WO2018004099A1 - 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 - Google Patents

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 Download PDF

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WO2018004099A1
WO2018004099A1 PCT/KR2017/001239 KR2017001239W WO2018004099A1 WO 2018004099 A1 WO2018004099 A1 WO 2018004099A1 KR 2017001239 W KR2017001239 W KR 2017001239W WO 2018004099 A1 WO2018004099 A1 WO 2018004099A1
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graphene
graphene oxide
composite fiber
carbon nanotube
nanotube composite
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French (fr)
Korean (ko)
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박상윤
신민균
김혁준
여창수
조윤제
조강래
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재단법인차세대융합기술연구원
주식회사 퓨리텍
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    • 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
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • 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
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/06—Washing or drying
    • 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
    • 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
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • 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
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/34—Core-skin structure; Spinnerette packs therefor
    • 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
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • 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
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06H—MARKING, INSPECTING, SEAMING OR SEVERING TEXTILE MATERIALS
    • D06H5/00—Seaming textile materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/40—Fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the present invention relates to a method for producing a graphene oxide / carbon nanotube composite fiber, graphene oxide / graphene composite fiber or graphene oxide / graphene / carbon nanotube composite fiber having a heterojunction structure (heterojunction structure) .
  • Nano-carbon-based materials such as graphene and carbon-nanotubes (CNT) are excellent in electrical properties, thermal properties, flexibility, and mechanical strength. It is an advanced material that is attracting attention as a material.
  • Graphene is a two-dimensional planar carbon allotrope in which hexagonal honeycomb is formed by sp 2 hybrids of carbon atoms.
  • the thickness of single layer graphene is 0.2 to 0.3 nm, the thickness of one carbon atom, and single layer graphene, as well as 10 layers
  • the stacked graphene structure of about two or three layers also belongs to the category of conventional graphene.
  • CVD chemical vapor deposition
  • epitaxial growth epitaxial growth
  • nonoxidative exfoliation chemical exfoliation
  • chemical exfoliation and the like are known.
  • CVD chemical vapor deposition
  • epitaxial growth and non-oxidation exfoliation have advantages of obtaining high quality pure graphene, but the yield of graphene is difficult to mass produce, and manufacturing costs are high.
  • manufacturing costs are high.
  • the chemical exfoliation method is graphene oxide (oxidized graphite) formed by oxidizing the graphite with a strong acid (nitric acid, sulfuric acid, etc.) and mechanically (ultrasonic grinding or homogenizer grinding) to form an oxygen functional group as shown in FIG. 'GO') [FIG. 1 (a)], followed by removal of oxygen functional groups through a series of chemical reduction [FIG. 1 (b)] and / or thermal reduction processes [FIG. 1 (c)].
  • a method for producing the fin it is called 'reduced GO (' rGO ') to distinguish it from pure graphene.
  • the 'reduced graphene oxide (rGO)' generates some carbon defects on the surface of graphene during oxidation and reduction of graphene, and it is difficult to completely remove oxygen functional groups, compared to pure graphene.
  • the electrical conductivity is somewhat inferior, it is the most widely used in that it can be mass-produced, the manufacturing cost is low, and there is no big difference in electrical conductivity and thermal conductivity compared to pure graphene.
  • Graphene oxide has completely different electrical properties from graphene due to oxygen functional groups generated during oxidation.
  • Graphene itself is a carbon allotrope, so it is nonpolar and hydrophobic, and has 100 times higher electrical conductivity than copper at room temperature, whereas graphene oxide is due to oxygen functional groups (epoxy, hydroxy, carboxyl, etc.) formed on the surface / edges. It is polar, hydrophilic and has insulators or extremely low electrical and thermal conductivity.
  • graphene oxide belongs to the intermediate of 'reduced graphene oxide (rGO)'
  • the oxygen functional groups formed on graphene oxide facilitate the surface modification and the bonding of functional materials for biological applications. Is regarded as a promising substance. For example, detection of a target substance (electrical signal or fluorescence, by conjugation of a biomolecule or a polymer such as nucleic acid, (single chain) DNA, RNA, aptamer, peptide, protein, antibody, growth factor, enzyme, etc. to the surface of graphene oxide) Quenching).
  • a target substance electrical signal or fluorescence, by conjugation of a biomolecule or a polymer such as nucleic acid, (single chain) DNA, RNA, aptamer, peptide, protein, antibody, growth factor, enzyme, etc.
  • Carbon nanotubes are cylindrical allotropic carbon allotropes in which hexagonal honeycombs are formed by sp 2 hybrids of carbon atoms, and single-walled CNTs (SWNT) depending on the number of bonds forming a wall. , Double-walled CNTs (DWNT), and multi-walled CNTs (MWNT).
  • Carbon nanotube production methods are known as chemical vapor deposition, arc discharge, laser evaporation, plasma torch, ion bombardment, and the like.
  • the chemical vapor deposition method has the advantage of controlling mass production and growth of carbon nanotubes.
  • Electrodes electrode active materials
  • touch panels flexible displays
  • high efficiency solar cells heat-dissipating films, coating materials, and seawater desalination It can be used in various fields such as filters, secondary battery electrodes, ultra fast chargers.
  • Figure 2 is a schematic diagram showing the process (b) of the graphene oxide (or graphene, nano carbon tube) is aligned in the wet spinning method (a) and wet spinning process of the graphene oxide.
  • the graphene oxide spinning solution is discharged into a coagulation bath through a spinneret (discharge nozzle) to be aggregated.
  • the alignment process of graphene oxide is non-directional and disorderedly located in a syringe.
  • Graphene oxide aligned with the axial direction of the nozzle by shear stress between the fluids moving along the fine inner diameter spinning nozzle (I), and discharged into the coagulation bath, and then aligned graphene oxide are solvent change in the coagulation bath.
  • Gel fibers are formed by self-assembly (II), and the gel fibers are made of graphene oxide fibers through a series of stretching, washing and drying processes.
  • the prepared graphene oxide fiber is subjected to an additional process of thermally or chemically reducing the graphene oxide fiber for electrical properties.
  • the wet spinning process of graphene and carbon nanotubes is also not significantly different from the above-described graphene oxide spinning process, but the coagulation bath properties are completely different as described below. Or it is virtually impossible to manufacture graphene oxide / carbon nanotube composite fiber.
  • Graphene and carbon nanotubes are nonpolar and hydrophobic, and are agglomerated with each other by an interlayer van der Waals force, so they do not disperse in water at all and do not disperse well in most organic solvents. Therefore, graphene and carbon nanotube dispersions are prepared by using a surfactant and ultrasonication, and used as a spinning solution.
  • polyvinyl alcohol PMMA
  • polymethyl methacrylate PMMA
  • polyethyleneimine PEI
  • polyvinylpyrrolidone PVP
  • polyethylene oxide PEO
  • Water-soluble polymers such as these, are known.
  • the graphene spinning solution or carbon nanotube spinning solution is spun into the coagulation bath through a nozzle, the water-soluble polymer penetrates on the spinning fiber to replace the surfactant to form a polymer matrix on the fiber, thereby forming graphene fibers and carbon nanotube fibers. More specifically, graphene / polymer composite fiber and carbon nanotube / polymer composite fiber are manufactured.
  • Korean Patent Publication No. 10-2012-0105179 discloses a) preparing a dispersion by dispersing graphene (reduced graphene or reduced graphene oxide) in a solvent with a surfactant; And b) it is disclosed a graphene / PVA composite fiber manufacturing method comprising the step of incorporating the dispersion into a polymer (PVA) solution, wet spinning and drying to produce a fiber,
  • PVA polymer
  • Republic of Korea Patent Publication No. 10-2012-0107026 discloses a method for producing a graphene fiber by removing the PVA polymer by additional heat treatment or strong acid treatment to the graphene / PVA composite fiber prepared in the patent.
  • Republic of Korea Patent No. 10-1182380 discloses a method for producing a graphene / carbon nanotube / PVA composite fiber by spinning the graphene / carbon nanotube dispersion in a PVA coagulation bath, the graphene oxide (graphene oxide ( Reduced graphene oxide (rGO) or chemically modified reduced graphene oxide (RCCG), rather than GO).
  • graphene oxide graphene oxide ( Reduced graphene oxide (rGO) or chemically modified reduced graphene oxide (RCCG)
  • Vigolo et al. Prepared a 0.35 wt% SWNT dispersion with a surfactant (1.0 wt% sodium dodecyl sulfonate (SDS)) and then spun it into a 5 wt% polyvinyl alcohol (PVA) / distilled water coagulation bath to produce carbon nanotube fibers for the first time.
  • a surfactant 1.0 wt% sodium dodecyl sulfonate (SDS)
  • PVA polyvinyl alcohol
  • SWNT dispersions using surfactants of cetyltrimethylammonium bromide (CTAB), sodium dodecylbenzenesulfonate (SDBS), and lithium dodecylsulfonate (LDS), followed by polyethyleneimine (PEI) / distilled water coagulation bath. Spinned to make SWNT / PEI fibers ( Adv. Mater . 2005, 17, No. 8, April 18). It was confirmed that the prepared SWNT / PEI fiber has increased electrical conductivity by 100 times compared to the SWNT / PVA composite fiber.
  • CTAB cetyltrimethylammonium bromide
  • SDBS sodium dodecylbenzenesulfonate
  • LDS lithium dodecylsulfonate
  • PEI polyethyleneimine
  • CTAB chitosan
  • CaCl 2 NaOH, KOH, and the like
  • coagulation baths of graphene oxide and CTAB is mainly used.
  • the aggregation process of graphene oxide is based on non-solvent precipitation using positively charged molecules such as CTAB and dispersion destabilization using reducing agent (NaOH) ( Nat. Comm. 2011, 2, 571.) , Polyelectrolyte complexation using graphene oxide cross-linking by divalent ions (Ca 2+ ), CaCl 2, etc. ( Adv. Mater. 2013, 25, 188.), chitosan, etc. ( Adv. Func. Mater . 2013, 23, 5345.) and the like are known.
  • graphene oxide and graphene / carbon nanotubes are different from each other in the coagulation bath characteristics, and conventionally known wet spinning processes are graphene oxide / carbon nanotube composite fibers, graphene oxide / graphene composite fibers or graphene Fin oxide / (graphene + carbon nanotube) composite fiber manufacturing is impossible.
  • CTAB a coagulant of graphene oxide
  • PVA acts as a coagulant of carbon nanotubes and graphene, but it acts as a dispersant in the case of graphene oxide.
  • the graphene oxide / carbon nanotube dispersion is spun into a PVA coagulation bath, carbon nanotubes and graphene Although it coagulates, the graphene oxide does not coagulate and thus no fibrosis occurs.
  • the graphene and carbon nanotubes have excellent electrical conductivity and thermal conductivity, and the fibers produced are also excellent in electrical conductivity and thermal conductivity.
  • graphene oxide has low electrical conductivity and thermal conductivity, and the fiber produced also has an insulator, low electrical conductivity, and thermal conductivity.
  • Graphene or carbon nanotube-based nanomaterials require high electrical conductivity and porosity (surface area, energy storage capacity) in order to be used in the electrode materials of batteries and supercapacitors. It can be improved through the composite of nanomaterials such as nanotubes.
  • Composite fibers composed of graphene oxide and carbon nanotubes (or graphene) can control electrical conductivity and thermal conductivity according to the content ratio of GO and CNT, and maximize mechanical properties such as tensile strength, elasticity, and elongation. Can be.
  • rGO and CNT inevitably cause defects and particle size reduction during the sonication process, whereas GO used in the wet process has good mechanical properties because it uses GO having a large average particle diameter of about several tens of um. Excellent conductivity
  • graphene oxide is capable of introducing various functional materials such as biomolecules (nucleic acid, aptamers, enzymes, etc.) and polymers, compared to graphene and carbon nanotubes, whereas for electrical conductivity, an additional chemical / thermal reduction process or post-treatment is possible. A process is required, and the reduction or aftertreatment process decomposes or destroys the functional material, thereby decreasing or losing the function. Therefore, development of graphene composite fibers having high physical properties without the above-described reduction process and post-treatment process is required.
  • An object of the present invention is to provide a method for producing a graphene oxide / carbon nanotube composite fiber, graphene oxide / graphene composite fiber or graphene oxide / graphene / carbon nanotube composite fiber.
  • the first coagulation component is preferably at least one selected from the group consisting of CTAB, chitosan, CaCl 2 , NaOH, KOH.
  • the second coagulation component is one selected from the group consisting of polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), polyethyleneimine (PEI), polyvinylpyrrolidone (PVP), polyethylene oxide (PEO) It is preferable that it is above.
  • PVA polyvinyl alcohol
  • PMMA polymethyl methacrylate
  • PEI polyethyleneimine
  • PVP polyvinylpyrrolidone
  • PEO polyethylene oxide
  • the bonding of the first gel fiber and the second gel fiber may be in side-by-side form.
  • the first gel fibers and the second gel fibers may have a twisted structure.
  • the bonding of the first gel fiber and the second gel fiber may be in the form of a sheath-core.
  • the hetero-bonded graphene oxide / carbon nanotube composite fiber, graphene oxide / graphene composite fiber or graphene oxide / graphene / carbon nanotube composite fiber prepared according to the present invention is a high porosity graphene oxide and electrical conductivity It contains both high carbon nanotubes or graphene and bonded in the form having a low interfacial resistance between these heterogeneous components it has a high porosity and conductivity can be usefully used as the electrode material of the battery, supercapacitor.
  • FIG. 1 is a schematic diagram of a graphene structure showing a process for generating a 'reduced graphene oxide (rGO)' from the graphene oxide (GO) according to the chemical peeling method.
  • FIG. 2 is a schematic diagram illustrating a process of arranging graphene oxide (or graphene, nano carbon tube) in a wet spinning method of graphene oxide (FIG. 2A) and a wet spinning process (FIG. 2B).
  • Figure 3 is a photograph showing the bonding process of the graphene oxide gel fibers and carbon nanotube gel fibers being manufactured by a roll-to-roll process.
  • Example 4 is an optical micrograph of a graphene oxide / carbon nanotube composite fiber having a heterojunction structure prepared according to Example 2 of the present invention.
  • Example 5 is an electron micrograph of the side of the graphene oxide / carbon nanotube composite fiber having a heterojunction structure prepared according to Example 2 of the present invention.
  • FIG. 6 is an electron micrograph of a cross section of a graphene oxide / carbon nanotube composite fiber having a heterojunction structure prepared according to Example 2 of the present invention.
  • the present inventors earnestly endeavored to develop a composite fiber in which graphene oxide and carbon nanotubes were bonded, and as a result, the cohesive force between gel fibers obtained by wet spinning graphene oxide and carbon nanotubes, respectively, was generated.
  • the present invention was completed by confirming that the bonded state was maintained as it was after bonding and washing with water.
  • heterojunction means that different components are bonded to each other.
  • hetero-bonded graphene oxide / carbon nanotube composite fiber, graphene oxide / graphene composite fiber or graphene oxide / graphene / carbon nanotube composite fiber manufacturing method according to the present invention
  • graphene oxide (GO) is prepared using a chemical exfoliation method.
  • Graphene oxide is prepared by oxidizing graphite using strong acid to produce expanded graphite oxide in which oxygen functional groups are introduced between graphene layers, and by ultrasonic pulverization or rapid heating on a solution.
  • Staudenmaier and Hamdi disclose a process for producing graphite oxide using a sulfuric acid / nitric acid mixture, but most graphene oxides oxidize graphite using a mixture of fuming sulfuric acid and sodium nitrate / potassium chlorate. It is prepared using the Hummers method or a variant thereof.
