[go: up one dir, main page]

WO2019182331A1 - Graphene composite fiber and manufacturing method therefor - Google Patents

Graphene composite fiber and manufacturing method therefor Download PDF

Info

Publication number
WO2019182331A1
WO2019182331A1 PCT/KR2019/003196 KR2019003196W WO2019182331A1 WO 2019182331 A1 WO2019182331 A1 WO 2019182331A1 KR 2019003196 W KR2019003196 W KR 2019003196W WO 2019182331 A1 WO2019182331 A1 WO 2019182331A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphene
composite fiber
fiber
solution
base
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2019/003196
Other languages
French (fr)
Korean (ko)
Inventor
한태희
성태현
엄원식
이은송
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Industry University Cooperation Foundation IUCF HYU
Original Assignee
Industry University Cooperation Foundation IUCF HYU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Industry University Cooperation Foundation IUCF HYU filed Critical Industry University Cooperation Foundation IUCF HYU
Publication of WO2019182331A1 publication Critical patent/WO2019182331A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/16—Physical properties antistatic; conductive

Definitions

  • the present invention relates to a graphene composite fiber and a method for producing the same, and to a graphene composite fiber and a method for producing the improved conductivity.
  • Graphene is a structure in which hexagonal shapes made of six carbons are connected to each other to form a two-dimensional single layer, similar to graphite.
  • Graphene is a material obtained by separating graphite one by one, and most easily by peeling off with scotch tape.
  • Graphene has excellent electrical properties such as high conductivity (1 x 10 -6 ⁇ cm), high electron mobility, as well as excellent surface area (2650 m 2 / g), high elastic force (1 TPa), chemical stability, etc. It has properties. Recently, it has been announced that it retains antibacterial properties to remove bacteria. For this reason, many studies using graphene have been conducted in the fields of display, anode material of lithium ion battery, electrode material of electric double layer capacitor, environmental filter, and biomaterial.
  • Korean Patent Registration No. 10-1386765 (Application No .: 10-2013-0058239, Applicant: Dongguk University Industry-Academic Cooperation Foundation) includes: 1) treating polyethylene yarn (PEI) on a cotton yarn; 2) reducing graphene oxide; 3) mixing the reduced graphene of step 2) with Eosin Y or Eosin B solution; And 4) supporting the PEI-treated cotton yarn of step 1) on the reduced graphene-Eosin Y solution or the reduced graphene-Eosin B solution of step 3).
  • PEI polyethylene yarn
  • One technical problem to be solved by the present invention is to provide a graphene composite fiber with improved electrical conductivity.
  • Another technical problem to be solved by the present invention is to provide a graphene composite fiber with reduced process cost.
  • Another technical problem to be solved by the present invention is to provide a graphene composite fiber with improved mechanical properties.
  • the technical problem to be solved by the present invention is not limited to the above.
  • the present invention provides a method for producing a graphene composite fiber.
  • the method for preparing graphene composite fibers may include preparing a base solution containing graphene oxide, preparing a composite solution by providing a functional material to the base solution, and Spinning a composite solution into a coagulation solution to produce a base fiber comprising the graphene oxide and the functional material, and reducing the graphene oxide in the base fiber to include a graphene sheet and the functional material.
  • the functional material can improve the attraction between the graphene sheet.
  • the functional material may have any one of a particle shape, a rod shape, a wire shape, and a nanosheet shape.
  • the electrical conductivity, strength, elongation, and modulus of the composite fiber are controlled according to the ratio of the graphene oxide and the functional material in the base solution. can do.
  • the concentration of the graphene oxide in the base solution may include increasing the elongation of the composite fiber.
  • the spinning speed of the composite solution may include increasing the elongation of the composite fiber.
  • the step of preparing the base fiber may include the step of separating the base fiber from the coagulation solution, and winding the separated base fiber.
  • the present invention provides a graphene composite fiber.
  • the graphene composite fiber comprises a plurality of graphene sheets, and a functional structure disposed between the plurality of graphene sheets, the functional structure, the functional material is a particle (particle) shape, rod It may have any one of a rod shape, a wire shape, and a nanosheet shape.
  • the functional material is carbon nanotube, silver nanowire, copper nanowire, graphene nanoribbon, h-BN, BP, MoS 2 , WS 2 , TiS 2 , TaS 2 , Ti 2 C, (Ti 0.5 Nb 0.5 ) 2 C, Nb 2 C, Mo 2 C, Ti 3 C 2 , Ti 3 CN, Zr 3 C 2 , Hf 3 C 2 , Ti 4 N 3 , Nb 4 C 3 , Ta 4 C 3 , Mo 2 TiC 2 , Cr 2 TiC 2 , and Mo 2 Ti 2 C 3 .
  • the electrical conductivity, strength, elongation, and modulus of the graphene composite fiber may be controlled according to the content of the material of the functional material.
  • preparing a base solution containing a graphene oxide preparing a composite solution by providing a functional material to the base solution, the composite solution Spinning in a coagulation solution to produce a base fiber comprising the graphene oxide and the functional material, and reducing the graphene oxide in the base fiber to produce a composite fiber including the graphene and the functional material. It may include the step. Accordingly, the graphene composite fiber with improved electrical conductivity may be manufactured in a simplified process.
  • FIG. 1 is a flow chart illustrating a method for producing a graphene composite fiber according to an embodiment of the present invention.
  • FIG 2 and 3 are views showing the manufacturing process of the graphene composite fiber according to an embodiment of the present invention.
  • FIG. 4 is a view for explaining the graphene composite fiber according to an embodiment of the present invention.
  • FIG. 5 is a view showing a manufacturing process of the graphene composite fiber according to a modification of the present invention.
  • Figure 6 is a photograph of the graphene composite fiber according to Example 1 of the present invention.
  • Figure 7 is a photograph of the graphene composite fiber according to Example 2 of the present invention.
  • Example 8 is a photograph of the graphene composite fiber according to Example 3 of the present invention.
  • FIG. 9 is a graph comparing the electrical conductivity of the graphene composite fiber according to embodiments and comparative examples of the present invention.
  • FIG. 10 is a graph comparing the tensile force of the graphene composite fibers according to embodiments and comparative examples of the present invention.
  • FIG. 11 is a graph comparing elongation of graphene composite fibers according to the Examples and Comparative Examples of the present invention.
  • FIG. 13 is a SEM photograph of the graphene composite fibers according to Examples 4 and 5 and the graphene fibers according to Comparative Example 2 of the present invention.
  • Example 15 is a graph evaluating the electrical properties of the graphene composite fibers according to Examples 4 and 5 and the graphene fibers according to Comparative Example 2 of the present invention.
  • FIG. 16 is a graph showing a tensile test result of the graphene composite fiber according to Example 4 of the present invention and the graphene fiber according to Comparative Example 2.
  • first, second, and third are used to describe various components, but these components should not be limited by these terms. These terms are only used to distinguish one component from another. Thus, what is referred to as a first component in one embodiment may be referred to as a second component in another embodiment.
  • first component in one embodiment may be referred to as a second component in another embodiment.
  • second component in another embodiment.
  • Each embodiment described and illustrated herein also includes its complementary embodiment.
  • the term 'and / or' is used herein to include at least one of the components listed before and after.
  • connection is used herein to mean both indirectly connecting a plurality of components, and directly connecting.
  • FIG. 1 is a flow chart illustrating a method for manufacturing a graphene composite fiber according to an embodiment of the present invention
  • Figures 2 and 3 are views showing the manufacturing process of the graphene composite fiber according to an embodiment of the present invention
  • Figure 4 Is a view for explaining the graphene composite fiber according to an embodiment of the present invention.
  • a base solution may be prepared (S100).
  • the base solution may include graphene oxide.
  • the base solution may be prepared by adding the graphene oxide to a solvent.
  • the solvent may be water or an organic solvent.
  • the organic solvent may be dimethyl sulfoxide (DMSO), ethylene glycol, ethylene glycol, N-methyl-2-pyrrolidone (NMP), dimethylformamide ( dimethylformamide, DMF).
  • the base solution may be prepared by adding the graphene oxide to the organic solvent at a concentration of 5 mg / mL.
  • the elongation percentage of the composite fiber to be described later can be controlled. Specifically, as the concentration of the graphene oxide in the base solution increases, the elongation of the composite fiber to be described later may increase. That is, when the concentration of the graphene oxide in the base solution is increased, the degree of orientation of the composite fiber described later may be reduced, the porosity may be increased. Accordingly, the elongation of the composite fiber described later can be increased.
  • a functional material may be provided in the base solution to prepare a complex solution 10 (S200).
  • the functional material may be a conductive material. Accordingly, the electrical conductivity of the composite fiber to be described later can be improved.
  • the functional material may have any one of a particle shape, a rod shape, a wire shape, and a nanosheet shape.
  • the functional material may be carbon nanotubes (CNTs).
  • the functional material is silver nanowire, copper nanowire, h-BN, BP, MoS 2 , WS 2 , TiS 2 , TaS 2 , Ti 2 C, (Ti 0.5 Nb 0.5 ) 2 C, Nb 2 C, Mo 2 C, Ti 3 C 2 , Ti 3 CN, Zr 3 C 2 , Hf 3 C 2 , Ti 4 N 3 , Nb 4 C 3 , Ta 4 C 3 , Mo 2 TiC 2 , Cr 2 TiC 2 , and Mo 2 Ti 2 C 3 It may include at least one. Accordingly, the functional material may not damage the structure of the graphene oxide in the base fiber in the manufacturing step of the base fiber described later.
  • different kinds of functional materials that is, two or more kinds of functional materials may be provided in the base solution, so that the complex solution 10 may be prepared.
  • the proportion of the graphene oxide and the functional material in the base solution can be controlled.
  • the ratio of the graphene oxide and the functional material in the base solution may be a ratio of 5: 7 wt%.
  • the electrical conductivity, strength, elongation, and elongation of the composite fiber described below, and Modulus can be improved.
  • the complex solution 10 may be spun into the coagulation solution 20 to produce a base fiber 30 (S300).
  • the base fiber 30 prepared by spinning the complex solution 10 in the coagulation solution 20 may be coagulated by the coagulant included in the coagulation solution 20.
  • the coagulant calcium chloride (CaCl2), potassium hydroxide (KOH), sodium hydroxide (NaOH), sodium chloride (NaCl), copper sulfate (CuSO4), cetyltrimethylammonium bromide (CTAB), or It may be any one of chitosan.
  • the complex solution 10 contained in the base container 100 through the spinneret 120 connected to the base container 100, the coagulation solution 20 This may be radiated into the coagulation bath (200).
  • the composite solution 10 that is spun into the coagulation solution 20 may control the spinning speed, thereby controlling the elongation of the composite fiber to be described later.
  • the spinning speed of the composite solution 10 spun into the coagulation solution 20 decreases, the elongation of the composite fiber to be described later may increase. That is, as the spinning speed of the composite solution 10 decreases, the degree of orientation of the composite fiber, which will be described later, may decrease, and the porosity may increase. Accordingly, the elongation of the composite fiber described later can be increased.
  • the manufacturing of the base fiber 30 may include separating the base fiber 30 from the coagulation solution 20, and winding the separated base fiber 30.
  • the base fiber 30 may be separated from the coagulation solution 20, washed, and dried.
  • the base fiber 30 may be separated from the coagulation bath 200 containing the coagulation solution 20 by a guide roller 130 and come out.
  • the base fiber 30 separated from the coagulation solution 20 may include the coagulant.
  • the washing solution used in the washing process may be an alcoholic aqueous solution.
  • the moisture contained in the base fiber 30 may be naturally dried in the air.
  • the base fiber 30 naturally dried in air may be secondaryly dried. That is, at least a portion of the water remaining in the base fiber 30 may be removed through the heating process.
  • the base fiber 30 may be wound and dried at the same time through the heating process. As shown in FIG. 2, after the washing process is finished, the base fiber 30 may be wound by a winding roller 140 while the drying process is performed.
  • the elongation of the composite fiber to be described later can be controlled. Specifically, when the spinning speed of the composite solution 10 is faster than the winding speed of the base fiber 30, the elongation of the composite fiber to be described later may be increased.
  • the degree of orientation of the composite fiber to be described later is reduced, the porosity may be increased. Accordingly, the elongation of the composite fiber described below can be increased.
  • the composite fiber 50 may include graphene and a functional material.
  • the composite fiber 50 may be in a form including a plurality of graphene sheets, and a functional structure disposed between the plurality of graphene sheets.
  • the functional structure may be one in which the functional material has a shape of any one of a particle shape, a rod shape, a wire shape, and a nanosheet shape. That is, the functional material may be maintained in shape in the process of manufacturing the composite fiber 50.
  • the functional structure may be a one-dimensional material, or as shown in (c) of FIG. 4, the functional structure may be a two-dimensional material.
  • Figure 4 (a) shows the graphene fibers composed of a plurality of graphene sheets, the functional structure is omitted.
  • the composite fiber 50 may control electric conductivity, strength, elongation, and modulus of the composite fiber 50 according to the content of the functional material. According to an embodiment, as the content of the composite fiber 50 and the functional material is increased, the electrical conductivity, durability, elongation, and modulus of the composite fiber 50 are improved. Can be.
  • the functional material may be a conductive material as described above. Accordingly, when the content of the functional material increases, the electrical conductivity of the composite fiber 50 can be improved.
  • the functional material may have any one of a particle shape, a rod shape, a wire shape, and a nanosheet shape as described above. Accordingly, the structure of the graphene oxide may not be damaged in the manufacturing process of the base fiber 30. As a result, when the structure of the graphene oxide is not damaged, the graphene included in the composite fiber 50 is also not damaged, thereby improving mechanical properties such as durability, elongation, and elasticity of the composite fiber 50. Can be.
  • the base solution 30 including graphene oxide may be In a simple way of providing a functional material, the electrical conductivity of the composite fiber 50 can be improved.
  • the manufacturing of the composite fiber 50 may include preparing a reducing solution 40 including a reducing agent, and immersing the base fiber 30 in the reducing solution 40.
  • the reducing agent may be Hydroiodic acid (HI).
  • the reducing solution 40 may be a solution in which HI having a concentration of 50 wt% and water having a concentration of 50 wt% are mixed.
  • the concentration of the reducing agent included in the reducing solution 40 and the time that the composite fiber 50 is immersed in the reducing solution is controlled,
  • the reduction level of the graphene included in the composite fiber 50 can be controlled.
  • the reduction level of the graphene included in the composite fiber 50 may be increased.
  • the time for which the base fiber 30 is immersed in the reducing solution is increased, the reduction level of the graphene included in the composite fiber 50 may be increased.
  • the concentration of the reducing agent included in the reducing solution 40 is reduced, the reduction level of the graphene included in the composite fiber 50 may be reduced.
  • the time for which the base fiber 30 is immersed in the reducing solution is reduced, so that the reduction level of the graphene included in the composite fiber 50 may be reduced.
  • the composite fiber 50 in the reducing gas atmosphere, the base fiber 30 is reduced, the composite fiber 50 can be produced.
  • the concentration of the reducing gas is increased or when the providing time of the reducing gas is increased, the reduction level of the graphene included in the composite fiber 50 may be increased.
  • the concentration of the reducing gas is reduced, or when the time for providing the reducing gas is reduced, the reduction level of the graphene included in the composite fiber 50 may be reduced.
  • preparing the base solution containing the graphene oxide, to provide the functional material to the base solution, to prepare the composite solution 10 Spinning the composite solution 10 into the coagulation solution 20 to produce the base fiber 30 comprising the graphene oxide and the functional material, and in the base fiber 30 Reducing the graphene oxide it may include the step of producing the composite fiber 50 containing the graphene and the functional material. Accordingly, the graphene composite fiber with improved electrical conductivity may be manufactured in a simplified process.
  • FIG. 5 is a view showing a manufacturing process of the graphene composite fiber according to a modification of the present invention.
  • a composite fiber 50 according to an embodiment of the present invention described with reference to FIGS. 1 to 3 is prepared.
  • the composite fiber 50 is joule heated, the graphene composite fiber 60 according to a modification of the present invention can be produced. That is, after the graphene oxide in the base fiber 30 is reduced, the composite fiber 50 including the reduced graphene oxide is lined, the graphene composite fiber 60 according to the modification Can be prepared.
  • the graphene composite fiber 60 according to the modified example in which the composite fiber 50 is lined and manufactured will be described in detail, but in the first modified example in which a continuous current is applied to the composite fiber 50,
  • the graphene composite fiber according to the present invention, and the graphene composite fiber according to the second modified example in which a pulse current is applied to the composite fiber 60 will be described.
  • the composite fiber 50 may be joule heated in a manner in which a continuous current is applied, and thus the graphene composite fiber 60 may be manufactured.
  • the joule heating apparatus for Joule heating the composite fiber 50 may include a chamber 300 and a power source 330.
  • the chamber 300 may include an electrode 310 and a gas injection hole 320.
  • the composite fiber 50 may be disposed between the electrodes 310 in the chamber 300 and line-heated.
  • the electrode 310 may include copper (Cu).
  • the interior of the chamber 300 may be filled with inert gas injected through the gas injection port 320.
  • the inert gas may be argon (Ar) gas.
  • amorphous carbons in the composite fiber 50 may be crystallized. That is, in the graphene composite fiber 60 according to the first modification, amorphous carbon in the composite fiber 50 may be crystallized. Accordingly, in the graphene composite fiber 60 according to the first modification, a plurality of graphene sheets may be aggregated and extended in one direction.
  • the composite fiber 50 and the graphene composite fiber 60 according to the first modification may include a laminated structure in which a plurality of graphene sheets are stacked.
  • the thickness of the laminated structure and the grain size of the graphene sheet may be changed. Specifically, as the composite fiber 50 is Joule heated, the thickness of the laminated structure and the grain size of the graphene sheet may be increased. Accordingly, the thickness of the laminated structure of the graphene composite fiber 60 and the grain size of the graphene sheet according to the first modified example are greater than the thickness of the laminated structure of the composite fiber 50 and the grain size of the graphene sheet. Can be large. In other words, the crystallinity of the composite fiber 50 may be lower than that of the graphene composite fiber 60 according to the first modification.
  • Graphene composite fiber 60 according to the first modification of the present invention is continuous to the composite fiber 50 containing the reduced graphene oxide after the graphene oxide in the base fiber 30 is reduced It may be manufactured by Joule heating in a manner in which a current is applied. Accordingly, the amorphous carbon in the composite fiber 50 is crystallized, the electrical conductivity of the graphene composite fiber 60 according to the first modification can be improved.
  • the composite fiber 50 may be joule heated in a manner in which a pulse current is applied, so that the graphene composite fiber 60 may be manufactured.
  • the pulse current may be a method in which a current is applied through a specific cycle.
  • the time of the pulse may be 0.3 seconds or more and 3 seconds or less.
  • the graphene composite fiber 60 according to the second modified example may be manufactured by applying a current to the composite fiber 50 at an interval of 15 seconds for 0.5 seconds.
  • the composite fiber 50 When the composite fiber 50 is lined by a method in which a pulse current is applied, residual oxygen in the composite fiber 50 may be foamed. That is, by reducing the graphene oxide included in the base fiber 30, in the process of manufacturing the composite fiber 50, unreduced oxygen may remain in the composite fiber 50. Subsequently, in the process of manufacturing the graphene composite fiber 60 according to the second modified example by heating the composite fiber 50, unreduced oxygen remaining in the composite fiber 50 may be foamed. Can be. Accordingly, the thickness of the graphene composite fiber 60 according to the second modified example may be thicker than the thickness of the composite fiber 50.
  • the composite fiber 50 when the composite fiber 50 is heated by a method in which a pulse current is applied, a sudden temperature rise may occur in the composite fiber 50. That is, when the pulse current is repeatedly applied to the composite fiber 50, the Joule heat of a relatively high temperature is repeated for a relatively short time compared to the case where a continuous current is applied to the composite fiber 50 May occur. As a result, oxygen remaining in the composite fiber 50 may be foamed. At this time, the thickness of the composite fiber 50 may be thickened by the force of the remaining oxygen is foamed. As a result, the thickness of the graphene composite fiber 60 according to the second modified example may be thicker than the thickness of the composite fiber 50.
  • the composite fiber 50 when the composite fiber 50 is heated in a manner in which a pulse current is applied, the fatigue applied to the composite fiber 50 by vibration can be eliminated between pulses.
  • the composite fiber 50 may perform a reduction reaction by Joule heat during a time when the pulse current is applied.
  • fatigue accumulated in the composite fiber 50 may be eliminated during a time between pulse currents in which the current is not applied to the composite fiber 50.
  • reduction reactions and accumulated fatigue relief by Joule heat may occur repeatedly.
  • the composite fiber 50 can be easily reduced while minimizing damage and breakage of the composite fiber 50.
  • the graphene composite fiber 60 according to the second modification with improved electrical conductivity can be produced.
  • Graphene composite fiber 60 according to the second modification of the present invention is the graphene oxide in the base fiber 30 is reduced, the pulse current to the composite fiber 50 containing the reduced graphene oxide May be manufactured by Joule heating in such a way that is applied. Accordingly, electrical conductivity of the graphene composite fiber 60 according to the second modified example may be improved.
  • a solution in which graphene oxide and carbon nanotubes (carbon nanotubes, CNTs) are mixed at a ratio of 5: 7 wt% is prepared.
  • the solution was spun into a CaCl 2 coagulation bath at 0.45 mol concentration to prepare a base fiber.
  • a hydroiodic aicd concentration of 30 wt%, and then reacted at a temperature of 80 ° C. for 1 hour to prepare graphene composite fiber according to Example 1.
  • a graphene composite fiber according to Example 1 was prepared, but was prepared after preparing graphene oxide and carbon nanotubes at a ratio of 5: 3.5 wt%.
  • a graphene composite fiber according to Example 1 was prepared, but was prepared after preparing graphene oxide and carbon nanotubes at a ratio of 5: 1.5 wt%.
  • Example 1 carbon nanotubes were omitted, and graphene fibers were prepared by reducing at 60 ° C.
  • FIG. 6 is a photograph taken of the graphene composite fiber according to the first embodiment of the present invention
  • Figure 7 is a photograph taken a graphene composite fiber according to the second embodiment of the present invention
  • Figure 8 is an embodiment of the present invention Photographs taken of graphene composite fiber according to 3.
  • graphene composite fibers according to Examples 1 to 3 of the present invention are shown by scanning electron microscope (SEM) imaging at different magnifications.
  • FIG. 9 is a graph comparing the electrical conductivity of the graphene composite fiber according to embodiments and comparative examples of the present invention.
  • the graphene composite fiber according to Example 1 shows an electrical conductivity of 1.5 X 10 2 S cm -1
  • the graphene composite fiber according to Example 2 is 4.2 X 10 1 S cm It shows an electrical conductivity of -1
  • the graphene composite fiber according to Example 3 shows an electrical conductivity of 6.2 X 10 1 S cm -1
  • the graphene composite fiber according to Comparative Example 1 is 2.7 X 10 1 S cm It was confirmed that the electrical conductivity of -1 . That is, it can be seen that the electrical conductivity of the graphene composite fiber according to the first embodiment is significantly improved compared to the electrical conductivity of the graphene composite fiber according to the other embodiments or the graphene fiber according to Comparative Example 1. .
  • the electrical conductivity of the graphene composite fibers according to Examples 1 to 3 is higher than the electrical conductivity of the graphene composite fibers according to Comparative Example 1. Accordingly, it can be seen that manufacturing the graphene composite fiber after mixing CNTs in the graphene oxide solution is a method of improving electrical conductivity.
  • FIG. 10 is a graph comparing the tensile force of the graphene composite fibers according to embodiments and comparative examples of the present invention.
  • the graphene composite fiber according to Example 1 exhibits a tensile force of about 780 MPa
  • the graphene composite fiber according to Example 2 exhibits a tensile force of about 700 MPa
  • the graphene composite fiber showed a tensile force of about 570 MPa
  • the graphene fiber according to Comparative Example 1 exhibits a tensile force of about 220 MPa. That is, it can be seen that the tensile force increases in the order of the graphene composite fiber according to Comparative Example 1, Example 3, Example 2, and Example 1.
  • FIG. 11 is a graph comparing elongation of graphene composite fibers according to the Examples and Comparative Examples of the present invention.
  • the graphene composite fiber according to Example 1 shows an elongation of about 1.6%
  • the graphene composite fiber according to Example 2 shows an elongation of about 0.9%
  • Example 3 According to the graphene composite fiber exhibits an elongation of about 0.6%, the graphene composite fiber according to Comparative Example 1 could be quoted that it shows an elongation of about 0.9%. That is, it can be seen that the elongation of the graphene composite fiber according to the first embodiment is significantly improved compared to the elongation of the graphene composite fiber according to other embodiments or the elongation of the graphene fiber according to Comparative Example 1.
  • the graphene composite fiber according to Example 1 exhibits an elastic force of about 115 GPa
  • the graphene composite fiber according to Example 2 exhibits an elastic force of about 85 GPa
  • the graphene composite fiber according to Comparative Example 1 was found to exhibit an elastic force of about 32 GPa.
  • the elastic force of the graphene composite fibers according to Example 1 is higher than the elastic force of the graphene composite fibers according to Examples 2, 3, and Comparative Example 1.
  • the elastic force of the graphene composite fiber according to Examples 1 to 3 is significantly higher than the elastic force of the graphene fiber according to Comparative Example 1.
  • Carbon nanotubes as one-dimensional materials were prepared.
  • a solution in which graphene oxide and carbon nanotubes are mixed at a ratio of 1: 4 wt% is prepared.
  • the solution was spun into a CaCl 2 coagulation bath at 0.45 mol concentration to prepare a base fiber.
  • Graphene nanoribbons which are two-dimensional materials, were prepared.
  • the solution was spun into a CaCl 2 coagulation bath at 0.45 mol concentration to prepare a base fiber.
  • Example 4 graphene fibers were prepared by omitting carbon nanotubes.
  • FIG. 13 is a SEM photograph of the graphene composite fibers according to Examples 4 and 5 and the graphene fibers according to Comparative Example 2 of the present invention.
  • FIG. 13 the surface of the graphene composite fibers according to Examples 4 and 5 and the graphene fibers according to Comparative Example 2 were SEM photographed.
  • Figure 13 (a) is a SEM photograph of the graphene fibers according to Comparative Example 2
  • Figure 13 (b) is a SEM photograph of the graphene composite fibers according to Example 4
  • Figure 13 (c) is an example SEM image of graphene composite fibers according to 5.
  • the graphene nanoribbons which are carbon nanotubes and two-dimensional materials, are provided with graphene sheets in the graphene composite fiber.
  • FIG. 14 is a graph evaluating the mechanical properties of the graphene composite fibers according to Examples 4 and 5 of the present invention, and the graphene fibers according to Comparative Example 2, and FIG. 15 shows Examples 4 and 4 of the present invention.
  • FIG. 16 is a graph showing a tensile test result of the graphene composite fiber according to Example 4 of the present invention and the graphene fiber according to Comparative Example 2.
  • the stress required according to the number of twists of the graphene composite fiber according to Example 4 and the graphene fiber according to Comparative Example 2 was measured.
  • carbon nanotubes were added according to Example 4 mechanical strength and tensile strength were increased. Modulus also increased, it can be seen that the added carbon nanotubules play a role of cross-linking between graphene sheets.
  • the electrical conductivity of the graphene composite fibers including various heterogeneous materials was measured and shown in Table 2 below.
  • the chemically reduced graphene is a graphene oxide reduced using a 30% HI solution at 80 ° C.
  • the high temperature reduced graphene is a graphene oxide reduced at 1100 ° C. in an argon atmosphere.
  • the ultra high temperature reduced graphene is a graphene oxide reduced in an argon atmosphere at 2800 ° C.
  • Graphene composite fiber according to an embodiment of the present invention can be used in a variety of industries, such as electric wire, electromagnetic shielding filler.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Inorganic Fibers (AREA)

