KR101837478B1 - Preparation method of grephene hybrid materials, Removal method of graphene materials impurities and graphene Materials - Google Patents
Preparation method of grephene hybrid materials, Removal method of graphene materials impurities and graphene Materials Download PDFInfo
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- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
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Abstract
The present invention maximizes the improvement of physical properties such as electrical conductivity due to the interplanar overlapping of materials by mixing two or more kinds of nano-plate materials including graphene materials, and by removing impurities from the graphene materials, .
The present invention relates to a method for producing a pretreatment material, comprising the steps of: (a) adding a critical energy capable of vaporizing the impurity to a graphene material containing an impurity to produce a pretreatment graphene material; And (b) a nano plate material having a thickness different from that of the pretreatment graphene material is mixed with the pretreatment graphene, whereby the thinner material of the pre-processing graphene material and the nano-plate material is inserted between the thicker materials, ; And a method for producing the graphene hybrid material.
Description
The present invention maximizes the improvement of physical properties such as electrical conductivity due to the interplanar overlapping of materials by mixing two or more kinds of nano-plate materials including graphene materials, and by removing impurities from the graphene materials, .
As shown in Fig. 1, the two-dimensional nano-plate material can cause overlapping of plates, that is, overlapping between planes, which is impossible in a zero-dimensional material or a one-dimensional material. Therefore, when a two-dimensional nano-plate material is coated on a base material to form a conductive film, thermal conductivity and electrical conductivity can be greatly improved compared to a case of coating a zero-dimensional powder material or a one-dimensional fibrous material.
However, if the thickness of the two-dimensional nanofibrous material is large, the adverse effect occurs. That is, when thick two-dimensional materials overlap each other, a step difference problem as shown in FIG. 2 occurs. Due to this group problem, a void space is created between the two-dimensional nano-plate material, so that the contact surface is in line contact, and the electrical conductivity, thermal conductivity, filling factor, barrier property, Physical properties such as thickness controllability, film uniformity and interfacial bonding property are all lowered.
The inventor of the present invention has proposed a method of manufacturing a two-dimensional hybrid material by applying a two-dimensional material having a different thickness through a method of manufacturing a two-dimensional hybrid material and a method of manufacturing a two-dimensional hybrid material for an electrically conductive film by the method of Japanese Patent Application Laid-Open No. 10-2015-0129137 By solving the step difference problem as described above, a method of improving the physical properties of the two-dimensional hybrid material was developed.
However, when a graphene material containing an impurity is used as a raw material for the two-dimensional hybrid material, improvement of the physical properties of the hybrid material due to the impurities has been limited, and a method for improving the properties has been demanded.
The present invention improves the physical properties of the graphene material itself by removing impurities from the graphene material and solves the step difference in mixing two or more types of nanoflouan materials including graphene materials to widen the interfacial contact area, Dimensional hybrid material, such as electrical conductivity, thermal conductivity, and the like.
The technical idea of the present invention introduced for solving the above-mentioned problems is as follows. (1) A technology for overcoming a step difference problem (hereinafter referred to as a 'technology 1') and (2) a technology for removing impurities from a graphene material .
The technique 1 is disclosed in Patent Application No. 2014-0054801 entitled " Method for manufacturing a two-dimensional hybrid material for an electrically conductive film "(Japanese Patent Application Laid-Open No. 10-2015-0129138, published on Nov. 19, 2015), Patent Application No. 2014-0054795 Patent Document No. 2015-0044173 "Method for manufacturing a carbon-based two-dimensional hybrid material" (unpublished), Patent Application No. 2015-0044174 (Unpublished), Patent Application No. 2015-0044183 entitled "Method for manufacturing graphene-nanoparticle hybrid material" (unpublished), Patent Application No. 2015-0142682 entitled "Method for producing a two-dimensional hybrid composite Method "(unpublished), and so on.
The present invention combines the following Technique 2 with the above Technique 1.