  • Graphene oxide has a structure in which various oxygen functional groups such as an epoxy group, a hydroxyl group, and a carboxyl group or a carbonyl group are formed at the surface or / and the terminal of the graphene.
  • the graphene oxide has an insulator, and has a low conductivity depending on the degree of oxidation and characteristics, but is insignificant compared to graphene or carbon nanotubes.
  • Graphene oxide according to the present invention includes a graphene oxide to which a functional material is attached.
  • the functional material is, for example, various sensing materials used for detection of a target material in the biosensor field.
  • the functional material may be a nucleic acid, DNA, RNA, aptamer, peptide, protein, antibody, growth factor, enzyme, fluorescent material, quencher, biomolecule, functional polymer.
  • the functional material may be formed in combination with a functional group of graphene oxide.
  • the electrical signal according to the functional material is provided through the graphene, carbon nanotubes of the conductive material of the composite fiber according to the present invention can provide a high detection force despite the low electrical signal.
  • the graphene oxide according to the present invention may include a chemically modified graphene oxide.
  • Chemical modification of graphene oxide can be prepared, for example, by reacting organic monomolecules with oxygen functional groups (epoxy groups, hydroxyl groups, carboxyl groups, etc.) of graphene oxide.
  • the organic monomolecule having an amine group reacts with the epoxy group of the graphene oxide to introduce the organic monomolecule into the graphene oxide as shown in the following reaction scheme ( Polymer (Korea), Vol. 35, No. 3, pp 265-271, 2011).
  • the graphene oxide is polar and hydrophilic by the oxygen functional group, it is well dispersed in a polar solvent such as water, an organic solvent, and a water / organic solvent.
  • Examples of the solvent for the graphene oxide include distilled water, dimethylformamide, methanol, ethanol, ethylene glycol, n-butanol, tert-butyl alcohol, isopropyl alcohol, n-propanol, ethyl acetate, dimethyl sulfoxide, tetrahydrofuran, and the like. Although it may be used, distilled water or distilled water / organic solvent is preferred.
  • Graphene oxide concentration is preferably 1 ⁇ 20 mg / mL (0.1 ⁇ 2wt%) compared to the spinning solution, but is not limited thereto.
  • the coagulation component of the graphene oxide (first coagulation component in the present invention) may be selected from the group consisting of CTAB, chitosan, CaCl 2 , NaOH, KOH, but is not limited thereto It doesn't work.
  • CTAB is most widely known as a coagulant of a cationic surfactant or graphene oxide. It is known that CaCl 2 cross-links and aggregates graphene oxides by divalent ions (Ca 2+ ) ( Adv. Mater. 2013, 25, 188.). NaOH and KOH are known to cause aggregation through reduction of graphene oxide as a reducing agent ( Nat. Comm. 2011, 2, 571.). Chitosan is known to aggregate graphene oxide by polyelectrolyte complexation ( Adv. Func. Mater . 2013, 23, 5345.)
  • the first coagulation component is water-soluble, and the coagulation bath of the present invention may be prepared by dissolving the first coagulation component in distilled water.
  • the solvent of the first coagulation component dimethylformamide, methanol, ethanol, ethylene glycol, n-butanol, tert-butyl alcohol, isopropyl alcohol, n-propanol, ethyl acetate, dimethyl sulfoxide, tetrahydrofuran, etc.
  • An organic solvent of may be used. Distilled water is preferred as the coagulation solvent in the present invention, but is not limited thereto.
  • the coagulant concentration of the first coagulation component may be used at a coagulation bath concentration (content wt%) known in the conventional wet spinning process of graphene oxide.
  • the CTAB concentration in the coagulation bath is 0.03 to 0.1 wt%, preferably 0.05 wt% (0.5 mg / mL), and CaCl 2 , NaOH, and KOH are 3-10 wt%, but are not limited thereto.
  • the first coagulation component When the graphene oxide dispersion is spun into a coagulation bath containing a first coagulation component through a spinneret (spinning nozzle), the first coagulation component gradually penetrates into the spinning solution, causing solvent substitution, thereby swelling the spinning solution and fibrosis (gelling). As it occurs, the soft graphene oxide gel fibers (the first gel fibers in the present invention) are formed.
  • Graphene according to the present invention can be prepared by mechanical peeling, chemical vapor deposition (CVD), epitaxial growth (Epitaxial Growth), non-oxidative exfoliation (Nonoxidative Exfoliation), but the above-described graphene oxide at high temperature heat treatment Or it is preferable to use reduced graphene oxide (rGO) prepared by chemical reduction.
  • CVD chemical vapor deposition
  • Epitaxial Growth epitaxial growth
  • Nonoxidative Exfoliation non-oxidative Exfoliation
  • rGO reduced graphene oxide
  • chemically modified graphene (CCG) and chemically modified reduced graphene (rCCG) may also be used. More preferably, the graphene according to the present invention is reduced graphene oxide (rGO).
  • reducing agents of graphene oxide include hydrazine, sodium hydrazine and hydrazine hydrate such as hydrazine, hydroquinone, sodium borohydride (NaBH 4 ), ascorbic acid, and glucose (glucose). Etc. may be used, but is not limited thereto.
  • Graphene (or reduced graphene oxide) has a nonpolar or very weak polarity and hydrophobicity, so it is dispersed in a solvent using a surfactant.
  • the surfactant may be sodium dodecylbenzenesulfonate (SDBS), sodium dodecylsulfonate (SDS), sodium lignosulfonate (SLS), sodium laureth sulfonate (SLES), lauryl ether sodium sulfonate (SLES), Sodium myreth sulfate, anionic surfactant having hydrophilic sulfonic acid group (SO 3 ⁇ ) of lithium dodecyl sulfonate (LDS), or cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC) , Cetylpyridinium chloride (CPC), dodecyltrimethylammonium bromide (DTAB), tetradecyltrimethylammonium
  • the graphene or graphene oxide is present in the form of a sheet piece, and may be referred to as "graphene flake”, “graphene sheet”, or “graphene crystal”.
  • the average diameter of the graphene flakes according to the present invention is several ⁇ m or more, and the number of layers of graphene or graphene oxide is preferably three or less layers.
  • Graphene concentration is preferably 1 ⁇ 20 mg / mL (0.1 ⁇ 2wt%) compared to the spinning solution, but is not limited thereto.
  • the coagulation component (second coagulation component in the present invention) of the carbon nanotube dispersion is polyvinyl alcohol (PVA), polymethylmethacrylate (PMMA), polyethyleneimine (PEI), polyvinylpyrrolidone (PVP). It may be selected from the group consisting of polyethylene oxide (PEO), but is not limited thereto.
  • PVA, PMMA, PEI, PVP, PEO is 2 to 40 wt%, preferably 5 to 10 wt%, but is not limited thereto.
  • the soft graphene gel fibers (second gel fibers in the present invention) are formed.
  • CNT carbon nanotubes
  • SWNT single-walled carbon nanotubes
  • DWNT double-walled carbon nanotubes
  • MWNT multi-walled carbon nanotubes
  • SWNT is more preferable in consideration of electrical conductivity and mechanical properties.
  • CNTs can be prepared by known methods such as chemical vapor deposition (CVD), arc discharge, laser evaporation, and the like.
  • Carbon nanotubes are non-polar and have strong van der Waals forces on the CNT sidewalls, so they are not easily dissolved or dispersed in polar solvents such as water and organic solvents. Therefore, in order to effectively disperse CNTs, it is desirable to disperse them using a surfactant and ultrasonic waves.
  • the above-described surfactants for dispersing graphene may be used in the same manner.
  • the surfactant concentration is important for CNT dispersion. If the concentration of surfactant is low, dispersion stability is low. If it is too high, osmotic pressure causes depletion-induced aggregation.
  • the wt% ratio of CNT and surfactant in the dispersion is preferably 1: 2 to 1: 3, but may vary depending on the type of surfactant.
  • the coagulation component of CNT is the same as the coagulation component of the graphene (second coagulation component).
  • the coagulation bath of the nano-carbon tube, graphene as the second coagulation component is known in various documents.
  • Vigolo et al. Prepared a 0.35 wt% SWNT dispersion with a surfactant (1.0 wt% sodium dodecyl sulfonate (SDS)) and then spun it into a 5 wt% polyvinyl alcohol (PVA) / distilled water coagulation bath to produce carbon nanotube fibers for the first time.
  • a surfactant 1.0 wt% sodium dodecyl sulfonate (SDS)
  • PVA polyvinyl alcohol
  • distilled water coagulation bath to produce carbon nanotube fibers for the first time.
  • SWNT dispersions using surfactants of cetyltrimethylammonium bromide (CTAB), sodium dodecylbenzenesulfonate (SDBS), and lithium dodecylsulfonate (LDS), followed by polyethyleneimine (PEI) / distilled water coagulation bath. Spinned to make SWNT / PEI fibers ( Adv. Mater . 2005, 17, No. 8, April 18). It was confirmed that the prepared SWNT / PEI fiber has increased electrical conductivity by 100 times compared to the SWNT / PVA composite fiber.
  • CTAB cetyltrimethylammonium bromide
  • SDBS sodium dodecylbenzenesulfonate
  • LDS lithium dodecylsulfonate
  • PEI polyethyleneimine
  • the concentration of CNT is preferably 1 to 30 mg / mL (0.1 to 3 wt%) relative to the spinning solution, but is not limited thereto.
  • the CNT concentration is more preferably 3 to 20 mg / mL (0.1 to 2 wt%), most preferably 5 to 10 mg / mL (0.5 to 1.0 wt%).
  • the second coagulation component When the CNT dispersion is spun into a coagulation bath containing a second coagulation component through a spinneret (spinning nozzle), the second coagulation component gradually penetrates into the spinning solution, causing solvent substitution, thereby causing the spinning solution to swell and fibrosis (gelling). While soft carbon nanotube (CNT) gel fibers (second gel fibers in the present invention) is formed.
  • CNT carbon nanotube
  • carbon nanotubes and graphene may be wet spinning alone as described above, but may be wet spinning using a mixture of graphene / carbon nanotubes as a spinning solution.
  • the total concentration of the mixed spinning solution is preferably 0.1 to 2 wt%.
  • the graphene / carbon nanotube mixed spinning solution according to the present invention may be prepared by dispersing and sonicating graphene, carbon nanotube, and surfactant in water or water / organic solvent at the same time, but the graphene dispersion liquid and carbon nanotube The dispersions may be prepared, respectively, and then mixed with each other.
  • the dispersion is used as a spinning solution.
  • the concentration of the spinning solution may be prepared by appropriate dilution of the dispersion.
  • the component ratio of graphene: carbon nanotubes is 4: 1 to 1: 4, preferably 3: 2 to 2: 3, more preferably 1: 1.
  • the coagulation component of the carbon nanotube / graphene mixed dispersion is the same as the second coagulation component.
  • the second coagulation component is water-soluble, and the coagulation bath of the present invention may be prepared by dissolving the first coagulation component and the second coagulation component in distilled water.
  • a solvent for the coagulation bath organic solvents such as dimethylformamide, methanol, ethanol, ethylene glycol, n-butanol, tert-butyl alcohol, isopropyl alcohol, n-propanol, ethyl acetate, dimethyl sulfoxide and tetrahydrofurancan be used.
  • Distilled water is preferred as the coagulation solvent in the present invention, but is not limited thereto.
  • the first gel fiber (graphene oxide gel fiber) and the second gel fiber (graphene gel fiber, tannonanotube gel fiber or carbon nanotube / graphene gel fiber) prepared according to the wet spinning are washed with water and dried. When physically bonded to each other previously, it was confirmed in the present invention that the effective bonding is achieved by the interaction between the gel fibers. The possibility of conjugation according to the invention has not been reported to date.
  • Bonding of the first gel fiber and the second gel fiber may be in a side-by-side form or a sheath-core form.
  • the side-by-side form converges each gel fiber that has passed through the coagulation bath into one concave roller so that the fibers are physically in close contact with the first gel fiber and the second gel. Due to the interaction of the fibers, the two fibers are joined in parallel form.
  • the first gel fiber and the second gel fiber may be bonded in a twisted shape. This is to rotate each of the gel fibers passed through the coagulation bath in the winding direction to twist the fibers together and then converge by joining the rollers.
  • the sheath-core shape is a core-shell heterojunction structure, and means a shape similar to a coaxial cable.
  • the core material is spun using a relatively small diameter spinning nozzle, the sheath material is spun in a ribbon form using a flat nozzle, and then converged on a roller so that the sheath fiber (ribbon form) surrounds the core fiber. It is made by bonding.
  • the graphene oxide / carbon nanotube composite fiber and the graphene oxide / graphene composite fiber according to the present invention are subjected to the stretching process, the washing process, and the drying process. Or graphene oxide / graphene / carbon nanotube composite fiber is effectively produced.
  • the composite fiber according to the present invention has electrical conductivity without a separate reduction process of graphene oxide. Therefore, in the case of using graphene oxides into which functional materials such as nucleic acids, DNA, RNA, and aptamer are introduced, these functional materials may have characteristics of electrical conductivity without being destroyed or degraded by chemical or thermal reduction processes. do.
  • the composite fiber of the present invention may be subjected to further reduction through a known thermal reduction method or chemical reduction method.
  • the thermal reduction method is not limited, but may be achieved by increasing the temperature at a rate of 0.1 to 10 °C / min from 200 to 1000 °C at room temperature.
  • the chemical reduction method is a known reducing agent such as hydrazine, hydroiodic acid, hydrobromic acid, sodium borohydride, lithium aluminum hydride, and sulfuric acid. Can be made.
  • aqueous graphene oxide dispersion After preparing an aqueous graphene oxide dispersion in the same manner as described above, the excess hydrazine was added thereto and reduced at 80 ° C. for 2 hours to obtain aggregated graphene. Concentrated graphene was added to the concentrated sulfuric acid and reacted at 180 ° C. for 12 hours to reduce the concentration, and washed and dried to obtain a reduced graphene oxide (rGO). 0.5 g of the obtained rGO and 0.25 g of sodium dodecylbenzenesulfonate (SDBS) were added to 100 mL of distilled water and sonicated for 30 minutes to prepare a 0.5 wt% rGO aqueous dispersion.
  • SDBS sodium dodecylbenzenesulfonate
  • SWNT Carbon Nanotube
  • SWNT and 0.25 g of surfactant SDBS were added to 100 mL of distilled water and sonicated for 30 minutes to prepare a 0.5 wt% SWNT aqueous dispersion.
  • CTAB first coagulation component
  • the aqueous dispersion of GO prepared above, and the carbon nanotube dispersion in syringe of 5 wt% PVA coagulation bath were rotated in each coagulation bath while maintaining the spinning speed of 1 mL / min or less.
  • the spinning solution was linearly injected to prepare graphene oxide gel fibers (first gel fibers) and carbon nanotube gel fibers (second gel fibers) simultaneously.
  • first gel fibers graphene oxide gel fibers
  • carbon nanotube gel fibers second gel fibers
  • Figure 4 is an optical micrograph of the graphene oxide / carbon nanotube gel fiber prepared by the above method, it can be seen that both fibers are firmly bonded in a side-by-side form.
  • FIGS. 5 and 6 are electron micrographs of the graphene oxide / carbon nanotube composite fiber having a heterojunction structure prepared according to Example 1, Figure 5 is a side photograph, Figure 6 is a cross-sectional photograph.
