KR20210052648A - Carbon fiber-graphene composite manufacturing apparatus and manufacturing method the same - Google Patents

Abstract

Disclosed are a carbon fiber-graphene composite manufacturing apparatus and a method for manufacturing the carbon fiber-graphene composite. In the carbon fiber-graphene composite manufactured by using the carbon fiber-graphene composite manufacturing apparatus, graphene is coated on carbon fibers, thereby exhibiting excellent performance by imparting excellent thermal conductivity, electrical conductivity, electromagnetic wave shielding, etc.

Description

Carbon fiber-graphene composite manufacturing apparatus and manufacturing method thereof {CARBON FIBER-GRAPHENE COMPOSITE MANUFACTURING APPARATUS AND MANUFACTURING METHOD THE SAME}

The present invention relates to a carbon fiber-graphene composite manufacturing apparatus and a method of manufacturing the carbon fiber-graphene composite.

Carbon nanotubes are microscopic molecules with a diameter of 1 nm in which carbons connected by hexagonal rings form a long round shape. The name is given because the carbon plane, which has a honeycomb-like structure by bonding three carbon atoms each, is rolled up into a tube shape. It is a futuristic new material with excellent flexibility and 100 times stronger tensile strength than steel. It is light because it is hollow, has electrical conductivity as well as copper, and thermal conductivity is known to be as good as diamond. In addition, carbon nanotubes are attracting attention as a next-generation semiconductor material as it has been found to be a conductor or a semiconductor depending on the diameter of the tube.

On the other hand, graphene (graphene) is a carbon-based new materials began receiving attention worldwide since 2007, graphite (graphite) with a layer of a single layer or less than 10 layers, isolated from the layered structure, the three electrons of sp ² bond And, one electron has a planar honeycomb structure with π-bonds on the top and bottom of the two-dimensional plane. So having such a structure pin is a metal, such as a two-dimensional movement of the electrons in the plane are given ballistic (Ballistic), copper and silver exhibits an electrical conductivity without regard to a length of allowable current density of 10 ⁹ a A / cm ² It exhibits a current density of 1,000 times or more, and is evaluated to have better electrical conductivity than carbon nanotubes. Due to these characteristics of graphene, it has been applied to conductive materials, electromagnetic wave shielding materials, solar cells, and polymer composite materials.

Among the various types of graphene, graphene oxide (GO) has many hydrophilic oxygen functional groups, and these oxygen functional groups can impart high workability to reinforce the composite material.

On the other hand, the carbon fiber composite material is a material that is superior to other types of fibers in physical properties such as specific strength, inelasticity, and heat resistance, and has the advantage of being lightweight and capable of making a high-strength, high-elastic composite. In the carbon fiber composite material, a matrix containing carbon fibers is referred to as a plastic carbon fiber-reinforced plastic, metal is referred to as a carbon fiber-reinforced metal, and carbon is referred to as a carbon composite material.

The carbon fiber composite material started in the 1950s and has been gradually increasing in use in various fields until today. In particular, the development of carbon fiber composites is the most widely used in the aviation industry at present due to the inherent characteristics of the material, such as non-rigidity, corrosion resistance, abrasion resistance, high strength, and excellent damping properties. I'm doing it.

The inventors of the present invention have been researching the carbon fiber composite material as described above, by coating graphene on the surface of the carbon fiber as a basic material, thereby producing a carbon fiber-graphene composite that has excellent thermal conductivity, electrical conductivity, and functions such as shielding electromagnetic waves. In order to do this, I started this study. Accordingly, after repeating the above studies, a device for coating graphene on carbon fibers using a roll-to-roll process was developed, and it was discovered that the manufacturing process time can be remarkably shortened when the device is used. Was completed.

In this regard, Korean Patent Registration No. 10-1386765 discloses a conductive electronic fiber coated with graphene and a method for manufacturing the same.

The present invention was conceived to solve the above-described problem, and an embodiment of the present invention provides a carbon fiber-graphene composite manufacturing apparatus through a roll-to-roll process.

In addition, another embodiment of the present invention provides a method of manufacturing a carbon fiber-graphene composite through a roll-to-roll process.

However, the technical problem to be achieved by the present invention is not limited to the technical problem mentioned above, and other technical problems not mentioned are clearly understood by those of ordinary skill in the technical field to which the present invention belongs from the following description. It will be possible.