The main content of Technology 2 is to remove impurities of graphene materials by energy introduction and then to mix them with the material of the nanofabric material or to introduce the energy into the mixture of two or more kinds of nanofabric materials including graphene material to remove the impurities of the graphene material .
Examples in which the present invention is applied can be classified as follows.
1) Mixture of graphene material and nano-plate material with energy removed impurities
2) A mixture of graphene material with impurities removed by applying energy and other graphene materials with energy removed and impurities removed
3) After mixing the graphene material containing the impurities and the nano-plate material, energy is removed to remove impurities.
4) Graphene materials containing impurities and other graphene materials including impurities are mixed and energy is removed to remove impurities
A common feature in these four applications is "to remove impurities from the graphene material by applying energy".
The impurities of the graphene material are divided into the following four types.
I) Non-graphene nanocarbon material produced with graphene production
Ii) the dried or amorphous portion of the graphene edge
Iii) oxidizing groups (-OH, -COOH, -O- (epoxy group)),
Iv) Non-carbon material impurities (sulfur, sodium, nitrate, etc.)
In the present invention, by applying critical energy to graphenes containing such impurities, the principle that graphene main body is able to withstand its energy and impurities are blown off as a gas is applied. In addition, when the impurities hidden between the multi-layer graphene materials are vaporized and blown off, the graphene layers are peeled off and the graphene material can be further thinned.
According to the present invention, graphene is thinned by the above two principles and effects (impurity removal and graphene layer peeling), impurities trapped between graphene layers are removed, and unnecessary oxidizing groups are removed to maximize graphene interplanar spacing , The level difference problem can be reduced extremely.
The threshold energy for removing the impurities may be generated by any one of thermal energy, plasma energy, discharge energy, and light energy.
The present invention improves the physical properties of the graphene material itself by removing impurities from the graphene material, and allows the layer of graphene material to peel off during impurity removal to produce a thinner material.
Further, by solving the step difference in mixing two or more kinds of nano-plate materials including graphene materials (before and after removal of impurities) and widening the area of contact between the planes, it is possible to improve the physical properties such as electric conductivity and thermal conductivity It is possible to maximize the improvement effect.
[Fig. 1] is a schematic cross-sectional view of a contact portion between 0-dimensional, 1-dimensional and 2-dimensional materials.
[Fig. 2] is a conceptual diagram of a step difference problem occurring in a two-dimensional nano-plate material.
[Fig. 3] is a schematic diagram of a process of removing impurities by applying critical energy to a graphene material containing impurities.
The present invention relates to a method for producing a pretreatment material, comprising the steps of: (a) adding a critical energy capable of vaporizing the impurity to a graphene material containing an impurity to produce a pretreatment graphene material; And (b) mixing a preformed graphene material and a nano-platelike material having different thicknesses from the pre-processing graphene material so that the thinner material of the pre-processing graphene material and the nanoflagelike material are inserted between the thicker materials, thereby widening the contact surface between the materials. And a method for producing the graphene hybrid material.
The nano-plate material may be prepared by pretreating a graphene material containing impurities with a critical energy to vaporize the impurities.
In the step (a), a graphene material containing impurities may be doped with a nitrogen element, and then a critical energy may be applied.
The present invention also provides a method for producing a graphene material, comprising the steps of: preparing a graphene material containing (a ') impurities; And (b ') mixing the graphene material and the nano-plate material having different thicknesses, and applying a critical energy capable of vaporizing the impurity to remove impurities from the graphene material and the nano- Making the contact surface between the materials wider while the material being between the thicker materials; And a method for producing the graphene hybrid material.
In the present invention, the non-graphene nano carbon material produced together with the graphene production, ii) the dried or amorphous portion of the graphene edge, iii) the oxidizing group formed during graphene production or naturally formed, iv) Wherein impurities are removed by adding a critical energy capable of vaporizing the impurities to a graphene material containing at least one impurity of the impurities, and a method of removing impurities from the graphene material, Provide the material together.