  • Example 1 using the graphene aqueous dispersion instead of carbon nanotubes in the same manner to prepare a composite fiber of graphene oxide / graphene heterojunction structure.
  • Graphene is a 0.5wt% reduced graphene (rGO) aqueous dispersion as a spinning solution, and the coagulation component was used 5wt% PVA (second coagulation component) the same as carbon nanotubes.
  • the prepared carbon nanotube aqueous dispersion and the graphene aqueous dispersion are mixed to form a carbon nanotube / graphene aqueous dispersion, and using this as a spinning solution, graphene oxide / (carbon nanotube) in the same manner as in Example 1. + Graphene) to produce a composite fiber of a heterojunction structure.
  • the present invention relates to a method for producing a graphene oxide / carbon nanotube composite fiber, graphene oxide / graphene composite fiber or graphene oxide / graphene / carbon nanotube composite fiber having a heterojunction structure.

Abstract

The present invention provides: a graphene oxide/carbon nanotube composite fiber having a heterojunction structure; and a method for manufacturing a graphene oxide/graphene composite fiber or a graphene oxide/graphene/carbon nanotube composite fiber, comprising: a) a step of preparing a first gel fiber by spinning a graphene oxide dispersion solution in a coagulation bath containing a first coagulation component and b) a step of preparing a second gel fiber by spinning a carbon nanotube dispersion solution, a graphene dispersion solution, or a mixture dispersion solution thereof in a coagulation bath containing a first coagulation component, wherein the steps are simultaneously carried out; and c) joining, washing, and drying the simultaneously prepared first gel fiber and second gel fiber.

Description

이종 접합구조를 가지는 그래핀산화물/탄소나노튜브 복합섬유, 그래핀산화물/그래핀 복합섬유 또는 그래핀산화물/그래핀/탄소나노튜브 복합섬유의 제조 방법Graphene oxide / carbon nanotube composite fiber, graphene oxide / graphene composite fiber or graphene oxide / graphene / carbon nanotube composite fiber having a heterojunction structure
본 발명은 이종 접합구조(heterojunction structure)를 가지는 그래핀산화물/탄소나노튜브 복합섬유, 그래핀산화물/그래핀 복합섬유 또는 그래핀산화물/그래핀/탄소나노튜브 복합섬유를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing a graphene oxide / carbon nanotube composite fiber, graphene oxide / graphene composite fiber or graphene oxide / graphene / carbon nanotube composite fiber having a heterojunction structure (heterojunction structure) .
그래핀(Graphene), 탄소나노튜브(Carbon-Nanotube, 이하 'CNT')와 같은 나노탄소계열 물질은 전기적 특성, 열적 특성, 유연성, 기계적 강도가 매우 우수하여 차세대 전자 재료, 방열 재료, 초고강도 구조 재료로 주목받고 있는 첨단 소재이다.Nano-carbon-based materials such as graphene and carbon-nanotubes (CNT) are excellent in electrical properties, thermal properties, flexibility, and mechanical strength. It is an advanced material that is attracting attention as a material.
그래핀은 탄소 원자들이 sp2 혼성으로 육각형 벌집 모양을 이루는 2차원 평면 구조의 탄소 동소체로서, 단층 그래핀의 두께는 탄소원자 1개의 두께인 0.2 ~ 0.3 nm이고, 단층 그래핀은 물론, 10층 이하, 바람직하게는 2, 3층 정도의 적층 그래핀 구조 역시 통상적인 그래핀의 범주에 속한다.Graphene is a two-dimensional planar carbon allotrope in which hexagonal honeycomb is formed by sp 2 hybrids of carbon atoms. The thickness of single layer graphene is 0.2 to 0.3 nm, the thickness of one carbon atom, and single layer graphene, as well as 10 layers Hereinafter, preferably, the stacked graphene structure of about two or three layers also belongs to the category of conventional graphene.
그래핀의 제조 방법으로는 화학기상증착법(CVD), 에피텍셜 성장법(Epitaxial Growth), 비산화 박리법(Nonoxidative Exfoliation), 화학적 박리법(Chemical Exfoliation) 등이 알려져 있다. 이 중 화학기상증착법, 에피텍셜 성장법, 비산화 박리법은 고품질의 순수 그래핀을 얻을 수 있는 장점이 있으나, 그래핀의 수율이 낮아 대량생산이 어렵고, 제조 비용이 높은 단점이 있어 현재 그 사용에 큰 제한이 있다. As a method for producing graphene, chemical vapor deposition (CVD), epitaxial growth, epitaxial growth, nonoxidative exfoliation, chemical exfoliation, and the like are known. Among them, chemical vapor deposition, epitaxial growth, and non-oxidation exfoliation have advantages of obtaining high quality pure graphene, but the yield of graphene is difficult to mass produce, and manufacturing costs are high. There is a big limitation.
한편, 화학적 박리법은 도 1에 도시된 바와 같이 흑연을 강산(질산,황산 등)으로 산화하고, 기계적(초음파 분쇄 또는 호모게나이저 분쇄)으로 박리시켜 산소관능기가 형성된 그래핀산화물(Graphene Oxide, 'GO')[도 1(a)]로 만든 다음, 일련의 화학적 환원(reduction)[도 1(b)] 및/또는 열적 환원 과정[도 1(c)]을 통해 산소관능기를 제거하여 그래핀[도 1(d)]을 제조하는 방법으로, 순수 그래핀과 구별되도록 '환원된 그래핀산화물(reduced GO, 'rGO')'로 호칭한다. 상기 '환원된 그래핀산화물(rGO)'는 그래핀의 산화 및 환원을 거치는 과정에서 그래핀 표면에 다소의 탄소 결함(carbon defection)이 발생되고, 산소관능기의 완전한 제거가 어려워 순수 그래핀에 비해서는 전기전도도 특성이 다소 떨어지지만, 대량 생산이 가능하고, 제조 비용이 낮다는 점과 순수 그래핀에 견주어 전기전도도, 열전도도에서 큰 차이가 없다는 점에서 현재 가장 널리 이용되고 있다.On the other hand, the chemical exfoliation method is graphene oxide (oxidized graphite) formed by oxidizing the graphite with a strong acid (nitric acid, sulfuric acid, etc.) and mechanically (ultrasonic grinding or homogenizer grinding) to form an oxygen functional group as shown in FIG. 'GO') [FIG. 1 (a)], followed by removal of oxygen functional groups through a series of chemical reduction [FIG. 1 (b)] and / or thermal reduction processes [FIG. 1 (c)]. As a method for producing the fin [Fig. 1 (d)], it is called 'reduced GO (' rGO ') to distinguish it from pure graphene. The 'reduced graphene oxide (rGO)' generates some carbon defects on the surface of graphene during oxidation and reduction of graphene, and it is difficult to completely remove oxygen functional groups, compared to pure graphene. Although the electrical conductivity is somewhat inferior, it is the most widely used in that it can be mass-produced, the manufacturing cost is low, and there is no big difference in electrical conductivity and thermal conductivity compared to pure graphene.
그래핀산화물(GO)은 산화과정에서 생성되는 산소관능기들로 인해 그래핀과는 전혀 다른 전기적 특성을 가진다. 그래핀 자체는 탄소동소체이므로 비극성, 소수성을 띠고, 상온에서 구리보다 100배 높은 전기전도성을 가지는 데 반해, 그래핀산화물은 표면/가장자리에 형성된 산소관능기들(에폭시, 하이드록시, 카르복시기 등)로 인해 극성, 친수성을 띠며, 절연체 또는 극히 낮은 전기전도, 열전도 특성을 지닌다.Graphene oxide (GO) has completely different electrical properties from graphene due to oxygen functional groups generated during oxidation. Graphene itself is a carbon allotrope, so it is nonpolar and hydrophobic, and has 100 times higher electrical conductivity than copper at room temperature, whereas graphene oxide is due to oxygen functional groups (epoxy, hydroxy, carboxyl, etc.) formed on the surface / edges. It is polar, hydrophilic and has insulators or extremely low electrical and thermal conductivity.
그래핀산화물(GO)은 비록 '환원된 그래핀산화물(rGO)'의 중간체에 속하지만, 그래핀산화물에 형성된 산소관능기로 인해 표면 개질이 용이할 뿐 아니라, 기능성 물질의 접합이 가능하여 생물학적 응용에 유망한 물질로 평가되고 있다. 예컨대, 그래핀산화물 표면에 핵산, (단일사슬) DNA, RNA, 압타머, 펩티드, 단백질, 항체, 성장인자, 효소 등의 생체분자 또는 고분자를 접합시킴으로써, 타겟물질의 검출(전기적 신호 또는 형광, 소광)에 이용할 수 있다.Although graphene oxide (GO) belongs to the intermediate of 'reduced graphene oxide (rGO)', the oxygen functional groups formed on graphene oxide facilitate the surface modification and the bonding of functional materials for biological applications. Is regarded as a promising substance. For example, detection of a target substance (electrical signal or fluorescence, by conjugation of a biomolecule or a polymer such as nucleic acid, (single chain) DNA, RNA, aptamer, peptide, protein, antibody, growth factor, enzyme, etc. to the surface of graphene oxide) Quenching).
탄소나노튜브(CNT)는 탄소 원자들이 sp2 혼성으로 육각형 벌집 모양을 이루는 원기둥 나노구조의 탄소 동소체로서, 벽을 이루고 있는 결합 수에 따라서 단일벽 탄소나노튜브(Single-walled CNT, 'SWNT'), 이중벽 탄소나노튜브(Double-walled CNT, 'DWNT'), 다중벽 탄소나노튜브(Multi-walled CNT, 'MWNT')로 구분된다.Carbon nanotubes (CNTs) are cylindrical allotropic carbon allotropes in which hexagonal honeycombs are formed by sp 2 hybrids of carbon atoms, and single-walled CNTs (SWNT) depending on the number of bonds forming a wall. , Double-walled CNTs (DWNT), and multi-walled CNTs (MWNT).
탄소나노튜브 제조법은 화학기상증착법, 아크 방전법, 레이저 증발법, 플라즈마 토치법, 이온 충격법 등이 알려져 있다. 이들 중 화학기상증착법은 탄소 나노튜브의 대량 생산과 성장 제어가 가능한 장점이 있다.Carbon nanotube production methods are known as chemical vapor deposition, arc discharge, laser evaporation, plasma torch, ion bombardment, and the like. Among them, the chemical vapor deposition method has the advantage of controlling mass production and growth of carbon nanotubes.
그래핀과 탄소나노튜브는 높은 전기전도성과 비표면적을 가지므로 슈퍼캐패시터, 센서, 배터리, 액추에이터 용도의 전극(전극 활물질), 터치패널, 플렉서블 디스플레이, 고효율 태양전지, 방열필름, 코팅 재료, 바닷물 담수화 필터, 이차전지용 전극, 초고속 충전기 등 다양한 분야에 이용될 수 있다.Graphene and carbon nanotubes have high electrical conductivity and specific surface area, so electrodes (electrode active materials) for supercapacitors, sensors, batteries, and actuators, touch panels, flexible displays, high efficiency solar cells, heat-dissipating films, coating materials, and seawater desalination It can be used in various fields such as filters, secondary battery electrodes, ultra fast chargers.
근래들어 그래핀, 그래핀산화물, 탄소나노튜브의 존재와 물리적 특성이 알려지면서 이들을 이용하여 섬유 또는 복합 섬유로 제작하려는 다양한 연구들이 진행되고 있다. 특히 습식 방사공정을 이용한 연구들이 활발히 이루어지고 있다.Recently, as the presence and physical properties of graphene, graphene oxide, and carbon nanotubes are known, various studies are being made to fabricate them using fibers or composite fibers. In particular, researches using wet spinning processes are being actively conducted.
도 2는 그래핀산화물의 습식 방사법(a) 및 습식 방사공정에서 그래핀산화물(또는 그래핀, 나노탄소튜브)이 정렬되는 과정(b)을 나타내는 모식도이다.Figure 2 is a schematic diagram showing the process (b) of the graphene oxide (or graphene, nano carbon tube) is aligned in the wet spinning method (a) and wet spinning process of the graphene oxide.
도 2를 참조하여 설명하면, 그래핀산화물 방사용액은 방사구금(토출노즐)을 통해 응고욕으로 토출되어 응집되는 데, 그래핀산화물의 정렬과정은 시린지 속에 무방향성과 무질서하게 위치한 그래핀산화물이 미세 내경의 방사 노즐을 따라 이동하면서 유체간의 전단응력(shear stress)에 의해 노즐의 축 방향으로 정렬되고(I), 응고욕에 토출된 후 정렬된 그래핀산화물은 응고욕에서 용매 교환(sovent change)과정을 통해 자기조립에 의해 젤 섬유(gel fibers)가 형성되고(II), 상기 젤 섬유는 일련의 연신, 수세, 건조 과정을 거쳐 그래핀산화물 섬유로 제조된다. 상기 제조된 그래핀산화물 섬유는 전기적 특성을 위해 그래핀산화물 섬유를 열적 또는 화학적 환원 처리하는 추가 공정을 거친다. 그래핀, 탄소나노튜브의 습식 방사공정 역시 상술한 그래핀산화물 방사공정과는 큰 차이가 없으나, 후술하는 바와 같이 응고욕 특성이 완전히 달라 종래 공지된 습식 방사법으로는 그래핀산화물/그래핀 복합섬유 또는 그래핀산화물/탄소나노튜브 복합섬유 제조가 사실상 불가능하다.Referring to FIG. 2, the graphene oxide spinning solution is discharged into a coagulation bath through a spinneret (discharge nozzle) to be aggregated. The alignment process of graphene oxide is non-directional and disorderedly located in a syringe. Graphene oxide aligned with the axial direction of the nozzle by shear stress between the fluids moving along the fine inner diameter spinning nozzle (I), and discharged into the coagulation bath, and then aligned graphene oxide are solvent change in the coagulation bath. Gel fibers are formed by self-assembly (II), and the gel fibers are made of graphene oxide fibers through a series of stretching, washing and drying processes. The prepared graphene oxide fiber is subjected to an additional process of thermally or chemically reducing the graphene oxide fiber for electrical properties. The wet spinning process of graphene and carbon nanotubes is also not significantly different from the above-described graphene oxide spinning process, but the coagulation bath properties are completely different as described below. Or it is virtually impossible to manufacture graphene oxide / carbon nanotube composite fiber.
습식 방사공정에서는 방사용액의 종류 및 특성과, 이에 적합한 응고욕 성분, 조성의 선정이 매우 중요한 데, 그래핀과 탄소나노튜브는 비극성, 비수용성으로 비슷한 응고욕 특성을 가지는 반면, 그래핀산화물은 극성, 수용성으로 그래핀, 탄소나노튜브와는 전혀 다른 응고욕 특성을 가진다.In the wet spinning process, it is very important to select the type and characteristics of the spinning solution, the appropriate coagulation bath components, and the composition. Graphene and carbon nanotubes have similar coagulation bath characteristics as nonpolar and water-insoluble, whereas graphene oxide Due to its polarity and water solubility, it has a completely different coagulation bath characteristic than graphene and carbon nanotubes.
그래핀, 탄소나노튜브의 응고욕 특성Characteristics of Coagulation Bath of Graphene and Carbon Nanotubes
그래핀, 탄소나노튜브는 비극성, 소수성을 띠고, 층간 반데르발스력에 의해 서로 응집되므로 물에 전혀 분산되지 않고, 대부분의 유기용매에도 잘 분산되지 않는다. 따라서 계면활성제와 초음파 처리를 통해 그래핀, 탄소나노튜브 분산액을 제조하여 방사용액으로 이용한다.Graphene and carbon nanotubes are nonpolar and hydrophobic, and are agglomerated with each other by an interlayer van der Waals force, so they do not disperse in water at all and do not disperse well in most organic solvents. Therefore, graphene and carbon nanotube dispersions are prepared by using a surfactant and ultrasonication, and used as a spinning solution.