Abstract

Provided is a manufacturing method for a graphene composite fiber. The manufacturing method for a graphene composite fiber may comprise the steps of: preparing a base solution containing graphene oxide; providing a functional substance for the base solution to prepare a composite solution; spinning the composite solution into a coagulation solution to prepare a base fiber; and reducing the graphene oxide in the base fiber to prepare a composite fiber.

Description

그래핀 복합 섬유 및 그 제조 방법Graphene Composite Fiber and Manufacturing Method Thereof

본 발명은 그래핀 복합 섬유 및 그 제조 방법에 관한 것으로서, 전도성이 향상된 그래핀 복합 섬유 및 그 제조 방법에 관련된 것이다. The present invention relates to a graphene composite fiber and a method for producing the same, and to a graphene composite fiber and a method for producing the improved conductivity.

인구 증가와 산업 발달로 인하여 섬유에 대한 수요가 급증하고, 천연 섬유에 비해 기능이 우수한 새로운 섬유에 대한 요구가 증대되고 있다. 1938년 미국 듀퐁사의 나일론이라는 새로운 합성섬유에 대한 발표를 시작으로, 폴리에스테르 섬유, 아크릴 섬유, 폴리우레탄 섬유 등이 개발되었다. 최근에는 기존 소재의 성능 한계를 초월하는 신소재를 이용한, 고성능 및 초고기능성 섬유와 나노 섬유의 개발이 진행되고 있다.Population growth and industrial development have led to a sharp increase in the demand for fibers and the demand for new fibers that are superior to natural fibers. Starting with the announcement of a new synthetic fiber called nylon, DuPont, USA in 1938, polyester fiber, acrylic fiber and polyurethane fiber were developed. Recently, the development of high-performance and ultra-high performance fibers and nanofibers using new materials that transcend the performance limitations of existing materials is in progress.

그래핀은 탄소 6개로 이루어진 육각형 모양이 서로 연결되어 2차원 단일층을 이루는 구조로, 흑연과 유사하다. 그래핀은 흑연을 한 장씩 분리하여 얻을 수 있는 물질로, 가장 쉽게는 스카치 테이프로 떼어내는 방법으로도 얻을 수 있다. 그래핀은 높은 전도성(1 x 10 -6Ωcm), 높은 전자이동성과 같은 전기적 특성뿐 아니라, 활성탄보다 2 배 이상 큰 표면적(2650 m 2 /g), 높은 탄성력(1 TPa), 화학적 안전성 등과 같은 우수한 물성들을 보유하고 있다. 최근에는 박테리아를 제거하는 향균성까지 보유한다는 사실이 발표되어 주목을 끌고 있다. 이러한 이유로, 디스 플레이, 리튬 이온 전지의 음극재, 전기이중층 캐패시터의 전극재, 환경 필터, 및 생체재료 등의 분야에서 그래핀을 이용한 많은 연구가 진행되고 있다Graphene is a structure in which hexagonal shapes made of six carbons are connected to each other to form a two-dimensional single layer, similar to graphite. Graphene is a material obtained by separating graphite one by one, and most easily by peeling off with scotch tape. Graphene has excellent electrical properties such as high conductivity (1 x 10 -6Ωcm), high electron mobility, as well as excellent surface area (2650 m 2 / g), high elastic force (1 TPa), chemical stability, etc. It has properties. Recently, it has been announced that it retains antibacterial properties to remove bacteria. For this reason, many studies using graphene have been conducted in the fields of display, anode material of lithium ion battery, electrode material of electric double layer capacitor, environmental filter, and biomaterial.

예를 들어, 대한민국 특허 등록 번호 10-1386765(출원번호: 10-2013-0058239, 출원인: 동국대학교 산학협력단)에는, 1) 면사(cotton yarn)에 PEI(polyethyleneimine)를 처리하는 단계; 2) 그래핀 산화물을 환원시키는 단계; 3) 단계 2)의 환원된 그래핀을, Eosin Y 또는 Eosin B 용액과 혼합하는 단계; 및 4) 상기 단계 3)의 환원 그래핀-Eosin Y 용액 또는 환원 그래핀-Eosin B 용액에 상기 단계 1)의 PEI 처리된 면사를 담지하는 단계를 포함하는 그래핀이 코팅된 전도성 전자섬유의 제조 방법이 개시된다. 이 밖에도 그래핀 섬유에 관한 많은 연구가 지속적으로 수행되고 있다. For example, Korean Patent Registration No. 10-1386765 (Application No .: 10-2013-0058239, Applicant: Dongguk University Industry-Academic Cooperation Foundation) includes: 1) treating polyethylene yarn (PEI) on a cotton yarn; 2) reducing graphene oxide; 3) mixing the reduced graphene of step 2) with Eosin Y or Eosin B solution; And 4) supporting the PEI-treated cotton yarn of step 1) on the reduced graphene-Eosin Y solution or the reduced graphene-Eosin B solution of step 3). The method is disclosed. In addition, many studies on graphene fibers are continuously conducted.

본 발명이 해결하고자 하는 일 기술적 과제는, 전기 전도도가 향상된 그래핀 복합 섬유를 제공하는 데 있다. One technical problem to be solved by the present invention is to provide a graphene composite fiber with improved electrical conductivity.

본 발명이 해결하고자 하는 다른 기술적 과제는, 공정 비용이 감소된 그래핀 복합 섬유를 제공하는 데 있다. Another technical problem to be solved by the present invention is to provide a graphene composite fiber with reduced process cost.