The nano-plate material may be a plate-like ceramic, nano-clay, ZnO nanoplate, TiO 2 nanoplate, WS 2 , MoS 2 , clamshell, calcium carbonate, silver flake, copper flake, carbon flake, carbon nanoplate, At least one of the resultant of electrical peeling of graphite, the result of physical peeling of graphite, the result of peeling of solvent of graphite, the result of peeling of physico-chemical peeling of graphite, and the result of mechanical peeling of graphite.
The graphene materials include graphene oxide (GO), reduced graphene (RGO), graphene nanoplate (GNP), graphene (GP) produced by peeling graphite, graphene CVD-GP), a graphene quantum dot (GP-QD) having a diameter of 30 nm or less, and the like.
Graphene Oxide (GO) maintains between 1 and 20 layers of graphite, has many defects and surface reactors, and is very well dispersed in water. These surface reactors can also be various substituents through simple reactions. These include the functional group bonded to the reaction before and after the graphite oxide as -OH, -COOH, -CONH 2, -NH 2, -COO-, -SO 3 -, -NR 3 +, -CH = O, C-OH, > O, CX and the like, and the binding of the functional group to graphene oxide also falls within the category of graphene oxide.
These graphene oxides (GO) can be produced in the form of graphene through a chemical reduction method (hydrazine treatment or the like) or a thermal reduction method. At this time, the reduced graphene is called Reduced Graphene Oxide (RGO).
On the other hand, graphene nanoplate (GNP) having a thickness of 5 to 100 nm obtained by physically peeling graphite or expanding graphite intercalation compound, graphite nanoplate (GNP) having a thickness of 5 to 10 nm obtained by peeling or physically peeling graphite from solvent (CVD-GP) produced by the CVD method, a graphene quantum dot (GP-QD) of 30 nm or less in diameter, and the like.
As described above, the graphene material is classified according to the thickness, the composition, the manufacturing method, and the like. The graphene derivative, the doping material, and the surface treatment structure are also included in the graphene material category.
Conventional graphene materials contain many impurities, and when used alone or in a composite state or in a solid state, they often do not exhibit graphene specific properties. These impurities are divided into the following four types.
I) Non-graphene nanocarbon material produced with graphene production
Ii) the dried or amorphous portion of the graphene edge
Iii) oxidizing groups (-OH, -COOH, -O- (epoxy group)),
Iv) Non-carbon material impurities (sulfur, sodium, nitrate, etc.)
Through the existing studies, the inventors of the present invention have developed a method of improving physical properties by hybridizing nano-plate materials (especially graphene) having different thicknesses. However, due to the above-mentioned impurity problem, the limit of the improvement of physical properties has been limited, and thus, a new limit breaking technique has been studied.
A detailed examination of the physical properties of the impurities described above revealed that the chemical stability of the impurities was relatively inferior to the chemical stability of the graphene materials. Accordingly, in the present invention, by applying critical energy to a graphene material containing one or more of the above four impurities, the main body of the graphene material is subjected to the energy, and the impurities are blown off as a gas , And impurities hidden between the multi-layer graphene materials are evaporated and flowed, the layers of the graphene material are peeled off and a thinner pretreatment graphene material can be obtained (see FIG. 3).
These two principles and effects can maximize the interplanar folding between nanofabric materials including graphene materials and can greatly reduce the level difference problem (since the thickness of the graphene material becomes thinner, The effect of removing impurities and eliminating unnecessary oxidizing groups).
The threshold energy for removing the impurities may be generated by any one of thermal energy, plasma energy, discharge energy, and light energy. Hereinafter, the energy that can be applied as the critical energy will be described for each type.
① Thermal energy
In order to apply the thermal energy, heat of 200 to 1500 ° C can be applied.
For example, in order to apply the thermal energy as critical energy, -COOH bonded with graphene is removed when heat of 200 DEG C or more is applied to a graphene material containing impurities. When heat of 400 DEG C or more is applied, -OH is removed do. That is, when the temperature is less than 200 ° C, -COOH and -OH are not removed or impurity vaporization does not occur.