그래핀, 탄소나노튜브의 응고(응집) 성분으로는 폴리비닐알코올(PVA), 폴리메틸메타아크릴레이트(PMMA), 폴리에틸렌이민(PEI), 폴리비닐필로리돈(PVP), 폴리에틸렌옥사이드(PEO) 등의 수용성 고분자가 알려져 있다. 그래핀 방사용액 또는 탄소나노튜브 방사용액이 노즐을 통해 응고욕에 방사되면, 상기 수용성 고분자는 방사 섬유 상에 침투하여 계면활성제를 대체하여 섬유상에 고분자 매트릭스를 형성함으로써 그래핀 섬유, 탄소나노튜브 섬유, 보다 정확히는 그래핀/고분자 복합섬유, 탄소나노튜브/고분자 복합섬유가 제조된다.As the coagulation (agglomeration) component of graphene and carbon nanotubes, polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), polyethyleneimine (PEI), polyvinylpyrrolidone (PVP), polyethylene oxide (PEO) Water-soluble polymers, such as these, are known. When the graphene spinning solution or carbon nanotube spinning solution is spun into the coagulation bath through a nozzle, the water-soluble polymer penetrates on the spinning fiber to replace the surfactant to form a polymer matrix on the fiber, thereby forming graphene fibers and carbon nanotube fibers. More specifically, graphene / polymer composite fiber and carbon nanotube / polymer composite fiber are manufactured.
대한민국 특허공개 제10-2012-0105179호는 a)그래핀(환원된 그래핀 또는 환원된 그래핀산화물)을 계면활성제와 함께 용매에 분산시켜 분산액을 제조하는 단계; 및 b) 상기 분산액을 고분자(PVA) 용액에 혼입하여 습식 방사한 후 건조시켜 섬유를 제조하는 단계를 포함하는 그래핀/PVA 복합섬유 제조 방법을 개시하고 있고, Korean Patent Publication No. 10-2012-0105179 discloses a) preparing a dispersion by dispersing graphene (reduced graphene or reduced graphene oxide) in a solvent with a surfactant; And b) it is disclosed a graphene / PVA composite fiber manufacturing method comprising the step of incorporating the dispersion into a polymer (PVA) solution, wet spinning and drying to produce a fiber,
대한민국 특허공개 제10-2012-0107026호는 상기 특허에서 제조된 그래핀/PVA 복합섬유에 추가적으로 열처리하거나 강산으로 처리하여 PVA 고분자를 제거하여 그래핀 섬유를 제조하는 방법을 개시하고 있다.Republic of Korea Patent Publication No. 10-2012-0107026 discloses a method for producing a graphene fiber by removing the PVA polymer by additional heat treatment or strong acid treatment to the graphene / PVA composite fiber prepared in the patent.
대한민국 특허등록 제10-1182380호는 그래핀/탄소나노튜브 분산액을 PVA 응고욕에 방사시켜 그래핀/탄소나노튜브/PVA 복합섬유를 제조하는 방법을 개시하고 있으나, 상기 그래핀은 그래핀산화물(GO)이 아닌, 환원된 그래핀산화물(rGO) 또는 화학적으로 개질된 환원된 그래핀산화물(RCCG)이 이용한다.Republic of Korea Patent No. 10-1182380 discloses a method for producing a graphene / carbon nanotube / PVA composite fiber by spinning the graphene / carbon nanotube dispersion in a PVA coagulation bath, the graphene oxide (graphene oxide ( Reduced graphene oxide (rGO) or chemically modified reduced graphene oxide (RCCG), rather than GO).
탄소나노튜브 섬유의 습식 방사공정은 하기와 같이 여러 문헌에 개시되어 있다.Wet spinning processes of carbon nanotube fibers have been described in several documents as follows.
Vigolo 등은 계면활성제(1.0wt% 도데실설폰산나트륨(SDS))를 이용하여 0.35wt% SWNT 분산액을 만든 다음, 5wt% 폴리비닐알코올(PVA)/증류수 응고욕에 방사시켜 탄소나노튜브 섬유를 최초로 제조하였다(Vigolo, B. et al. Macroscopic fibers and ribbons of oriented carbon nanotubes. Science 290, 1331-1334 (2000)).Vigolo et al. Prepared a 0.35 wt% SWNT dispersion with a surfactant (1.0 wt% sodium dodecyl sulfonate (SDS)) and then spun it into a 5 wt% polyvinyl alcohol (PVA) / distilled water coagulation bath to produce carbon nanotube fibers for the first time. (Vigolo, B. et al. Macroscopic fibers and ribbons of oriented carbon nanotubes. Science 290, 1331-1334 (2000)).
Munoz 등은 세틸트리메틸암모늄 브로마이드(CTAB), 도데실벤젠설폰산나트륨(SDBS), 도데실설폰산리튬(LDS)의 계면활성제를 이용하여 SWNT 분산액을 만든 다음, 폴리에틸렌이민(PEI)/증류수 응고욕에 방사시켜 SWNT/PEI 섬유를 제조하였다(Adv. Mater. 2005, 17, No.8, April 18). 제조된 SWNT/PEI 섬유는 SWNT/PVA 복합섬유에 비해 전기전도성이 100배 증가되는 것이 확인되었다.Munoz et al. Prepared SWNT dispersions using surfactants of cetyltrimethylammonium bromide (CTAB), sodium dodecylbenzenesulfonate (SDBS), and lithium dodecylsulfonate (LDS), followed by polyethyleneimine (PEI) / distilled water coagulation bath. Spinned to make SWNT / PEI fibers ( Adv. Mater . 2005, 17, No. 8, April 18). It was confirmed that the prepared SWNT / PEI fiber has increased electrical conductivity by 100 times compared to the SWNT / PVA composite fiber.
그래핀산화물의 응고욕 특성Characteristics of Coagulation Bath of Graphene Oxide
상술한 그래핀, 탄소나노튜브와 달리, 그래핀산화물의 응고욕으로는 CTAB, 키토산, CaCl2, NaOH, KOH 등이 알려져 있고, 이들 중에서도 CTAB이 주로 이용된다.Unlike graphene and carbon nanotubes described above, CTAB, chitosan, CaCl 2 , NaOH, KOH, and the like are known as coagulation baths of graphene oxide, and CTAB is mainly used.
그래핀산화물의 응집과정은 CTAB 등 양전하로 대전된 분자를 이용한 비용매 침전(non-solvent precipitation), 환원제(NaOH)를 이용한 분산 불안정(dispersion destabilization)(Nat. Comm. 2011, 2, 571.), CaCl2 등을 이용한 2가 이온(Ca2 +)에 의한 그래핀산화물 가교(ionic cross-linking)(Adv. Mater.2013, 25, 188.), 키토산 등을 이용한 고분자전해질 착물화(polyelectrolyte complexation)(Adv. Func. Mater.2013, 23, 5345.) 등이 알려져 있다.The aggregation process of graphene oxide is based on non-solvent precipitation using positively charged molecules such as CTAB and dispersion destabilization using reducing agent (NaOH) ( Nat. Comm. 2011, 2, 571.) , Polyelectrolyte complexation using graphene oxide cross-linking by divalent ions (Ca 2+ ), CaCl 2, etc. ( Adv. Mater. 2013, 25, 188.), chitosan, etc. ( Adv. Func. Mater . 2013, 23, 5345.) and the like are known.
상기에서 주목할 점은 그래핀산화물과 그래핀/탄소나노튜브는 서로 응고욕 특성이 달라 종래 공지의 습식 방사공정으로는 그래핀산화물/탄소나노튜브 복합섬유, 그래핀산화물/그래핀 복합섬유 또는 그래핀산화물/(그래핀+탄소나노튜브) 복합섬유 제조가 불가능하다는 것이다.It should be noted that the graphene oxide and graphene / carbon nanotubes are different from each other in the coagulation bath characteristics, and conventionally known wet spinning processes are graphene oxide / carbon nanotube composite fibers, graphene oxide / graphene composite fibers or graphene Fin oxide / (graphene + carbon nanotube) composite fiber manufacturing is impossible.
예를 들어, 그래핀산화물의 응고매인 CTAB은 탄소나노튜브에서는 반대로 분산제 역할을 하므로, 그래핀산화물/탄소나노튜브 분산액을 CTAB 응고욕에 방사할 경우 그래핀산화물은 응고되지만 탄소나노튜브는 응고되지 않고, 분사되어 정량비를 갖는 그래핀산화물/탄소나노튜브 섬유화(젤화)가 발생되지 않는다. 반면, PVA는 탄소나노튜브, 그래핀의 응고매로 작용하지만, 그래핀산화물에서는 반대로 분산제 역할을 하므로, 그래핀산화물/탄소나노튜브 분산액을 PVA 응고욕에 방사할 경우 탄소나노튜브, 그래핀은 응고되지만 그래핀산화물은 응고되지 않아 역시 섬유화(젤화)가 발생되지 않는다.For example, CTAB, a coagulant of graphene oxide, acts as a dispersant in the case of carbon nanotubes. Therefore, when graphene oxide / carbon nanotube dispersion is spun into CTAB coagulation bath, graphene oxide coagulates but carbon nanotubes do not coagulate. And no graphene oxide / carbon nanotube fibrosis (gelling) having a quantitative ratio is sprayed out. On the other hand, PVA acts as a coagulant of carbon nanotubes and graphene, but it acts as a dispersant in the case of graphene oxide. Thus, when the graphene oxide / carbon nanotube dispersion is spun into a PVA coagulation bath, carbon nanotubes and graphene Although it coagulates, the graphene oxide does not coagulate and thus no fibrosis occurs.
전술한 바와 같이 그래핀, 탄소나노튜브는 전기전도성, 열전도성이 매우 우수하여 제조되는 섬유 역시 전기전도도, 열전도도가 매우 우수하다. 이와 반대로 그래핀산화물은 전기전도성, 열전도성이 낮아 제조되는 섬유 역시 절연체이거나 낮은 전기전도도, 열전도를 가진다.As described above, the graphene and carbon nanotubes have excellent electrical conductivity and thermal conductivity, and the fibers produced are also excellent in electrical conductivity and thermal conductivity. On the contrary, graphene oxide has low electrical conductivity and thermal conductivity, and the fiber produced also has an insulator, low electrical conductivity, and thermal conductivity.
그래핀이나 탄소나노튜브 기반의 나노소재가 배터리, 슈퍼커패시터의 전극소재에 이용되기 위해서는 높은 전기전도도와 다공성(표면적, 에너지 저장능력)이 요구되는 데, 이러한 특성은 그래핀산화물, 그래핀, 탄소나노튜브 등의 나노소재의 복합를 통해 향상될 수 있다.Graphene or carbon nanotube-based nanomaterials require high electrical conductivity and porosity (surface area, energy storage capacity) in order to be used in the electrode materials of batteries and supercapacitors. It can be improved through the composite of nanomaterials such as nanotubes.
그래핀산화물과 탄소나노튜브(또는 그래핀)로 이루어진 복합섬유는 GO와 CNT의 함량비에 따라 전기전도도, 열전도도를 제어할 수 있으며, 인장강도, 탄성도, 신율등의 기계적 특성을 극대화할 수 있다. 그리고 rGO, CNT는 초음파처리 과정 중, 불가피하게 결함, 입경크기 감소가 발생하는데 비해, 습식공정에 사용되는 GO는 평균입경이 수십 um내외로 큰 GO를 사용하므로 기계적 특성이 우수하고, 환원시 전기전도도가 우수하다.Composite fibers composed of graphene oxide and carbon nanotubes (or graphene) can control electrical conductivity and thermal conductivity according to the content ratio of GO and CNT, and maximize mechanical properties such as tensile strength, elasticity, and elongation. Can be. In addition, rGO and CNT inevitably cause defects and particle size reduction during the sonication process, whereas GO used in the wet process has good mechanical properties because it uses GO having a large average particle diameter of about several tens of um. Excellent conductivity
또한, 그래핀산화물은 그래핀, 탄소나노튜브에 비해 생체분자(핵산, 압타머, 효소 등), 고분자 등 다양한 기능성 물질의 도입이 가능한 반면, 전기전도성을 위해서는 추가적인 화학적/열적 환원공정 또는 후처리 공정이 요구되는 데, 이러한 환원공정, 후처리 공정에 의해 상기 기능성 물질이 분해되거나 파괴되어 기능이 감쇄되거나 상실된다. 따라서, 상술한 환원공정, 후처리 공정없이도 높은 물성을 가지는 그래핀 복합섬유의 개발이 요구된다.In addition, graphene oxide is capable of introducing various functional materials such as biomolecules (nucleic acid, aptamers, enzymes, etc.) and polymers, compared to graphene and carbon nanotubes, whereas for electrical conductivity, an additional chemical / thermal reduction process or post-treatment is possible. A process is required, and the reduction or aftertreatment process decomposes or destroys the functional material, thereby decreasing or losing the function. Therefore, development of graphene composite fibers having high physical properties without the above-described reduction process and post-treatment process is required.
본 발명은 그래핀산화물/탄소나노튜브 복합섬유, 그래핀산화물/그래핀 복합섬유 또는 그래핀산화물/그래핀/탄소나노튜브 복합섬유를 제조하는 방법을 제공하는 데 그 목적이 있다.An object of the present invention is to provide a method for producing a graphene oxide / carbon nanotube composite fiber, graphene oxide / graphene composite fiber or graphene oxide / graphene / carbon nanotube composite fiber.
상기 기술적 과제를 해결하기 위하여, 본 발명은, In order to solve the above technical problem, the present invention,
a) 그래핀산화물 분산액을 제1 응고성분을 포함하는 응고욕에 방사시켜 제1 젤 섬유를 제조하는 공정; 및 b) 탄소나노튜브 분산액 또는 그래핀 분산액 또는 이의 혼합 분산액을 제1 응고성분을 포함하는 응고욕에 방사시켜 제2 젤 섬유를 제조하는 공정이 동시에 이루어지고, c) 상기 동시 제조된 제1 젤 섬유와 제2 젤 섬유를 서로 접합하고, 수세, 건조하는 것을 특징으로 하는, 이종 접합구조를 가지는 그래핀산화물/탄소나노튜브 복합섬유, 그래핀산화물/그래핀 복합섬유 또는 그래핀산화물/그래핀/탄소나노튜브 복합섬유 제조 방법을 제공한다.a) preparing a first gel fiber by spinning the graphene oxide dispersion into a coagulation bath containing a first coagulation component; B) spinning a carbon nanotube dispersion or graphene dispersion or a mixed dispersion thereof in a coagulation bath comprising a first coagulation component to produce a second gel fiber, and c) simultaneously preparing the first gel. Graphene oxide / carbon nanotube composite fibers, graphene oxide / graphene composite fibers or graphene oxide / graphene having a heterojunction structure, characterized in that the fibers and the second gel fibers are bonded to each other, washed, and dried It provides a method for producing a carbon nanotube composite fiber.
상기 제1 응고성분은 CTAB, 키토산, CaCl2, NaOH, KOH 으로 구성된 군에서 선택되는 1종 이상인 것이 바람직하다.The first coagulation component is preferably at least one selected from the group consisting of CTAB, chitosan, CaCl 2 , NaOH, KOH.