As a technical means for achieving the above-described technical problem, one aspect of the present invention,

A surface treatment unit for pretreating the surface of the carbon fiber; A graphene coating unit for coating graphene on the surface-treated carbon fiber; A drying unit for drying the graphene-coated carbon fiber; And it provides a carbon fiber-graphene composite manufacturing apparatus through a roll-to-roll process comprising a; and a reduction treatment unit for reducing the graphene by treating the dried graphene-coated carbon fiber at a high temperature.

The pretreatment may be performed using plasma.

The intensity of the plasma may be 300 W to 1.5 kW.

The pretreatment may be performed for 5 to 10 minutes.

The graphene coated in the graphene coating part is graphene oxide, and the graphene may be dissolved in an aqueous solution.

The drying may be performed at a temperature of 100°C to 200°C.

The high-temperature treatment of the reduction treatment unit may be performed at a temperature of 500°C to 800°C.

The high-temperature treatment of the reduction treatment unit may be performed for 30 minutes to 2 hours.

In addition, another aspect of the present invention,

Pre-treating the surface of the carbon fiber; Coating graphene on the surface-treated carbon fiber; Drying the graphene-coated carbon fiber; And reducing the graphene by subjecting the dried graphene-coated carbon fiber to a high temperature.

According to an embodiment of the present invention, the carbon fiber-graphene composite manufactured using the apparatus for manufacturing a carbon fiber-graphene composite through the roll-to-roll process is coated with graphene on the carbon fiber to provide excellent thermal and electrical conductivity. , Electromagnetic wave shielding, and the like are imparted to show excellent performance.

In addition, since the carbon fiber-graphene composite is manufactured through a roll-to-roll process, the manufacturing time is remarkably shortened, and mass production is possible in a short time. In addition, since the surface of the carbon fiber is pretreated using plasma, the outer coating material coated on the carbon fiber can be removed before the graphene is coated, and the surface area of the carbon fiber can be increased. Can be coated.

The effects of the present invention are not limited to the above effects, and should be understood to include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.

1 is a schematic diagram of an apparatus for manufacturing a carbon fiber-graphene composite according to an embodiment of the present invention.
2 is a top view of an apparatus for manufacturing a carbon fiber-graphene composite according to an embodiment of the present invention.
3 is a front view of an apparatus for manufacturing a carbon fiber-graphene composite according to an embodiment of the present invention.
4A and 4B are SEM photographs showing the surface of carbon fibers after plasma treatment prepared according to an embodiment of the present invention.
5A and 5B are SEM photographs showing the surface of a carbon fiber-graphene composite manufactured according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail. However, the present invention may be implemented in various different forms, and the present invention is not limited by the embodiments described herein, and the present invention is only defined by the claims to be described later.

In addition, terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the entire specification of the present invention, "including" a certain component means that other components may be further included, rather than excluding other components unless specifically stated to the contrary.

The first aspect of the present application,

A surface treatment unit for pretreating the surface of the carbon fiber; A graphene coating unit for coating graphene on the surface-treated carbon fiber; A drying unit for drying the graphene-coated carbon fiber; And it provides a carbon fiber-graphene composite manufacturing apparatus through a roll-to-roll process comprising a; and a reduction treatment unit for reducing the graphene by treating the dried graphene-coated carbon fiber at a high temperature.

Hereinafter, an apparatus for manufacturing a carbon fiber-graphene composite according to the first aspect of the present application will be described in detail with reference to FIGS. 1 to 3. 1 is a schematic diagram of a carbon fiber-graphene composite manufacturing apparatus, FIG. 2 is a top view of the manufacturing apparatus, and FIG. 3 is a front view of the manufacturing apparatus.

In one embodiment of the present application, the carbon fiber-graphene composite manufacturing apparatus may be performed through a roll-to-roll process. That is, as shown in FIGS. 1 to 3, since each process is performed in a roll-to-roll process, the carbon fiber-graphene composite may be continuously manufactured. Accordingly, when a carbon fiber-graphene composite is manufactured using the carbon fiber-graphene composite manufacturing apparatus, mass production may be possible because continuous production is possible.

