer, reactive monofunctional monomer, reactive bifunctional monomer, reactive trifunctional monomer, and photoinitiator.

① Reactive oligomer

The reactive oligomer may be at least one of an epoxy acrylate, a polyester acrylate, a urethane acrylate, a polyether acrylate, a thiolate, an organosilicon polymer, and an organosilicon copolymer.

② Reactive monofunctional monomer

The reactive monofunctional monomer may be selected from the group consisting of 2-ethylhexyl acrylate, orthyldecyl acrylate, isodecyl acrylate, didecyl methacrylate, 2-phenoxyethyl acrylate, nonylphenol ethoxy lake monoacrylate, Acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, or hydroxybutyl methacrylate is used as the initiator. Or more.

③ Reactive bifunctional monomer

The reactive bifunctional monomer may be selected from the group consisting of 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, At least one of pentyl glycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycol methacrylate, polyethylene glycol dimethacrylate, tripropylene glycol diacrylate and 1,6-hexanediol diacrylate is applied .

④ Reactive trifunctional monomer

The reactive trifunctional monomer may be any one or more of trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, glycidylpentatriacrylate and glycidylpentatriacrylate. have.

⑤ Photo initiator

The photoinitiator may be at least one selected from the group consisting of benzophenone, benzyldimethylketal, acetophenone, anthraquinone, and thioxanthone.

(3) Silane compound

The silane compound may be any one or more of silanes, aminosilanes, silanes containing an organic functional group, TEOS, tetraalkoxysilanes, trialkoxysilanes, and dialkoxysilanes, which may cause a sol-gel reaction . In addition, compounds that can cause a sol-gel reaction among non-silicon compounds such as Ti can also be added.

① tetraalkoxysilanes

The tetraalkoxysilanes may be at least one of tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane and tetra-n-butoxysilane.

② Trialkoxysilanes

The trialkoxysilanes may be selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltriethoxysilane, Propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxy Silane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3- Chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydride Hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltri At least one of methoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane can be applied.

③ Dialkoxysilanes

Examples of the dialkoxysilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di- Butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di- Di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, At least one of diethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane can be applied.

(4) Thermoplastic resin

The thermoplastic resin may be at least one selected from the group consisting of polystyrene, polystyrene derivatives, polystyrene butadiene copolymers, polycarbonate, polyvinyl chloride, polysulfone, polyethersulfone, polyetherimide, polyacrylate, polyester, polyimide, polyamic acid, cellulose acetate, , Polyolefin, polymethyl methacrylate, polyether ketone, and polyoxyethylene can be applied.

(5) Conductive polymer

The conductive polymer may be at least one selected from the group consisting of a polythiophene-based homopolymer, a polythiophene-based copolymer, polyacetylene, polyaniline, polypyrrole, poly (3,4-ethylenedioxythiophene) and pentacene.

2. Metal nanowire

The metal nanowires may be copper nanowires or silver nanowires. The addition of such metal nanowires can improve the electrical conductivity of the coating. The copper nanowire may be coated with a protective layer, and the protective layer may be formed of a polymer or a metal.

3. Dispersant

Examples of the dispersing agent include BYK, block copolymer, BTK-Chemie, Triton X-100, polyethylene oxide, polyethylene oxide-polypropylene oxide copolymer, polyvinylpyrrole, polyvinyl alcohol, (Eg, sodium dodecylsulfonate, sodium dodecyl benzene sulfonate (NaDDBS), sodium dodecylsulfonate, sodium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, SDS), 4-vinylbenzoic acid cetyltrimethylammounium 4-vinylbenzoate, pyrene derivatives, Gum Arabic, GA, and nafion.

4. Surfactants

Examples of the surfactant include LDS (lithium dodecyl sulfate), CTAC (Cetyltrimethyl ammonium chloride), DTAB (Dodecyl-trimethyl ammonium bromide), nonionic C12E5 (Pentaoxoethylenedocyl ether), Dextrin (polysaccharide) GA (Gum Arabic), and ethylene carbonate (EC).

Hereinafter, the present invention will be described in detail with reference to examples. It should be noted that the following embodiments are provided so that those skilled in the art will be able to fully understand the present invention, and thus the scope of the present invention is not limited to the embodiments described.

≪ Examples of graphite oxide production &

Examples of the method for producing the graphite oxide include the modified Hummers method, the Hummers method, the Brodie method, the Hofman & Frenzel method, the Hamdi method, and the Staus method.