본 발명이 해결하고자 하는 또 다른 기술적 과제는, 기계적 특성이 향사된 그래핀 복합 섬유를 제공하는 데 있다. Another technical problem to be solved by the present invention is to provide a graphene composite fiber with improved mechanical properties.

본 발명이 해결하고자 하는 기술적 과제는 상술된 것에 제한되지 않는다. The technical problem to be solved by the present invention is not limited to the above.

상술된 기술적 과제들을 해결하기 위해 본 발명은 그래핀 복합 섬유의 제조 방법을 제공한다. In order to solve the above technical problem, the present invention provides a method for producing a graphene composite fiber.

일 실시 예에 따르면, 상기 그래핀 복합 섬유의 제조 방법은 그래핀 산화물(graphene oxide)을 포함하는 베이스 용액을 준비하는 단계, 상기 베이스 용액에, 기능성 물질을 제공하여 복합 용액을 제조하는 단계, 상기 복합 용액을 응고 용액 내에 방사시켜, 상기 그래핀 산화물 및 상기 기능성 물질을 포함하는 베이스 섬유를 제조하는 단계, 및 상기 베이스 섬유 내의 상기 그래핀 산화물을 환원시켜, 그래핀 시트 및 상기 기능성 물질을 포함하는 복합 섬유를 제조하는 단계를 포함하되, 상기 기능성 물질은 상기 그래핀 시트 사이의 인력을 향상시킬 수 있다. According to an embodiment, the method for preparing graphene composite fibers may include preparing a base solution containing graphene oxide, preparing a composite solution by providing a functional material to the base solution, and Spinning a composite solution into a coagulation solution to produce a base fiber comprising the graphene oxide and the functional material, and reducing the graphene oxide in the base fiber to include a graphene sheet and the functional material. Comprising a step of producing a composite fiber, the functional material can improve the attraction between the graphene sheet.

일 실시 예에 따르면, 상기 기능성 물질은, 파티클(particle) 형상, 로드(rod) 형상, 와이어(wire) 형상, 및 나노시트(nanosheet) 형상 중 어느 하나의 형상을 가질 수 있다. According to an embodiment, the functional material may have any one of a particle shape, a rod shape, a wire shape, and a nanosheet shape.

일 실시 예에 따르면, 상기 베이스 용액 내의 상기 그래핀 산화물 및 상기 기능성 물질의 비율에 따라, 상기 복합 섬유의 전기 전도도, 내구성(strength), 신장률(elongation), 및 탄성률(modulus)이 제어되는 것을 포함할 수 있다. According to one embodiment, the electrical conductivity, strength, elongation, and modulus of the composite fiber are controlled according to the ratio of the graphene oxide and the functional material in the base solution. can do.

일 실시 예에 따르면, 상기 베이스 용액 내의 상기 그래핀 산화물의 농도가 증가함에 따라, 상기 복합 섬유의 신장률이 증가하는 것을 포함할 수 있다. According to one embodiment, as the concentration of the graphene oxide in the base solution, it may include increasing the elongation of the composite fiber.

일 실시 예에 따르면, 상기 복합 용액의 방사 속도가 감소함에 따라, 상기 복합 섬유의 신장률이 증가하는 것을 포함할 수 있다. According to one embodiment, as the spinning speed of the composite solution is reduced, it may include increasing the elongation of the composite fiber.

일 실시 예에 따르면, 상기 베이스 섬유를 제조하는 단계는, 상기 베이스 섬유를 상기 응고 용액으로부터 분리하는 단계, 및 분리된 상기 베이스 섬유를 권취하는 단계를 포함할 수 있다. According to one embodiment, the step of preparing the base fiber may include the step of separating the base fiber from the coagulation solution, and winding the separated base fiber.

상술된 기술적 과제들을 해결하기 위해 본 발명은 그래핀 복합 섬유를 제공한다. In order to solve the above technical problem, the present invention provides a graphene composite fiber.

일 실시 예에 따르면, 상기 그래핀 복합 섬유는 복수의 그래핀 시트, 및 복수의 상기 그래핀 시트 사이에 배치되는 기능성 구조체를 포함하되, 상기 기능성 구조체는, 기능성 물질이 파티클(particle) 형상, 로드(rod) 형상, 와이어(wire) 형상, 및 나노시트(nanosheet) 형상 중 어느 하나의 형상을 가질 수 있다. According to one embodiment, the graphene composite fiber comprises a plurality of graphene sheets, and a functional structure disposed between the plurality of graphene sheets, the functional structure, the functional material is a particle (particle) shape, rod It may have any one of a rod shape, a wire shape, and a nanosheet shape.

일 실시 예에 따르면, 상기 기능성 물질은, carbon nanotube, silver nanowire, copper nanowire, graphene nanoribbon, h-BN, BP, MoS2, WS2, TiS2, TaS2, Ti2C, (Ti0.5Nb0.5)2C, Nb2C, Mo2C, Ti3C2, Ti3CN, Zr3C2, Hf3C2, Ti4N3, Nb4C3, Ta4C3, Mo2TiC2, Cr2TiC2, 및 Mo2Ti2C3 중 적어도 어느 하나를 포함할 수 있다. According to one embodiment, the functional material is carbon nanotube, silver nanowire, copper nanowire, graphene nanoribbon, h-BN, BP, MoS 2 , WS 2 , TiS 2 , TaS 2 , Ti 2 C, (Ti 0.5 Nb 0.5 ) 2 C, Nb 2 C, Mo 2 C, Ti 3 C 2 , Ti 3 CN, Zr 3 C 2 , Hf 3 C 2 , Ti 4 N 3 , Nb 4 C 3 , Ta 4 C 3 , Mo 2 TiC 2 , Cr 2 TiC 2 , and Mo 2 Ti 2 C 3 .

일 실시 예에 따르면, 상기 기능성 물질의 물질의 함량에 따라, 상기 그래핀 복합 섬유의 전기 전도도, 내구성(strength), 신장률(elongation), 및 탄성률(modulus)이 제어되는 것을 포함할 수 있다. According to one embodiment, the electrical conductivity, strength, elongation, and modulus of the graphene composite fiber may be controlled according to the content of the material of the functional material.

본 발명의 실시 예에 따른 그래핀 복합 섬유의 제조 방법은, 그래핀 산화물을 포함하는 베이스 용액을 준비하는 단계, 상기 베이스 용액에, 기능성 물질을 제공하여 복합 용액을 제조하는 단계, 상기 복합 용액을 응고 용액 내에 방사시켜, 상기 그래핀 산화물 및 상기 기능성 물질을 포함하는 베이스 섬유를 제조하는 단계, 및 상기 베이스 섬유 내의 상기 그래핀 산화물을 환원시켜, 그래핀 및 상기 기능성 물질을 포함하는 복합 섬유를 제조하는 단계를 포함할 수 있다. 이에 따라, 간소화된 공정으로 전기 전도도가 향상된 그래핀 복합 섬유가 제조될 수 있다. In the method for producing a graphene composite fiber according to an embodiment of the present invention, preparing a base solution containing a graphene oxide, preparing a composite solution by providing a functional material to the base solution, the composite solution Spinning in a coagulation solution to produce a base fiber comprising the graphene oxide and the functional material, and reducing the graphene oxide in the base fiber to produce a composite fiber including the graphene and the functional material. It may include the step. Accordingly, the graphene composite fiber with improved electrical conductivity may be manufactured in a simplified process.

도 1은 본 발명의 실시 예에 따른 그래핀 복합 섬유의 제조 방법을 설명하는 순서도이다. 1 is a flow chart illustrating a method for producing a graphene composite fiber according to an embodiment of the present invention.

도 2 및 도 3은 본 발명의 실시 예에 따른 그래핀 복합 섬유의 제조 공정을 나타내는 도면들이다. 2 and 3 are views showing the manufacturing process of the graphene composite fiber according to an embodiment of the present invention.

도 4는 본 발명의 실시 예에 따른 그래핀 복합 섬유를 설명하기 위한 도면이다.4 is a view for explaining the graphene composite fiber according to an embodiment of the present invention.

도 5는 본 발명의 변형 예에 따른 그래핀 복합 섬유의 제조 공정을 나타내는 도면이다. 5 is a view showing a manufacturing process of the graphene composite fiber according to a modification of the present invention.

도 6은 본 발명의 실시 예 1에 따른 그래핀 복합 섬유를 촬영한 사진이다. Figure 6 is a photograph of the graphene composite fiber according to Example 1 of the present invention.

도 7은 본 발명의 실시 예 2에 따른 그래핀 복합 섬유를 촬영한 사진이다. Figure 7 is a photograph of the graphene composite fiber according to Example 2 of the present invention.

도 8은 본 발명의 실시 예 3에 따른 그래핀 복합 섬유를 촬영한 사진이다. 8 is a photograph of the graphene composite fiber according to Example 3 of the present invention.

도 9는 본 발명의 실시 예들 및 비교 예에 따른 그래핀 복합 섬유의 전기 전도도를 비교한 그래프이다. 9 is a graph comparing the electrical conductivity of the graphene composite fiber according to embodiments and comparative examples of the present invention.

도 10은 본 발명의 실시 예들 및 비교 예에 따른 그래핀 복합 섬유의 인장력을 비교한 그래프이다.10 is a graph comparing the tensile force of the graphene composite fibers according to embodiments and comparative examples of the present invention.

도 11은 본 발명의 실시 예들 및 비교 예에 따른 그래핀 복합 섬유의 신장률을 비교한 그래프이다.11 is a graph comparing elongation of graphene composite fibers according to the Examples and Comparative Examples of the present invention.

도 12는 본 발명의 실시 예들 및 비교 예에 따른 그래핀 복합 섬유의 탄성률을 비교한 그래프이다.12 is a graph comparing the elastic modulus of the graphene composite fibers according to the embodiments and comparative examples of the present invention.

도 13은 본 발명의 실시 예 4 및 실시 예 5에 따른 그래핀 복합 섬유, 및 비교 예 2에 따른 그래핀 섬유를 촬영한 SEM 사진이다.13 is a SEM photograph of the graphene composite fibers according to Examples 4 and 5 and the graphene fibers according to Comparative Example 2 of the present invention.

도 14는 본 발명의 실시 예 4 및 실시 예 5에 따른 그래핀 복합 섬유, 및 비교 예 2에 따른 그래핀 섬유의 기계적 특성을 평가한 그래프이다. 14 is a graph evaluating the mechanical properties of the graphene composite fibers according to Examples 4 and 5, and the graphene fibers according to Comparative Example 2.

도 15는 본 발명의 실시 예 실시 예 4 및 실시 예 5에 따른 그래핀 복합 섬유, 및 비교 예 2에 따른 그래핀 섬유의 전기적 특성을 평가한 그래프이다.15 is a graph evaluating the electrical properties of the graphene composite fibers according to Examples 4 and 5 and the graphene fibers according to Comparative Example 2 of the present invention.

도 16은 본 발명의 실시 예 4에 따른 그래핀 복합 섬유 및 비교 예 2에 따른 그래핀 섬유의 인장 테스트 결과 그래프이다.16 is a graph showing a tensile test result of the graphene composite fiber according to Example 4 of the present invention and the graphene fiber according to Comparative Example 2.

도 17은 본 발명의 실시 예 4에 따른 그래핀 복합 섬유 및 비교 예 2에 따른 그래핀 섬유의 꼬임 테스트 결과이다.17 is a twist test results of the graphene composite fiber according to Example 4 and the graphene fiber according to Comparative Example 2 of the present invention.

이하, 첨부된 도면들을 참조하여 본 발명의 바람직한 실시 예를 상세히 설명할 것이다. 그러나 본 발명의 기술적 사상은 여기서 설명되는 실시 예에 한정되지 않고 다른 형태로 구체화 될 수도 있다. 오히려, 여기서 소개되는 실시 예는 개시된 내용이 철저하고 완전해질 수 있도록 그리고 당업자에게 본 발명의 사상이 충분히 전달될 수 있도록 하기 위해 제공되는 것이다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the technical idea of the present invention is not limited to the exemplary embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided to ensure that the disclosed contents are thorough and complete, and that the spirit of the present invention can be sufficiently delivered to those skilled in the art.

본 명세서에서, 어떤 구성요소가 다른 구성요소 상에 있다고 언급되는 경우에 그것은 다른 구성요소 상에 직접 형성될 수 있거나 또는 그들 사이에 제 3의 구성요소가 개재될 수도 있다는 것을 의미한다. 또한, 도면들에 있어서, 막 및 영역들의 두께는 기술적 내용의 효과적인 설명을 위해 과장된 것이다. In the present specification, when a component is mentioned to be on another component, it means that it may be formed directly on the other component or a third component may be interposed therebetween. In addition, in the drawings, the thicknesses of films and regions are exaggerated for effective explanation of technical contents.

또한, 본 명세서의 다양한 실시 예 들에서 제1, 제2, 제3 등의 용어가 다양한 구성요소들을 기술하기 위해서 사용되었지만, 이들 구성요소들이 이 같은 용어들에 의해서 한정되어서는 안 된다. 이들 용어들은 단지 어느 구성요소를 다른 구성요소와 구별시키기 위해서 사용되었을 뿐이다. 따라서, 어느 한 실시 예에 제 1 구성요소로 언급된 것이 다른 실시 예에서는 제 2 구성요소로 언급될 수도 있다. 여기에 설명되고 예시되는 각 실시 예는 그것의 상보적인 실시 예도 포함한다. 또한, 본 명세서에서 '및/또는'은 전후에 나열한 구성요소들 중 적어도 하나를 포함하는 의미로 사용되었다.In addition, in various embodiments of the present specification, terms such as first, second, and third are used to describe various components, but these components should not be limited by these terms. These terms are only used to distinguish one component from another. Thus, what is referred to as a first component in one embodiment may be referred to as a second component in another embodiment. Each embodiment described and illustrated herein also includes its complementary embodiment. In addition, the term 'and / or' is used herein to include at least one of the components listed before and after.

명세서에서 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한 복수의 표현을 포함한다. 또한, "포함하다" 또는 "가지다" 등의 용어는 명세서상에 기재된 특징, 숫자, 단계, 구성요소 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징이나 숫자, 단계, 구성요소 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 배제하는 것으로 이해되어서는 안 된다. 또한, 본 명세서에서 "연결"은 복수의 구성 요소를 간접적으로 연결하는 것, 및 직접적으로 연결하는 것을 모두 포함하는 의미로 사용된다.In the specification, the singular encompasses the plural unless the context clearly indicates otherwise. In addition, the terms "comprise" or "having" are intended to indicate that there is a feature, number, step, element, or combination thereof described in the specification, and one or more other features or numbers, steps, configurations It should not be understood to exclude the possibility of the presence or the addition of elements or combinations thereof. In addition, the term "connection" is used herein to mean both indirectly connecting a plurality of components, and directly connecting.

또한, 하기에서 본 발명을 설명함에 있어 관련된 공지 기능 또는 구성에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명은 생략할 것이다.In addition, in the following description of the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted.

도 1은 본 발명의 실시 예에 따른 그래핀 복합 섬유의 제조 방법을 설명하는 순서도이고, 도 2 및 도 3은 본 발명의 실시 예에 따른 그래핀 복합 섬유의 제조 공정을 나타내는 도면들이고, 도 4는 본 발명의 실시 예에 따른 그래핀 복합 섬유를 설명하기 위한 도면이다. 1 is a flow chart illustrating a method for manufacturing a graphene composite fiber according to an embodiment of the present invention, Figures 2 and 3 are views showing the manufacturing process of the graphene composite fiber according to an embodiment of the present invention, Figure 4 Is a view for explaining the graphene composite fiber according to an embodiment of the present invention.

도 1 및 도 2를 참조하면, 베이스 용액이 준비될 수 있다(S100). 상기 베이스 용액은 그래핀 산화물(graphene oxide)을 포함할 수 있다. 상기 베이스 용액은, 상기 그래핀 산화물이 용매에 첨가되어 제조될 수 있다. 일 실시 예에 따르면, 상기 용매는, 물 또는 유기 용매일 수 있다. 예를 들어, 상기 유기 용매는, 디메틸석폭사이드(dimethyl sulfoxide, DMSO), 에틸렌글리콜(ethylene glycol), N-메틸-2-피페리돈(n-methyl-2-pyrrolidone, NMP), 디메틸포름아미드(dimethylformamide, DMF) 중 어느 하나일 수 있다. 일 실시 예에 따르면, 상기 베이스 용액은, 상기 그래핀 산화물이 상기 유기 용매에 5 mg/mL의 농도로 첨가되어 제조될 수 있다. 1 and 2, a base solution may be prepared (S100). The base solution may include graphene oxide. The base solution may be prepared by adding the graphene oxide to a solvent. According to one embodiment, the solvent may be water or an organic solvent. For example, the organic solvent may be dimethyl sulfoxide (DMSO), ethylene glycol, ethylene glycol, N-methyl-2-pyrrolidone (NMP), dimethylformamide ( dimethylformamide, DMF). According to an embodiment, the base solution may be prepared by adding the graphene oxide to the organic solvent at a concentration of 5 mg / mL.