In one embodiment of the present application, the carbon fiber-graphene composite manufacturing apparatus may include a surface treatment unit for pretreating the surface of the carbon fiber. The surface treatment may be performed to remove an external coating material coated on the outer surface of the carbon fiber and increase the surface area of the carbon fiber. Therefore, since the carbon fiber is subjected to the pretreatment process as described above before coating the graphene, the graphene coated in the subsequent process may be uniformly coated with a high content. Meanwhile, the pretreatment may be preferably performed using plasma, and a chemical functional group is attached to the surface of the carbon fiber by the plasma treatment, and the bonding structure and roughness of carbon are adjusted. The plasma treatment may be atmospheric pressure plasma treatment or vacuum plasma treatment, and preferably may be performed using atmospheric pressure plasma treatment. Specifically, the atmospheric pressure plasma treatment is performed using air or argon gas under atmospheric pressure, and through this, chemical functional groups such as CC, C=C, -CH, CH, OH may be formed on the surface of the carbon fiber. . In addition, the surface of the carbon fiber may be modified by the plasma to deform carbon bonds. Specifically, the sp ² bond of the graphite structure may be transformed into ^{the sp 3} bond structure of the diamond structure. Meanwhile, the carbon fiber may be one or more selected from a PAN system, a pitch system, or a Rayon system.

In one embodiment of the present application, the intensity of the plasma may be 300 W to 1.5 kW, preferably 500 W to 1 kW. In addition, the pretreatment may be performed for 5 to 10 minutes. Accordingly, the pretreatment may be performed for an appropriate time according to the intensity of the plasma, and the process time may be remarkably shortened compared to the conventional pretreatment process. In addition, since the surface treatment unit is performed by plasma treatment, ozone may be generated, and may further include an atmospheric treatment device for removing the generated ozone.

In one embodiment of the present application, the carbon fiber-graphene composite manufacturing apparatus may include a graphene coating unit for coating graphene on the surface-treated carbon fiber. The surface-treated carbon fiber may be transferred to the graphene coating part by a roll-to-roll process, and after the carbon fiber is immersed in a graphene aqueous solution in which graphene is dissolved, the carbon fiber is moved to the drying part, thereby forming the graphene on the surface of the carbon fiber. It may be coated with an aqueous fin solution. At this time, the graphene aqueous solution may preferably be a mixed solution of distilled water and graphene, and the content of the graphene relative to 100 parts by weight of the distilled water may be 10 parts by weight to 30 parts by weight.

Specifically, the graphene aqueous solution may be accommodated in a container, and the surface-treated carbon fiber may be immersed in the graphene aqueous solution accommodated in the container through an input roll. Thereafter, the carbon fibers immersed in the graphene aqueous solution may move to the outside of the container through a desorption roll, and the carbon fibers moved to the outside of the container may move to the drying unit. At this time, the carbon fiber before being moved to the drying unit may be formed by contacting the atmosphere so that the graphene coated on the surface causes an oxidation reaction to form graphene oxide. On the other hand, the process time of the graphene coating unit may be performed in less than 1 hour, preferably may be performed for about 10 minutes.

In one embodiment of the present application, the carbon fiber-graphene composite manufacturing apparatus may include a drying unit for drying the graphene-coated carbon fiber. The drying unit is a process for removing distilled water contained in graphene coated on the carbon fiber, and the drying method is not limited, but at a temperature of about 100°C to 200°C, preferably at a temperature of about 150°C for 1 hour It may be performed for less than, preferably about 10 minutes.

In one embodiment of the present application, the carbon fiber-graphene composite manufacturing apparatus may include a reduction treatment unit for reducing the graphene by processing the dried graphene-coated carbon fiber at a high temperature. That is, the graphene, specifically, the graphene oxide may be reduced by subjecting the carbon fiber coated with graphene oxide to a high temperature, and through this, the graphene may be more strongly adhered to the surface of the carbon fiber. . In this case, the high-temperature treatment may be performed at a temperature of 500°C to 800°C in an argon (Ar) and nitrogen (N _{2) atmosphere, and may be performed for about 1 hour.} On the other hand, as described above, the reduction processing unit may have a slightly longer processing time than other processes, and thus a reduction gear may be installed between the drying unit and the reduction processing unit to adjust the processing time. In addition, the reduction treatment unit may generate ozone by high-temperature treatment, and may further include an atmospheric treatment device for removing the generated ozone.