In the present embodiment, the Modified Hummers method is used. Specifically, 50 g of micro graphite powder and 40 g of NaNO ₃ are put into a 200 mL H ₂ SO ₄ solution, and while cooling, 250 g of KMnO ₄ is slowly added over 1 hour. Then slowly add ₅ L of _4-7 % H ₂ SO ₄ over 1 hour and add H ₂ O ₂ . After that, the precipitate is centrifuged and washed with 3% H ₂ SO ₄ -0.5% H ₂ O ₂ and distilled water to obtain a yellowish brown water-based graphene slurry. At this time, the number of graphene oxides obtained is 1 to 20 layers.

≪ Example of chemical reduction method >

For the chemical reduction method, 2 ml of 3% GO slurry is added with 100 ml of distilled water, and then 1 ml of hydrazine hydrate is added and reduced at 100 for 3 to 24 hours. The black reduced graphene Filter it using water and methanol. Before treating a strong reducing agent such as high-dry chalcopyrite, it is possible to use a process of treating a salt of an alkali metal or alkaline earth metal such as KI or NaCl to partially remove H ₂ O from the GO and partially restoring the carbon-carbon double bond.

As a specific experimental example, 6 g of KI is added to a 5% GO slurry and left for 6 days to complete the reaction. It is then rinsed with distilled water and filtered. In addition to the hydrazine method and the KI method, other methods for introducing a reducing agent into the GO aqueous solution include NaBH 4, Pyrogallol, HI, KOH, Lawesson's reagnet, Vitamin C, and Ascorbic acid.

≪ Example of thermally reducing graphene powder production &

The water-based graphene slurry obtained in the above <graphite oxide production example> is heat-treated at 300 ° C or higher to obtain graphene powder. In the present invention, heat-reduced graphene powder was prepared by heat treatment at 600 ° C for 10 minutes in an inert gas atmosphere of nitrogen.

&Lt; GNP Production Example &

The commercial GIC was treated with microwave for 30 seconds to obtain EP, and then treated with ultrasonic waves for 30 minutes to obtain CNP. As a further step, GIC was instantaneously put in an inert atmosphere at 500 캜, EP was obtained, and treated with ultrasonic waves for 30 seconds to obtain CNP. The EP obtained in the intermediate stage of the present invention is also in a state in which CNPs are partially bonded, and thus can be included in the CNP of the present invention. In this case, the carbon-based two-dimensional hybrid material is manufactured by mixing the EP-state CNP and other plate-like materials, that is, graphene or graphite, without using the separate ultrasonic process, can do.

&Lt; Example of thickness determination TRY-ERROR >

The mixed material obtained in the CNP, the graphite oxide production example and the chemical reduction method example obtained in the above <GNP production example> was classified into a natural precipitate (T1), a classification according to the centrifugal force intensity (T2 10 to 50 nm CNP, 50 to 100 nm CNP, 100 to 200 nm CNP, 200 to 300 nm CNP, 300 to 500 nm CNP, 1 to 500 nm CNP, 10 layers of RGO graphene (1 to 3 nm thick) and 10 to 20 layers of RGO graphene (3 to 6 nm thick). (S1), 3-6 nm (S2), 5-10 nm (S3), 10-50 nm (S4), 50-100 nm (S5), 100-200 nm (S6), 200-300 nm (S7), 300-500 nm (S8), and the resistance value was measured (50:50). The data on these are shown in [Table 1]. The heat treatment was performed at 200 to 500 ° C. [Table 1] clearly shows two trends. As the first tendency, when only S1 is mixed with S3 to S6, the resistance value is lowered, and it is visually confirmed that the film is formed without breakage. As a second trend, S2 to S8 samples do not have a low resistivity value when mixed with one-step larger diameter samples, S3 to S8, and the phenomenon of breaking the film is visually observed. Therefore, this experiment is a result that shows the principle of the present invention described above well. Therefore, the valid area is the part corresponding to the underlined red character in [Table 1].

[Table 1]

<Diameter determination TRY-ERROR example>

Unlike thicknesses, graphene diameters have not been developed effectively. Thus, Example 1 was performed on the basis of the raw material to prepare a GO, a first sheet material was obtained through Example 2, and Example 4 was carried out to obtain CNPs having different diameters and then the experiment was conducted. 1 to 10 layers of RGO graphene were used as the first layer material, and CNPs of about 5 to 200 nm were used as the second layer material, and the resistance values were measured by mixing the materials in a weight ratio of 5: 5. The graphite used in the first sheet material has a diameter of 200 to 500 nm (T1), 0.5 to 2 m (T2), 2 to 5 m (T3), 5 to 30 m (T4), 30 to 50 m (C1), 50 to 200 占 퐉 (C3), 200 to 500 占 퐉 (C4), and the diameter of the raw material GIC used in the production of CNP is 50 to 500 占 퐉 (T6) , And 500 to 5000 占 퐉 (C5). Table 2 shows that graphite materials of 0.5 to 50 μm are used as the first sheet material and GIC materials having a size of 0.5 to 5000 μm are used as the second sheet material, It can be seen that the hybrid effect of [Table 1] appears in the area of underlined red letter.