일 실시 예에 따르면, 상기 베이스 용액 내의 상기 그래핀 산화물의 농도를 제어하여, 후술되는 복합 섬유의 신장률(elongation percentage)이 제어될 수 있다. 구체적으로, 상기 베이스 용액 내의 상기 그래핀 산화물의 농도가 증가함에 따라, 후술되는 복합 섬유의 신장률이 증가할 수 있다. 즉, 상기 베이스 용액 내의 상기 그래핀 산화물의 농도가 증가하는 경우, 후술되는 복합 섬유의 배향도는 감소되고, 기공도는 증가할 수 있다. 이에 따라, 후술되는 복합 섬유의 신장률은 증가할 수 있다. According to one embodiment, by controlling the concentration of the graphene oxide in the base solution, the elongation percentage of the composite fiber to be described later can be controlled. Specifically, as the concentration of the graphene oxide in the base solution increases, the elongation of the composite fiber to be described later may increase. That is, when the concentration of the graphene oxide in the base solution is increased, the degree of orientation of the composite fiber described later may be reduced, the porosity may be increased. Accordingly, the elongation of the composite fiber described later can be increased.

상기 베이스 용액에 기능성 물질이 제공되어 복합 용액(10)이 제조될 수 있다(S200). 일 실시 예에 따르면, 상기 기능성 물질은 전도성 물질일 수 있다. 이에 따라, 후술되는 복합 섬유의 전기 전도도(conductivity)가 향상될 수 있다. A functional material may be provided in the base solution to prepare a complex solution 10 (S200). According to one embodiment, the functional material may be a conductive material. Accordingly, the electrical conductivity of the composite fiber to be described later can be improved.

일 실시 예에 따르면, 상기 기능성 물질은 파티클(particle) 형상, 로드(rod) 형상, 와이어(wire) 형상, 및 나노시트(nanosheet) 형상 중 어느 하나의 형상을 가질 수 있다. 예를 들어, 상기 기능성 물질은 carbon nanotube(CNT)일 수 있다. 다른 예를 들어, 상기 기능성 물질은 silver nanowire, copper nanowire, h-BN, BP, MoS2, WS2, TiS2, TaS2, Ti2C, (Ti0.5Nb0.5)2C, Nb2C, Mo2C, Ti3C2, Ti3CN, Zr3C2, Hf3C2, Ti4N3, Nb4C3, Ta4C3, Mo2TiC2, Cr2TiC2, 및 Mo2Ti2C3 중 적어도 어느 하나를 포함할 수 있다. 이에 따라, 상기 기능성 물질은 후술되는 베이스 섬유의 제조 단계에서, 상기 베이스 섬유 내의 상기 그래핀 산화물의 구조를 손상시키지 않을 수 있다. According to an embodiment, the functional material may have any one of a particle shape, a rod shape, a wire shape, and a nanosheet shape. For example, the functional material may be carbon nanotubes (CNTs). In another example, the functional material is silver nanowire, copper nanowire, h-BN, BP, MoS 2 , WS 2 , TiS 2 , TaS 2 , Ti 2 C, (Ti 0.5 Nb 0.5 ) 2 C, Nb 2 C, Mo 2 C, Ti 3 C 2 , Ti 3 CN, Zr 3 C 2 , Hf 3 C 2 , Ti 4 N 3 , Nb 4 C 3 , Ta 4 C 3 , Mo 2 TiC 2 , Cr 2 TiC 2 , and Mo 2 Ti 2 C 3 It may include at least one. Accordingly, the functional material may not damage the structure of the graphene oxide in the base fiber in the manufacturing step of the base fiber described later.

일 실시 예에 따르면, 서로 다른 종류의 기능성 물질, 다시 말하면 2종 이상의 기능성 물질이 상기 베이스 용액에 제공되어, 상기 복합 용액(10)이 제조될 수 있다. According to an embodiment, different kinds of functional materials, that is, two or more kinds of functional materials may be provided in the base solution, so that the complex solution 10 may be prepared.

상기 베이스 용액 내의 상기 그래핀 산화물 및 상기 기능성 물질의 비율은 제어될 수 있다. 예를 들어, 상기 베이스 용액 내의 상기 그래핀 산화물 및 상기 기능성 물질의 비율은 5:7 wt%의 비율일 수 있다. The proportion of the graphene oxide and the functional material in the base solution can be controlled. For example, the ratio of the graphene oxide and the functional material in the base solution may be a ratio of 5: 7 wt%.

또한, 상기 베이스 용액 내의 상기 그래핀 산화물 및 상기 기능성 물질의 비율이 제어됨에 따라, 후술되는 복합 섬유의 전기 전도도, 내구성(strength), 신장률(elongation), 및 탄성률(modulus)이 제어될 수 있다. In addition, as the ratio of the graphene oxide and the functional material in the base solution is controlled, electrical conductivity, durability, elongation, and modulus of the composite fiber, which will be described later, may be controlled.

구체적으로, 상기 베이스 용액 내의 상기 그래핀 산화물의 비율과 비교하여, 상기 베이스 용액 내의 상기 기능성 물질의 비율이 증가함에 따라, 후술되는 복합 섬유의 전기 전도도, 내구성(strength), 신장률(elongation), 및 탄성률(modulus)이 향상될 수 있다. Specifically, as compared with the ratio of the graphene oxide in the base solution, as the ratio of the functional material in the base solution increases, the electrical conductivity, strength, elongation, and elongation of the composite fiber described below, and Modulus can be improved.

상기 복합 용액(10)은, 응고 용액(20) 내에 방사되어 베이스 섬유(30)가 제조될 수 있다(S300). 상기 응고 용액(20) 내에 상기 복합 용액(10)이 방사되어 제조된 상기 베이스 섬유(30)는, 상기 응고 용액(20) 내에 포함된 상기 응고제에 의해 응고될 수 있다. The complex solution 10 may be spun into the coagulation solution 20 to produce a base fiber 30 (S300). The base fiber 30 prepared by spinning the complex solution 10 in the coagulation solution 20 may be coagulated by the coagulant included in the coagulation solution 20.

일 실시 예에 따르면, 상기 응고제는, 염화칼슘(CaCl2), 수산화칼륨(KOH), 수산화나트륨(NaOH), 염화나트륨(NaCl), 황산구리(CuSO4), 세틸트리메틸암모늄브로미드(Cetyltrimethylammonium bromide, CTAB), 또는 키토산(chitosan) 중 어느 하나일 수 있다.According to one embodiment, the coagulant, calcium chloride (CaCl2), potassium hydroxide (KOH), sodium hydroxide (NaOH), sodium chloride (NaCl), copper sulfate (CuSO4), cetyltrimethylammonium bromide (CTAB), or It may be any one of chitosan.

일 실시 예에 따르면, 도 2에서 알 수 있듯이, 베이스 용기(100)에 담긴 상기 복합 용액(10)은, 상기 베이스 용기(100)에 연결된 방사구(120)를 통해, 상기 응고 용액(20)이 담긴 응고욕(200)으로 방사될 수 있다. According to one embodiment, as shown in Figure 2, the complex solution 10 contained in the base container 100, through the spinneret 120 connected to the base container 100, the coagulation solution 20 This may be radiated into the coagulation bath (200).

일 실시 예에 따르면, 상기 응고 용액(20) 내로 방사되는 상기 복합 용액(10)이 방사 속도를 제어하여, 후술되는 복합 섬유의 신장률을 제어할 수 있다. 구체적으로, 상기 응고 용액(20) 내로 방사되는 상기 복합 용액(10)의 방사 속도가 감소함에 따라, 후술되는 복합 섬유의 신장률이 증가할 수 있다. 즉, 상기 복합 용액(10)의 방사 속도가 감소함에 따라, 후술되는 복합 섬유의 배향도는 감소되고, 기공도는 증가할 수 있다. 이에 따라, 후술되는 복합 섬유의 신장률은 증가할 수 있다. According to one embodiment, the composite solution 10 that is spun into the coagulation solution 20 may control the spinning speed, thereby controlling the elongation of the composite fiber to be described later. Specifically, as the spinning speed of the composite solution 10 spun into the coagulation solution 20 decreases, the elongation of the composite fiber to be described later may increase. That is, as the spinning speed of the composite solution 10 decreases, the degree of orientation of the composite fiber, which will be described later, may decrease, and the porosity may increase. Accordingly, the elongation of the composite fiber described later can be increased.

상기 베이스 섬유(30)를 제조하는 단계는, 상기 베이스 섬유(30)를 상기 응고 용액(20)으로부터 분리하는 단계, 및 분리된 상기 베이스 섬유(30)를 권취하는 단계를 포함할 수 있다. The manufacturing of the base fiber 30 may include separating the base fiber 30 from the coagulation solution 20, and winding the separated base fiber 30.

구체적으로, 상기 베이스 섬유(30)는 상기 응고 용액(20)으로부터 분리되어 세척, 및 건조될 수 있다. 상기 베이스 섬유(30)는, 가이드 롤러(guide roller, 130)에 의해 상기 응고 용액(20)이 담긴 상기 응고욕(200)으로부터 분리되어 외부로 나올 수 있다. 상기 응고 용액(20)으로부터 분리된 상기 베이스 섬유(30)는, 상기 응고제를 포함할 수 있다. Specifically, the base fiber 30 may be separated from the coagulation solution 20, washed, and dried. The base fiber 30 may be separated from the coagulation bath 200 containing the coagulation solution 20 by a guide roller 130 and come out. The base fiber 30 separated from the coagulation solution 20 may include the coagulant.

이에 따라, 세척 공정에 의해, 상기 베이스 섬유(30)에 잔존하는 상기 응고제의 적어도 일부가 제거될 수 있다. 일 실시 예에 따르면, 상기 세척 공정에 사용되는 세척 용액은, 알코올성 수용액일 수 있다. Accordingly, at least a portion of the coagulant remaining in the base fiber 30 may be removed by the washing process. According to one embodiment, the washing solution used in the washing process may be an alcoholic aqueous solution.

일 실시 예에 따르면, 상기 분리 및 세척 공정을 통해, 상기 베이스 섬유(30)에 포함된 수분이 공기 중에서 자연 건조될 수 있다. 또한, 가열 공정을 통해, 공기 중에서 자연 건조된 상기 베이스 섬유(30)가 이차적으로 건조될 수 있다. 즉, 상기 가열 공정을 통해, 상기 베이스 섬유(30)에 잔존하는 물의 적어도 일부가 제거될 수 있다. According to one embodiment, through the separation and washing process, the moisture contained in the base fiber 30 may be naturally dried in the air. In addition, through the heating process, the base fiber 30 naturally dried in air may be secondaryly dried. That is, at least a portion of the water remaining in the base fiber 30 may be removed through the heating process.

일 실시 예에 따르면, 상기 베이스 섬유(30)는, 상기 가열 공정을 통해 건조되는 동시에, 권취될 수 있다. 도 2에 도시된 바와 같이, 상기 세척 공정이 종료된 후, 상기 베이스 섬유(30)는, 상기 건조 공정이 수행되는 동시에, 와인딩 롤러(winding roller, 140)에 의하여 권취될 수 있다. According to an embodiment, the base fiber 30 may be wound and dried at the same time through the heating process. As shown in FIG. 2, after the washing process is finished, the base fiber 30 may be wound by a winding roller 140 while the drying process is performed.

일 실시 예에 따르면, 상기 베이스 섬유(30)의 권취 속도를 제어함에 따라, 후술되는 복합 섬유의 신장률이 제어될 수 있다. 구체적으로, 상기 베이스 섬유(30)의 권취 속도보다 상기 복합 용액(10)의 방사 속도가 더 빠른 경우, 후술되는 복합 섬유의 신장률이 증가될 수 있다. According to one embodiment, by controlling the winding speed of the base fiber 30, the elongation of the composite fiber to be described later can be controlled. Specifically, when the spinning speed of the composite solution 10 is faster than the winding speed of the base fiber 30, the elongation of the composite fiber to be described later may be increased.

즉, 상기 베이스 섬유(30)의 권취 속도보다 상기 복합 용액(10)의 방사 속도가 더 빠른 경우, 후술되는 복합 섬유의 배향도는 감소되고, 기공도는 증가할 수 있다. 이에 따라, 후술되는 복합 섬유의 신장률은 증가될 수 있다. That is, when the spinning speed of the composite solution 10 is faster than the winding speed of the base fiber 30, the degree of orientation of the composite fiber to be described later is reduced, the porosity may be increased. Accordingly, the elongation of the composite fiber described below can be increased.

도 1, 도 3, 및 도 4를 참조하면, 상기 베이스 섬유(30) 내의 상기 그래핀 산화물이 환원되어, 복합 섬유(50)가 제조될 수 있다(S400). 이에 따라, 상기 복합 섬유(50)는 그래핀 및 기능성 물질을 포함할 수 있다. 구체적으로, 상기 복합 섬유(50)는 복수의 그래핀 시트, 및 복수의 상기 그래핀 시트 사이에 배치되는 기능성 구조체를 포함하는 형태일 수 있다. 상기 기능성 구조체는, 상기 기능성 물질이 파티클(particle) 형상, 로드(rod) 형상, 와이어(wire) 형상, 및 나노시트(nanosheet) 형상 중 어느 하나의 형상을 갖는 것일 수 있다. 즉, 상기 기능성 물질은, 상기 복합 섬유(50)가 제조되는 과정에서 형상이 유지될 수 있다. 1, 3, and 4, the graphene oxide in the base fiber 30 is reduced, the composite fiber 50 can be produced (S400). Accordingly, the composite fiber 50 may include graphene and a functional material. Specifically, the composite fiber 50 may be in a form including a plurality of graphene sheets, and a functional structure disposed between the plurality of graphene sheets. The functional structure may be one in which the functional material has a shape of any one of a particle shape, a rod shape, a wire shape, and a nanosheet shape. That is, the functional material may be maintained in shape in the process of manufacturing the composite fiber 50.

구체적으로, 도 4의 (b)에 도시된 것과 같이, 상기 기능성 구조체는 1차원 물질일 수 있고, 또는 도 4의 (c)에 도시된 것과 같이, 상기 기능성 구조체는 2차원 물질일 수 있다. 도 4의 (a)는 상기 기능성 구조체가 생략되어, 복수의 그래핀 시트로 구성된 그래핀 섬유를 도시한 것이다. Specifically, as shown in (b) of FIG. 4, the functional structure may be a one-dimensional material, or as shown in (c) of FIG. 4, the functional structure may be a two-dimensional material. Figure 4 (a) shows the graphene fibers composed of a plurality of graphene sheets, the functional structure is omitted.

상기 복합 섬유(50)는, 상기 기능성 물질의 함량에 따라, 상기 복합 섬유(50)의 전기 전도도, 내구성(strength), 신장률(elongation), 및 탄성률(modulus)이 제어될 수 있다. 일 실시 예에 따르면, 상기 복합 섬유(50), 상기 기능성 물질의 함량이 증가함에 따라, 상기 복합 섬유(50)의 전기 전도도, 내구성(strength), 신장률(elongation), 및 탄성률(modulus)이 향상될 수 있다. The composite fiber 50 may control electric conductivity, strength, elongation, and modulus of the composite fiber 50 according to the content of the functional material. According to an embodiment, as the content of the composite fiber 50 and the functional material is increased, the electrical conductivity, durability, elongation, and modulus of the composite fiber 50 are improved. Can be.

구체적으로, 상기 기능성 물질은 상술된 바와 같이 전도성 물질일 수 있다. 이에 따라, 상기 기능성 물질의 함량이 증가하는 경우, 상기 복합 섬유(50)의 전기 전도도가 향상될 수 있다. Specifically, the functional material may be a conductive material as described above. Accordingly, when the content of the functional material increases, the electrical conductivity of the composite fiber 50 can be improved.

또한, 상기 기능성 물질은 상술된 바와 같이 파티클(particle) 형상, 로드(rod) 형상, 와이어(wire) 형상, 및 나노시트(nanosheet) 형상 중 어느 하나의 형상을 가질 수 있다. 이에 따라, 상기 베이스 섬유(30)의 제조 과정에서 상기 그래핀 산화물의 구조를 손상시키지 않을 수 있다. 결과적으로, 상기 그래핀 산화물의 구조가 손상되지 않는 경우, 상기 복합 섬유(50)가 포함하는 그래핀 또한 손상받지 않게 되어, 상기 복합 섬유(50) 내구성, 신장률, 및 탄성률과 같은 기계적 특성이 향상될 수 있다. In addition, the functional material may have any one of a particle shape, a rod shape, a wire shape, and a nanosheet shape as described above. Accordingly, the structure of the graphene oxide may not be damaged in the manufacturing process of the base fiber 30. As a result, when the structure of the graphene oxide is not damaged, the graphene included in the composite fiber 50 is also not damaged, thereby improving mechanical properties such as durability, elongation, and elasticity of the composite fiber 50. Can be.