상기 제2 응고성분은 폴리비닐알코올(PVA), 폴리메틸메타아크릴레이트(PMMA), 폴리에틸렌이민(PEI), 폴리비닐필로리돈(PVP), 폴리에틸렌옥사이드(PEO)으로 이루어진 군에서 선택되는 1종 이상인 것이 바람직하다.The second coagulation component is one selected from the group consisting of polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), polyethyleneimine (PEI), polyvinylpyrrolidone (PVP), polyethylene oxide (PEO) It is preferable that it is above.
제1 젤 섬유와 제2 젤 섬유의 접합은 사이드-바이-사이드(side-by-side) 형태일 수 있다. 또한 제1 젤 섬유와 제2 젤 섬유는 꼬임 구조를 가질 수 있다.The bonding of the first gel fiber and the second gel fiber may be in side-by-side form. In addition, the first gel fibers and the second gel fibers may have a twisted structure.
한편, 제1 젤 섬유와 제2 젤 섬유의 접합은 쉬쓰-코어(sheath-core) 형태일 수 있다.Meanwhile, the bonding of the first gel fiber and the second gel fiber may be in the form of a sheath-core.
본 발명에 따라 제조된 이종 접합된 그래핀산화물/탄소나노튜브 복합섬유, 그래핀산화물/그래핀 복합섬유 또는 그래핀산화물/그래핀/탄소나노튜브 복합섬유는 다공도가 높은 그래핀산화물과 전기전도도가 높은 탄소나노튜브 또는 그래핀이 모두 포함하고 이들 이종 성분 간에 낮은 계면저항을 가지는 형태로 접합되므로 높은 다공성과 전도성을 가져 배터리, 슈퍼커패시터의 전극 소재로 유용하게 이용될 수 있다.The hetero-bonded graphene oxide / carbon nanotube composite fiber, graphene oxide / graphene composite fiber or graphene oxide / graphene / carbon nanotube composite fiber prepared according to the present invention is a high porosity graphene oxide and electrical conductivity It contains both high carbon nanotubes or graphene and bonded in the form having a low interfacial resistance between these heterogeneous components it has a high porosity and conductivity can be usefully used as the electrode material of the battery, supercapacitor.
도 1은 화학박리법에 따른 그래핀산화물(GO)으로부터 '환원된 그래핀산화물(rGO)'을 생성하는 과정을 나타낸 그래핀 구조의 모식도이다.1 is a schematic diagram of a graphene structure showing a process for generating a 'reduced graphene oxide (rGO)' from the graphene oxide (GO) according to the chemical peeling method.
도 2는 그래핀산화물의 습식 방사법(도 2a) 및 습식 방사공정에서 그래핀산화물(또는 그래핀, 나노탄소튜브)이 정렬되는 과정(도 2b)을 나타내는 모식도이다.FIG. 2 is a schematic diagram illustrating a process of arranging graphene oxide (or graphene, nano carbon tube) in a wet spinning method of graphene oxide (FIG. 2A) and a wet spinning process (FIG. 2B).
도 3은 Roll-to-roll 공정으로 제조 중인 그래핀산화물 젤 섬유와 탄소나노튜브 젤 섬유의 접합과정을 나타내는 사진이다.Figure 3 is a photograph showing the bonding process of the graphene oxide gel fibers and carbon nanotube gel fibers being manufactured by a roll-to-roll process.
도 4는 본 발명의 실시예 2에 따라 제조된 이종 접합구조를 가지는 그래핀산화물/탄소나노튜브 복합섬유의 광학현미경 사진이다.4 is an optical micrograph of a graphene oxide / carbon nanotube composite fiber having a heterojunction structure prepared according to Example 2 of the present invention.
도 5는 본 발명의 실시예 2에 따라 제조된 이종 접합구조를 가지는 그래핀산화물/탄소나노튜브 복합섬유 측면의 전자현미경 사진이다.5 is an electron micrograph of the side of the graphene oxide / carbon nanotube composite fiber having a heterojunction structure prepared according to Example 2 of the present invention.
도 6은 본 발명의 실시예 2에 따라 제조된 이종 접합구조를 가지는 그래핀산화물/탄소나노튜브 복합섬유 단면의 전자현미경 사진이다.6 is an electron micrograph of a cross section of a graphene oxide / carbon nanotube composite fiber having a heterojunction structure prepared according to Example 2 of the present invention.
본 발명자들은 그래핀산화물과 탄소나노튜브가 접합된 복합섬유 개발에 예의 노력한 결과, 그래핀산화물과 탄소나노튜브를 각각 습식 방사하여 얻어진 젤 섬유(gel fibers) 끼리 응집력이 발생하여, 젤 섬유화 상태에서 접합시키고, 수세 건조 후에도 접합상태가 그대로 유지되는 것을 확인하여 본 발명을 완성하였다.The present inventors earnestly endeavored to develop a composite fiber in which graphene oxide and carbon nanotubes were bonded, and as a result, the cohesive force between gel fibers obtained by wet spinning graphene oxide and carbon nanotubes, respectively, was generated. The present invention was completed by confirming that the bonded state was maintained as it was after bonding and washing with water.
본 발명에 있어 "이종 접합"은 서로 다른 성분이 상호 접합된 것을 의미한다.In the present invention, "heterojunction" means that different components are bonded to each other.
본 발명에 따른 이종 접합된 그래핀산화물/탄소나노튜브 복합섬유, 그래핀산화물/그래핀 복합섬유 또는 그래핀산화물/그래핀/탄소나노튜브 복합섬유 제조 방법은,The hetero-bonded graphene oxide / carbon nanotube composite fiber, graphene oxide / graphene composite fiber or graphene oxide / graphene / carbon nanotube composite fiber manufacturing method according to the present invention,
a) 그래핀산화물 분산액을 제1 응고성분을 포함하는 응고욕에 방사시켜 제1 젤 섬유를 제조하는 공정; 및a) preparing a first gel fiber by spinning the graphene oxide dispersion into a coagulation bath containing a first coagulation component; And
b) 탄소나노튜브 분산액 또는 그래핀 분산액 또는 이의 혼합 분산액을 제2 응고성분을 포함하는 응고욕에 방사시켜 제2 젤 섬유를 제조하는 공정이 동시에 이루어지고,b) simultaneously spinning the carbon nanotube dispersion or the graphene dispersion or a mixed dispersion thereof into a coagulation bath containing a second coagulation component to produce a second gel fiber;
c) 상기 동시 제조된 제1 젤 섬유와 제2 젤 섬유를 서로 접합하고, 수세, 건조하는 공정을 포함하여 이루어진다.c) bonding the first gel fiber and the second gel fiber, which are simultaneously manufactured, to each other, and washing with water and drying.
그래핀산화물(GO)의 습식 방사Wet Spinning of Graphene Oxide (GO)
본 발명에 있어서, 그래핀산화물(GO)은 화학적 박리법을 이용하여 제조된다.In the present invention, graphene oxide (GO) is prepared using a chemical exfoliation method.
그래핀산화물은 강산을 이용해 흑연을 산화시켜 그래핀 층간에 산소관능기가 도입된 팽창 산화흑연을 만들고, 용액 상에서 초음파분쇄나 급속가열을 하는 것으로 제조된다.Graphene oxide is prepared by oxidizing graphite using strong acid to produce expanded graphite oxide in which oxygen functional groups are introduced between graphene layers, and by ultrasonic pulverization or rapid heating on a solution.
Staudenmaier와 Hamdi는 황산/질산 혼합물을 이용하여 산화흑연을 제조하는 방법을 개시하고 있으나, 현재 대부분의 그래핀산화물은 농황산(fuming sulfuric acid)에 질산나트륨/염소산칼륨을 섞은 혼합물을 이용하여 흑연을 산화시키는 Hummers 방법 또는 이의 변형 방법을 주로 이용하여 제조된다.Staudenmaier and Hamdi disclose a process for producing graphite oxide using a sulfuric acid / nitric acid mixture, but most graphene oxides oxidize graphite using a mixture of fuming sulfuric acid and sodium nitrate / potassium chlorate. It is prepared using the Hummers method or a variant thereof.
그래핀산화물은 그래핀의 표면 또는/및 말단에 에폭시기, 하이드록시기, 말단에 카르복시기 또는 카르보닐기 등 다양한 산소관능기 그룹이 형성된 구조를 가진다.Graphene oxide has a structure in which various oxygen functional groups such as an epoxy group, a hydroxyl group, and a carboxyl group or a carbonyl group are formed at the surface or / and the terminal of the graphene.
상기 그래핀산화물은 절연체를 가지며, 산화 정도, 특성에 따라 낮은 전도성을 가지나, 그래핀 또는 탄소나노튜브에 비해서는 극히 미미한 수준이다.The graphene oxide has an insulator, and has a low conductivity depending on the degree of oxidation and characteristics, but is insignificant compared to graphene or carbon nanotubes.
본 발명에 따른 그래핀산화물은 기능성 물질이 부착된 그래핀산화물을 포함한다. 상기 기능성 물질은 예컨대, 바이오센서 분야에서 타겟물질의 검출을 위해 이용하는 다양한 감지물질이다. 상기 기능성 물질은 핵산, DNA, RNA, 압타머, 펩티드, 단백질, 항체, 성장인자, 효소, 형광물질, 소광물질, 생체분자, 기능성 고분자일 수 있다. 상기 기능성 물질은 그래핀산화물의 관능기와 결합되어 형성될 수 있다. 상기 감지물질이 타겟물질과 결합 또는 반응하면 전기적 신호 또는 형광(또는 소광)을 관찰함으로써 특정 핵산, 단백질, 성장인자와 같은 중요한 생체분자를 성공적으로 검출할 수 있게 된다. 상기 기능성 물질에 따른 전기적 신호는 본 발명에 따른 복합섬유의 전기전도성 물질인 그래핀, 탄소나노튜브를 통해 전달됨으로써 낮은 전기적 신호에도 불구하고 높은 검출력을 제공할 수 있다.Graphene oxide according to the present invention includes a graphene oxide to which a functional material is attached. The functional material is, for example, various sensing materials used for detection of a target material in the biosensor field. The functional material may be a nucleic acid, DNA, RNA, aptamer, peptide, protein, antibody, growth factor, enzyme, fluorescent material, quencher, biomolecule, functional polymer. The functional material may be formed in combination with a functional group of graphene oxide. When the detection material binds to or reacts with the target material, it is possible to successfully detect important biomolecules such as specific nucleic acids, proteins and growth factors by observing an electrical signal or fluorescence (or quenching). The electrical signal according to the functional material is provided through the graphene, carbon nanotubes of the conductive material of the composite fiber according to the present invention can provide a high detection force despite the low electrical signal.
한편, 본 발명에 따른 그래핀산화물은 화학적으로 개질된 그래핀산화물을 포함할 수 있다. 그래핀산화물의 화학적 개질은 예컨대, 유기 단분자들을 그래핀산화물의 산소관능기(에폭시기, 하이드록시기, 카르복시기 등)들과 반응시켜 제조될 수 있다. 아민기를 가지는 유기 단분자는 하기 반응식에 보이는 바와 같이 그래핀산화물의 에폭시기와 반응하여 유기 단분자가 그래핀산화물에 도입된다(Polymer(Korea), Vol. 35, No. 3, pp 265-271, 2011).On the other hand, the graphene oxide according to the present invention may include a chemically modified graphene oxide. Chemical modification of graphene oxide can be prepared, for example, by reacting organic monomolecules with oxygen functional groups (epoxy groups, hydroxyl groups, carboxyl groups, etc.) of graphene oxide. The organic monomolecule having an amine group reacts with the epoxy group of the graphene oxide to introduce the organic monomolecule into the graphene oxide as shown in the following reaction scheme ( Polymer (Korea), Vol. 35, No. 3, pp 265-271, 2011).
Figure PCTKR2017001239-appb-I000001
Figure PCTKR2017001239-appb-I000001
이소시아네이트로 기능기화된 그래핀산화물은 극성용매에서 분산성이 크게 향상되는 것으로 보고된다(S. Stankovich, R. D. Piner, S. T. Nguyen, and R. S. Ruoff, Carbon, 44, 3342 (2006)).Graphene oxides functionalized with isocyanates are reported to greatly improve dispersibility in polar solvents (S. Stankovich, R. D. Piner, S. T. Nguyen, and R. S. Ruoff, Carbon, 44, 3342 (2006)).
상기 그래핀산화물은 상기 산소관능기 그룹에 의해 극성, 친수성을 띠므로 물, 유기용매, 물/유기용매와 같은 극성용매에 잘 분산된다.Since the graphene oxide is polar and hydrophilic by the oxygen functional group, it is well dispersed in a polar solvent such as water, an organic solvent, and a water / organic solvent.
상기 그래핀산화물의 용매로는 증류수, 디메틸포름아미드, 메탄올, 에탄올, 에틸렌글리콜, n-부탄올, tert-부틸알코올, 이소프로필알코올, n-프로판올, 에틸아세테이트, 디메틸설폭사이드, 테트라하이드로퓨란 등이 이용될 수 있으나, 이 중에서 증류수 또는 증류수/유기용매가 바람직하다.Examples of the solvent for the graphene oxide include distilled water, dimethylformamide, methanol, ethanol, ethylene glycol, n-butanol, tert-butyl alcohol, isopropyl alcohol, n-propanol, ethyl acetate, dimethyl sulfoxide, tetrahydrofuran, and the like. Although it may be used, distilled water or distilled water / organic solvent is preferred.
그래핀산화물 농도는 방사용액 대비 1 ~ 20 mg/mL(0.1 ~ 2wt%)인 것이 바람직하나 이에 한정되지는 않는다.Graphene oxide concentration is preferably 1 ~ 20 mg / mL (0.1 ~ 2wt%) compared to the spinning solution, but is not limited thereto.
그래핀산화물 방사액은 통상의 습식 방사법에 따르고, 그래핀산화물의 응고성분(본 발명에서 제1 응고성분)은 CTAB, 키토산, CaCl2, NaOH, KOH 으로 구성된 군에서 선택될 수 있으나, 이에 한정되지는 않는다. Graphene oxide spinning solution according to the conventional wet spinning method, the coagulation component of the graphene oxide (first coagulation component in the present invention) may be selected from the group consisting of CTAB, chitosan, CaCl 2 , NaOH, KOH, but is not limited thereto It doesn't work.
상기 제1 응고성분 중에서 CTAB은 양이온성 계면활성제이나 그래핀산화물의 응고매로서 가장 널리 알려져 있다. CaCl2는 2가 이온(Ca2 +)에 의해 그래핀산화물이 서로 가교되어 응집되는 것을 알려져 있다(Adv. Mater.2013, 25, 188.). NaOH, KOH는 환원제로서 그래핀산화물의 환원을 통한 응집을 발생시키는 것으로 알려져 있다(Nat. Comm. 2011, 2, 571.). 키토산은 고분자전해질 착물화(polyelectrolyte complexation)에 의해 그래핀산화물을 응집하는 것으로 알려져 있다(Adv. Func. Mater.2013, 23, 5345.)Among the first coagulation components, CTAB is most widely known as a coagulant of a cationic surfactant or graphene oxide. It is known that CaCl 2 cross-links and aggregates graphene oxides by divalent ions (Ca 2+ ) ( Adv. Mater. 2013, 25, 188.). NaOH and KOH are known to cause aggregation through reduction of graphene oxide as a reducing agent ( Nat. Comm. 2011, 2, 571.). Chitosan is known to aggregate graphene oxide by polyelectrolyte complexation ( Adv. Func. Mater . 2013, 23, 5345.)