When heat exceeding 1500 ° C is applied, the graphene main body is oxidized due to reaction with residual oxygen, and the properties of graphene disappear.
In addition, annealing effect and defect healing (defect restoration) effect can be given to the graphene crystal through application of heat energy for removing impurities.
② Plasma energy
The plasma energy generated by the application of DC voltage, RF power, and discharge can be directly applied to the graphene. Indirect hot thermal energy around the plasma can also contribute to the manifestation of the effects described above.
Plasma is a gas state separated by electrons with negative charge and positively charged ions at ultra-high temperature. It is called the "fourth state of matter", which is distinguished from solid, liquid and gas. In order to produce a plasma state, a plasma, It is necessary to generate a plasma by an electric means such as an electron beam and then maintain the plasma state by using a magnetic field or the like.
To use plasma in everyday life, you have to make it artificially, but plasma is the most common state in the entire universe. It is estimated that 99% of the entire universe is in a plasma state.
In the present invention, a mechanism (sputter mechanism) in which high energy electrons and ion species in a plasma state are directly irradiated to a graphen impurity to vaporize them, and a chemical coupling cleavage phenomenon of impurities due to a high temperature thermal energy state around the plasma.
③ Discharge energy
The discharge energy may be energy generated by any one of a gas discharge, a vacuum discharge, a glow discharge, an arc discharge, a corona discharge, and a high frequency discharge.
Generally, discharge refers to a phenomenon in which an electromotive force (electromotive force) decreases due to a current flowing from a charged battery. It is easy to say that the battery wears out in everyday life. However, in a narrow sense, when an insulator, such as a gas, in which electricity hardly flows, is in a strong electric field, it is often referred to as a phenomenon in which an insulator is lost and a current flows into the insulator. Examples of such discharge phenomena include gas discharge, vacuum discharge, glow discharge, arc discharge, corona discharge, and high frequency discharge.
④ Light energy
As the light energy, any one of ultraviolet rays, visible rays, and infrared rays may be used.
In the present invention, when the photon energy of the ultraviolet ray is 3.0 to 134 eV, the chemical bond of the impurity can be directly broken by photon energy. When the energy source of light energy is infrared ray, it is described as the principle of absorbing photons (less than 1.6 eV) condensed by graphene to generate thermal energy to vaporize impurities. This case is similar to the principle of thermal energy application. In the case of visible light, impurities are removed due to the mixing effect of photon energy and thermal energy.
When the critical energy is applied as described above, elements such as nitrogen may be doped to improve physical properties such as electrical conductivity. In order to vaporize the impurities according to the application of the critical energy, it is preferable to prepare the graphene material in powder form.
By mixing the pretreatment graphene material produced through the above process with the nano plate material thicker than the pre-treatment graphene material, the contact surface between the nano plate materials can be widened while the pre-treatment graphene is inserted between the nano plate materials.
When a pretreatment graphene material is produced prior to the removal of the impurities of the graphene material by energy application, a nano-plate material having a thickness different from that of the pre-treatment graphene material is mixed with the pretreated graphene material, And the nano-plate material becomes thinner between the thick material and the contact surface between the materials becomes wider.
When a nanoflagic material having a thickness different from that of the graphene material is mixed with the graphene material and then the critical energy capable of vaporizing the impurity is applied, the graphene material and the nanofibrous material The contact surface between the material becomes wider while the thin material enters between the thick material.
The graphene material and nanofibrous material can be hybridized in solid or liquid phase.
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. Hybridized materials in the solid phase can be supplied into a solvent to provide shock waves to maximize dispersion and hybridization.
Liquid-phase hybridization is performed in a liquid state such as ink, paste, etc., and a blending process and a shock wave providing process are added to hybridize the pre-treatment graphene material and the nano-plate material. In particular, the molecular shock wave providing process is very important in liquid-phase hybridization, and this process replaces water-based graphene or water-based graphene oxide with alcohol-based solvent or oil-based solvent.