상술된 본 발명의 실시 예와 달리, 그래핀 섬유의 전기 전도도를 향상시키기 위해서, 그래핀 섬유의 환원도를 향상시킬 수 있다. 하지만, 환원도를 향상시키기 위해서는 고온의 열처리, 레이저 처리 등과 같은 후속 공정이 요구될 수 있다. 이에 따라, 시간 및 가격이 증가하여, 경제적 문제가 발생하는 단점이 있다. Unlike the embodiment of the present invention described above, in order to improve the electrical conductivity of the graphene fibers, it is possible to improve the reduction of the graphene fibers. However, in order to improve the degree of reduction, subsequent processes such as high temperature heat treatment and laser treatment may be required. Accordingly, the time and the price increase, there is a disadvantage that the economic problem occurs.

하지만 본 발명의 실시 예에 따른 그래핀 복합 섬유의 제조 방법은, 그래핀 산화물을 포함하는 상기 베이스 섬유(30)가 제조되기 전 단계에서, 그래핀 산화물을 포함하는 상기 베이스 용액(30) 내에 상기 기능성 물질을 제공하는 간단한 방법으로, 상기 복합 섬유(50)의 전기 전도도를 향상시킬 수 있다. However, in the graphene composite fiber manufacturing method according to the embodiment of the present invention, before the base fiber 30 including graphene oxide is manufactured, the base solution 30 including graphene oxide may be In a simple way of providing a functional material, the electrical conductivity of the composite fiber 50 can be improved.

일 실시 예에 따르면, 상기 복합 섬유(50)를 제조하는 단계는, 환원제를 포함하는 환원 용액(40)을 준비하는 단계, 및 상기 환원 용액(40) 내에 상기 베이스 섬유(30)를 침지시키는 단계를 포함할 수 있다. 예를 들어, 상기 환원제는 Hydroiodic acid(HI)일 수 있다. 예를 들어, 상기 환원 용액(40)은, 50 wt%의 농도를 갖는 HI 와 50 wt%의 농도를 갖는 물이 혼합된 용액일 수 있다. According to an embodiment, the manufacturing of the composite fiber 50 may include preparing a reducing solution 40 including a reducing agent, and immersing the base fiber 30 in the reducing solution 40. It may include. For example, the reducing agent may be Hydroiodic acid (HI). For example, the reducing solution 40 may be a solution in which HI having a concentration of 50 wt% and water having a concentration of 50 wt% are mixed.

일 실시 예에 따르면, 상기 복합 섬유(50)를 제조하는 단계에서, 상기 환원 용액(40)이 포함하는 상기 환원제의 농도 및 상기 환원 용액 내에 상기 복합 섬유(50)가 침지되는 시간이 제어되어, 상기 복합 섬유(50)가 포함하는 상기 그래핀의 환원 레벨이 제어될 수 있다. According to one embodiment, in the step of manufacturing the composite fiber 50, the concentration of the reducing agent included in the reducing solution 40 and the time that the composite fiber 50 is immersed in the reducing solution is controlled, The reduction level of the graphene included in the composite fiber 50 can be controlled.

구체적으로, 상기 환원 용액(40)이 포함하는 상기 환원제의 농도가 증가되는 경우, 상기 복합 섬유(50)가 포함하는 상기 그래핀의 환원 레벨이 증가될 수 있다. 또한, 상기 환원 용액 내에 상기 베이스 섬유(30)가 침지되는 시간이 증가되어, 상기 복합 섬유(50)가 포함하는 상기 그래핀의 환원 레벨이 증가될 수 있다. Specifically, when the concentration of the reducing agent included in the reducing solution 40 is increased, the reduction level of the graphene included in the composite fiber 50 may be increased. In addition, the time for which the base fiber 30 is immersed in the reducing solution is increased, the reduction level of the graphene included in the composite fiber 50 may be increased.

반면, 상기 환원 용액(40)이 포함하는 상기 환원제의 농도가 감소되는 경우, 상기 복합 섬유(50)가 포함하는 상기 그래핀의 환원 레벨이 감소될 수 있다. 또한, 상기 환원 용액 내에 상기 베이스 섬유(30)가 침지되는 시간이 감소되어, 상기 복합 섬유(50)가 포함하는 상기 그래핀의 환원 레벨이 감소될 수 있다. On the other hand, when the concentration of the reducing agent included in the reducing solution 40 is reduced, the reduction level of the graphene included in the composite fiber 50 may be reduced. In addition, the time for which the base fiber 30 is immersed in the reducing solution is reduced, so that the reduction level of the graphene included in the composite fiber 50 may be reduced.

또는, 다른 실시 예에 따르면, 환원 가스 분위기에서, 상기 베이스 섬유(30)가 환원되어, 상기 복합 섬유(50)가 제조될 수 있다. 이때, 상기 환원 가스의 농도가 증가되거나, 상기 환원 가스의 제공시간이 증가되는 경우 복합 섬유(50)가 포함하는 상기 그래핀의 환원 레벨이 증가될 수 있다. 반면, 상기 환원 가스의 농도가 감소되거나, 상기 환원 가스가 제공되는 시간이 감소되는 경우 상기 복합 섬유(50)가 포함하는 상기 그래핀의 환원 레벨이 감소될 수 있다.Alternatively, according to another embodiment, in the reducing gas atmosphere, the base fiber 30 is reduced, the composite fiber 50 can be produced. In this case, when the concentration of the reducing gas is increased or when the providing time of the reducing gas is increased, the reduction level of the graphene included in the composite fiber 50 may be increased. On the other hand, when the concentration of the reducing gas is reduced, or when the time for providing the reducing gas is reduced, the reduction level of the graphene included in the composite fiber 50 may be reduced.

본 발명의 실시 예에 따른 그래핀 복합 섬유의 제조 방법은, 상기 그래핀 산화물을 포함하는 상기 베이스 용액을 준비하는 단계, 상기 베이스 용액에, 상기 기능성 물질을 제공하여 상기 복합 용액(10)을 제조하는 단계, 상기 복합 용액(10)을 상기 응고 용액(20) 내에 방사시켜, 상기 그래핀 산화물 및 상기 기능성 물질을 포함하는 상기 베이스 섬유(30)를 제조하는 단계, 및 상기 베이스 섬유(30) 내의 상기 그래핀 산화물을 환원시켜, 그래핀 및 상기 기능성 물질을 포함하는 상기 복합 섬유(50)를 제조하는 단계를 포함할 수 있다. 이에 따라, 간소화된 공정으로 전기 전도도가 향상된 그래핀 복합 섬유가 제조될 수 있다. In the method for producing a graphene composite fiber according to an embodiment of the present invention, preparing the base solution containing the graphene oxide, to provide the functional material to the base solution, to prepare the composite solution 10 Spinning the composite solution 10 into the coagulation solution 20 to produce the base fiber 30 comprising the graphene oxide and the functional material, and in the base fiber 30 Reducing the graphene oxide, it may include the step of producing the composite fiber 50 containing the graphene and the functional material. Accordingly, the graphene composite fiber with improved electrical conductivity may be manufactured in a simplified process.

이상, 본 발명의 실시 예에 따른 그래핀 복합 섬유의 제조 방법이 설명되었다. 이하, 도 5를 참조하여 그래핀 산화물이 환원된 상기 복합 섬유가, 줄히팅 되어 형성되는 본 발명의 변형 예에 따른 그래핀 복합 섬유의 제조 방법이 설명된다.The graphene composite fiber manufacturing method according to an embodiment of the present invention has been described above. Hereinafter, a method of manufacturing a graphene composite fiber according to a modified example of the present invention in which the composite fiber in which graphene oxide is reduced is formed by Joule heating with reference to FIG.

도 5는 본 발명의 변형 예에 따른 그래핀 복합 섬유의 제조 공정을 나타내는 도면이다. 5 is a view showing a manufacturing process of the graphene composite fiber according to a modification of the present invention.

도 5를 참조하면, 도 1 내지 도 3을 참조하여 설명된 본 발명의 실시 예에 따른 복합 섬유(50)가 준비된다. 상기 복합 섬유(50)는 줄히팅(joule heating)되어, 본 발명의 변형 예에 따른 그래핀 복합 섬유(60)가 제조될 수 있다. 즉, 상기 베이스 섬유(30) 내의 상기 그래핀 산화물이 환원된 후, 환원된 그래핀 산화물을 포함하는 상기 복합 섬유(50)가 줄히팅 되어, 상기 변형 예에 따른 그래핀 복합 섬유(60)가 제조될 수 있다. Referring to FIG. 5, a composite fiber 50 according to an embodiment of the present invention described with reference to FIGS. 1 to 3 is prepared. The composite fiber 50 is joule heated, the graphene composite fiber 60 according to a modification of the present invention can be produced. That is, after the graphene oxide in the base fiber 30 is reduced, the composite fiber 50 including the reduced graphene oxide is lined, the graphene composite fiber 60 according to the modification Can be prepared.

이와 달리, 상기 베이스 섬유(30)내의 상기 그래핀 산화물이 환원되지 않은 상태에서, 상기 베이스 섬유(30)에 전류가 인가되어 줄히팅 되는 경우, 상기 베이스 섬유(30)가 끊어지는 현상이 발생될 수 있다. On the contrary, in the state in which the graphene oxide in the base fiber 30 is not reduced, when the current is applied to the base fiber 30 and is heated, the phenomenon in which the base fiber 30 is broken may occur. Can be.

이하, 상기 복합 섬유(50)가 줄히팅 되어 제조되는 상기 변형 예에 따른 그래핀 복합 섬유(60)를 구체적으로 설명하되, 상기 복합 섬유(50)에 연속적인 전류가 인가되는 제1 변형 예에 따른 그래핀 복합 섬유, 및 상기 복합 섬유(60)에 펄스(pulse) 전류가 인가되는 제2 변형 예에 따른 그래핀 복합 섬유가 각각 설명된다.Hereinafter, the graphene composite fiber 60 according to the modified example in which the composite fiber 50 is lined and manufactured will be described in detail, but in the first modified example in which a continuous current is applied to the composite fiber 50, The graphene composite fiber according to the present invention, and the graphene composite fiber according to the second modified example in which a pulse current is applied to the composite fiber 60 will be described.

제1 변형 예에 따르면, 상기 복합 섬유(50)는 연속적인 전류가 인가되는 방법으로 줄히팅(joule heating)되어, 그래핀 복합 섬유(60)가 제조될 수 있다. According to the first modified example, the composite fiber 50 may be joule heated in a manner in which a continuous current is applied, and thus the graphene composite fiber 60 may be manufactured.

일 실시 예에 따르면, 상기 복합 섬유(50)를 줄히팅하기 위한 줄히팅 장치는, 챔버(300), 및 전원(330)으로 구성될 수 있다. 상기 챔버(300)는, 전극(310), 및 가스 주입구(320)를 포함할 수 있다. According to an embodiment of the present disclosure, the joule heating apparatus for Joule heating the composite fiber 50 may include a chamber 300 and a power source 330. The chamber 300 may include an electrode 310 and a gas injection hole 320.

상기 복합 섬유(50)는 상기 챔버(300) 내의 상기 전극(310) 사이에 배치되어 줄히팅 될 수 있다. 예를 들어, 상기 전극(310)은 구리(Cu)를 포함할 수 있다. 일 실시 예에 따르면, 상기 챔버(300)의 내부는 상기 가스 주입구(320)를 통해 주입된 비활성 가스로 채워질 수 있다. 예를 들어, 상기 비활성 가스는 아르곤(Ar) 가스일 수 있다. The composite fiber 50 may be disposed between the electrodes 310 in the chamber 300 and line-heated. For example, the electrode 310 may include copper (Cu). According to one embodiment, the interior of the chamber 300 may be filled with inert gas injected through the gas injection port 320. For example, the inert gas may be argon (Ar) gas.

상기 복합 섬유(50)는, 줄히팅 됨에 따라, 상기 복합 섬유 (50)내의 비정질 탄소들이 결정화될 수 있다. 즉, 상기 제1 변형 예에 따른 그래핀 복합 섬유(60)는, 상기 복합 섬유(50) 내의 비정질 탄소들이 결정화된 것일 수 있다. 이에 따라, 상기 제1 변형 예에 따른 그래핀 복합 섬유(60)는, 복수의 그래핀 시트가 응집되어 일 방향으로 연장될 수 있다. As the composite fiber 50 is Joule heated, amorphous carbons in the composite fiber 50 may be crystallized. That is, in the graphene composite fiber 60 according to the first modification, amorphous carbon in the composite fiber 50 may be crystallized. Accordingly, in the graphene composite fiber 60 according to the first modification, a plurality of graphene sheets may be aggregated and extended in one direction.

상기 복합 섬유(50) 및 상기 제1 변형 예에 따른 그래핀 복합 섬유(60)는 각각 복수의 그래핀 시트가 적층된, 적층 구조체를 포함할 수 있다. 이때, 상기 복합 섬유(50)는, 줄히팅 됨에 따라, 적층 구조체의 두께 및 그래핀 시트의 결정립 크기가 변화될 수 있다. 구체적으로, 상기 복합 섬유(50)는, 줄히팅 됨에 따라, 적층 구조체의 두께 및 그래핀 시트의 결정립 크기가 증가될 수 있다. 이에 따라, 상기 제1 변형 예에 따른 그래핀 복합 섬유(60)의 적층 구조체의 두께 및 그래핀 시트의 결정립 크기는, 상기 복합 섬유(50)의 적층 구조체의 두께 및 그래핀 시트의 결정립 크기보다 클 수 있다. 다시 말해, 상기 복합 섬유(50)의 결정화도는, 상기 제1 변형 예에 따른 그래핀 복합 섬유(60)의 결정화도 보다 낮을 수 있다. The composite fiber 50 and the graphene composite fiber 60 according to the first modification may include a laminated structure in which a plurality of graphene sheets are stacked. In this case, as the composite fiber 50 is lined, the thickness of the laminated structure and the grain size of the graphene sheet may be changed. Specifically, as the composite fiber 50 is Joule heated, the thickness of the laminated structure and the grain size of the graphene sheet may be increased. Accordingly, the thickness of the laminated structure of the graphene composite fiber 60 and the grain size of the graphene sheet according to the first modified example are greater than the thickness of the laminated structure of the composite fiber 50 and the grain size of the graphene sheet. Can be large. In other words, the crystallinity of the composite fiber 50 may be lower than that of the graphene composite fiber 60 according to the first modification.

본 발명의 제1 변형 예에 따른 그래핀 복합 섬유(60)는 상기 베이스 섬유(30) 내의 상기 그래핀 산화물이 환원된 후, 환원된 그래핀 산화물을 포함하는 상기 복합 섬유(50)에 연속적인 전류가 인가되는 방법으로 줄히팅 되어 제조될 수 있다. 이에 따라, 상기 복합 섬유(50) 내의 비정질 탄소들이 결정화 되어, 상기 제1 변형 예에 따른 그래핀 복합 섬유(60)의 전기 전도도가 향상될 수 있다. Graphene composite fiber 60 according to the first modification of the present invention is continuous to the composite fiber 50 containing the reduced graphene oxide after the graphene oxide in the base fiber 30 is reduced It may be manufactured by Joule heating in a manner in which a current is applied. Accordingly, the amorphous carbon in the composite fiber 50 is crystallized, the electrical conductivity of the graphene composite fiber 60 according to the first modification can be improved.

제2 변형 예에 따르면, 상기 복합 섬유(50)는 펄스(pulse) 전류가 인가되는 방법으로 줄히팅(joule heating)되어, 그래핀 복합 섬유(60)가 제조될 수 있다. 상기 펄스 전류는, 특정 주기(cycle)를 통해 전류가 가해지는 방식일 수 있다. 일 실시 예에 따르면, 상기 펄스의 시간은 0.3초 이상 3초 이하일 수 있다. 예를 들어, 상기 복합 섬유(50)에 15초의 간격으로 0.5초 동안 전류가 인가되어 상기 제2 변형 예에 따른 그래핀 복합 섬유(60)가 제조될 수 있다. According to a second modified example, the composite fiber 50 may be joule heated in a manner in which a pulse current is applied, so that the graphene composite fiber 60 may be manufactured. The pulse current may be a method in which a current is applied through a specific cycle. According to one embodiment, the time of the pulse may be 0.3 seconds or more and 3 seconds or less. For example, the graphene composite fiber 60 according to the second modified example may be manufactured by applying a current to the composite fiber 50 at an interval of 15 seconds for 0.5 seconds.