상기 제1 응고성분은 수용성을 띠며, 본 발명의 응고욕은 상기 제1 응고성분 을 증류수에 용해시켜 제조될 수 있다. 또한, 상기 제1 응고성분의 용매로는 디메틸포름아미드, 메탄올, 에탄올, 에틸렌글리콜, n-부탄올, tert-부틸알코올, 이소프로필알코올, n-프로판올, 에틸아세테이트, 디메틸설폭사이드, 테트라하이드로퓨란 등의 유기 용매가 이용될 수 있다. 본 발명에서 응고용 용매로는 증류수가 바람직하나 이에 제한되지는 않는다.The first coagulation component is water-soluble, and the coagulation bath of the present invention may be prepared by dissolving the first coagulation component in distilled water. In addition, as the solvent of the first coagulation component, dimethylformamide, methanol, ethanol, ethylene glycol, n-butanol, tert-butyl alcohol, isopropyl alcohol, n-propanol, ethyl acetate, dimethyl sulfoxide, tetrahydrofuran, etc. An organic solvent of may be used. Distilled water is preferred as the coagulation solvent in the present invention, but is not limited thereto.
상기 제1 응고성분의 응고액 농도는 그래핀산화물의 종래 습식 방사공정에서 공지된 응고욕 농도(함량wt%)에서 이용될 있다.The coagulant concentration of the first coagulation component may be used at a coagulation bath concentration (content wt%) known in the conventional wet spinning process of graphene oxide.
예를 들어, 응고욕에서 CTAB 농도는 0.03~0.1wt%, 바람직하게는 0.05wt%(0.5 mg/mL)이며, CaCl2, NaOH, KOH은 3~10wt%이나, 이에 제한되지는 않는다.For example, the CTAB concentration in the coagulation bath is 0.03 to 0.1 wt%, preferably 0.05 wt% (0.5 mg / mL), and CaCl 2 , NaOH, and KOH are 3-10 wt%, but are not limited thereto.
상기 그래핀산화물 분산액을 방사구금(방사노즐)을 통해 제1 응고성분을 포함하는 응고욕에 방사시키면 제1 응고성분이 방사용액에 서서히 침투, 용매 치환을 일으켜 방사용액이 부풀면서 섬유화(젤화)가 일어나면서 말랑말랑한 그래핀산화물 젤 섬유(본 발명에서 제1 젤 섬유)가 형성된다.When the graphene oxide dispersion is spun into a coagulation bath containing a first coagulation component through a spinneret (spinning nozzle), the first coagulation component gradually penetrates into the spinning solution, causing solvent substitution, thereby swelling the spinning solution and fibrosis (gelling). As it occurs, the soft graphene oxide gel fibers (the first gel fibers in the present invention) are formed.
그래핀(Graphene, rGO 포함)의 습식 방사Wet Spinning of Graphene (including Graphene, rGO)
본 발명에 따른 그래핀은 기계적 박리법, 화학기상증착법(CVD), 에피텍셜 성장법(Epitaxial Growth), 비산화 박리법(Nonoxidative Exfoliation) 등으로 제조될 수 있으나, 상술한 그래핀산화물을 고온열처리 또는 화학적으로 환원시켜 제조되는 환원된 그래핀산화물(rGO)을 이용하는 것이 바람직하다. 본 발명에 따른 그래핀으로는 화학적으로 개질된 그래핀(Chemically converted graphene, CCG), 화학적으로 개질된 환원 그래핀(rCCG)도 이용될 수 있다. 본 발명에 따른 그래핀은 환원된 그래핀산화물(rGO)인 것이 더욱 바람직하다.Graphene according to the present invention can be prepared by mechanical peeling, chemical vapor deposition (CVD), epitaxial growth (Epitaxial Growth), non-oxidative exfoliation (Nonoxidative Exfoliation), but the above-described graphene oxide at high temperature heat treatment Or it is preferable to use reduced graphene oxide (rGO) prepared by chemical reduction. As the graphene according to the present invention, chemically modified graphene (CCG) and chemically modified reduced graphene (rCCG) may also be used. More preferably, the graphene according to the present invention is reduced graphene oxide (rGO).
상기 환원공정에서 열처리, 화학적 환원처리는 이미 다양한 방법이 공지되어 있다. 그래핀산화물의 대표적 환원제로는 하이드라진, 소듐 하이드라진, 하이드라진 하이드레이트(hydrazine hydrate) 등의 하이드라진계, 하이드로퀴논(hydroquinone), 소듐 보로하이드라이드(NaBH4), 아스코빅산(ascorbic acid), 글루코스(glucose) 등이 이용될 수 있으나, 이에 제한되지는 않는다.Heat treatment and chemical reduction treatment in the reduction process is already known a variety of methods. Representative reducing agents of graphene oxide include hydrazine, sodium hydrazine and hydrazine hydrate such as hydrazine, hydroquinone, sodium borohydride (NaBH 4 ), ascorbic acid, and glucose (glucose). Etc. may be used, but is not limited thereto.
그래핀(또는 환원된 그래핀산화물)은 비극성 또는 매우 약한 극성, 소수성을 가지므로 계면활성제를 이용하여 용매에 분산시킨다. 상기 계면활성제로는 도데실벤젠설폰산나트륨(SDBS), 도데실설폰산나트륨(SDS), 리그노설폰산나트륨(SLS), 라우레스설폰산나트륨(SLES), 라우릴 에테르 설폰산나트륨(SLES), 미레스설폰산나트륨(Sodium myreth sulfate), 도데실설폰산리튬(LDS)의 친수성 설폰산기(SO3 -)를 가지는 음이온성 계면활성제, 또는 세틸트리메틸암모늄 브로마이드(CTAB), 세틸트리메틸암모늄클로라이드(CTAC), 세틸피리디늄클로라이드(CPC), 도데실트리메틸암모늄 브로마이드(DTAB), 테트라데실트리메틸암모늄 브로마이드(TTAB), 테트라트리메틸암모늄 브로마이드(TMB), 디옥타데실디메틸암모늄브로마이드(DODAB), 디메틸디옥타데실암모늄클로라이드(DODMAC)의 양이온 계면활성제, 또는 Tween 20, 40, 60, 80, Triton X-100, 글리세롤알킬에스테르(Glycerol alkyl esters), 글리세릴라우릴에스테르(Glyceryl laurate esters), 폴리에틸렌글리콜소르비탄알킬에스테르(Polyoxyethylene glycol sorbitan alkyl esters), 폴리에틸렌글리콜옥타데실에테르의 비이온성 계면활성제가 이용될 수 있다. 본 발명에서는 제한되지는 않으나 친수성 설폰산기(SO3 -)를 가지는 음이온성 계면활성제를 이용하여 수분산시키는 것이 바람직하다. 본 발명에 따른 그래핀을 효과적으로 분산하기 위하여 초음파 처리가 추가될 수 있다.Graphene (or reduced graphene oxide) has a nonpolar or very weak polarity and hydrophobicity, so it is dispersed in a solvent using a surfactant. The surfactant may be sodium dodecylbenzenesulfonate (SDBS), sodium dodecylsulfonate (SDS), sodium lignosulfonate (SLS), sodium laureth sulfonate (SLES), lauryl ether sodium sulfonate (SLES), Sodium myreth sulfate, anionic surfactant having hydrophilic sulfonic acid group (SO 3 − ) of lithium dodecyl sulfonate (LDS), or cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC) , Cetylpyridinium chloride (CPC), dodecyltrimethylammonium bromide (DTAB), tetradecyltrimethylammonium bromide (TTAB), tetratrimethylammonium bromide (TMB), dioctadecyldimethylammonium bromide (DODAB), dimethyldiooctadecylammonium Cationic surfactants of chloride (DODMAC), or Tween 20, 40, 60, 80, Triton X-100, glycerol alkyl esters, glyceryl laurate esters, Li a glycol sorbitan alkyl ester nonionic surfactant (Polyoxyethylene glycol sorbitan alkyl esters), polyethylene glycol octadecyl ether may be used. Although not limited in the present invention, it is preferable to disperse using an anionic surfactant having a hydrophilic sulfonic acid group (SO 3 − ). Sonication may be added to effectively disperse the graphene according to the present invention.
상기 그래핀 또는 그래핀산화물은 시트 조각 형태로 존재하는 데, "그래핀 플레이크"(Graphene flake), "그래핀 시트", "그래핀 결정"으로 지칭될 수 있다. 본 발명에 따른 그래핀 플레이크의 평균 직경은 수 μm 이상이고, 그래핀 또는 그래핀산화물의 층수가 3층 이하인 것이 바람직하다.The graphene or graphene oxide is present in the form of a sheet piece, and may be referred to as "graphene flake", "graphene sheet", or "graphene crystal". The average diameter of the graphene flakes according to the present invention is several μm or more, and the number of layers of graphene or graphene oxide is preferably three or less layers.
그래핀 농도는 방사용액 대비 1 ~ 20 mg/mL(0.1 ~ 2wt%)인 것이 바람직하나 이에 한정되지는 않는다.Graphene concentration is preferably 1 ~ 20 mg / mL (0.1 ~ 2wt%) compared to the spinning solution, but is not limited thereto.
본 발명에서 탄소나노튜브 분산액의 응고성분(본 발명에서 제2 응고성분)은 폴리비닐알코올(PVA), 폴리메틸메타아크릴레이트(PMMA), 폴리에틸렌이민(PEI), 폴리비닐필로리돈(PVP), 폴리에틸렌옥사이드(PEO)으로 이루어진 군에서 선택될 수 있으나 이에 한정되지는 않는다. 상기 PVA, PMMA, PEI, PVP, PEO는 2~40wt%, 바람직하게는 5~10wt%이나, 이에 제한되지는 않는다.In the present invention, the coagulation component (second coagulation component in the present invention) of the carbon nanotube dispersion is polyvinyl alcohol (PVA), polymethylmethacrylate (PMMA), polyethyleneimine (PEI), polyvinylpyrrolidone (PVP). It may be selected from the group consisting of polyethylene oxide (PEO), but is not limited thereto. The PVA, PMMA, PEI, PVP, PEO is 2 to 40 wt%, preferably 5 to 10 wt%, but is not limited thereto.
상기 그래핀 분산액을 방사구금(방사노즐)을 통해 제2 응고성분을 포함하는 응고욕에 방사시키면 제2 응고성분이 방사용액에 서서히 침투, 용매 치환을 일으켜 방사용액이 부풀면서 섬유화(젤화)가 일어나면서 말랑말랑한 그래핀 젤 섬유(본 발명에서 제2 젤 섬유)가 형성된다.When the graphene dispersion is spun into a coagulation bath containing a second coagulation component through a spinneret (spinning nozzle), the second coagulation component gradually penetrates into the spinning solution, causing solvent substitution, thereby swelling the spinning solution and fibrosis (gelling). As it occurs, the soft graphene gel fibers (second gel fibers in the present invention) are formed.
탄소나노튜브(Carbon-Nanotube, CNT)의 습식 방사Wet Spinning of Carbon-Nanotubes (CNTs)
본 발명에 있어서, 탄소나노튜브(CNT)는 단일벽 탄소나노튜브(SWNT, Single-walled CNT), 이중벽 탄소나노튜브(DWNT, Double-walled CNT), 다중벽 탄소나노튜브(MWNT, Multi-walled CNT)이 가능하나, 전기전도성과 기계적 특성을 고려하여 SWNT가 더욱 바람직하다. CNT는 화학기상증착법(CVD), 아크 방전법, 레이저 증발법 등 공지의 방법을 통해 제조될 수 있다.In the present invention, carbon nanotubes (CNT) are single-walled carbon nanotubes (SWNT, Single-walled CNT), double-walled carbon nanotubes (DWNT, Double-walled CNT), multi-walled carbon nanotubes (MWNT, Multi-walled) CNT) is possible, but SWNT is more preferable in consideration of electrical conductivity and mechanical properties. CNTs can be prepared by known methods such as chemical vapor deposition (CVD), arc discharge, laser evaporation, and the like.
탄소나노튜브는 비극성이며, CNT 측벽 상호에 강한 반데르발스력(van der Waals forces)을 가지므로 물과 같은 극성용매, 유기용매에는 잘 용해되거나 분산되지 않는다. 따라서 CNT의 효과적인 분산을 위해 계면활성제와 초음파를 이용하여 분산하는 것이 바람직하다.Carbon nanotubes are non-polar and have strong van der Waals forces on the CNT sidewalls, so they are not easily dissolved or dispersed in polar solvents such as water and organic solvents. Therefore, in order to effectively disperse CNTs, it is desirable to disperse them using a surfactant and ultrasonic waves.
상기 계면활성제로는 상술한 그래핀 분산을 위한 계면활성제들이 동일하게 이용될 수 있다.As the surfactant, the above-described surfactants for dispersing graphene may be used in the same manner.
상기 계면활성제 농도는 CNT 분산에 있어 중요하다. 계면활성제의 농도가 낮으면 분산 안정성이 떨어지고, 너무 높으면 삼투압은 depletion-induced aggregation을 일으킨다. 상기 분산액에서 CNT와 계면활성제의wt% 비율는 1:2~1:3 인 것이 바람직하나, 계면활성제의 종류에 따라 변동될 수 있다.The surfactant concentration is important for CNT dispersion. If the concentration of surfactant is low, dispersion stability is low. If it is too high, osmotic pressure causes depletion-induced aggregation. The wt% ratio of CNT and surfactant in the dispersion is preferably 1: 2 to 1: 3, but may vary depending on the type of surfactant.
CNT의 응고성분은 상기 그래핀의 응고성분과 동일하다(제2 응고성분).The coagulation component of CNT is the same as the coagulation component of the graphene (second coagulation component).
상기 제2 응고성분인 나노탄소튜브, 그래핀의 응고욕으로는 다양한 문헌에 공지되어 있다. Vigolo 등은 계면활성제(1.0wt% 도데실설폰산나트륨(SDS))를 이용하여 0.35wt% SWNT 분산액을 만든 다음, 5wt% 폴리비닐알코올(PVA)/증류수 응고욕에 방사시켜 탄소나노튜브 섬유를 최초로 제조하였다(Vigolo, B. et al. Macroscopic fibers and ribbons of oriented carbon nanotubes. Science 290, 1331-1334 (2000)).The coagulation bath of the nano-carbon tube, graphene as the second coagulation component is known in various documents. Vigolo et al. Prepared a 0.35 wt% SWNT dispersion with a surfactant (1.0 wt% sodium dodecyl sulfonate (SDS)) and then spun it into a 5 wt% polyvinyl alcohol (PVA) / distilled water coagulation bath to produce carbon nanotube fibers for the first time. (Vigolo, B. et al. Macroscopic fibers and ribbons of oriented carbon nanotubes. Science 290, 1331-1334 (2000)).
Munoz 등은 세틸트리메틸암모늄 브로마이드(CTAB), 도데실벤젠설폰산나트륨(SDBS), 도데실설폰산리튬(LDS)의 계면활성제를 이용하여 SWNT 분산액을 만든 다음, 폴리에틸렌이민(PEI)/증류수 응고욕에 방사시켜 SWNT/PEI 섬유를 제조하였다(Adv. Mater. 2005, 17, No.8, April 18). 제조된 SWNT/PEI 섬유는 SWNT/PVA 복합섬유에 비해 전기전도성이 100배 증가되는 것이 확인되었다.Munoz et al. Prepared SWNT dispersions using surfactants of cetyltrimethylammonium bromide (CTAB), sodium dodecylbenzenesulfonate (SDBS), and lithium dodecylsulfonate (LDS), followed by polyethyleneimine (PEI) / distilled water coagulation bath. Spinned to make SWNT / PEI fibers ( Adv. Mater . 2005, 17, No. 8, April 18). It was confirmed that the prepared SWNT / PEI fiber has increased electrical conductivity by 100 times compared to the SWNT / PVA composite fiber.