[Table 2]

&Lt; Experimental Example of Effect of Content of Graphene as the First Plate Material and Carbon Nano Plate as the Second Plate Material >

The effect of the content of graphene on the first plate and the carbon nanoplate on the second plate was investigated. The CNP obtained in the <GNP Production Example> and the graphene RGO mixed material obtained in the <Chemical Reduction Method Example> were mixed in IPA, and ultrasonic dispersion was performed for 30 seconds to measure the electric conductivity according to the weight content. 3]. The heat treatment was performed at 200 to 500 ° C. As a result, it can be confirmed that the carbon nanoflake-graphene hybrid material shows no linear change according to the content change, and shows a nonlinear tendency in which the resistance decreases sharply when the carbon nanoflower is put over 5% (by weight) . This nonlinear tendency can be explained by the step difference overcoming process described in the present invention. That is, it is understood that thin and flexible graphene greatly increases the contact area of the stepped portion generated in the CNP, and as shown in FIG. 4, the CNP voids and the rough surfaces are two-dimensionally hybridized and smoothed .

In addition, the resistance value which can not be achieved in the first plate material (25 Ω / sq) and the second plate material CNP (20 Ω / sq) shows the smallest value of 6 Ω / sq at 60% of CNP + 40% of graphene oxide . This value shows the effectiveness of the present invention and is the best in the world even in the case of coating a thick film without a binder to date. Therefore, it can be expected that, when the solvent, the dispersion process, the coating process and the like are optimized based on the embodiment of the present invention, better physical properties can be exhibited. [Table 3] shows that when the content of CNP is below 60%, the physical properties tend to deteriorate, and that the effective contact is saturated and the remaining graphene acts as a defect like impurities.

[Table 3]

&Lt; Additional Example of Graphene Third Sheet Material >

The weight of the graphene oxide as the first plate material and the carbon nanoplate as the second plate material were fixed at 15:85, and then the graphene as the third plate material was added to test the hybrid effect. The graphene used was the RGO 1 to 10 layer material obtained in the <Chemical Reduction Method Example>. Table 4 shows that as the graphene is added to the third sheet material, the cell resistance is lowered, which means that step problems and individual material problems are greatly improved.

[Table 4]

&Lt; CNP-graphene hybrid film surface resistance test example >

CNP (85%) - graphene oxide (15%) As a result of measuring the sheet resistance of the film by ultrasonically dispersing 0.5% in a hybrid material, the electric resistance was improved to about 3.5 times / sq by 4 times ] Reference). This allows us to confirm that silver nanoparticles play an important role in solving the step differences in sheet materials. That is, it is interpreted as a result of improving the filling rate (not the contact area) at the interface. In fact, it can be confirmed that the nanoparticles are separately dispersed in the gap between the plate-shaped material through the transmission electron microscope photograph shown in FIG. 5 .

In addition, silver nanowires (30 nm in diameter, 5 microns in length) and 0.5% of silver nanoparticles of 30 nm in size were dispersed by ultrasonic dispersion in a CNP (85%) - graphene oxide (15%) hybrid material to measure the sheet resistance As a result, the electric resistance was improved by 15 times or more (refer to [Table 4]) at 0.9 Ω / sq. This enables us to confirm that silver nanowires and silver nanoparticles play a very important role in solving group problems in sheet materials. In other words, it serves to extend the contact length (not the contact area) at the interface, and it is interpreted as complementing the contact length problem (especially in the case of conductivity) at the nano plate interface through the nanowire.

To improve electrical conductivity, nanowires can use metal nanowires such as silver nanowires and copper nanowires, and carbon nanotubes can also be used. In addition, the nanoparticles serve to fill void spaces generated in the step difference problem as described above. Thus, secondary problems arising in carbon-based 2D hybrid materials can be supplemented further through other nanoparticles and nanowires. For reference, silver nanowires and silver nanoparticles have a sand-like property. Therefore, it is very difficult to produce a thick film by using only these materials. As in the present invention, these materials are used for forming a two-dimensional plate-like material And exhibits new and excellent properties when fused with thin film and thick film properties. FIG. 6 is an FE-SEM photograph of a material in which silver nanowires and silver nanoparticles are added to the carbon nanoplate-graphene hybrid plate material.

