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WO2018004099A1 - Fibre composite d'oxyde de graphène/de nanotube de carbone ayant une structure à hétérojonction, et procédé de fabrication de fibre composite d'oxyde de graphène/de graphène ou fibre composite d'oxyde de graphène/de graphène/de nanotube de carbone - Google Patents

Fibre composite d'oxyde de graphène/de nanotube de carbone ayant une structure à hétérojonction, et procédé de fabrication de fibre composite d'oxyde de graphène/de graphène ou fibre composite d'oxyde de graphène/de graphène/de nanotube de carbone 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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Prior art keywords
graphene
graphene oxide
composite fiber
carbon nanotube
nanotube composite
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Korean (ko)
Inventor
박상윤
신민균
김혁준
여창수
조윤제
조강래
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PURITECH CO Ltd
Advanced Institute of Convergence Technology AICT
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PURITECH CO Ltd
Advanced Institute of Convergence Technology AICT
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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, LIGHT-SENSITIVE OR TEMPERATURE-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.

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Abstract

La présente invention concerne : une fibre composite d'oxyde de graphène/de nanotube de carbone ayant une structure à hétérojonction; et un procédé de fabrication d'une fibre composite d'oxyde de graphène/de graphène ou d'une fibre composite d'oxyde de graphène/de graphène/de nanotube de carbone, comprenant : a) une étape de préparation d'une première fibre de gel par filage d'une solution de dispersion d'oxyde de graphène dans un bain de coagulation contenant un premier élément de coagulation et b) une étape de préparation d'une seconde fibre de gel par filage d'une solution de dispersion de nanotubes de carbone, d'une solution de dispersion de graphène, ou d'une solution de dispersion de leur mélange dans un bain de coagulation contenant un premier élément de coagulation, les étapes étant effectuées simultanément; et c) l'assemblage, le lavage et le séchage de la première fibre de gel et de la seconde fibre de gel préparées simultanément.
PCT/KR2017/001239 2016-06-27 2017-02-04 Fibre composite d'oxyde de graphène/de nanotube de carbone ayant une structure à hétérojonction, et procédé de fabrication de fibre composite d'oxyde de graphène/de graphène ou fibre composite d'oxyde de graphène/de graphène/de nanotube de carbone Ceased WO2018004099A1 (fr)

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