(Respectively 100)
Growth rate
(%)
[Table 1] are examples for showing the effect of the present invention.
As graphene used, GO (Graphene Oxide made by liquid phase oxidation of graphite) has a thickness of less than 1 nm, RGO1 is graphene with 3 ~ 5 layer thickness made by chemically reducing GO, and RGO2 is thermally reduced Graphene with a thickness of 7-20 layers.
GNP1 is a graphene with a thickness of 5 ~ 30nm which is formed by expanding and delaminating ICC (intercalated carbon compound) between layers of graphite. GNP2 is a layer of 3 ~ It is about 200 nm graphene.
In order to demonstrate the effect of the present invention, the conductivities of GO and RGO1, RGO1 and RGO2, GNP1 and RGO1, GNP2 and RGO1 were dispersed in ICP solvent, respectively,
(PE-CVD apparatus, RF plasma torch, atmospheric plasma apparatus, arc discharge apparatus, heat treatment at 250 ° C., IR irradiation at 400 ° C., or the like) before mixing GO / RGO 1, RGO 1 / RGO 2, GNP 1 / RGO 1 and GNP 2 / RGO 1 Table 1 shows the electrical conductivity improvement ( %) of the coating film prepared by applying the dispersion process and the coating process as in the case of the non-energy treatment after the treatment through the lamp treatment.
The energy application method applied to the test is as follows.
Plasma-enhanced chemical vapor deposition (PE-CVD) devices produce plasma at very low, low pressures. The graphene material powder was placed on the substrate and subjected to plasma treatment.
The RF plasma torch is industrially important and exhibits the best effects of the present invention for graphene powder.
Atmospheric plasma (atmospheric plasma) and arc discharge processing equipment were all commercialized equipment.
As the heat treatment method, heat treatment in a 250 ° C atmosphere and heat treatment in an IR lamp at 400 ° C were applied respectively.
In Table 1, it can be seen that the electric conductivity is improved in all the test examples before the energy treatment although there is a difference depending on the kind of the material to be tested and the energy application method. Particularly, in the case of the PE-CVD apparatus, the RF plasma torch, the atmospheric pressure plasma apparatus, and the arc discharge apparatus, the electric conductivity is improved by more than 1000% according to the material to be tested. It is considered to be caused by removal of impurities in graphene materials, improvement of graphene purity, recovery of graphene defects, and generation of thin graphene through peeling of thick graphene.
The electric conduction improvement rate was the lowest when heat treated at 250 ℃ by energy application method. This is interpreted to be because the energy is too small to exhibit the effect of -COOH or adsorbed H 2 O removal on the surface of the graphene material, and the electrical conductivity value that is relatively increased by the 400 ° C. IR lamp treatment is -OH Removal, impurity removal, and annealing effects.
none
Claims (9)
(b) mixing the pretreated graphene material with nanoflagic materials having different thicknesses so that a thinner material of the pre-processing graphene material and a nanoflagelike material is inserted between the thicker materials, thereby widening the contact surface between the materials; ≪ / RTI >
Wherein the graphene material containing an impurity is doped with a nitrogen element and then a critical energy is applied in the step (a).
(b ') mixing the graphene material with a nano-plate material having a different thickness, applying a critical energy to vaporize the impurity, and while the graphene main body is resistant to the critical energy, A step of allowing a thinner material between the graphene material and the nano-plate material to be interposed between the thicker materials to widen the contact surface between the materials; ≪ / RTI >
The nano-plate material may be at least one selected from the group consisting of plate-like ceramics, nano-clay, ZnO nanoplate, TiO 2 nanoplate, WS 2 , MoS 2 , clamshell, calcium carbonate, silver flake, copper flake, carbon flake, The result of the physical stripping of graphite, the result of physical stripping of graphite, the stripping result of graphite, the result of physical stripping of graphite, and the result of mechanical stripping of graphite.
Wherein the critical energy is generated by one of thermal energy, plasma energy, discharge energy, and light energy.
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