상기 복합 섬유(50)가 펄스 전류가 인가되는 방법으로 줄히팅 되는 경우, 상기 복합 섬유(50) 내의 잔존하는 산소들이 발포될 수 있다. 즉, 상기 베이스 섬유(30)가 포함하는 상기 그래핀 산화물을 환원시켜, 상기 복합 섬유(50)를 제조하는 과정에서 상기 복합 섬유(50)의 내부에는 환원되지 못한 산소들이 잔존할 수 있다. 이후, 상기 복합 섬유(50)가 줄히팅 되어 상기 제2 변형 예에 따른 그래핀 복합 섬유(60)가 제조되는 과정에서, 상기 복합 섬유(50)의 내부에 남아있던 환원되지 못한 산소들이 발포될 수 있다. 이에 따라, 상기 제2 변형 예에 따른 그래핀 복합 섬유(60)의 두께는 상기 복합 섬유(50)의 두께보다 두꺼워질 수 있다. When the composite fiber 50 is lined by a method in which a pulse current is applied, residual oxygen in the composite fiber 50 may be foamed. That is, by reducing the graphene oxide included in the base fiber 30, in the process of manufacturing the composite fiber 50, unreduced oxygen may remain in the composite fiber 50. Subsequently, in the process of manufacturing the graphene composite fiber 60 according to the second modified example by heating the composite fiber 50, unreduced oxygen remaining in the composite fiber 50 may be foamed. Can be. Accordingly, the thickness of the graphene composite fiber 60 according to the second modified example may be thicker than the thickness of the composite fiber 50.

구체적으로, 상기 복합 섬유(50)가 펄스 전류가 인가되는 방법으로 줄히팅 되는 경우, 상기 복합 섬유(50)에 급격한 온도 상승이 발생될 수 있다. 즉, 상기 복합 섬유(50)에 펄스 전류가 반복적으로 인가되는 경우, 상기 복합 섬유(50)에 연속적인 전류가 인가되는 경우와 비교하여 상대적으로 높은 온도의 줄 열이 상대적으로 짧은 시간 동안 반복하여 발생할 수 있다. 이로 인하여, 상기 복합 섬유(50) 내부에 잔존하는 산소들은 발포될 수 있다. 이때, 잔존하는 산소들이 발포되는 힘에 의하여, 상기 복합 섬유(50)의 두께가 두꺼워 질 수 있다. 결과적으로, 상기 제2 변형 예에 따른 그래핀 복합 섬유(60)의 두께는 상기 복합 섬유(50)의 두께보다 두꺼워질 수 있다.Specifically, when the composite fiber 50 is heated by a method in which a pulse current is applied, a sudden temperature rise may occur in the composite fiber 50. That is, when the pulse current is repeatedly applied to the composite fiber 50, the Joule heat of a relatively high temperature is repeated for a relatively short time compared to the case where a continuous current is applied to the composite fiber 50 May occur. As a result, oxygen remaining in the composite fiber 50 may be foamed. At this time, the thickness of the composite fiber 50 may be thickened by the force of the remaining oxygen is foamed. As a result, the thickness of the graphene composite fiber 60 according to the second modified example may be thicker than the thickness of the composite fiber 50.

또한, 상기 복합 섬유(50)가 펄스 전류가 인가되는 방법으로 줄히팅 되는 경우, 진동에 의하여 상기 복합 섬유(50)에 가해지는 피로가, 펄스 사이에 해소될 수 있다. 구체적으로, 상기 복합 섬유(50)에 펄스 전류가 반복적으로 인가되는 경우, 상기 복합 섬유(50)는 펄스 전류가 인가되는 시간 동안에는 줄열에 의한 환원 반응이 수행될 수 있다. 반면, 상기 복합 섬유(50)에 전류가 인가되지 않는 펄스 전류 사이의 시간 동안에는 상기 복합 섬유(50)에 축적된 피로가 해소될 수 있다. 또한, 줄열에 의한 환원 반응 및 축적된 피로 해소는 반복하여 발생될 수 있다.In addition, when the composite fiber 50 is heated in a manner in which a pulse current is applied, the fatigue applied to the composite fiber 50 by vibration can be eliminated between pulses. Specifically, when a pulse current is repeatedly applied to the composite fiber 50, the composite fiber 50 may perform a reduction reaction by Joule heat during a time when the pulse current is applied. On the other hand, fatigue accumulated in the composite fiber 50 may be eliminated during a time between pulse currents in which the current is not applied to the composite fiber 50. In addition, reduction reactions and accumulated fatigue relief by Joule heat may occur repeatedly.

이에 따라, 상기 복합 섬유(50)의 손상 및 끊김 현상을 최소화하면서, 상기 복합 섬유(50)를 용이하게 환원할 수 있다. 결과적으로, 전기 전도도가 향상된 상기 제2 변형 예에 따른 그래핀 복합 섬유(60)가 제조될 수 있다. Accordingly, the composite fiber 50 can be easily reduced while minimizing damage and breakage of the composite fiber 50. As a result, the graphene composite fiber 60 according to the second modification with improved electrical conductivity can be produced.

본 발명의 제2 변형 예에 따른 그래핀 복합 섬유(60)는 상기 베이스 섬유(30) 내의 상기 그래핀 산화물이 환원된 후, 환원된 그래핀 산화물을 포함하는 상기 복합 섬유(50)에 펄스 전류가 인가되는 방법으로 줄히팅 되어 제조될 수 있다. 이에 따라, 제2 변형 예에 따른 그래핀 복합 섬유(60)의 전기 전도도가 향상될 수 있다. Graphene composite fiber 60 according to the second modification of the present invention is the graphene oxide in the base fiber 30 is reduced, the pulse current to the composite fiber 50 containing the reduced graphene oxide May be manufactured by Joule heating in such a way that is applied. Accordingly, electrical conductivity of the graphene composite fiber 60 according to the second modified example may be improved.

이상, 본 발명이 변형 예에 따른 그래핀 복합 섬유 및 그 제조 방법이 설명되었다. 이하, 본 발명의 실시 예에 따른 그래핀 복합 섬유의 구체적인 실험 예 및 특성 평가 결과가 설명된다. In the above, the graphene composite fiber according to a modified example of the present invention and a method of manufacturing the same have been described. Hereinafter, specific experimental examples and characteristics evaluation results of the graphene composite fiber according to the embodiment of the present invention will be described.

실시 예 1에 따른 그래핀 복합 섬유의 제조Preparation of Graphene Composite Fiber according to Example 1

그래핀 산화물 및 탄소나노튜브(carbon nanotube, CNT)가 5:7의wt% 비율로 혼합된 용액이 준비된다. 상기 용액을 0.45 mol 농도의 CaCl2 응고욕에 방사하여 베이스 섬유를 제조하였다. 제조된 베이스 섬유의 환원을 위해 30 wt% 농도의 hydroiodic aicd가 있는 용기에 담근 후, 80℃의 온도에서 1시간 동안 반응시켜 실시 예 1에 따른 그래핀 복합 섬유를 제조하였다. A solution in which graphene oxide and carbon nanotubes (carbon nanotubes, CNTs) are mixed at a ratio of 5: 7 wt% is prepared. The solution was spun into a CaCl 2 coagulation bath at 0.45 mol concentration to prepare a base fiber. In order to reduce the prepared base fiber, it was immersed in a container with a hydroiodic aicd concentration of 30 wt%, and then reacted at a temperature of 80 ° C. for 1 hour to prepare graphene composite fiber according to Example 1.

실시 예 2에 따른 그래핀 복합 섬유의 제조Preparation of Graphene Composite Fiber according to Example 2

상기 실시 예 1에 따른 그래핀 복합 섬유를 제조하되, 그래핀 산화물 및 탄소나노튜브를 5:3.5 wt%의 비율로 준비한 후 제조하였다. A graphene composite fiber according to Example 1 was prepared, but was prepared after preparing graphene oxide and carbon nanotubes at a ratio of 5: 3.5 wt%.

실시 예 3에 따른 그래핀 복합 섬유의 제조Preparation of Graphene Composite Fiber according to Example 3

상기 실시 예 1에 따른 그래핀 복합 섬유를 제조하되, 그래핀 산화물 및 탄소나노튜브를 5:1.5 wt%의 비율로 준비한 후 제조하였다. A graphene composite fiber according to Example 1 was prepared, but was prepared after preparing graphene oxide and carbon nanotubes at a ratio of 5: 1.5 wt%.

비교 예 1에 따른 그래핀 섬유 준비Graphene fiber preparation according to Comparative Example 1

상술된 실시 예 1에서, 탄소나노튜브를 생략하고, 60℃ 조건에서 환원하여 그래핀 섬유를 제조하였다.In Example 1 described above, carbon nanotubes were omitted, and graphene fibers were prepared by reducing at 60 ° C.

상기 실시 예 1 내지 3 및 비교 예 1에 따른 그래핀 복합 섬유 및 그래핀 섬유가 아래 <표 1>을 통해 정리된다. Graphene composite fibers and graphene fibers according to Examples 1 to 3 and Comparative Example 1 are summarized through Table 1 below.

구분division 구조rescue 비율ratio 실시 예 1Example 1 그래핀 복합 섬유Graphene composite fiber 그래핀 산화물: 탄소나노튜브 = 5:7Graphene oxide: carbon nanotubes = 5: 7 실시 예 2Example 2 그래핀 복합 섬유Graphene composite fiber 그래핀 산화물: 탄소나노튜브 = 5:3.5Graphene Oxide: Carbon Nanotubes = 5: 3.5 실시 예 3Example 3 그래핀 복합 섬유Graphene composite fiber 그래핀 산화물: 탄소나노튜브 = 5:1.5Graphene Oxide: Carbon Nanotubes = 5: 1.5 비교 예 1Comparative Example 1 환원된 그래핀 산화물Reduced graphene oxide --

도 6은 본 발명의 실시 예 1에 따른 그래핀 복합 섬유를 촬영한 사진이고, 도 7은 본 발명의 실시 예 2에 따른 그래핀 복합 섬유를 촬영한 사진이고, 도 8은 본 발명의 실시 예 3에 따른 그래핀 복합 섬유를 촬영한 사진이다. 6 is a photograph taken of the graphene composite fiber according to the first embodiment of the present invention, Figure 7 is a photograph taken a graphene composite fiber according to the second embodiment of the present invention, Figure 8 is an embodiment of the present invention Photographs taken of graphene composite fiber according to 3.

도 6 내지 8을 참조하면, 본 발명의 실시 예 1 내지 실시 예 3에 따른 그래핀 복합 섬유들을 서로 다른 배율에서 SEM(Scanning electron microscope) 촬영하여 나타내었다. 6 to 8, graphene composite fibers according to Examples 1 to 3 of the present invention are shown by scanning electron microscope (SEM) imaging at different magnifications.

도 6 내지 도 8에서 확인할 수 있듯이, 상기 실시 예 1 내지 실시 예 3에 따른 그래핀 복합 섬유들은, 끊어지지 않고 섬유 형태로 최종적으로 형성된 것을 알 수 있다. 즉, 그래핀 산화물 및 CNT의 비율이 5:7, 5:3.5, 및 5:1.5인 경우, 본 발명의 실시 예에 따른 그래핀 복합 섬유가 용이하게 제조되는 것을 알 수 있다. 6 to 8, it can be seen that the graphene composite fibers according to Examples 1 to 3 are finally formed in a fiber form without breaking. That is, when the ratio of graphene oxide and CNT is 5: 7, 5: 3.5, and 5: 1.5, it can be seen that the graphene composite fiber according to the embodiment of the present invention is easily manufactured.

도 9는 본 발명의 실시 예들 및 비교 예에 따른 그래핀 복합 섬유의 전기 전도도를 비교한 그래프이다. 9 is a graph comparing the electrical conductivity of the graphene composite fiber according to embodiments and comparative examples of the present invention.

도 9를 참조하면, 상기 실시 예 1 내지 실시 예 3에 따른 그래핀 복합 섬유 및 상기 비교 예 1에 따른 그래핀 섬유의 전기 전도도(electrical conductivity, S cm-1)를 측정하여 나타내었다. 9, the electrical conductivity (S cm -1 ) of the graphene composite fibers according to Examples 1 to 3 and the graphene fibers according to Comparative Example 1 was measured and shown.

도 9에서 확인 할 수 있듯이, 상기 실시 예 1에 따른 그래핀 복합 섬유는 1.5 X 102 S cm-1의 전기 전도도를 나타내고, 상기 실시 예 2에 따른 그래핀 복합 섬유는 4.2 X 101 S cm-1의 전기 전도도를 나타내고, 상기 실시 예 3에 따른 그래핀 복합 섬유는 6.2 X 101 S cm-1의 전기 전도도를 나타내고, 상기 비교 예 1에 따른 그래핀 복합 섬유는 2.7 X 101 S cm-1의 전기 전도도를 나타내는 것을 확인할 수 있었다. 즉, 상기 실시 예 1에 따른 그래핀 복합 섬유의 전기 전도도는 다른 실시 예들에 따른 그래핀 복합 섬유의 전기 전도도 또는 비교 예 1에 따른 그래핀 섬유의 전기 전도도와 비교하여 현저하게 향상된 것을 알 수 있다. As can be seen in Figure 9, the graphene composite fiber according to Example 1 shows an electrical conductivity of 1.5 X 10 2 S cm -1 , the graphene composite fiber according to Example 2 is 4.2 X 10 1 S cm It shows an electrical conductivity of -1 , the graphene composite fiber according to Example 3 shows an electrical conductivity of 6.2 X 10 1 S cm -1 , the graphene composite fiber according to Comparative Example 1 is 2.7 X 10 1 S cm It was confirmed that the electrical conductivity of -1 . That is, it can be seen that the electrical conductivity of the graphene composite fiber according to the first embodiment is significantly improved compared to the electrical conductivity of the graphene composite fiber according to the other embodiments or the graphene fiber according to Comparative Example 1. .

이에 따라, 본 발명의 실시 예에 따른 그래핀 복합 섬유를 제조하는 경우, 상기 그래핀 복합 섬유 내의 CNT 함량을 증가시키는 것이, 상기 그래핀 복합 섬유의 전기 전도도를 향상시키는 방법임을 알 수 있다. Accordingly, when manufacturing the graphene composite fiber according to an embodiment of the present invention, it can be seen that increasing the CNT content in the graphene composite fiber, a method of improving the electrical conductivity of the graphene composite fiber.

또한, 상기 실시 예 1 내지 3에 따른 그래핀 복합 섬유의 전기 전도도가 상기 비교 예 1에 따른 그래핀 복합 섬유의 전기 전도도와 비교하여 높은 것을 알 수 있다. 이에 따라, 그래핀 산화물 용액에 CNT를 혼합한 후 그래핀 복합 섬유를 제조하는 것이, 전기 전도도를 향상시키는 방법임을 알 수 있다. In addition, it can be seen that the electrical conductivity of the graphene composite fibers according to Examples 1 to 3 is higher than the electrical conductivity of the graphene composite fibers according to Comparative Example 1. Accordingly, it can be seen that manufacturing the graphene composite fiber after mixing CNTs in the graphene oxide solution is a method of improving electrical conductivity.

도 10은 본 발명의 실시 예들 및 비교 예에 따른 그래핀 복합 섬유의 인장력을 비교한 그래프이다.10 is a graph comparing the tensile force of the graphene composite fibers according to embodiments and comparative examples of the present invention.

도 10을 참조하면, 상기 실시 예 1 내지 3에 따른 그래핀 복합 섬유 및 비교 예 1에 따른 그래핀 섬유의 인장력(tensile strength, MPa)을 측정하여 나타내었다. 10, the tensile strength (MPa) of the graphene composite fibers according to Examples 1 to 3 and the graphene fibers according to Comparative Example 1 were measured and shown.

도 10에서 확인할 수 있듯이, 상기 실시 예 1에 따른 그래핀 복합 섬유는 약 780 MPa의 인장력을 나타내고, 상기 실시 예 2에 따른 그래핀 복합 섬유는 약 700 MPa의 인장력을 나타내고, 상기 실시 예 3에 따른 그래핀 복합 섬유는 약 570 MPa의 인장력을 나타내고, 상기 비교 예 1에 따른 그래핀 섬유는 약 220 MPa의 인장력을 나타내는 것을 확인할 수 있었다. 즉, 상기 비교 예 1, 상기 실시 예 3, 상기 실시 예 2, 및 상기 실시 예 1 에 따른 그래핀 복합 섬유의 순서로 인장력이 증가하는 것을 알 수 있다. 10, the graphene composite fiber according to Example 1 exhibits a tensile force of about 780 MPa, and the graphene composite fiber according to Example 2 exhibits a tensile force of about 700 MPa. According to the graphene composite fiber showed a tensile force of about 570 MPa, it was confirmed that the graphene fiber according to Comparative Example 1 exhibits a tensile force of about 220 MPa. That is, it can be seen that the tensile force increases in the order of the graphene composite fiber according to Comparative Example 1, Example 3, Example 2, and Example 1.