The second aspect of the present application,

Pre-treating the surface of the carbon fiber; Coating graphene on the surface-treated carbon fiber; Drying the graphene-coated carbon fiber; And reducing the graphene by subjecting the dried graphene-coated carbon fiber to a high temperature.

Detailed descriptions of parts overlapping with the first aspect of the present application have been omitted, but the description of the first aspect of the present application may be equally applied even if the description is omitted in the second aspect.

Hereinafter, a method of manufacturing a carbon fiber-graphene composite according to the second aspect of the present application will be described in detail step by step.

First, in one embodiment of the present application, the method of manufacturing the carbon fiber-graphene composite includes a step of pre-treating the surface of the carbon fiber. The surface treatment may be performed to remove an external coating material coated on the outer surface of the carbon fiber and increase the surface area of the carbon fiber. Therefore, since the carbon fiber is subjected to the pretreatment process as described above before coating the graphene, the graphene coated in the subsequent process may be uniformly coated with a high content. Meanwhile, the pretreatment may be preferably performed using plasma, and a chemical functional group is attached to the surface of the carbon fiber by the plasma treatment, and the bonding structure and roughness of carbon are adjusted. The plasma treatment may be atmospheric pressure plasma treatment or vacuum plasma treatment, and preferably may be performed using atmospheric pressure plasma treatment. Specifically, the atmospheric pressure plasma treatment is performed using air or argon gas under atmospheric pressure, and through this, chemical functional groups such as CC, C=C, -CH, CH, OH may be formed on the surface of the carbon fiber. . In addition, the surface of the carbon fiber may be modified by the plasma to deform carbon bonds. Specifically, the sp ² bond of the graphite structure may be transformed into ^{the sp 3} bond structure of the diamond structure. Meanwhile, the carbon fiber may be one or more selected from a PAN system, a pitch system, or a Rayon system.

In one embodiment of the present application, the intensity of the plasma may be 300 W to 1.5 kW, preferably 500 W to 1 kW. In addition, the pretreatment may be performed for 5 to 10 minutes. Accordingly, the pretreatment may be performed for an appropriate time according to the intensity of the plasma, and the process time may be remarkably shortened compared to the conventional pretreatment process. In addition, since the surface treatment unit is performed by plasma treatment, ozone may be generated, and may further include an atmospheric treatment device for removing the generated ozone.

Next, in one embodiment of the present application, the method of manufacturing the carbon fiber-graphene composite includes a step of coating graphene on the surface-treated carbon fiber. The surface-treated carbon fiber may be transferred to the graphene coating part by a roll-to-roll process, and after the carbon fiber is immersed in a graphene aqueous solution in which graphene is dissolved, the carbon fiber is moved to the drying part, thereby forming the graphene on the surface of the carbon fiber. It may be coated with an aqueous fin solution. At this time, the graphene aqueous solution may preferably be a mixed solution of distilled water and graphene, and the content of the graphene relative to 100 parts by weight of the distilled water may be 10 parts by weight to 30 parts by weight.

Specifically, the graphene aqueous solution may be accommodated in a container, and the surface-treated carbon fiber may be immersed in the graphene aqueous solution accommodated in the container through an input roll. Thereafter, the carbon fibers immersed in the graphene aqueous solution may move to the outside of the container through a desorption roll, and the carbon fibers moved to the outside of the container may move to the drying unit. At this time, the carbon fiber before being moved to the drying unit may be formed by contacting the atmosphere so that the graphene coated on the surface causes an oxidation reaction to form graphene oxide. On the other hand, the process time of the graphene coating unit may be performed in less than 1 hour, preferably may be performed for about 10 minutes.

Next, in one embodiment of the present application, the method of manufacturing the carbon fiber-graphene composite includes drying the carbon fiber coated with the graphene. The drying step is a process for removing distilled water contained in graphene coated on the carbon fiber, and the drying method is not limited, but at a temperature of about 100°C to 200°C, preferably at a temperature of about 150°C. It may be performed for less than 1 hour, preferably about 10 minutes.