Winey 등은 폴리메틸메타크릴레이트(PMMA)을 응고매로 하는 CNT 복합필름 제조 방법을 개시하였다(Winey et al., Macromolecules, 2004, 37, 9048).Winey et al. Disclosed a method for producing CNT composite film using copolymethyl polymethyl methacrylate (PMMA) (Winey et al., Macromolecules , 2004, 37, 9048).
Smalley 등은 PVA/PVP을 응고매로 하는 CNT 복합필름 제조 방법을 개시하였다.Smalley et al. Disclosed a CNT composite film production method using PVA / PVP as a coagulant.
CNT의 농도는 방사용액 대비 1 ~ 30 mg/mL(0.1 ~ 3wt%)이 것이 바람직하난 이에 한정되지는 않는다. CNT 농도는 더욱 바람직하게는 3 ~ 20 mg/mL(0.1 ~ 2 wt%)이고, 가장 바람직하게는 5 ~ 10 mg/mL(0.5 ~ 1.0wt%)이다.The concentration of CNT is preferably 1 to 30 mg / mL (0.1 to 3 wt%) relative to the spinning solution, but is not limited thereto. The CNT concentration is more preferably 3 to 20 mg / mL (0.1 to 2 wt%), most preferably 5 to 10 mg / mL (0.5 to 1.0 wt%).
상기 CNT 분산액을 방사구금(방사노즐)을 통해 제2 응고성분을 포함하는 응고욕에 방사시키면 제2 응고성분이 방사용액에 서서히 침투, 용매 치환을 일으켜 방사용액이 부풀면서 섬유화(젤화)가 일어나면서 말랑말랑한 탄소나노튜브(CNT) 젤 섬유(본 발명에서 제2 젤 섬유)가 형성된다.When the CNT dispersion is spun into a coagulation bath containing a second coagulation component through a spinneret (spinning nozzle), the second coagulation component gradually penetrates into the spinning solution, causing solvent substitution, thereby causing the spinning solution to swell and fibrosis (gelling). While soft carbon nanotube (CNT) gel fibers (second gel fibers in the present invention) is formed.
탄소나노튜브/그래핀 혼합용액의 습식 방사Wet Spinning of Carbon Nanotube / Graphene Mixtures
본 발명에 있어서, 탄소나노튜브, 그래핀은 상술한 바와 같이 단독으로 습식 방사가 가능하나, 그래핀/탄소나노튜브의 혼합물을 방사용액으로 하여 습식 방사할 수 있다. 이때 혼합 방사액의 전체 농도는 0.1 ~ 2 wt%인 것이 바람직하다.In the present invention, carbon nanotubes and graphene may be wet spinning alone as described above, but may be wet spinning using a mixture of graphene / carbon nanotubes as a spinning solution. At this time, the total concentration of the mixed spinning solution is preferably 0.1 to 2 wt%.
본 발명에 따른 그래핀/탄소나노튜브 혼합 방사액은 그래핀과 탄소나노튜브,계면활성제를 물 또는 물/유기용매에 넣고 동시에 분산, 초음파 처리하여 제조될 수 있으나, 그래핀 분산액, 탄소나노튜브 분산액을 각각 제조한 후, 서로 혼합하는 것으로 제조될 수도 있다.The graphene / carbon nanotube mixed spinning solution according to the present invention may be prepared by dispersing and sonicating graphene, carbon nanotube, and surfactant in water or water / organic solvent at the same time, but the graphene dispersion liquid and carbon nanotube The dispersions may be prepared, respectively, and then mixed with each other.
상기 분산액은 방사용액으로 사용된다. 상기 방사용액의 농도는 분산액을 적절히 희석하는 것으로 제조될 수도 있다.The dispersion is used as a spinning solution. The concentration of the spinning solution may be prepared by appropriate dilution of the dispersion.
상기 그래핀/탄소나노튜브 혼합 분산액에서 그래핀:탄소나노튜브의 성분비는 4:1 ~ 1:4, 바람직하게는 3:2 ~ 2:3, 더욱 바람하게는 1:1이다.In the graphene / carbon nanotube mixed dispersion, the component ratio of graphene: carbon nanotubes is 4: 1 to 1: 4, preferably 3: 2 to 2: 3, more preferably 1: 1.
본 발명에서 탄소나노튜브/그래핀 혼합 분산액의 응고성분은 상기 제2 응고성분과 동일하다.In the present invention, the coagulation component of the carbon nanotube / graphene mixed dispersion is the same as the second coagulation component.
상기 제2 응고성분은 수용성을 띠며, 본 발명의 응고욕은 상기, 제1 응고성분 및 제2 응고성분을 증류수에 용해시켜 제조될 수 있다. 또한, 응고욕의 용매로는 디메틸포름아미드, 메탄올, 에탄올, 에틸렌글리콜, n-부탄올, tert-부틸알코올, 이소프로필알코올, n-프로판올, 에틸아세테이트, 디메틸설폭사이드, 테트라하이드로퓨란 등의 유기 용매가 이용될 수 있다. 본 발명에서 응고용 용매로는 증류수가 바람직하나 이에 제한되지는 않는다.The second coagulation component is water-soluble, and the coagulation bath of the present invention may be prepared by dissolving the first coagulation component and the second coagulation component in distilled water. As a solvent for the coagulation bath, organic solvents such as dimethylformamide, methanol, ethanol, ethylene glycol, n-butanol, tert-butyl alcohol, isopropyl alcohol, n-propanol, ethyl acetate, dimethyl sulfoxide and tetrahydrofuran Can be used. Distilled water is preferred as the coagulation solvent in the present invention, but is not limited thereto.
제1 젤 섬유와 제2 젤 섬유의 접합Bonding the First Gel Fiber and the Second Gel Fiber
상기 습식방사에 따라 제조된 제1 젤 섬유(그래핀산화물 젤 섬유), 제2 젤 섬유(그래핀 젤 섬유, 탄노나노튜브 젤 섬유 또는 탄소나노튜브/그래핀 젤 섬유)를 수세, 건조 공정에 앞서 서로 물리적으로 접합시키면, 젤 섬유간의 상호 작용으로 효과적인 접합이 이루어짐이 본 발명에서 확인되었다. 본 발명에 따른 접합 가능성은 현재까지 보고된 바 없다.The first gel fiber (graphene oxide gel fiber) and the second gel fiber (graphene gel fiber, tannonanotube gel fiber or carbon nanotube / graphene gel fiber) prepared according to the wet spinning are washed with water and dried. When physically bonded to each other previously, it was confirmed in the present invention that the effective bonding is achieved by the interaction between the gel fibers. The possibility of conjugation according to the invention has not been reported to date.
상기 제1 젤 섬유와 제2 젤 섬유의 접합은 사이드-바이-사이드(side-by-side) 형태나 쉬쓰-코어(sheath-core) 형태가 모두 가능하다.Bonding of the first gel fiber and the second gel fiber may be in a side-by-side form or a sheath-core form.
사이드-바이-사이드(side-by-side) 형태는 응고욕을 통과한 각 젤 섬유를 하나의 오목한 롤러(roller)에 수렴시켜 이들 섬유가 물리적으로 밀착되도록 하면, 제1 젤 섬유와 제2 젤 섬유의 상호 작용에 의하여 두 섬유는 평행한 형태로 접합된다.The side-by-side form converges each gel fiber that has passed through the coagulation bath into one concave roller so that the fibers are physically in close contact with the first gel fiber and the second gel. Due to the interaction of the fibers, the two fibers are joined in parallel form.
상기 사이드-바이-사이드(side-by-side) 형태의 변형예로는 제1 젤 섬유와 제2 젤 섬유가 꼬인 형태로 접합될 수도 있다. 이는 응고욕을 통과한 각 젤 섬유를 권취 방향에서 회전을 시키는 것으로 섬유를 서로 꼰 다음 롤러에 수렴시켜 접합시킨다.As a variation of the side-by-side shape, the first gel fiber and the second gel fiber may be bonded in a twisted shape. This is to rotate each of the gel fibers passed through the coagulation bath in the winding direction to twist the fibers together and then converge by joining the rollers.
상기 쉬쓰-코어(sheath-core) 형태는 코어쉘(core-shell) 이종 접합구조로서, 동축(coaxial) 케이블과 유사한 형태를 의미한다. 코어 물질은 상대적으로 구경이 작은 방사노즐을 사용하여 방사하고, 쉬쓰 물질은 납작한 형태의 노즐을 사용하여 리본 형태로 방사를 한 다음, 롤러 상에 수렴시키면 쉬쓰 섬유(리본 형태)이 코어 섬유를 감싸면서 접합됨으로서 이루어진다.The sheath-core shape is a core-shell heterojunction structure, and means a shape similar to a coaxial cable. The core material is spun using a relatively small diameter spinning nozzle, the sheath material is spun in a ribbon form using a flat nozzle, and then converged on a roller so that the sheath fiber (ribbon form) surrounds the core fiber. It is made by bonding.
상술한 바와 같이 제1 젤 섬유와 제2 섬유의 접합이 이루어지면 연신공정, 수세 공정, 건조 공정을 거침으로써 본 발명에 따른 그래핀산화물/탄소나노튜브 복합섬유, 그래핀산화물/그래핀 복합섬유 또는 그래핀산화물/그래핀/탄소나노튜브 복합섬유가 효과적으로 제조된다.As described above, when the first gel fiber and the second fiber are bonded, the graphene oxide / carbon nanotube composite fiber and the graphene oxide / graphene composite fiber according to the present invention are subjected to the stretching process, the washing process, and the drying process. Or graphene oxide / graphene / carbon nanotube composite fiber is effectively produced.
본 발명에 따른 복합섬유는 별도의 그래핀산화물의 환원공정 없이 전기전도 특성을 가진다. 따라서, 핵산, DNA, RNA, 압타머 등의 기능성 물질이 도입된 그래핀산화물을 사용하는 경우 이들 기능성 물질이 화학적, 열적 환원공정에 의해 파괴, 또는 분해되지 않으면서 전기전도의 특성을 가질 수 있게 한다.The composite fiber according to the present invention has electrical conductivity without a separate reduction process of graphene oxide. Therefore, in the case of using graphene oxides into which functional materials such as nucleic acids, DNA, RNA, and aptamer are introduced, these functional materials may have characteristics of electrical conductivity without being destroyed or degraded by chemical or thermal reduction processes. do.
다만, 본 발명의 그래핀산화물이 기능성 물질이 없는 경우에는 본 발명의 복합섬유는 공지의 열적 환원 방법 또는 화학적 환원 방법을 통해 추가 환원공정을 거칠 수 있다. 상기 열적 환원 방법은 제한되지는 않으나, 상온에서 200 ~ 1000 ℃로 0.1 ~ 10 ℃/분의 속도로 승온하여 이루어질 수 있다. 상기 화학적 환원 방법은 히드라진(hydrazine), 요오드화수소산(Hydroiodic acid), 브롬화수소산(hydrobromic acid), 수소화붕소나트륨(sodiumborohyride), 수소화리튬알루미늄(lithium aluminum hydride) 그리고 황산(surfuric acid) 등 공지의 환원제를 이용하여 이루어질 수 있다.However, when the graphene oxide of the present invention does not have a functional material, the composite fiber of the present invention may be subjected to further reduction through a known thermal reduction method or chemical reduction method. The thermal reduction method is not limited, but may be achieved by increasing the temperature at a rate of 0.1 to 10 ℃ / min from 200 to 1000 ℃ at room temperature. The chemical reduction method is a known reducing agent such as hydrazine, hydroiodic acid, hydrobromic acid, sodium borohydride, lithium aluminum hydride, and sulfuric acid. Can be made.
이하 실시예를 통하여 본 발명에 따른 이종 접합구조를 가지는 그래핀산화물/탄소나노튜브 복합섬유, 그래핀산화물/그래핀 복합섬유 또는 그래핀산화물/그래핀/탄소나노튜브 복합섬유 제조 방법을 상세히 설명한다.Hereinafter, the method for producing graphene oxide / carbon nanotube composite fiber, graphene oxide / graphene composite fiber or graphene oxide / graphene / carbon nanotube composite fiber according to the present invention will be described in detail through the following examples. do.
재료 준비Material preparation
그래핀산화물(GO) 분산액 제조Graphene Oxide (GO) Dispersion Preparation
흑연 플레이크 2.4 g을 과황산포타슘 2.0g, 오산화인 2.0g이 용해된 황산 10mL에 넣은 후 80℃에서 72시간 동안 반응시켰다. 상기 흑연을 희석시킨 후 진공 여과를 통해 수득한 후, 24시간동안 진공에서 상온 건조시킴으로써 팽창 흑연(expanded graphite)를 수득하였다. 수득된 팽창 흑연을 92mL의 황산에 분산시킨 후, 과망간산포타슘 12.0g을 녹여 35℃에서 2시간 30분동안 반응시킨 다음 증류수 1.0L를 전체 분산액의 온도가 45℃를 넘지 않도록 30분간 첨가한 후, 30% 과산화수소수 20mL를 첨가함으로써 반응을 종결시켰다. 상기 반응 혼합물을 10,000rpm의 속도로 10분간 원심분리시킨 후 1.0M 염산 수용액을 첨가하여 원심분리하는 과정을 3회 이상 반복하고, 물을 첨가하여 13,000rpm의 속도로 40분간 원심분리하는 과정을 5회 이상 반복하고, 건조하여 그래핀산화물을 수득하였다. 상기 수득된 그래핀산화물 1g을 증류수 200 mL에 넣고 용해하여 0.5wt% GO 수분산액을 수득하였다.2.4 g of graphite flakes were added to 10 mL of sulfuric acid in which 2.0 g of potassium persulfate and 2.0 g of phosphorus pentoxide were dissolved, followed by reacting at 80 ° C. for 72 hours. After diluting the graphite, obtained through vacuum filtration, expanded graphite was obtained by drying at room temperature in a vacuum for 24 hours. After the obtained expanded graphite was dispersed in 92 mL of sulfuric acid, 12.0 g of potassium permanganate was dissolved and reacted at 35 ° C. for 2 hours and 30 minutes, and then 1.0L of distilled water was added for 30 minutes so that the temperature of the entire dispersion liquid did not exceed 45 ° C., The reaction was terminated by adding 20 mL of 30% hydrogen peroxide water. After centrifuging the reaction mixture at a speed of 10,000 rpm for 10 minutes, the process of centrifugation was repeated three more times with the addition of 1.0M aqueous hydrochloric acid solution. Repeated more than once and dried to obtain a graphene oxide. 1 g of the obtained graphene oxide was added to 200 mL of distilled water and dissolved to obtain a 0.5 wt% GO aqueous dispersion.