이에 따라, 본 발명의 실시 예에 따른 그래핀 복합 섬유를 제조하는 경우, 상기 그래핀 복합 섬유 내의 CNT 함량을 증가시키는 것이, 상기 그래핀 복합 섬유의 인장력을 향상시키는 방법임을 알 수 있다.Accordingly, when manufacturing the graphene composite fiber according to an embodiment of the present invention, it can be seen that increasing the CNT content in the graphene composite fiber is a method of improving the tensile force of the graphene composite fiber.

도 11은 본 발명의 실시 예들 및 비교 예에 따른 그래핀 복합 섬유의 신장률을 비교한 그래프이다.11 is a graph comparing elongation of graphene composite fibers according to the Examples and Comparative Examples of the present invention.

도 11을 참조하면, 상기 실시 예 1 내지 3에 따른 그래핀 복합 섬유 및 비교 예 1에 따른 그래핀 섬유의 신장률(elongation, %)을 측정하여 나타내었다. 11, the elongation (%) of the graphene composite fibers according to Examples 1 to 3 and the graphene fibers according to Comparative Example 1 were measured and shown.

도 11에서 확인할 수 있듯이, 상기 실시 예 1에 따른 그래핀 복합 섬유는 약 1.6%의 신장률을 나타내고, 상기 실시 예 2에 따른 그래핀 복합 섬유는 약 0.9%의 신장률을 나타내고, 상기 실시 예 3에 따른 그래핀 복합 섬유는 약 0.6%의 신장률을 나타내고, 상기 비교 예 1에 따른 그래핀 복합 섬유는 약 0.9%의 신장률을 나타내는 것을 호가인할 수 있었다. 즉, 상기 실시 예 1에 따른 그래핀 복합 섬유의 신장률은 다른 실시 예들에 따른 그래핀 복합 섬유의 신장률 또는 비교 예 1에 따른 그래핀 섬유의 신장률과 비교하여 현저하게 향상된 것을 알 수 있다.As can be seen in Figure 11, the graphene composite fiber according to Example 1 shows an elongation of about 1.6%, the graphene composite fiber according to Example 2 shows an elongation of about 0.9%, in Example 3 According to the graphene composite fiber exhibits an elongation of about 0.6%, the graphene composite fiber according to Comparative Example 1 could be quoted that it shows an elongation of about 0.9%. That is, it can be seen that the elongation of the graphene composite fiber according to the first embodiment is significantly improved compared to the elongation of the graphene composite fiber according to other embodiments or the elongation of the graphene fiber according to Comparative Example 1.

이에 따라, 본 발명의 실시 예에 따른 그래핀 복합 섬유를 제조하는 경우, 상기 그래핀 복합 섬유 내의 CNT 함량을 증가시키는 것이, 상기 그래핀 복합 섬유의 신장률을 향상시키는 방법임을 알 수 있다.Accordingly, when manufacturing the graphene composite fiber according to an embodiment of the present invention, it can be seen that increasing the CNT content in the graphene composite fiber is a method of improving the elongation of the graphene composite fiber.

도 12는 본 발명의 실시 예들 및 비교 예에 따른 그래핀 복합 섬유의 탄성률을 비교한 그래프이다.12 is a graph comparing the elastic modulus of the graphene composite fibers according to the embodiments and comparative examples of the present invention.

도 12를 참조하면, 상기 실시 예 1 내지 3에 따른 그래핀 복합 섬유 및 비교 예 1에 따른 그래핀 섬유의 탄성력(modulus, GPa)을 측정하여 나타내었다. 12, the elastic force (modulus, GPa) of the graphene composite fibers according to Examples 1 to 3 and the graphene fibers according to Comparative Example 1 were measured and shown.

도 12에서 확인할 수 있듯이, 상기 실시 예 1에 따른 그래핀 복합 섬유는 약 115 GPa의 탄성력을 나타내고, 상기 실시 예 2에 따른 그래핀 복합 섬유는 약 85 GPa의 탄성력을 나타내고, 상기 실시 예 3에 따른 그래핀 복합 섬유는 약 87 GPa의 탄성력을 나타내고, 상기 비교 예 1에 따른 그래핀 섬유는 약 32 GPa의 탄성력을 나타내는 것을 알 수 있었다. As shown in FIG. 12, the graphene composite fiber according to Example 1 exhibits an elastic force of about 115 GPa, and the graphene composite fiber according to Example 2 exhibits an elastic force of about 85 GPa. According to the graphene composite fiber showed an elastic force of about 87 GPa, the graphene fiber according to Comparative Example 1 was found to exhibit an elastic force of about 32 GPa.

즉, 상기 실시 예 1에 따른 그래핀 복합 섬유의 탄성력이 상기 실시 예 2, 실시 예 3, 및 비교 예 1에 따른 그래핀 복합 섬유들의 탄성력 보다 높은 것을 알 수 있다. 또한, 상기 실시 예 1내지 실시 예 3에 따른 그래핀 복합 섬유의 탄성력이 상기 비교 예 1에 따른 그래핀 섬유의 탄성력보다 현저히 높은 것을 알 수 있다. That is, it can be seen that the elastic force of the graphene composite fibers according to Example 1 is higher than the elastic force of the graphene composite fibers according to Examples 2, 3, and Comparative Example 1. In addition, it can be seen that the elastic force of the graphene composite fiber according to Examples 1 to 3 is significantly higher than the elastic force of the graphene fiber according to Comparative Example 1.

이에 따라, 본 발명의 실시 예에 따른 그래핀 복합 섬유를 제조하는 경우, 상기 그래핀 복합 섬유 내의 CNT 함량을 증가시키는 것이, 상기 그래핀 복합 섬유의 탄성력을 향상시키는 방법임을 알 수 있다.Accordingly, when manufacturing the graphene composite fiber according to an embodiment of the present invention, it can be seen that increasing the CNT content in the graphene composite fiber, a method of improving the elastic force of the graphene composite fiber.

결과적으로, 도 10 내지 도 12를 통해 알 수 있듯이 본 발명의 실시 예에 따른 그래핀 복합 섬유의 제조 방법과 같이, 그래핀 산화물에 CNT를 혼합한 후, 그래핀 복합 섬유를 제조하는 것이, 인장력, 신장률, 및 탄성력과 같은 기계적 특성을 향상시키는 방법임을 알 수 있다. As a result, as can be seen through FIGS. 10 to 12, as in the method for producing a graphene composite fiber according to an embodiment of the present invention, after mixing CNT with graphene oxide, to produce a graphene composite fiber, the tensile force It can be seen that the method of improving the mechanical properties such as elongation, elastic force.

실시 예 4에 따른 그래핀 복합 섬유 제조Graphene Composite Fiber Preparation According to Example 4

1차원 물질인 탄소나노튜브를 준비하였다. 그래핀 산화물 및 탄소나노튜브가 1:4wt%의 비율로 혼합된 용액이 준비된다. 상기 용액을 0.45mol 농도의 CaCl2 응고욕에 방사하여 베이스 섬유를 제조하였다. 제조된 베이스 섬유의 환원을 위해 30 wt% 농도의 hydroiodic aicd가 있는 용기에 담근 후, 80℃의 온도에서 1시간 동안 반응시켜 실시 예 4에 따른 그래핀 복합 섬유를 제조하였다.Carbon nanotubes as one-dimensional materials were prepared. A solution in which graphene oxide and carbon nanotubes are mixed at a ratio of 1: 4 wt% is prepared. The solution was spun into a CaCl 2 coagulation bath at 0.45 mol concentration to prepare a base fiber. In order to reduce the prepared base fiber, it was immersed in a container containing 30 wt% hydroiodic aicd, and then reacted at a temperature of 80 ° C. for 1 hour to prepare a graphene composite fiber according to Example 4.

실시 예 5에 따른 그래핀 복합 섬유 제조Graphene Composite Fiber Preparation According to Example 5

2차원 물질인 그래핀 나노리본을 준비하였다. 그래핀 산화물 및 그래핀나노리본이 7:3wt%의 비율로 혼합된 용액이 준비된다. 상기 용액을 0.45mol 농도의 CaCl2 응고욕에 방사하여 베이스 섬유를 제조하였다. 제조된 베이스 섬유의 환원을 위해 30 wt% 농도의 hydroiodic aicd가 있는 용기에 담근 후, 80℃의 온도에서 1시간 동안 반응시켜 실시 예 4에 따른 그래핀 복합 섬유를 제조하였다.Graphene nanoribbons, which are two-dimensional materials, were prepared. A solution in which graphene oxide and graphene nanoribbons are mixed at a ratio of 7: 3 wt% is prepared. The solution was spun into a CaCl 2 coagulation bath at 0.45 mol concentration to prepare a base fiber. In order to reduce the prepared base fiber, it was immersed in a container containing 30 wt% hydroiodic aicd, and then reacted at a temperature of 80 ° C. for 1 hour to prepare a graphene composite fiber according to Example 4.

비교 예 2에 따른 그래핀 섬유 제조Graphene fiber preparation according to Comparative Example 2

상술된 실시 예 4에서, 탄소나노튜브를 생략하여 그래핀 섬유를 제조하였다. In Example 4 described above, graphene fibers were prepared by omitting carbon nanotubes.

도 13은 본 발명의 실시 예 4 및 실시 예 5에 따른 그래핀 복합 섬유, 및 비교 예 2에 따른 그래핀 섬유를 촬영한 SEM 사진이다. 13 is a SEM photograph of the graphene composite fibers according to Examples 4 and 5 and the graphene fibers according to Comparative Example 2 of the present invention.

도 13을 참조하면, 본 발명의 실시 예 4 및 실시 예 5에 따른 그래핀 복합 섬유 및 비교 예 2에 따른 그래핀 섬유의 표면을 SEM 촬영하였다. 도 13의 (a)는 비교 예 2에 따른 그래핀 섬유의 SEM 사진이고, 도 13의 (b)는 실시 예 4에 따른 그래핀 복합 섬유의 SEM 사진이고, 도 13의 (c)는 실시 예 5에 따른 그래핀 복합 섬유의 SEM 사진이다. 도 13에서 알 수 있듯이, 1차원 물질인 탄소나노튜브 및 2차원 물질인 그래핀 나노리본이 그래핀 복합 섬유 내에 그래핀 시트와 함께 제공된 것을 확인할 수 있다. Referring to FIG. 13, the surface of the graphene composite fibers according to Examples 4 and 5 and the graphene fibers according to Comparative Example 2 were SEM photographed. Figure 13 (a) is a SEM photograph of the graphene fibers according to Comparative Example 2, Figure 13 (b) is a SEM photograph of the graphene composite fibers according to Example 4, Figure 13 (c) is an example SEM image of graphene composite fibers according to 5. As can be seen in FIG. 13, it can be seen that the graphene nanoribbons, which are carbon nanotubes and two-dimensional materials, are provided with graphene sheets in the graphene composite fiber.

도 14는 본 발명의 실시 예 4 및 실시 예 5에 따른 그래핀 복합 섬유, 및 비교 예 2에 따른 그래핀 섬유의 기계적 특성을 평가한 그래프이고, 도 15는 본 발명의 실시 예 실시 예 4 및 실시 예 5에 따른 그래핀 복합 섬유, 및 비교 예 2에 따른 그래핀 섬유의 전기적 특성을 평가한 그래프이다. 14 is a graph evaluating the mechanical properties of the graphene composite fibers according to Examples 4 and 5 of the present invention, and the graphene fibers according to Comparative Example 2, and FIG. 15 shows Examples 4 and 4 of the present invention. Graphene composite fiber according to Example 5, and graphene to evaluate the electrical properties of the graphene fiber according to Comparative Example 2.

도 14및 도 15를 참조하면, 실시 예 4 및 실시 예 5에 따른 그래핀 복합 섬유, 및 비교 예 2에 따른 그래핀 섬유에 대해서, 기계적 전단 물성 및 전기적 특성을 평가하였다. 도 14및 도 15에서 알 수 있듯이, 탄소나노튜브 및 그래핀 나노리본이 첨가된 실시 예 4 및 5에 따른 그래핀 복합 섬유의 경우, 비교 예 2에 따른 복합 섬유와 비교하여, 기계적 물성 및 전기적 특성이 우수한 것을 확인할 수 있다. 14 and 15, the mechanical shear and electrical properties of the graphene composite fibers according to Examples 4 and 5 and the graphene fibers according to Comparative Example 2 were evaluated. As can be seen in Figures 14 and 15, in the case of the graphene composite fibers according to Examples 4 and 5 to which carbon nanotubes and graphene nanoribbons are added, compared to the composite fibers according to Comparative Example 2, mechanical properties and electrical It can be confirmed that the characteristics are excellent.

도 16은 본 발명의 실시 예 4에 따른 그래핀 복합 섬유 및 비교 예 2에 따른 그래핀 섬유의 인장 테스트 결과 그래프이다. 16 is a graph showing a tensile test result of the graphene composite fiber according to Example 4 of the present invention and the graphene fiber according to Comparative Example 2.

도 16을 참조하면, 실시 예 4에 따른 그래핀 복합 섬유 및 비교 예 2에 따른 그래핀 섬유에 대해서 인장 테스트를 수행하였다. 실시 예 4에 따라서 탄소나노튜브를 첨가하는 경우, 기계적 강도와 인장도가 증가한 것을 확인할 수 있다. Modulus 또한 증가한 것을 통해, 첨가된 탄소나토뷰브가 그래핀 시트간 인력을 강하게 보강해주는 것을 알 수 있다. Referring to FIG. 16, a tensile test was performed on the graphene composite fiber according to Example 4 and the graphene fiber according to Comparative Example 2. When adding carbon nanotubes according to Example 4, it can be seen that the mechanical strength and tensile strength increased. Modulus has also increased, indicating that the added carbon nanotubules strongly reinforce the inter-graphene attraction.

도 17은 본 발명의 실시 예 4에 따른 그래핀 복합 섬유 및 비교 예 2에 따른 그래핀 섬유의 꼬임 테스트 결과이다. 17 is a twist test results of the graphene composite fiber according to Example 4 and the graphene fiber according to Comparative Example 2 of the present invention.

도 17을 참조하면, 실시 예 4에 따른 그래핀 복합 섬유 및 비교 예 2에 따른 그래핀 섬유의 꼬임 횟수에 따라 소요되는 스트레스를 측정하였다. 실시 예 4에 따라서 탄소나노튜브를 첨가하는 경우, 기계적 강도와 인장도가 증가하였다. Modulus 또한 증가한 것을 통해, 첨가된 탄소나토뷰브가 그래핀 시트간 가교 역할을 수행하는 것을 알 수 있다.Referring to FIG. 17, the stress required according to the number of twists of the graphene composite fiber according to Example 4 and the graphene fiber according to Comparative Example 2 was measured. When carbon nanotubes were added according to Example 4, mechanical strength and tensile strength were increased. Modulus also increased, it can be seen that the added carbon nanotubules play a role of cross-linking between graphene sheets.

탄소나노튜브 및 그래핀 나노리본 외에, 다양한 이종 물질을 포함하는 그래핀 복합 섬유에 대해서 전기 전도도를 측정하여, 아래의 [표 2]에 도시하였다. [표 2]에서 화학적 환원 그래핀은 80℃ 조건에서 30%의 HI 용액을 이용하여 그래핀 산화물을 환원한 것이고, 고온 환원 그래핀은 1100℃ 조건에서 아르곤 분위기에서 그래핀 산화물을 환원한 것이고, 초 고온 환원 그래핀은 2800℃ 조건에서 아르곤 분위기에서 그래핀 산화물을 환원한 것이다.In addition to carbon nanotubes and graphene nanoribbons, the electrical conductivity of the graphene composite fibers including various heterogeneous materials was measured and shown in Table 2 below. In Table 2, the chemically reduced graphene is a graphene oxide reduced using a 30% HI solution at 80 ° C., and the high temperature reduced graphene is a graphene oxide reduced at 1100 ° C. in an argon atmosphere. The ultra high temperature reduced graphene is a graphene oxide reduced in an argon atmosphere at 2800 ° C.