&Lt; Example of decorating nanoparticles >

7 shows electron micrographs of nanoparticles decorated with graphene, which is the first plate material, and CNP, which is the second plate material. The first plate material was prepared by attaching a silver-based organometallic compound to graphene grains by a liquid phase reduction method and adsorbing a nickel-based organometallic compound to the CNP surface of the second plate material, followed by heat treatment. When these materials were mixed and dispersed at 8.5: 1.5 (CNP system: graphene system), the magnetic properties were remarkably lowered to 4.7 Ω / sq and new magnetic properties were exhibited. The coercivity was 12 Oe and the saturation magnetization The magnetization ratio was 2.8%. This shows that a hybrid film having good electrical conductivity properties while exhibiting soft magnetic properties can be realized by using the principle of the present invention.

&Lt; Example of addition of additives &

The membranes were prepared by adding BYK series dispersant and PVP binder in IPA dispersion process (ultrasonic treatment) to make more stable film with 85% CNP85% - graphene oxide 15% hybrid sheet material. Through this, it was confirmed that the hybridization of nano plate materials having different thicknesses became more uniform through the dispersant and packing of the membrane became high density through a small amount of binder. These additives show that they can help solve the additional problems in 2D hybrid materials. In addition, the resistance is 9.2? / Sq, the resistance is rather low, and the film strength is improved by 12 times, because the binder and dispersant also fulfill the general role and efficiently fill the empty space according to the step difference problem. An electron micrograph of the densified film is shown in FIG. As a result, it can be confirmed that the novel properties, such as other silane binders and organic materials, which have not been previously provided, can be expressed using the principle of the present invention.

none

Claims (16)

(a) preparing a first sheet material which is a graphene oxide material having 10 or less layers;
(b) preparing a second sheet-like material that is a carbon nanoplate material thicker than the first sheet-like material;
(c) preparing a mixed solution obtained by mixing the first and second sheet materials in a liquid phase; And
(d) adsorbing or coating the mixed liquid on the base material; Based hybrid material.
The method of claim 1,
Wherein the first plate-like material is made of a graphite raw material having an average diameter of 0.5 to 50 탆.
The method of claim 1,
Wherein the second plate-like material is manufactured by stripping expanded graphite having expanded GIC (Graphite Intercalated Compound).
4. The method of claim 3,
Wherein the GIC has a diameter of 0.5 to 5,000 mu m.
The method of claim 1,
Wherein the second plate-like material has a thickness of 5 to 100 nm and not less than 60 wt%.
The method of claim 1,
Wherein the step (a) comprises preparing the first plate-like material in solid or liquid form.
The method of claim 1,
Wherein the first and second plate-shaped materials are chemically modulated or doped on the surface of the carbon-based two-dimensional hybrid material.

The method of claim 1,
Wherein the first and second plate-like materials are decorated with nanoparticles on their surfaces.
The method of claim 1,
The method of claim 1, wherein the step (c) comprises the step of applying a liquid phase hybridization process to the first and second plate-like materials in a solvent, wherein shock waves are provided to the solvent.
The method of claim 9,
The method for providing the shock wave may be at least one of a micro cavity method, an ultrasonic wave applying method, a molecular unit shearing force applying method, an ultrafast blading method, an ultra high speed stirling method, a beads ball stuttering method, a high pressure jetting method, Based two-dimensional hybrid material.
11. The method according to any one of claims 1 to 10,
(e) further mixing the additive; Based hybrid material. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;
12. The method of claim 11,
Wherein the additive is a graphene having 1 to 20 layers.
12. The method of claim 11,
Wherein the additive is at least one of a zero-dimensional nanomaterial or a one-dimensional nanomaterial.
The method of claim 13,
Wherein the one-dimensional nanomaterial is a metal nanowire or a carbon nanotube.
12. The method of claim 11,
The additive may be selected from the group consisting of a binder, a monomer, a polymer, a resin, a copolymer, a ceramic precursor, a polyimide precursor, a metal binder, a ceramic binder, a nanoparticle binder, a surfactant, a dispersant, a BYK, a functional material, Wherein the carbon-based two-dimensional hybrid material is at least one selected from the group consisting of a base, a salt, an ionic species, a labeling agent, a pressure-sensitive adhesive, an oxide, a ceramic, a magnetic material, an organic material and a biomaterial.
16. The method according to any one of claims 1 to 15,
(c-1) heat treating the obtained product after the step (c); Based hybrid material. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;

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