그래핀(rGO) 분산액 제조Graphene (rGO) Dispersion Preparation
상기와 같이 방법으로 그래핀산화물 수분산액을 준비한 다음, 여기에 과량의 하이드라진을 넣고 80℃에서 2시간 동안 환원시켜 응집된 그래핀을 수득하였다. 상기 응집된 그래핀에 진한 황산을 첨가하여 180℃에서 12시간 동안 반응시켜 환원시키고, 수세, 건조 과정을 거쳐 환원된 그래핀산화물(rGO)를 얻었다. 증류수 100 mL에 상기 수득된 rGO 0.5g 및 도데실벤젠설폰산나트륨(SDBS) 0.25g을 넣고 30분간 초음파 처리를 하여 0.5wt% rGO 수분산액을 제조하였다.After preparing an aqueous graphene oxide dispersion in the same manner as described above, the excess hydrazine was added thereto and reduced at 80 ° C. for 2 hours to obtain aggregated graphene. Concentrated graphene was added to the concentrated sulfuric acid and reacted at 180 ° C. for 12 hours to reduce the concentration, and washed and dried to obtain a reduced graphene oxide (rGO). 0.5 g of the obtained rGO and 0.25 g of sodium dodecylbenzenesulfonate (SDBS) were added to 100 mL of distilled water and sonicated for 30 minutes to prepare a 0.5 wt% rGO aqueous dispersion.
탄소나노튜브(SWNT) 분산액 제조Carbon Nanotube (SWNT) Dispersion Preparation
증류수 100mL에 SWNT 0.5g 및 계면활성제 SDBS 0.25g을 넣고, 30분간 초음파 처리하여 0.5wt% SWNT 수분산액을 제조하였다.0.5 g of SWNT and 0.25 g of surfactant SDBS were added to 100 mL of distilled water and sonicated for 30 minutes to prepare a 0.5 wt% SWNT aqueous dispersion.
응고액 제조Coagulant preparation
증류수 2L에 CTAB 1g을 넣고 용해시켜 0.05wt% CTAB(제1 응고성분) 응고액을 제조하였다.1 g of CTAB was added and dissolved in 2 L of distilled water to prepare a 0.05 wt% CTAB (first coagulation component) coagulation solution.
증류수 2L에 PVA 111g을 넣고 용해시켜 5wt% PVA(제2 응고성분) 응고액을 제조하였다.111 g of PVA was added and dissolved in 2 L of distilled water to prepare a 5 wt% PVA (second coagulation component) coagulation solution.
실시예 1 : 그래핀산화물/탄소나노튜브 이종 접합구조의 복합섬유 제조Example 1 Preparation of Composite Fiber of Graphene Oxide / Carbon Nanotube Heterojunction
2개의 응고조를 준비하고, 한 곳에는 상기 제조된 0.05wt% CTAB 응고액을, 다른 한 곳에는 5wt% PVA 응고액을 넣어 2개의 응고욕을 만들고, 각 응고조에 내경 0.3 mm 방사노즐과 시린지를 위치시켰다.Prepare two coagulation baths, one at 0.05wt% CTAB coagulant and the other at 5wt% PVA coagulant to make two coagulation baths, and each coagulation bath with an internal diameter 0.3 mm spinning nozzle and syringe Was placed.
0.05wt% CTAB 응고욕의 시린지에는 상기 제조된 GO 수분산액을, 5wt% PVA 응고욕의 시린지에는 탄소나노튜브 수분산액을 넣고, 각각 1 mL/min 이하의 방사 속도를 유지하면서 각 응고욕에 회전 또는 선형으로 방사용액을 주입하여 그래핀산화물 젤 섬유(제1 젤 섬유)와 탄소나노튜브 젤 섬유(제2 젤 섬유)를 각각 동시에 제조하였다. 방사용액 주입 30분 후에 각각 제조된 도 3에 보이는 바와 같이 제1 젤 섬유와 제2 젤 섬유를 증류수 내에서 서로 꼬이도록 하면서 roll-to-roll 방식으로 그래핀산화물 섬유와 탄소나노튜브 섬유가 상호 접합된 젤 섬유를 제조하였다.In the syringe of 0.05 wt% CTAB coagulation bath, the aqueous dispersion of GO prepared above, and the carbon nanotube dispersion in syringe of 5 wt% PVA coagulation bath, were rotated in each coagulation bath while maintaining the spinning speed of 1 mL / min or less. Alternatively, the spinning solution was linearly injected to prepare graphene oxide gel fibers (first gel fibers) and carbon nanotube gel fibers (second gel fibers) simultaneously. As shown in FIG. 3 prepared 30 minutes after injection of the spinning solution, the graphene oxide fibers and the carbon nanotube fibers were mutually twisted in a roll-to-roll manner while twisting the first gel fibers and the second gel fibers in distilled water. Bonded gel fibers were prepared.
도 4는 상기 방법으로 제조된 그래핀산화물/탄소나노튜브 젤 섬유의 광학현미경 사진으로, 사이드-바이-사이드 형태로 양 섬유가 견고히 접합된 것을 확인할 수 있다.Figure 4 is an optical micrograph of the graphene oxide / carbon nanotube gel fiber prepared by the above method, it can be seen that both fibers are firmly bonded in a side-by-side form.
이후 연신 공정을 거친후 증류수 상에서 수세하고, 상온에서 24시간 건조시켜 그래핀산화물/탄소나노튜브가 접합된 복합섬유를 제조하였다.After the stretching process and washed with distilled water, and dried at room temperature for 24 hours to prepare a composite fiber bonded graphene oxide / carbon nanotubes.
도 5 및 6은 상기 실시예 1에 따라 제조된 이종 접합구조를 가지는 그래핀산화물/탄소나노튜브 복합섬유의 전자현미경 사진으로 도 5는 측면 사진, 도 6은 단면 사진이다.5 and 6 are electron micrographs of the graphene oxide / carbon nanotube composite fiber having a heterojunction structure prepared according to Example 1, Figure 5 is a side photograph, Figure 6 is a cross-sectional photograph.
도 5 및 도 6에 보이는 바와 같이, 그래핀산화물과 탄소나노튜브 섬유는 매우 견고하게 접합되었음을 확인할 수 있다.As shown in Figure 5 and 6, it can be confirmed that the graphene oxide and carbon nanotube fibers are very firmly bonded.
실시예 2 : 그래핀산화물/그래핀 이종 접합구조의 복합섬유 제조Example 2 Preparation of Composite Fiber of Graphene Oxide / Graphene Heterostructure
상기 실시예 1에서 탄소나노튜브 대신 그래핀 수분산액을 이용하여 동일한 방법으로 실시하여 그래핀산화물/그래핀 이종 접합구조의 복합섬유를 제조하였다.In Example 1 using the graphene aqueous dispersion instead of carbon nanotubes in the same manner to prepare a composite fiber of graphene oxide / graphene heterojunction structure.
그래핀은 0.5wt% 환원된 그래핀(rGO) 수분산액을 방사용액으로 하였으며, 응고성분은 탄소나노튜브와 동일하게 5wt% PVA(제2 응고성분)를 이용하였다.Graphene is a 0.5wt% reduced graphene (rGO) aqueous dispersion as a spinning solution, and the coagulation component was used 5wt% PVA (second coagulation component) the same as carbon nanotubes.
실시예 3 : 그래핀산화물 /(탄소나노튜브+ 그래핀 ) 이종 접합구조의 복합섬유 제조 Example 3 Preparation of Composite Fiber of Graphene Oxide / (Carbon Nanotube + Graphene ) Heterojunction
상기 제조된 탄소나노튜브 수분산액과 그래핀 수분산액을 혼합하여 탄소나노튜브/그래핀 수분산액을 만들고, 이를 방사용액으로 이용하여, 상기 실시예 1과 동일한 방법으로 그래핀산화물/(탄소나노튜브+그래핀) 이종 접합구조의 복합섬유를 제조하였다.The prepared carbon nanotube aqueous dispersion and the graphene aqueous dispersion are mixed to form a carbon nanotube / graphene aqueous dispersion, and using this as a spinning solution, graphene oxide / (carbon nanotube) in the same manner as in Example 1. + Graphene) to produce a composite fiber of a heterojunction structure.
본 발명은 이종 접합구조를 가지는 그래핀산화물/탄소나노튜브 복합섬유, 그래핀산화물/그래핀 복합섬유 또는 그래핀산화물/그래핀/탄소나노튜브 복합섬유를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing a graphene oxide / carbon nanotube composite fiber, graphene oxide / graphene composite fiber or graphene oxide / graphene / carbon nanotube composite fiber having a heterojunction structure.

Claims (9)

  1. a) 그래핀산화물 분산액을 제1 응고성분을 포함하는 응고욕에 방사시켜 제1 젤 섬유를 제조하는 공정; 및a) preparing a first gel fiber by spinning the graphene oxide dispersion into a coagulation bath containing a first coagulation component; And
    b) 탄소나노튜브 분산액 또는 그래핀 분산액 또는 이의 혼합 분산액을 제1 응고성분을 포함하는 응고욕에 방사시켜 제2 젤 섬유를 제조하는 공정이 동시에 이루어지고,b) spinning the carbon nanotube dispersion or graphene dispersion or a mixed dispersion thereof into a coagulation bath containing the first coagulation component to produce a second gel fiber at the same time,
    c) 상기 동시 제조된 제1 젤 섬유와 제2 젤 섬유를 서로 접합하고, 수세, 건조하는 것을 특징으로 하는,c) bonding the first gel fiber and the second gel fiber produced at the same time to each other, washed with water, and dried,
    이종 접합구조를 가지는 그래핀산화물/탄소나노튜브 복합섬유, 그래핀산화물/그래핀 복합섬유 또는 그래핀산화물/그래핀/탄소나노튜브 복합섬유의 제조 방법.Graphene oxide / carbon nanotube composite fiber, graphene oxide / graphene composite fiber or graphene oxide / graphene / carbon nanotube composite fiber having a heterojunction structure.
  2. 제1항에 있어서,The method of claim 1,
    상기 제1 응고성분은 CTAB, 키토산, CaCl2, NaOH, KOH 으로 구성된 군에서 선택되는 1종 이상인 것인, The first coagulation component is one or more selected from the group consisting of CTAB, chitosan, CaCl 2 , NaOH, KOH,
    이종 접합구조를 가지는 그래핀산화물/탄소나노튜브 복합섬유, 그래핀산화물/그래핀 복합섬유 또는 그래핀산화물/그래핀/탄소나노튜브 복합섬유의 제조 방법.Graphene oxide / carbon nanotube composite fiber, graphene oxide / graphene composite fiber or graphene oxide / graphene / carbon nanotube composite fiber having a heterojunction structure.
  3. 제1항에 있어서,The method of claim 1,
    상기 제2 응고성분은 폴리비닐알코올(PVA), 폴리메틸메타아크릴레이트(PMMA), 폴리에틸렌이민(PEI), 폴리비닐필로리돈(PVP), 폴리에틸렌옥사이드(PEO)으로 이루어진 군에서 선택되는 1종 이상인 것인,The second coagulation component is one selected from the group consisting of polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), polyethyleneimine (PEI), polyvinylpyrrolidone (PVP), polyethylene oxide (PEO) It is ideal
    이종 접합구조를 가지는 그래핀산화물/탄소나노튜브 복합섬유, 그래핀산화물/그래핀 복합섬유 또는 그래핀산화물/그래핀/탄소나노튜브 복합섬유의 제조 방법.Graphene oxide / carbon nanotube composite fiber, graphene oxide / graphene composite fiber or graphene oxide / graphene / carbon nanotube composite fiber having a heterojunction structure.
  4. 제1항에 있어서,The method of claim 1,
    제1 젤 섬유와 제2 젤 섬유이 접합된 형태는 사이드-바이-사이드(side-by-side)형인 것을 특징으로 하는, The first gel fibers and the second gel fibers are bonded to each other, characterized in that the side-by-side type,
    이종 접합구조를 가지는 그래핀산화물/탄소나노튜브 복합섬유, 그래핀산화물/그래핀 복합섬유 또는 그래핀산화물/그래핀/탄소나노튜브 복합섬유의 제조 방법.Graphene oxide / carbon nanotube composite fiber, graphene oxide / graphene composite fiber or graphene oxide / graphene / carbon nanotube composite fiber having a heterojunction structure.
  5. 제1항에 있어서,The method of claim 1,
    제1 젤 섬유와 제2 젤 섬유이 접합된 형태는 사이드-바이-사이드(side-by-side)형으로 꼬임을 가지는 것을 특징으로 하는, The first gel fibers and the second gel fibers are bonded to each other, the side-by-side (side-by-side) characterized in that the twisted,
    이종 접합구조를 가지는 그래핀산화물/탄소나노튜브 복합섬유, 그래핀산화물/그래핀 복합섬유 또는 그래핀산화물/그래핀/탄소나노튜브 복합섬유의 제조 방법.Graphene oxide / carbon nanotube composite fiber, graphene oxide / graphene composite fiber or graphene oxide / graphene / carbon nanotube composite fiber having a heterojunction structure.
  6. 제1항에 있어서,The method of claim 1,
    제1 젤 섬유와 제2 젤 섬유이 접합된 형태는 쉬쓰-코어(sheath-core)형인 것을 특징으로 하는, The first gel fibers and the second gel fibers are bonded to each other, characterized in that the sheath-core type,
    이종 접합구조를 가지는 그래핀산화물/탄소나노튜브 복합섬유, 그래핀산화물/그래핀 복합섬유 또는 그래핀산화물/그래핀/탄소나노튜브 복합섬유의 제조 방법.Graphene oxide / carbon nanotube composite fiber, graphene oxide / graphene composite fiber or graphene oxide / graphene / carbon nanotube composite fiber having a heterojunction structure.
  7. 제1항에 있어서,The method of claim 1,
    상기 그래핀산화물은 타겟물질 검출능을 가지는 기능성 물질이 도입된 그래핀산화물인 것을 특징으로 하는,The graphene oxide is characterized in that the graphene oxide introduced with a functional material having a target material detection ability,
    이종 접합구조를 가지는 그래핀산화물/탄소나노튜브 복합섬유, 그래핀산화물/그래핀 복합섬유 또는 그래핀산화물/그래핀/탄소나노튜브 복합섬유 제조 방법.Graphene oxide / carbon nanotube composite fiber, graphene oxide / graphene composite fiber or graphene oxide / graphene / carbon nanotube composite fiber having a heterojunction structure.
  8. 제7항에 있어서,The method of claim 7, wherein
    상기 기능성 물질은 핵산, DNA, RNA, 압타머, 펩티드, 단백질, 항체, 성장인자, 효소, 형광물질, 소광물질인 것을 특징으로 하는,The functional material is a nucleic acid, DNA, RNA, aptamers, peptides, proteins, antibodies, growth factors, enzymes, fluorescent material, characterized in that the quencher,
    이종 접합구조를 가지는 그래핀산화물/탄소나노튜브 복합섬유, 그래핀산화물/그래핀 복합섬유 또는 그래핀산화물/그래핀/탄소나노튜브 복합섬유 제조 방법.Graphene oxide / carbon nanotube composite fiber, graphene oxide / graphene composite fiber or graphene oxide / graphene / carbon nanotube composite fiber having a heterojunction structure.
  9. 제1항에 있어서,The method of claim 1,
    상기 건조된 복합섬유를 화학적 또는 열적 환원시키는 단계를 더 포함하는 것을 특징으로 하는,Further comprising the step of chemically or thermally reducing the dried composite fiber,
    이종 접합구조를 가지는 그래핀산화물/탄소나노튜브 복합섬유, 그래핀산화물/그래핀 복합섬유 또는 그래핀산화물/그래핀/탄소나노튜브 복합섬유 제조 방법.Graphene oxide / carbon nanotube composite fiber, graphene oxide / graphene composite fiber or graphene oxide / graphene / carbon nanotube composite fiber having a heterojunction structure.
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