Next, in one embodiment of the present application, the method of manufacturing the carbon fiber-graphene composite includes reducing the graphene by subjecting the dried graphene-coated carbon fiber to a high temperature. That is, the graphene, specifically, the graphene oxide may be reduced by subjecting the carbon fiber coated with graphene oxide to a high temperature, and through this, the graphene may be more strongly adhered to the surface of the carbon fiber. . In this case, the high-temperature treatment may be performed at a temperature of 500°C to 800°C in an argon (Ar) and nitrogen (N _{2) atmosphere, and may be performed for about 1 hour.} On the other hand, the reducing step may be to adjust the process time by installing a reducer between the drying part of the drying step and the reduction treatment part of the reducing step, as the process time is somewhat longer than that of other processes, as described above. . In addition, the reduction treatment unit may generate ozone by high-temperature treatment, and may further include an atmospheric treatment device for removing the generated ozone.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily implement the present invention. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

Example. Preparation of carbon fiber-graphene composite

In order to manufacture the carbon fiber-graphene composite according to the present invention, a roll-to-roll device as shown in FIGS. 1 to 3 was used. First, the pretreatment process was performed by irradiating the carbon fiber with plasma of 1 kW intensity for 10 minutes. After the pretreatment process, carbon fibers were introduced into a container containing an aqueous solution of graphene using an input roll, and moved to the outside of the container using a desorption roll. At this time, the graphene aqueous solution is a solution containing distilled water and graphene, and the graphene aqueous solution was coated on the outside of the carbon fiber by immersing the carbon fiber in the aqueous solution, and the coating was performed for 10 minutes. Thereafter, the carbon fiber coated with the graphene aqueous solution was moved to a drying unit and dried at a temperature of 150° C. for 10 minutes to remove all distilled water contained in the graphene aqueous solution. Finally, graphene was reduced by moving the dried carbon fiber to a reduction treatment unit and high-temperature treatment at a temperature of 500°C to 800°C for 1 hour, and graphene-coated carbon fiber, that is, a carbon fiber-graphene composite Was obtained.

Experimental Example 1. Observation of the surface of carbon fiber after pretreatment process

In the above example, the surface of the carbon fiber after performing the plasma pretreatment process was observed, and SEM photographs thereof are shown in FIGS. 4A and 4B. As shown in FIGS. 4A and 4B, the plasma-treated carbon fiber had a smooth surface, and it was confirmed that all foreign substances coated on the carbon fiber were removed through this.

Experimental Example 2. Surface observation of carbon fiber-graphene composite

The surface of the carbon fiber-graphene composite prepared in the above example was observed, and SEM photographs thereof are shown in FIGS. 5A and 5B. 5A and 5B, it was confirmed that the prepared carbon fiber-graphene composite was uniformly coated with graphene on the surface of the carbon fiber.

Claims (9)

A surface treatment unit for pretreating the surface of the carbon fiber;
A graphene coating unit for coating graphene on the surface-treated carbon fiber;
A drying unit for drying the graphene-coated carbon fiber; And
A reduction treatment unit for reducing the graphene by processing the dried graphene-coated carbon fiber at a high temperature;
Carbon fiber through a roll-to-roll process comprising a-graphene composite manufacturing apparatus.
The method of claim 1,
The pretreatment is a carbon fiber-graphene composite manufacturing apparatus that is performed using plasma.
The method of claim 2,
The intensity of the plasma is 300 W to 1.5 kW of carbon fiber-graphene composite manufacturing apparatus.
The method of claim 1,
The pretreatment is a carbon fiber-graphene composite manufacturing apparatus that is performed for 5 to 10 minutes.
The method of claim 1,
The graphene coated in the graphene coating part is graphene oxide,
The graphene is a carbon fiber-graphene composite manufacturing apparatus that is dissolved in an aqueous solution.
The method of claim 1,
The drying is carried out at a temperature of 100 ℃ to 200 ℃ carbon fiber-graphene composite manufacturing apparatus.
The method of claim 1,
The high-temperature treatment of the reduction treatment unit is carried out at a temperature of 500 ℃ to 800 ℃ carbon fiber-graphene composite manufacturing apparatus.
The method of claim 1,
The high-temperature treatment of the reduction treatment unit is a carbon fiber-graphene composite manufacturing apparatus that is performed for 30 minutes to 2 hours.
Pre-treating the surface of the carbon fiber;
Coating graphene on the surface-treated carbon fiber;
Drying the graphene-coated carbon fiber; And
Reducing the graphene by treating the dried graphene-coated carbon fiber at a high temperature;
A method of manufacturing a carbon fiber-graphene composite through a roll-to-roll process comprising a.

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