이종 물질의 종류Type of heterogeneous substance Conductivity(S/cm)Conductivity (S / cm) 화학적 환원 그래핀Chemically reduced graphene 1.0E+021.0E + 02 Double wall carbon nanotube/화학적 환원 그래핀Double wall carbon nanotube / chemical reduced graphene 1.4E+021.4E + 02 질소 도핑된 그래핀Nitrogen Doped Graphene 2.5E+022.5E + 02 Double wall carbon nanotube/고온 환원 그래핀Double wall carbon nanotube / high temperature reduced graphene 4.0E+024.0E + 02 질소 도핑된 Double wall carbon nanotube/화학적 환원 그래핀Nitrogen doped double wall carbon nanotube / chemically reduced graphene 4.8E+024.8E + 02 은 나노와이어/고온 환원 그래핀Silver Nanowires / High Temperature Reduced Graphene 5.4E+025.4E + 02 은 나노와이어/초 고온 환원 그래핀Silver Nanowires / Ultra High Temperature Reduced Graphene 7.1E+027.1E + 02 Double wall carbon nanotube/초 고온 환원 그래핀Double wall carbon nanotube / ultra high temperature reduced graphene 7.9E+027.9E + 02 Multi wall carbon nanotube/고온 환원 그래핀Multi wall carbon nanotube / high temperature reduced graphene 8.5E+028.5E + 02 고온 환원 그래핀High temperature graphene 8.9E+028.9E + 02 Single wall carbon nanotube/고온 환원 그래핀Single wall carbon nanotube / high temperature reduced graphene 9.0E+029.0E + 02 질소 도핑된 Single wall carbon nanotube/고온 환원 그래핀Nitrogen doped single wall carbon nanotube / high temperature reduced graphene 1.3E+031.3E + 03 초고온 환원 그래핀Ultra High Temperature Graphene 1.7E+031.7E + 03

이상, 본 발명을 바람직한 실시 예를 사용하여 상세히 설명하였으나, 본 발명의 범위는 특정 실시 예에 한정되는 것은 아니며, 첨부된 특허청구범위에 의하여 해석되어야 할 것이다. 또한, 이 기술분야에서 통상의 지식을 습득한 자라면, 본 발명의 범위에서 벗어나지 않으면서도 많은 수정과 변형이 가능함을 이해하여야 할 것이다.As mentioned above, although this invention was demonstrated in detail using the preferable embodiment, the scope of the present invention is not limited to a specific embodiment, Comprising: It should be interpreted by the attached Claim. In addition, those skilled in the art should understand that many modifications and variations are possible without departing from the scope of the present invention.

본 발명의 실시 예에 따른 그래핀 복합 섬유는, 전선, 전자파 차폐 필러 등 다양한 산업 분야에 이용될 수 있다. Graphene composite fiber according to an embodiment of the present invention can be used in a variety of industries, such as electric wire, electromagnetic shielding filler.

Claims (9)

그래핀 산화물(graphene oxide)을 포함하는 베이스 용액을 준비하는 단계; Preparing a base solution including graphene oxide; 상기 베이스 용액에, 기능성 물질을 제공하여 복합 용액을 제조하는 단계; Preparing a complex solution by providing a functional material to the base solution; 상기 복합 용액을 응고 용액 내에 방사시켜, 상기 그래핀 산화물 및 상기 기능성 물질을 포함하는 베이스 섬유를 제조하는 단계; 및Spinning the composite solution into a coagulation solution to produce a base fiber comprising the graphene oxide and the functional material; And 상기 베이스 섬유 내의 상기 그래핀 산화물을 환원시켜, 그래핀 시트 및 상기 기능성 물질을 포함하는 복합 섬유를 제조하는 단계를 포함하되,Reducing the graphene oxide in the base fiber to produce a composite fiber comprising a graphene sheet and the functional material, 상기 기능성 물질은 상기 그래핀 시트 사이의 인력을 향상시키는 것을 포함하는 그래핀 복합 섬유의 제조 방법. The functional material is a graphene composite fiber manufacturing method comprising improving the attractive force between the graphene sheet. 제1 항에 있어서, The method of claim 1, 상기 기능성 물질은, 파티클(particle) 형상, 로드(rod) 형상, 와이어(wire) 형상, 및 나노시트(nanosheet) 형상 중 어느 하나의 형상을 갖는 그래핀 복합 섬유의 제조 방법.The functional material is a graphene composite fiber manufacturing method of any one of particle shape, rod shape, wire shape, and nanosheet (nanosheet) shape. 제1 항에 있어서,The method of claim 1, 상기 베이스 용액 내의 상기 그래핀 산화물 및 상기 기능성 물질의 비율에 따라, 상기 복합 섬유의 전기 전도도, 내구성(strength), 신장률(elongation), 및 탄성률(modulus)이 제어되는 것을 포함하는 그래핀 복합 섬유의 제조 방법. The electrical conductivity, strength, elongation, and modulus of the composite fiber are controlled according to the ratio of the graphene oxide and the functional material in the base solution. Manufacturing method. 제1 항에 있어서, The method of claim 1, 상기 베이스 용액 내의 상기 그래핀 산화물의 농도가 증가함에 따라, 상기 복합 섬유의 신장률이 증가하는 것을 포함하는 그래핀 복합 섬유의 제조 방법. As the concentration of the graphene oxide in the base solution, the method of producing a graphene composite fiber comprising increasing the elongation of the composite fiber. 제1 항에 있어서, The method of claim 1, 상기 복합 용액의 방사 속도가 감소함에 따라, 상기 복합 섬유의 신장률이 증가하는 것을 포함하는 그래핀 복합 섬유의 제조 방법.Method of producing a graphene composite fiber comprising increasing the elongation of the composite fiber as the spinning speed of the composite solution decreases. 제1 항에 있어서, The method of claim 1, 상기 베이스 섬유를 제조하는 단계는, Producing the base fiber, 상기 베이스 섬유를 상기 응고 용액으로부터 분리하는 단계; 및Separating the base fiber from the coagulation solution; And 분리된 상기 베이스 섬유를 권취하는 단계를 포함하는 그래핀 복합 섬유의 제조 방법. Graphene composite fiber manufacturing method comprising the step of winding the separated base fiber. 복수의 그래핀 시트, 및 복수의 상기 그래핀 시트 사이에 배치되는 기능성 구조체를 포함하되, A plurality of graphene sheets, and a functional structure disposed between the plurality of graphene sheets, 상기 기능성 구조체는, 기능성 물질이 파티클(particle) 형상, 로드(rod) 형상, 와이어(wire) 형상, 및 나노시트(nanosheet) 형상 중 어느 하나의 형상을 갖는 것을 포함하고, 복수의 상기 그래핀 시트 사이의 인력을 증가시키는 것을 포함하는 그래핀 복합 섬유.The functional structure may include a functional material having any one of a particle shape, a rod shape, a wire shape, and a nanosheet shape, and the plurality of graphene sheets Graphene composite fiber comprising increasing the attraction between. 제1 항에 있어서, The method of claim 1, 상기 기능성 물질은, carbon nanotube, silver nanowire, copper nanowire, graphene nanoribbon, h-BN, BP, MoS2, WS2, TiS2, TaS2, Ti2C, (Ti0.5Nb0.5)2C, Nb2C, Mo2C, Ti3C2, Ti3CN, Zr3C2, Hf3C2, Ti4N3, Nb4C3, Ta4C3, Mo2TiC2, Cr2TiC2, 및 Mo2Ti2C3 중 적어도 어느 하나를 포함하는 그래핀 복합 섬유의 제조 방법.The functional material is carbon nanotube, silver nanowire, copper nanowire, graphene nanoribbon, h-BN, BP, MoS 2 , WS 2 , TiS 2 , TaS 2 , Ti 2 C, (Ti 0.5 Nb 0.5 ) 2 C, Nb 2 C, Mo 2 C, Ti 3 C 2 , Ti 3 CN, Zr 3 C 2 , Hf 3 C 2 , Ti 4 N 3 , Nb 4 C 3 , Ta 4 C 3 , Mo 2 TiC 2 , Cr 2 TiC 2 , And Mo 2 Ti 2 C 3 A method for producing a graphene composite fiber comprising at least one. 제1 항에 있어서, The method of claim 1, 상기 기능성 물질의 함량에 따라, 상기 그래핀 복합 섬유의 전기 전도도, 내구성(strength), 신장률(elongation), 및 탄성률(modulus)이 제어되는 것을 포함하는 그래핀 복합 섬유의 제조 방법.According to the content of the functional material, the graphene composite fiber electrical conductivity, strength (strength), elongation (elongation), and modulus (modulus) of manufacturing a graphene composite fiber comprising controlling.
PCT/KR2019/003196 2018-03-19 2019-03-19 Graphene composite fiber and manufacturing method therefor Ceased WO2019182331A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR20180031395 2018-03-19
KR10-2018-0031395 2018-03-19

Publications (1)

Publication Number Publication Date
WO2019182331A1 true WO2019182331A1 (en) 2019-09-26

Family

ID=67986292

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2019/003196 Ceased WO2019182331A1 (en) 2018-03-19 2019-03-19 Graphene composite fiber and manufacturing method therefor

Country Status (2)

Country Link
KR (1) KR102712431B1 (en)
WO (1) WO2019182331A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112376121A (en) * 2020-10-27 2021-02-19 山东科技大学 Preparation method and application of folded graphene fibers for improving shear orientation of graphene sheets
CN113270588A (en) * 2020-02-17 2021-08-17 天津大学 Graphene-carbon nanotube composite film material and preparation method and application thereof
CN113737302A (en) * 2021-07-22 2021-12-03 常州恒利宝纳米新材料科技有限公司 Method for modifying nylon 6 fibers by using graphene oxide
CN115198394A (en) * 2022-07-14 2022-10-18 山东科技大学 A kind of graphene composite fiber modified by nitrogen-doped hollow carbon sphere, preparation method and application
CN119340016A (en) * 2024-12-18 2025-01-21 湖南华菱线缆股份有限公司 Astronaut out-of-vehicle cable
CN120590123A (en) * 2025-06-26 2025-09-05 揭阳市好夫曼建材有限公司 Environmentally friendly building material regenerated from organic waste and preparation method thereof

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102268153B1 (en) * 2019-11-29 2021-06-21 한양대학교 산학협력단 Fabrication method for graphene fiber using organic solvent as cogulant and graphene fiber fabricated by the same
KR102440348B1 (en) * 2020-10-07 2022-09-05 한양대학교 산학협력단 Graphene/CNT composite fiber and fabrication method for the same
KR102582289B1 (en) * 2020-10-26 2023-09-26 한국화학연구원 Composite material for flexible electrode and manufacturing method thereof
CN115132990B (en) * 2022-07-04 2025-02-18 江苏科技大学 MoS (MoS)2Graphene/Mxene composite film and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101182380B1 (en) * 2011-03-15 2012-09-12 한양대학교 산학협력단 Hybrid polymer composite fibers comprising graphene and carbon nanotubes
KR20170125444A (en) * 2016-05-04 2017-11-15 재단법인차세대융합기술연구원 Wet spinningMethod for preparing GO-CNT composite fibers, GO-Graphene composite fibers, GO-Grephene-CNT composite fibers
KR101812534B1 (en) * 2016-06-27 2017-12-29 재단법인 차세대융합기술연구원 Method for preparing GO-CNT composite fibers, GO-Graphene composite fibers, GO-Graphene-CNT composite fibers
KR20180019130A (en) * 2018-01-19 2018-02-23 재단법인차세대융합기술연구원 Method for preparing graphene oxide fibers, graphene fibers or their composite fibers by using wet spinning induced by electric field
KR20180021360A (en) * 2016-08-19 2018-03-02 한양대학교 산학협력단 Graphene fiber composite and method of fabricating of the same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101386765B1 (en) 2013-05-23 2014-04-21 동국대학교 산학협력단 Graphene-coated conductive fibers and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101182380B1 (en) * 2011-03-15 2012-09-12 한양대학교 산학협력단 Hybrid polymer composite fibers comprising graphene and carbon nanotubes
KR20170125444A (en) * 2016-05-04 2017-11-15 재단법인차세대융합기술연구원 Wet spinningMethod for preparing GO-CNT composite fibers, GO-Graphene composite fibers, GO-Grephene-CNT composite fibers
KR101812534B1 (en) * 2016-06-27 2017-12-29 재단법인 차세대융합기술연구원 Method for preparing GO-CNT composite fibers, GO-Graphene composite fibers, GO-Graphene-CNT composite fibers
KR20180021360A (en) * 2016-08-19 2018-03-02 한양대학교 산학협력단 Graphene fiber composite and method of fabricating of the same
KR20180019130A (en) * 2018-01-19 2018-02-23 재단법인차세대융합기술연구원 Method for preparing graphene oxide fibers, graphene fibers or their composite fibers by using wet spinning induced by electric field

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113270588A (en) * 2020-02-17 2021-08-17 天津大学 Graphene-carbon nanotube composite film material and preparation method and application thereof
CN112376121A (en) * 2020-10-27 2021-02-19 山东科技大学 Preparation method and application of folded graphene fibers for improving shear orientation of graphene sheets
CN113737302A (en) * 2021-07-22 2021-12-03 常州恒利宝纳米新材料科技有限公司 Method for modifying nylon 6 fibers by using graphene oxide
CN115198394A (en) * 2022-07-14 2022-10-18 山东科技大学 A kind of graphene composite fiber modified by nitrogen-doped hollow carbon sphere, preparation method and application
CN115198394B (en) * 2022-07-14 2024-02-06 山东科技大学 Nitrogen-doped hollow carbon sphere modified graphene composite fiber, preparation method and application
CN119340016A (en) * 2024-12-18 2025-01-21 湖南华菱线缆股份有限公司 Astronaut out-of-vehicle cable
CN120590123A (en) * 2025-06-26 2025-09-05 揭阳市好夫曼建材有限公司 Environmentally friendly building material regenerated from organic waste and preparation method thereof

Also Published As

Publication number Publication date
KR102712431B1 (en) 2024-10-02
KR20190110056A (en) 2019-09-27

Similar Documents

Publication Publication Date Title
WO2019182331A1 (en) Graphene composite fiber and manufacturing method therefor
WO2017191887A1 (en) Method for producing graphene oxide/carbon nanotube composite fiber, graphene oxide/graphene composite fiber or graphene oxide/graphene/carbon nanotube composite fiber using wet spinning process
WO2017188564A1 (en) Method for manufacturing graphene oxide fiber, graphene fiber, and graphene or graphene (oxide) composite fiber by using electric field-induced wet spinning process
JP5633821B2 (en) Graphene oxide sheet, article containing graphene-containing material obtained by reducing the same, and method for producing the same
WO2016182100A1 (en) Three-dimensional mesh structure form electrode for electrochemical device, method for producing same, and electrochemical device comprising same
WO2018004099A1 (en) Graphene oxide/carbon nanotube composite fiber having heterojunction structure, and method for manufacturing graphene oxide/graphene composite fiber or graphene oxide/graphene/carbon nanotube composite fiber
WO2014189270A1 (en) Electromagnetic wave shielding sheet comprising carbon composite fiber manufactured by electrospinning and method for manufacturing same
CN1109114A (en) Polyvinyl Alcohol Based Water Soluble Fiber
WO2012108607A1 (en) Manufactured carbon nanotube fibers
WO2010056061A2 (en) A single-crystalline germanium cobalt nanowire, a germanium cobalt nanowire structure, and a fabrication method thereof
KR101928911B1 (en) Method for preparing graphene oxide fibers, graphene fibers or their composite fibers by using wet spinning induced by electric field
WO2015083860A1 (en) Method of manufacturing transparent electrode using electrospinning method, and transparent electrode formed using same
WO2018004092A1 (en) Nanostructure network and method for manufacturing same
WO2015163595A1 (en) Method for producing graphene-based nano carbon fiber using inter-layer self-assembly
WO2022075565A1 (en) Lithium-sulfur battery cathode using fabric material, lithium-sulfur battery comprising same, and manufacturing method therefor
WO2010140853A2 (en) Sea-island fibres and artificial leather, and a production method therefor
WO2017150770A1 (en) Fibrous electrode having buckle structure, production method therefor and supercapacitor using same
WO2019177223A1 (en) Manufacturing method comprising multiple conductive treatments for highly conductive polymer thin film
WO2013095045A1 (en) Novel secondary structure of carbon nanostructures, assembly thereof, and composite comprising same
US20240318358A1 (en) Polytetrafluoroethylene porous fiber and manufacturing and modifying process thereof
WO2020032403A1 (en) Conductive composite using conductive composite solution, and method for producing same
WO2023013938A1 (en) Conductive thin film production method using expandable graphite
KR20150070468A (en) Transparent electrode using transparent polyimide layer embedded with silver nanowire network and fabrication method thereof
WO2019182362A1 (en) Graphene oxide-dyed fiber and manufacturing method therefor
WO2020076113A1 (en) Conductive fiber and manufacturing method therefor

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19772162

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19772162

Country of ref document: EP

Kind code of ref document: A1